1 STRUCTURE-REACTIVITY PRINCIPLES OF SODIUM HEXAMETHYLDISILAZIDE AND SODIUM ALKYL(TRIMETHYLSILYL)AMIDES A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Qiulin You August 2024 2 STRUCTURE-REACTIVITY PRINCIPLES OF SODIUM HEXAMETHYLDISILAZIDE AND SODIUM ALKYL(TRIMETHYLSILYL)AMIDES Qiulin You, Ph. D. Cornell University 2024 The solvent-dependent reactivity of sodium hexamethyldisilazide (NaHMDS) toward carbon-centered electrophiles reveals reactions that are poorly represented or unrepresented in the literature including direct aminolysis of aromatic methyl esters to give carboxamides, nitriles, or amidines, depending on the choice of solvent. SNAr substitutions of aryl halides and terminal epoxides are also examined. A combination of 1H and 29Si NMR spectroscopic studies using [15N]NaHMDS, kinetic studies, and computational studies reveal the complex mechanistic basis of the preference for simple aryl carboxamides in toluene and dimethylethylamine promote and arylnitriles or amidines in THF. A prevalence of dimer- and mixed dimer-based chemistry even from the observable NaHMDS monomer in THF solution is notable. Following extensive studies on sodium hexamethyldisilazide (NaHMDS), the solution structures and reactivity of sodium isopropyl(trimethylsilyl)amide (NaPTA), sodium (2-phenylethyl)amide (NaPETA), sodium tert- butyl(trimethylsilyl)amide (NaBTA), and their isotopomers [15N]NaBTA have been investigated. Solution structural studies using a combination of 29Si NMR spectroscopy, the Method of Continuous Variations (MCV), and density functional theory (DFT) computations provided insights into aggregation and solvation in a range of solvents including toluene, N,N-dimethylethylamine, triethylamine, MTBE, THF, dimethoxyethane (DME), diglyme, N,N,N’,N’- 3 tetramethylethylenediamine (TMEDA), N,N,N’,N’-tetramethylcyclohexanediamine (TMCDA), N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (PMDTA), 12-crown-4, 15-crown-5, and 18-crown-6 revealed solvent- and substituent-dependent dimer- monomer mixtures with affiliated solvation numbers. Complexation of the three crown ethers documented both crown and substituent dependencies. Qualitative studies of reactivity showed a variety of reactions of NaPETA. Aminolysis of methyl benzoate with dialkylamines mediated by NaPTA afforded high yields of benzamides. Quantitative rate studies of aminolysis of methyl benzoate by NaPTA revealed a 47,000-old range of rates. Detailed rate studies in toluene and THF showed dimer-based mechanisms. The role of primary- and secondary-shell solvation by THF is discussed, including nuances of methods used to separate the two contributions. PMDTA-solvated NaPTA monomer reacts as a monomer whereas bis-diglyme solvated monomer reacts as a dimer. Rate studies exploring the structure-reactivity correlations of the three crown ethers show mono- and bis- crown-based pathways in which 15-crown-5—the crown ether often said to be of choice for sodium—was decidedly inferior as an accelerant. 4 BIOGRAPHICAL SKETCH The author was born on October 5th, 1996 in Chengdu, China. After completing his secondary education at Chengdu No. 7 High School, he attended Sichuan University. Under the guidance of Professor Jingbo Lan, he studied organic synthesis utilizing transition metal catalyzed C–H activation. The author received his B.S. in Chemistry after defending his thesis in June 2019. Later in 2019 he began his graduate career at Cornell University where he joined the laboratory of Professor David B. Collum. His graduate work focused on structural, kinetic and reactivity of sodium hexamethyldisilazide and sodium alkyl(trimethylsilyl)amides. The author received an M.S. in July 2021 and Ph.D. in July 2024. 5 STRUCTURE-REACTIVITY PRINCIPLES OF SODIUM HEXAMETHYLDISILAZIDE AND SODIUM ALKYL(TRIMETHYLSILYL)AMIDES The work is dedicated for my parents, Jinsong You and Jinsong Qiu For the unconditional support during my Ph.D. career 6 ACKNOWLEDGEMENTS I will begin the acknowledgements with my sincere gratitude to Professor David B. Collum for his continuous support during my Ph. D. research. He supported me academically with his rich knowledge in organic synthesis, brilliant ideas on kinetics and structural studies. His guidance helped me become a better scientist and improve my personality. I appreciate all his efforts in coaching me in organic chemistry. I could not do better in any other lab for my graduate study. I would also like to express my gratitude to my special committee, Prof. Song Lin and Prof. Tristan Lambert for their encouragements and helpful advice. I would like to express my deepest gratitude to my committee members for their invaluable guidance and support throughout my research. Additionally, I extend my heartfelt thanks to the members of the Collum group for providing a pleasant environment, helpful training, and insightful discussions that greatly contributed to my growth as a researcher. Special thanks go to Dr. Ma Yun, a specialist in synthetic organic chemistry, who taught me unique knowledge and skills that are not widely known but extraordinarily useful. I am grateful to Dr. Ryan Woltornist, who worked with me for a year before graduating; he introduced me to the basic lab procedures and provided helpful advice on conducting research. I would also like to thank Dr. Jessy Spivey, who joined the lab in the same year as I did and offered valuable guidance for my research. Lastly, I am deeply indebted to Dr. Nathan Lui, with whom I worked closely for over three years. He not only taught me fundamental lab skills hands-on but also guided me through computational techniques essential to my work. My research would not have been possible without his assistance and mentorship. The facilities staff, administrative support, and remainder of the faculty in the department of Chemistry and Chemical Biology at Cornell University supplied 7 valuable assistance during my graduate study. The NMR Staff, Dr. Ivan Keresztes, was remarkably helpful with experimental design, structural deconvolution and technical trouble shooting. His assistance was crucial to the completion of my work. I cannot recall how many times I sought his help to analyze concepts I did not understand. His guidance and patience have been invaluable throughout my research. Finally, I would like to acknowledge my parents, Jinsong You and Jinsong Qiu. They have shown continuous encouragement and love to me. 8 TABLE OF CONTENTS Biological Sketch 4 Dedication 5 Acknowledgements 6 Table of Contents 8 Chapter 1 Carbon-Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms 9 Chapter 1 Appendix 53 Chapter 1 References and Footnotes 431 Chapter 2 Sodium Alkyl(trimethylsilyl)amides: Substituent- and Solvent-Dependent Solution Structures and Reactivities 445 Chapter 2 Appendix 516 Chapter 2 References and Footnotes 787 Chapter 2 DFT Cartesian Coordinates 809 9 CHAPTER 1 CARBON-NITROGEN BOND FORMATION USING SODIUM HEXAMETHYLDISILAZIDE: SOLVENT-DEPENDENT REACTIVITIES AND MECHANISMS 10 Carbon-Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms Abstract The solvent-dependent reactivity of sodium hexamethyldisilazide (NaHMDS) toward carbon-centered electrophiles reveals reactions that are poorly represented or unrepresented in the literature including direct aminolysis of aromatic methyl esters to give carboxamides, nitriles, or amidines, depending on the choice of solvent. SNAr substitutions of aryl halides and terminal epoxides are also examined. A combination of 1H and 29Si NMR spectroscopic studies using [15N]NaHMDS, kinetic studies, and computational studies reveal the complex mechanistic basis of the preference for simple aryl carboxamides in toluene and dimethylethylamine promote and arylnitriles or amidines in THF. A prevalence of dimer- and mixed dimer-based chemistry even from the observable NaHMDS monomer in THF solution is notable. Introduction After decades of communal disinterest in organosodium chemistry, we began trying to shine a light on its potential by expanding the toolbox for generating and using organosodium species.1–3 This involved some minor adjustments to protocols for generating and handling sodium diisopropylamide (NaDA) 2,3 as well as developing a new reagent, sodium isopropyl(trimethyl)silyl amide (NaPTA), that manifests desirable solubilities and reactivities as a strong base.4 Our primary approach, however, is decidedly structural and mechanistic with the faith that understanding how solvation and aggregation influence reactivity and selectivity will propel applications through a combination of serendipity in our lab and need- driven progress by others. Even the most prominent organosodium reagent, sodium 11 hexamethyldisilazide (NaHMDS),5 while garnering the attention of crystallographers,6 had evaded spectroscopic, mechanistic, and computational scrutiny until recent studies of solvent-dependent structure and reactivity toward enolization.7 This brings us to the current work. Aminolyses illustrated with generic examples in Scheme 1.1 are legion. SNAr substitutions and peptide bond formations are of unquestioned importance in pharmaceutical chemistry.8,9 With that said, any reaction in which the electrophile is merely heated in ammonia or simple alkylamine will be difficult to improve upon. However, should these simple protocols fail, whether owing to low reactivity or poor selectivity, the experimentalist is left with few options. In these instances, metal amides could offer solutions through control of their coordination spheres. Scheme 1.1. Generic aminolyses We describe herein a survey of the reactivity of NaHMDS toward carbon- centered electrophiles of potential interest in synthesis accompanied by detailed structural and mechanistic studies. NaHMDS plays the role of a highly reactive analog of ammonia and a preface to expanding investigations of sodium alkylsilazides.4 Some of the transformations surveyed as opportunities for E X CONHR X RNH2 RNH2 E = CO2Me E NHR E = O X NHR OH 12 mechanistic studies piqued our interest as synthetically promising have surprisingly little or no presence in the NaHMDS literature. The more mechanistically inclined will find the prevalence of dimer- and mixed aggregate- based reactivity surprising.10 We also inadvertently stumbled into the complex world of organosilicon chemistry. Results and Discussion Aminolyses. Substitutions of representative organic substrates by NaHMDS are summarized in Table 1. The yields are of isolated, purified products that have been desilylated during workup. 1H and 29Si NMR spectroscopic monitoring (vide infra) shows the reactions are often pristine and reveals unisolated silylated and sodiated intermediates. The times and temperatures listed in Table 1 are those required to achieve high conversion as confirmed by in situ monitoring using NMR or IR spectroscopies. Table 1.1. Reactions of NaHMDS with electrophiles in various solvents. entry substrate conditions product yield 1 1 2.0 equiv NaHMDS 25 oC, 5 h toluene 2 72% 2 3 3.0 equiv NaHMDS 25 oC, 0.3 h DMEA 4 95% Ph OMe O Ph NH2 O N O OMe N O NH2 13 3 5 3.0 equiv NaHMDS 25 oC, 0.3 h toluene 4 90% 4 3 1.0 equiv NaHMDS 50 oC, 1.0 h THF 6 86% 5 3 3.0 equiv NaHMDS 50 oC, 0.3 h THF 7 92% 6 8 3.0 equiv NaHMDS 70 oC, 0.3 h toluenea 9 85% 7 8 3.0 equiv NaHMDS 70 oC, 1.0 h THF 10 96% 8 11 2.0 equiv NaHMDS 70 oC, 1.0 h toluene 12 76% 9 3.0 equiv NaHMDS 95% N O OEt N O NH2 N O OMe N CN N O OMe N NH NH2 N O OMe N O NH2 N O OMe N NH NH2 N O OMe N O NH2 N O OMe N NH NH2 14 11 70 oC, 1.0 h THF 13 10 14 3 equiv NaHMDS 50 oC, 1 h DMEA 15 78% 11 14 3.0 equiv NaHMDS/ THF 70 oC, 2.0 h 25 °C, 24 h 16 92% 12 17 2.0 equiv NaHMDS 25 °C, 0.05 h DMEA 16 95% 13 18 2.0 equiv NaHMDS 25 °C, 2 h toluene 19 85% 14 20 2.0 equiv NaHMDS 25 oC, 1.0 h toluene 21 77% O OMe O NH2 O OMe NH NH2 CN NH NH2 NO2 F NO2 NH2 NO2 F Cl NO2 NH2 Cl 15 a Forms a gel-like mixture during the reaction. For context, the aminolysis of methyl cinnamate to form carboxamide (entry 1) rather than alternatives such as 1,4-addition,11,12 enolization,5 or generalized destruction caught our attention. Ester aminolyses by LiHMDS and NaHMDS may populate pharmaceutical notebooks, but they are poorly represented in the 15 22 2.0 equiv NaHMDS 25 oC, 1.0 h toluene 23 83% 16 24 2.0 equiv NaHMDS 110 °C, 2 h toluene 25 55% 17 26 2.0 equiv NaHMDS 110 oC, 3 h toluene 27 76% 18 28 2 equiv NaHMDS 60 oC, 24 h toluene (>50:1) 29 86% 19 30 2 equiv NaHMDS 25 oC, 24 h THF 31 76% NO2 F F NO2 NH2 F N F N NH2 N FF NF NH2 Ph O Ph NH2 OH n-C6H13 O NH2 OH n-C6H13 16 published literature. In 1963, Kruger et al. aminolyzed an aryl ester with NaHMDS to form an O-methyloximino ether, an intermediate en route to carboxamides (as in entry 2) detected in mechanistic studies below.13 In 1998, Hwu and coworkers reported a NaHMDS-mediated conversion of aryl esters to nitriles with NaHMDS at 110–185 °C (as in entry 4), attributing a central importance to phenolic groups.14 One-pot conversions of aryl esters to amidines or carboxamides by NaHMDS are unreported. Additions to nitriles to form amidinates (as in entry 12) are well known for LiHMDS.15 Mechanistic studies below offer some thoughts on why analogous additions of NaHMDS to nitriles are rare.16 The potentially useful selectivities for the formation of carboxamides, nitriles, and amidines directly from esters have complex mechanistic underpinnings dependent on solvent, temperature, and equivalents of NaHMDS (vide infra). The 3- and 4-picoline methyl esters form gels in weak solvents (entries 9 and 11), presumably owing to head-to-tail oligomeric substrate-NaHMDS dimer complexes but without negative consequences. SNAr reactions (entries 15–19) represent a reaction class of unquestioned importance.8 We find it somewhat confounding that SNAr reactions seem to be more effective with soft nucleophiles. Malonates, for example, are far superior nucleophiles17 than unstabilized enolates.18 We can find only one report of direct (uncatalyzed) SNAr substitution by LiHMDS19 and none for NaHMDS, while RNH2-based aminolyses facilitated by LiHMDS are legion albeit with an unknown role of the LiHMDS.20 We expended considerable effort trying to glean mechanistic insights (entry 15–17) only to be thwarted by deeply colored debris that appears to be diazo derivatives arising from NaHMDS reacting with the nitro moiety noted years ago (eq 1).21 Nitroarenes are spartan in the voluminous literature of lithium amide-mediated ortholithiations,22 possibly for similar reasons. 17 A few problematic substrates are illustrated in Chart 1. Arenes 1–3 gave complex products suggestive of orthometalations and possibly pyridyne intermediates. Halopyridines (35,36) and chloroisoquinoline 37 aminated but were prone to transfer a silyl group to the 3-position by a Fries-like process.23 Nitrobenzene 38 underwent a clean halogen dance,24 forming 2-fluoro-3- iodonitrobenzene.25 Chart 1.1. Failed and troublesome substrates We replicated the highly regioselective epoxide openings reported by Withnall and coworkers in 200826 (entries 20 and 21) to evaluate them as candidates for mechanistic work and include their potentially useful results have gone largely unnoticed.27 To assist the reader, Scheme 1.2 represents a roadmap to what is forthcoming in the following mechanistic studies. We explore the reaction coordinates to convert NaHMDS and methyl picolinate 3 to carboxamide 4 in NO2 N N O NaHMDS (1) N F(H) F N Cl N X N N ClCl NO2 FF 32 37 33 34 35 X = Cl 36 X = Br F 38 I NO2 18 DMEA (Part 1), to nitrile 6 in THF (Part 2), and conversion of nitrile 6 to amidine 7 in DMEA (Part 3) and THF (Part 4). Each part delves into the underlying organosodium and organosilicon chemistry by examining spectroscopically observable structural events, kinetic studies to evaluate solvation and aggregation in the rate-limiting transition structures,28 and computational probes of solvation, aggregation, critical transition structures, and elusive details along the reaction coordinates.29,30 Scheme 1.2. Focus of the four studies examined spectroscopically, kinetically, and computationally. Monitoring the reactions by 1H and 29Si NMR spectroscopies showed the reactions to be very clean and provided detailed structural assignments. [15N]NaHMDS7 distinguished O–Si and 15N–Si species owing to 15N–29Si coupling whereas combinations of [15N]NaHMDS and NaHMDS were exploited to examine reversible steps. DFT computations exploiting Me3N in place of Me2NEt to reduce unnecessary degrees of freedom revealed an exothermic substitution of DMEA on dimer 39. We take the liberty of using the original numbers assigned to DMEA 3 N N 6 Part 1 NaHMDS DMEA N O NH2 4 Part 2 NaHMDS THF N NH NH2 7 Part 4 NaHMDS THF N O OMe Part 3 NaHMDS DMEA 19 solvates in the schemes showing Me3N solvates. The shorthand of general form A- mSn alludes to the hexamethyldisilazide fragment (A) and solvent (S). Part 1: Mechanism of aminolysis of methyl-2-picolinate (3) with NaHMDS/DMEA. We focused structure-reactivity studies on additions to methyl- 2-picolinate in DMEA and THF. Toluene acts similarly to DMEA but affords broader resonances. The reaction coordinate for the addition of NaHMDS to picoline 3 in DMEA observable by NMR spectroscopy is summarized Scheme 1.3. Mono- and dichelated dimers 40 and 41 observable at –80 °C reflect the behavior of NaHMDS with other bifunctional ligands studied previously.7 Both dimers display coupling constants (1JN-Si = 8.5 and 8.7 Hz, respectively) and chemical shifts (–15.8 and –16.4 ppm, respectively) characteristic of [15N]NaHMDS dimers.7 Addition of excess 3 affords computationally doubly chelated monomer 42 with an upfield 29Si chemical shift and large coupling constant (–21.41 ppm, 1JN-Si = 13.1 Hz) characteristic of a NaHMDS monomer.7 Rate studies (below) place dimer 40 on the reaction coordinate. The stability of 43 allows carboxamide 431 to be isolated in high yield (Table 1, entry 5).32 Scheme 1.3. Spectroscopically observed species on the reaction of methyl-2- picolinate with NaHMDS/DMEA.33 20 The computed structure of 40 (Figure 1.1) reveals a geometry that more closely approximates square planar than tetrahedral sodium. Serial substitution from 39 to 41 is computed to be mildly exothermic for both steps (ignoring translational entropy).34 DFT supports monomer stereoisomer 42 with the alternative stereoisomeric monomer (not drawn) to be 10.4 kcal/mol less stable. N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt N OMe O 40 N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt 39 3 N Na NaMe3Si Me3Si Me2NEt N SiMe3 —Me3SiOMe O N N Na N Na SiMe3Me3Si SiMe3Me3Si N OMe O 3 N MeO O 41 3 N Me3Si Me3Si N O Na O N OMe OMe 25 °C 15 min N O NH2 4 43 42 Workup N O OMe 21 Figure 1.1. Ball and stick depictions of DFT-computed dimer 40 displaying an approximate 10° rotation of the chelate and Na2N2 planes from coplanarity. The only observable species during the aminolysis in DMEA are mixed aggregate 43 (Figure 1.2A) and Me3SiOMe with the latter confirmed by comparison with an authentic sample (29Si, δ 17.49 ppm). Two 29Si resonances of 43 at –16.0 ppm (1JN-Si = 9.7 Hz) and –16.6 ppm (1JN-Si = 10.3 Hz) are similar to [15N]NaHMDS dimer 39 (–15.2 ppm, JN-Si = 8.5 Hz) and coalesce into a single broad resonance at –20 °C. The imino 29Si resonance is markedly downfield (–9.70 ppm, JN-Si = 11.2 Hz). Addition of excess unlabelled NaHMDS to pre-formed [15N2]43 at –80 °C shows immediate incorporation of unlabelled silazide fragments (Figure 1.2B). DFT computations illustrate the magnetic inequivalence of the two silazide-derived Me3Si moieties in 43 (Figure 1.3). Figure 1.2. Spectrum A is 29Si NMR spectrum of 0.05 M ester 3 with 0.10 M added [15N]NaHMDS in DMEA after reaction containing only mixed aggregate -16.8-16.4-16.0-15.6-15.2 29Si (ppm) -10.0-9.6-9.2 29Si (ppm) A B 43 1J N-Si = 9.7 Hz 43 1J N-Si = 11.2 Hz 39 1J N-Si = 8.5 Hz 43 1J N-Si = 10.3 Hz 29Si (ppm) 22 [15N]43 and residual NaHMDS dimer [15N]39 (Scheme 1.3). Spectrum B is the sample from spectrum A with 1.0 equiv (relative to ester 3) of unlabelled NaHMDS. Figure 1.3. Ball and stick depictions of DFT-computed and artist’s rendition of mixed aggregate 43 with Me3N as a DMEA surrogate. We probed the mechanism for the addition of NaHMDS to picolinate 3 in DMEA-pentane mixtures using in situ IR spectroscopy35 under pseudo-first-order conditions (excess NaHMDS) following the loss of monochelated dimer 40 (1737 cm–1) to form mixed dimer 43 (1584 cm–1). Clean first-order decays (Figure 1.4) afford pseudo-first-order rate constants, kobsd, that are independent of the initial concentration of 40. Plotting kobsd versus DMEA concentration with pentane cosolvent (Figure 1.5) and versus NaHMDS dimer 39 concentration (Figure 1.6) both show zeroth-order dependencies. The resulting rate law (eq 2) is consistent with a rate-limiting addition via a transition structure of stoichiometry A2S(substrate). (Recall that A an amide subunit and S is solvent.) The dimer-based reaction coordinate is a hallmark of alkali metal amides in poorly coordinating solvents.2,7c,36 Figure 1.7 depicts the computed transition structure TS-1 displaying a developing Na2(O)(N) mixed dimer core. SicMe3 N Na N Na SibMe3 SiaMe3 ON NMe3 NMe3 Sic Sib Sia 23 Figure 1.4. Addition of 0.10 M NaHMDS to methyl-2-picolinate (3, 0.005 M) at 25 °C measured with IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ae–bx (a = 8.1 x 10–3 ± 0.1 x 10–3; b = 1.5 x 10–3 ± 0.1 x 10–3). 5 4 3 2 1 0 [m et hy l p ic ol in at e] x 1 03 (M ) 160012008004000 time (s) 5 4 3 2 1 0 k o bs d x 10 3 / se c-1 43210 [DMEA] (M) 24 Figure 1.5. A plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.005 M) at 25 °C measured with IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b (a = 2.4 x 10–3 ± 0.2 x 10–3; b = 8.3 x 10–6 ± 0.3 x 10–6). Figure 1.6. A plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate (3, 0.050 M) in 3.8 M (neat) DMEA at 25 °C measured with IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b (a = 2.7 x 10–3 ± 0.2 x 10–3; b = –1.3 x 10–3 ± 0.1 x 10–3). 4 3 2 1 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaHMDS] (M) 25 Figure 1.7. DFT-computed transition structure TS-1 for the NaHMDS-based addition to methyl-2-picolinate (3) with Me3N as a DMEA surrogate. –d[40]/dt = k’[40]1[A2S2]0[S]0 (2) Probing the reaction coordinate en route to observable product 43 (carboxamide 13 after workup) and Me3SiOMe using DFT computations served up a nuanced and quite complex story (Scheme 1.4). To reiterate, Me3N is used as a surrogate of DMEA to reduce unnecessary degrees of freedom while taking the liberty of reusing the original numbers for 40, 43, and 46. Transition structures TS- 1, TS-2, TS-3, and TS-4 all have single negative frequencies. Intrinsic reaction coordinate (IRC) calculations37 were used to determine the minima flanking each transition structure. Minima connected without connecting transition structures represent structural minima corresponding to reorganizations of insufficient interest to probe further. There are likely more minima and barriers resulting from other minor adjustments. These same caveats also apply to the reaction coordinate depicted in Scheme 1.6 (below). N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me3N O OMe N TS-1 26 Scheme 1.4. DFT-computed reaction coordinate for the aminolysis of methyl-2- picolinate (3) by NaHMDS using Me3N as a DMEA surrogate. Following the formation of open dimer 45,36 the 1,2-addition proceeds via rate-limiting transition structure TS-1 (depicted in Figure 1.7) to form the tetrahedral adduct as mixed aggregate 46. Structures beyond TS-1 represent kinetically and spectroscopically invisible post-rate-limiting events. The collapse of the adduct 46 via transition structure TS-2 affords NaOMe–NaHMDS mixed dimer 47. Following a readjustment via TS-3 to position the methoxy as a MeO–Si Lewis acid-base complex 48, silyl transfer via transition structure TS-4 extrudes Me3SiOMe via complex 49 to form mixed dimer 50 (same structure compared to mixed aggregate 43 instead of utilizing Me3N as a solvent surrogate in DFT- computation) as the spectroscopically observable product (albeit with an exothermic addition of a second solvent.) N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 N OMe O N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me3N O OMe N N Na NaMe3Si Me3Si Me3N O OMe N(SiMe3)2 N N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me3N O OMe N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N ∆G° = +13.8 kcal/mol ∆G° = +9.2 kcal/mol ∆G° = –20.9 kcal/mol ∆G° = +12.3 kcal/mol ∆G° = –7.4 kcal/mol ∆G° = +7.5 kcal/mol ∆G° = –0.6 kcal/mol ∆G° = +8.0 kcal/mol ∆G° = –41.2 kcal/mol N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N 44 45 TS-1 46 TS-2 47 TS-3 48 TS-4 N Me3Si Me3Si Na Na O N SiMe3 Me3N N MeOSiMe3 + 50 49 ∆G° = –3.2 kcal/mol 27 As drawn, the NaOMe silylation is an intra-aggegate reaction. We cannot exclude the possibility that NaOMe is released into solution before silyl transfer but have no reason to invoke it either. We also probed for a methoxy-silyl coupling directly from the tetrahedral adduct 46 without first expelling NaOMe (see 51, path a) but were unable to locate such a transfer. Similarly, a silyl transfer to extrude NaOSiMe3 from 46 (see 51, path b) was located but had an unreasonably high (23 kcal/mol) barrier consistent with our failure to observe Me3SiONa spectroscopically. Part 2: Mechanism of aminolysis of methyl-2-picolinate (3) with NaHMDS/THF. The aminolysis in THF follows a distinctly different pathway. The spectroscopically observable forms summarized in Scheme 1.5 bely mechanistic complexity lurking beneath the surface. At the outset, we note that the excess NaHMDS undergoes a THF-dependent deaggregation of disolvated dimer 52 to provide tetrasolvated monomer 53 described previously,7a,b which proves to be mechanistically important. Picolinate-complexed dimer 54 (analogous to 9) and THF-complexed monomer 55 can be observed at –110 °C at both low and high THF concentrations, respectively, using pentane cosolvent. Evidence of complexation is gleaned from distinct chemical shift differences in the 1H and 29Si NMR when compared with the uncomplexed substrate 3 and free NaHMDS (Supporting Information). The assigned THF solvation numbers derive from DFT computations. NaO MeO Ar N SiMe3 SiMe3 51 a b 28 Scheme 1.5. Spectroscopically observed species for the reaction of NaHMDS to methyl-2-picolinate 3 in THF. Warming mixtures of 3 and NaHMDS to room temperature affords imino ether 56, analogous to that isolated previously,13 within 1.0 min. The concomittant formation of Me3SiONa was confirmed by comparison with an authentic sample (17.70 ppm). In the absence of excess NaHMDS, 56 gives nitrile 6 over 24 h at RT or in 30 minutes at 50 °C in good yield (Table 1, entry 7) with concomitant formation of Me3SiOMe, confirmed with an authentic sample. The conversion of 56 to 6 is somewhat mysterious in that it does not appear to require NaHMDS and is not accelerated by excess NaHMDS, yet it does not occur by heating a crude isolated sample of 56. N OMe N SiMe3 N N 25 °C, 24 hr or 50 °C, 30 min NaHMDS (excess)N N N SiMe3 Me3Si Na N NH NH2 56 7 657 H2O – Me3SiOMe N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N Me3Si Me3Si N O Na THF THF OMe 55 NNa(THF)4 Me3Si Me3Si 52 53 25 °C 1 min – Me3SiONa N Na N Na SiMe3Me3Si SiMe3Me3Si THF 54 N O OMe 1/2 29 Reaction of 3 with excess NaHMDS renders nitrile 6 unobservable because it is quickly scavenged to give amidinate 5738 with noteworthy spectroscopic properties. The 29Si resonance of [15N2]57 appears as a clean triplet owing to second-order effects referred to as “virtual coupling.” The two magnetically equivalent 29Si nuclei experience equivalent coupling by the 15N nuclei despite one being proximal and one being distal to each silicon nucleus (Figure 1.8). Similar virtual coupling is observed in bridging transition metal phosphides (M2P2 core)39 and has been observed in a Li2P2 lithium phosphide dimer.40 In theory, we could have observed this in NaHMDS (Na2N2) dimers as well but have not.7 If the symmetry is broken by generating [15N1]57 from unlabelled nitrile 6 and [15N]NaHMDS, the 29Si resonance appears as a doublet of doublets owing to a large 1JN-Si coupling and small 3JN-Si coupling with a slight isotopic perturbation visible.41 -15.7-15.5-15.3-15.1-14.9-14.7-14.5 29Si (ppm) [15N2]57 1JN-Si = 8.8 Hz [15N1]57 1JN-Si = 8.9 Hz 3JN-Si = 2.8 Hz 30 Figure 1.8. 29Si NMR spectra of [15N2]57 showing virtual coupling (1JN–Si = 8.8 Hz) and standard coupling in [15N1]57 (1JN–Si = 8.9 Hz and 3JN–Si = 2.8 Hz). The requisite silyl transfer from the initially formed unsymmetric N,N- disilylamidine to N,N’-disilylamidine 56 is discussed in the context of DFT computations below. The depicted 6–57 nitrile-amidinate equilibrium cannot be observed directly, but adding [14N]NaHMDS to labelled amidinate 57 results in label exchange (eq 3). An analogous addition of NaHMDS to PhCO2Me (Table 1, entry 13) to generate phenyl-substituted amidinate 58 was approximately 60-fold (see in supporting information) slower than for 3. It also revealed the elusive nitrile- amidinate exchange as a temperature-dependent equilibrium (eq 4). Heating excess NaHMDS (3.0 equiv) and PhCO2Me to 80 °C followed by rapid thermal quenching to –80 °C affords predominantly benzonitrile (17). Alternatively, cooling the reaction to 25 °C and letting it stand for 12 h generates amidinate 58. Heating- cooling cycles show the changes are temperature dependent and reversible. Adding [15N]NaHMDS to unlabelled benzonitrile, 17, shows label incorporation in both 17 and 58. Thus, benzonitrile can be isolated in 86% yield using 1.1 equiv of NaHMDS and elevated temperatures (Table 1, entry 13), while amidine 58 can be isolated in 98% yield using 3.0 equiv NaHMDS at 80 °C for 3 h, then 25 °C for 12 h. This odd temperature dependence in which heating accelerates the aminolysis N 15N 15N SiMe3 Me3Si Na [15N2]57 (3) [14N]NaHMDS N 15N N SiMe3 Me3Si Na [15N1]57 31 but retards addition to the intermediate nitrile might be why nitrile-to-amidine conversions largely exploit LiHMDS15 rather than NaHMDS.16 Alternatively, it could just be a cultural preference for LiHMDS. There are no extraneous silazide signals in the 29Si spectrum that would implicate a mixed aggregate. Rate studies for the addition of NaHMDS to picolinate 3 to afford imino ether 56 provided yet another nuanced story. We anticipated that the first-order dependence—the first-order decay—on complexed monomer 55 measured in neat THF would be accompanied by a zeroth-order NaHMDS dependence. To the contrary, a plot of kobsd vs NaHMDS shows a half-order dependence on the free NaHMDS monomer (Figure 1.9). The partial rate law (deferring discussion of solvent-concentration dependencies momentarily) is described by eq 5. To be clear on a critical point: A dimer-based addition involving contributions of a standard NaHMDS monomer would manifest a first-order NaHMDS dependence.42 The half-order on a monomer demands a full ionization of the sodium cation.43 C N NaHMDS (2.0 equiv) N N SiMe3 Me3Si Na 80 °C: 1:1.5 25 °C: 1:22 5817 (4)PhCO2Me NaHMDS THF 80 °C 32 Figure 1.9. The plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate (3, 0.005 M) in 12.8 M (neat) THF at 0 °C measured with IR spectroscopy (1731 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 2.4 x 10–3 ± 0.1 x 10–3; n = 0.44 ± 0.01). –d[55]/dt = k’[55]1[AS4]1/2 (5) such that 55 = AS2(3) We may not yet fully understand the role of solvation. The forthcoming discussion may even seem excessive, but we are still groping to understand how organosodium solvation and aggregation differ from those of organolithiums. A plot of kobsd vs THF in pentane (Figure 1.10, curve A) manifests a maximum in the rates at intermediate THF concentrations. By contrast, analogous data using 2,5- dimethyltetrahydrofuran (2,5-Me2THF) or the decidedly more expensive 2,2,5,5- tetramethyltetrahydrofuran (2,2,5,5-Me4THF) as poorly coordinating polar cosolvents44–47 eliminate the maximum. The solvent dependencies suggest that medium effects are in play. We remind the reader that two deaggregations are 15 10 5 0 k o bs d x 1 03 / se c-1 0.50.40.30.20.10.0 [NaHMDS] (M) 33 occurring concurrently. At low THF concentrations, the dimeric reactant A2S(substrate) (54) exists concurrently with A2S2 (NaHMDS dimer 52), and the rise in rates indicates they are collectively under-solvated relative to the rate- limiting transition structure. At high THF concentrations in polar cosolvents, the observable reactants AS2(substrate) (54) and AS47c (53) appear optimally solvated—six THF ligands total—but under-aggregated relative to the dimeric rate- limiting transition structure. Figure 1.10. A plot of kobsd vs [THF] (M) for the addition of NaHMDS to methyl- 2-picolinate (3, 0.005 M) in 0.10 M NaHMDS at 0 °C measured with IR spectroscopy (1732 cm–1). Curve A derives from pentane cosolvent and depicts an unweighted least-squares fit to y = [axn/(1+bxn)](1/1+cx2) (a = 2.4 × 10–3 ± 0.1 × 10–3; b = 1.3 × 10–1 ± 0.1 × 10–1; c = 0.6 × 10–3 ± 0.1 × 10–4; n = 5). Curve B derives from 2,5-Me2THF cosolvent and depicts an unweighted least-squares fit to y = axn/(1+bxn) (a = 1.6 × 10–1 ± 0.1 × 10–1; b = 1.6 × 10–1 ± 0.1 × 10–1; n = 5). Curve C derives from 2,2,5,5-Me4THF cosolvent and depicts an unweighted least- 20 15 10 5 0 k o bs d x 1 03 / se c-1 121086420 [THF] (M) A B C 34 squares fit to y = axn/(1+bxn) (a = 8.2 × 10–4 ± 0.1 × 10–1; b = 7.9 × 10–2 ± 0.1 × 10–2; n = 2.2 ± 0.2). The problem we confronted in this study was that 2,5-Me2THF was binding cooperatively with THF to promote monomer formation as illustrated in eq 6. At low THF concentration, an unusually elevated concentration of NaHMDS monomer in 2,5-Me2THF compared with pentane implicates a (Me3Si)2N(THF)- x(Me2THF)y mixed. However, there is almost no chance that 2,2,5,5-Me4THF cooperatively solvates monomers, and DFT computations support this assertion. We still, however, observe the promotion of the monomer. Thus, the flattening of the curve is at least partially attributable to such an unproductive side equilibrium to form a mixed solvate according to the Principle of Detailed Balance.48 We must confess that the function used to fit the THF/pentane data (caption in Figure 1.10) contains a correction for inhibitory medium effects, 1/(1+cx2), that was derived empirically with no formal molecular basis. The challenge posed by these medium effects rears its ugly head below. With all that said, the rate law in eq 5 provides an adequate picture of a mechanism requiring 6 solvents and two silazide subunits—a hexasolvated dimer- N Na N Na SiMe3Me3Si SiMe3Me3Si S S NNaSn Me3Si Me3Si 2.0 M S 50 °C cosolvent, S (°C) pentane (50 °C) Me2THF (50 °C) Me2THF (–110 °C) Me4THF (50 °C) monomer/ dimer (6) 1 : 23 1.3 : 1 >50 : 1 1 : 3 35 based transition structure TS-5 (Figure 1.11) with a +Na(THF)6 gegenion (Figure 1.12).36 Figure 1.11. DFT-computed transition structure TS-5 for the NaHMDS-based addition to methyl-2-picolinate (3) solvated by THF. The implicit +Na(THF)6 cation7b (Figure 1.12) is not included. Figure 1.12. DFT computed +Na(THF)6. We computationally examined the overall reaction coordinate using a triple- ion-based framework (Scheme 1.6). The cation (Figure 1.12) is omitted for all N O OMe N SiMe3 SiMe3 TS-5 N Me3Si SiMe3 Na 36 structures in Scheme 1.6. Triple ions are well precedented,36 including for LiHMDS. Inspection of Figure 1.11, however, reveals that it is a triple-ion-based reference state (59) because the lowest-energy rate-limiting transition structure TS- 5 has lost all semblance of the N–Na–N triple ion connectivity as has the IRC- derived minimum 61 preceding it. 37 Scheme 1.6. DFT-computed reaction coordinate aminolysis of methyl-2-picolinate (3) with NaHMDS in THF with the +Na(THF)6 omitted for all structures. There is plenty of room for alternative interpretation. One could, for example, imagine 61 stemming directly from a chelated monomer and ionized NaHMDS fragment. It is also possible, however, that the conversion of 60 to transition structure TS-5 proceeds via 61 in which the (Me3Si)2N– in 61 remains “bound.” (The dissociation of 61 is calculated to be +5.5 kcal/mol.) Transition structure TS-5 gives way to tetrahedral adduct 62. The sequence follows an aza- Brook-like silicon transfer akin to that presumed to occur in an aza-Peterson-like imine formation49 via transition structure TS-6, elimination of 63 via transition structure TS-7 to form arene p complex 64, and arene dissociation to afford the observed imino ether 56 and unobserved (fleeting) mixed triple ion 65.36,50 N O OMeNaN N Me3Si Me3Si N O OMe Na N NMe3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 ONaN Me3Si Me3Si SiMe3 N MeO N SiMe3 OSiMe3NaN Me3Si Me3Si N + OMe N SiMe3 ∆G° = +4.7 kcal/mol ∆G° = +10.7 kcal/mol ∆G° = +2.8 kcal/mol ∆G° = –11.7 kcal/mol ∆G° = –3.6 kcal/mol ∆G° = +6.0 kcal/mol ∆G° = +7.7 kcal/mol ∆G° = –16.1 kcal/mol ∆G° = –5.5 kcal/mol TS-5 61 60 59 3 62 TS-6 63 TS-7 64 5665 SiMe3 SiMe3 N Me3Si SiMe3 Na N Me3Si SiMe3 Na N Me3Si SiMe3 Na N Me3Si SiMe3 Na 38 Part 3: Mechanism of aminolysis of 2-pyridinecarbonitrile (6) with NaHMDS/DMEA. Motivated as much by an obsessive need to complete the story as by curiosity, we examined the addition of NaHMDS to nitrile 6 to form amidinate 57 (Scheme 1.5) and were rewarded for our persistence. IR and NMR spectroscopy showed no evidence that nitrile 6 binds to NaHMDS at low or high DMEA concentrations. The addition occurs to give mixed amidinate 66 within seconds at 25 °C (eq 7) manifesting a silazide fragment that is well resolved from NaHMDS homodimer 39 displaying dimer-like coupling (1JN–Si = 8.5 Hz; Figure 1.13). As described above, further heating at 50 °C additional scrambling of the 14N–15N was observed. Figure 1.13. 29Si NMR spectra of [15N2]NaHMDS dimer (39, 1JN–Si = 8.5 Hz) and mixed aggregate [15N1]66 (1JN–Si = 7.3 Hz, 3JN–Si = 2.0 Hz). -9.4-9.3-9.2-9.1 29Si (ppm) -15.6-15.4-15.2-15.0 29Si (ppm) 39 1J N-Si = 8.5 Hz 66 1J N-Si = 9.0 Hz [ 15 N1]66 1J N-Si = 7.3 Hz 3J N-Si = 2.0 Hz 29Si (ppm) 39 Rate studies show an inverse-second-order dependence on DMEA (Figure 1.14) and first-order dependence on NaHMDS dimer 39 (Figure 1.15) consistent with a disolvated-dimer-based 1,2-addition. A full computational workup is found in the Supporting Information. An abbreviated version is illustrated in Scheme 1.7. For example, the conversion of 70 to 66 requires several additional mundane readjustments. Also, we examined the role of solvation of the intermediates and found minima that were higher energy than the unsolvated forms except for 70, whose Me3N-solvated form is –2.5 kcal/mol more stable. Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 Me2NEt Me2NEt 66 N CN 6 DMEA / 25 °C (7)N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt 39 7 6 5 4 3 2 1 0 k o bs d x 1 03 / se c-1 43210 [DMEA] (M) 40 Figure 1.14. A plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS to pyridinecarbonitrile (6, 0.005 M) at –40 °C measured with IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn/(1+bxn) (n = –1.9 ± 0.1; a = 2.7 × 10–2 ± 0.1 × 10–2; b = 7.1 × 10–3 ± 0.1 × 10– 2). Figure 1.15. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to 2- pyridinecarbonitrile (6, 0.005 M) in 3.85 M (neat) DMEA at –40 °C measured with IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 2.1 x 10–2 ± 0.1 x 10–2; n = 1.1 ± 0.1). 10 8 6 4 2 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaHMDS] (M) 41 Scheme 1.7. DFT-computed reaction coordinate aminolysis of 2- pyridinecarbonitrile (6) by NaHMDS using Me3N as a DMEA surrogate. Part 4. Mechanism of aminolysis of 2-pyridinecarbonitrile (6) with NaHMDS/THF. IR and NMR spectroscopy showed no evidence that nitrile 6 binds to NaHMDS (eq 8). The only adduct observable by 1H and 29Si NMR spectroscopy was free NaHMDS (52 and 53, Scheme 1.5) and sodium amidinate 57 to the exclusion of any mixed aggregate. DFT computations suggest 57 is a disolvate. + N CN + Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 NMe3 NMe3 ∆G° = 7.1 kcal/mol + NMe3 ∆G° = –15.1 kcal/mol ∆G° = 4.2 kcal/mol + NMe3 ∆G° = –17.0 kcal/mol– 2NMe3 ∆G° = 7.2 kcal/mol 67 6 68 69 TS-8 70 66 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3N CN N Na N Na SiMe3 SiMe3 NMe3Si Me3Si N Na N Na SiMe3 SiMe3 N Me3Si Me3Si N Na N Na SiMe3 Me3Si SiMe3 SiMe3 NC N NMe3 N N 42 Rate studies showed first-order decays and concentration-independent values of kobsd, consistent with a first-order dependence on nitrile 6. A plot of kobsd vs THF concentration shows a distinct sigmoidal dependence affording a pronounced inhibition at high THF (Figure 1.16, curve A). Any doubt that this correlates with the NaHMDS dimer-monomer deaggregation (52 and 53, Scheme 1.5) was put to rest by superimposing the rate data on a plot of the equilibrium population of dimer (curve B) measured in 2020 by a different experimentalist.7b Clearly, deaggregation inhibits the reaction. A plot of kobsd vs NaHMDS in neat THF where NaHMDS is >98% monomer shows a clean second-order dependence (Figure 1.17), consistent with a requisite monomer-to-dimer aggregation before rate-limiting addition. The crudely defined zeroth-order THF dependence implicates the partial rate law in eq 9, pointing to the overall dimer-based transition structure, [A2S2(ArCN)] ‡.51,52 The DFT computed transition structure TS-10 is illustrated in Figure 1.18. 6 THF, 25 °C (8) NaHMDS N N N SiMe3 Me3Si Na 57 N C N 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 k o bs d / s ec -1 121086420 [THF] (M) -21 -20 -19 -18 -17 -16 δ 29S i chem ical shift (ppm ) A B C 43 Figure 1.16. A plot of kobsd vs [THF] (M) for the addition of NaHMDS to 2- pyridinecarbonitrile in pentane cosolvent (curve A, red) and 29Si chemical shift (curve B, green) plotted versus [THF] in 2:1 pentane/toluene as cosolvent measured at −20 °C. The latter function fits to a model based on an A2S2−AS4 equilibrium (Supporting Information).7b,52 The blue data (Curve C) derives from 2,5-Me2THF rather than pentane as cosolvent (vide infra). Figure 1.17. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to picolinonitrile (6, 0.005 M) in 12.8 M (neat) THF at –20 °C measured with IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 4.3 x 10–2 ± 0.1 x 10–2; n = 2.0 ± 0.1). –d[6]/dt = k’[6]1[AS4]2 (9) 10 8 6 4 2 0 k o bs d x 1 03 / se c-1 0.50.40.30.20.10.0 [NaHMDS] (M) 44 Figure 1.18. DFT computed transition structure TS-10 for the NaHMDS-dimer- based addition to nitrile 6. The DFT-computed reaction coordinate for addition to nitrile 6 in THF shows many parallels with that in DMEA that are relegated to the supporting information. The notable differences are the exothermic solvation of all key species including transition structure TS-10 in Figure 1.18, mixed dimer-based transition structure TS-9 for silicon transfer, and unobserved mixed aggregate 71 whose analog (66, eq 7) was fully characterized in DMEA.53 We have accumulated evidence of pre-aggregation-based reactions originating from monomers, but none have ever been so poignant.36 Why is the N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 TS-10 C N SiMe3N Na N Na THF THF N Me3Si SiMe3 Me3Si Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 THF THF TS-9 71 45 dimer-based addition to nitriles dominant? A partial answer is that the trajectory of the silazide attack on the nitrile p system in TS-10 (Figure 1.18) appears optimal. The most stable transition structure TS-11 (Figure 1.19) for monomer-based addition is decidedly less favorable energetically (4.4 kcal/mol using a monomer reference state), which appears to be a consequence of an inferior trajectory. Figure 1.19. DFT computed transition structure TS-11 for the unfavorable NaHMDS-monomer-based addition to nitrile 6. We would be remiss to not comment on the influence of 2,5-Me2THF rather than pentane as the cosolvent for nitrile addition (curve C in Figure 1.16). It provided further evidence of cooperative solvation. While checking for polarity effects we detected and subsequently documented cooperative monomer solvation, (Me3Si)2NNa(THF)x(Me2THF)y, noted in eq 6. The details are obscured in Figure 1.16 by an overlaying THF concentration dependence. The complete suppression of the rate suggested that the mixed solvated monomers persisted as an unproductive side equilibrium at stunningly low THF concentrations. Indeed, this was caused by a steep temperature dependence on the deaggregation. The message N C N NaN Me3Si Me3Si THF THF TS-11 46 for us is that 2,5-Me2THF is a far better non-coordinating THF surrogate for lithium than sodium. Summary. The studies described above proved to be four discrete mechanistic studies in which the choice of solvent and conditions markedly influence the outcome of the reactions. We offer an overview in which the results are grouped according to choice solvent—THF or DMEA. This summary is organosodium centric; there is a considerable body organolsilicon chemistry (largely addressed computationally) that is left to the four parts described above. The arrows in Schemes 8 and 9 encompass many discrete steps including the organosilicon chemistry. The THF results are summarized in Scheme 1.8. While NaHMDS in neat THF solution exists exclusively as tetrasolvated monomer 53, it reacts with methyl-2-picolinate, 3, via a dimer-based pathway in which a triple ion motif TS-5 is invoked at the rate-limiting transition structure. The critical chemoselectivity stems from a post-rate-limiting extrusion of NaOSiMe3 to form spectroscopically observable imino ether 56, which further to give nitrile 6 and sodium amidinate 57 en route to a high-yielding one-pot synthesis of amidine 7. This ester-to-amidine conversion seems potentially important synthetically. Addition of NaHMDS to nitrile 6 is also dimer-based as depicted in computationally viable transition structure TS-10. The dominance of dimer-based reactivity under conditions affording monomeric NaHMDS should pique the interest of those interested in mechanistic alkali metal chemistry. Scheme 1.8. Summary of NaHMDS mechanistic studies in THF solution. 47 The chemistry of NaHMDS in poorly coordinating DMEA7b (Scheme 1.9) shows some parallels with the results in THF, but the differences are consequential. Although we do not consider a dimeric NaHMDS to be the proximate cause of dimer-based reactivity—many if not most monomer-based organoalkali metal reactions emanate from aggregates—the dominance of a dimer-based transition structure, TS-1, leading to observable mixed aggregate 43 aligns with previous studies of both LiHMDS and NaHMDS in DMEA.7c,54 In contrast to THF, however, a critical post-rate-limiting extrusion of MeOSiMe3 rather than NaOSiMe3 dictates the chemoselective formation of carboxamide 4. Observable mixed aggregate 43 is robust but finds a path to 66 (DMEA solvated mixed aggregate form of amidine 57) over a month at 25 °C. Although this is clearly an inferior route to amidine 57 we examined the addition to nitrile 6 and, once again, uncovered dimer-based chemistry via an unsolvated transition structure, TS-8. Scheme 1.9. Summary of NaHMDS mechanistic studies in DMEA solution. Na(THF)6 N OMe N SiMe3 56 N N N SiMe3 Me3Si Na(THF)2 57 N O OMe N SiMe3 SiMe3 TS-5 N Me3Si SiMe3 Na N NH NH2 7 N C N 6 – NaOSiMe3 NNa(THF)4 Me3Si Me3Si2 workup NaHMDS ArCO2Me 3 N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 TS-10 48 Conclusion While casting about for case studies to investigate solvent-structure- reactivity relationships in NaHMDS we happened across several potentially useful reactions that are poorly represented in the literature and provided mechanistic insights that were wholly unexpected. The potential utility stems from C-N bond formations directly from aryl methyl esters, bypassing more activated forms. For us, however, they provided clean examples illustrating the role of solvation and aggregation in the chemistry of sodium amides in general and NaHMDS in particular. The NaHMDS itself serves as a preface to ongoing studies of sodium alkyl(trimethylsilyl) amides with potentially greater utility as strong bases and for C-N bond-forming reactions. The dimer- and mixed dimer-based reactivity has precedent,7c,36 but the total dominance of aggregate-based reactivity still came as a surprise. From a mechanistically tactical perspective, the work underscores both the power of 29Si– 15N coupling to determine solution structures and the general merits of 29Si NMR spectroscopy. (We asserted previously that 29Si NMR spectroscopy is underutilized by those outside the organosilicon community.) We offer a final caveat to those who might be tempted to probe primary- versus secondary-shell solvation by using 2,5-Me2THF as a polar, non-coordinating cosolvent. Despite its success in TS-8 N Na N Na SiMe3 SiMe3 N Me3Si Me3Si N Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 Me2NEt Me2NEt 66 N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt 39 N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me2NEt O OMe N TS-1 N Me3Si Me3Si Na Na O N SiMe3 Me2NEt N 50 N O NH2 4 workup N NH NH2 7 – MeOSiMe3 workup ArCO2Me 3 ArCN 6 49 organolithium chemistry, the larger sodium ion may call for the more expensive 2,2,5,5-Me4THF. On the truism that an effect is either sterics or electronics, ours’ and others’ experience with metal ion solvation is that sterics dominates.55 Experimental Reagents and solvents. NaHMDS and [15N]NaHMDS were prepared as white crystalline solids.7b Toluene, hexanes, THF, MTBE, cyclopentane, 2,5- Me2THF, and HMPA were distilled from blue or purple solutions containing sodium benzophenone ketyl. All substrates and products in Table 1 are commercially available.31,32 General Procedure A: picolinamide 4. Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2 mL of DMEA at 25 °C. 2 mL of the NaHMDS solution was added to a dry 5 mL Kimble vial equipped with a magnetic stir bar. Methyl picolinate (3, 36 µl, 0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.3 h. DI water (1 mL) was added, and the resulting biphasic mixture was partitioned between water (1 mL) and ethyl ether (2 mL). The aqueous layer was separated and extracted further with three 2 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80 % ethyl acetate in hexanes) afforded picolinamide 4 as a white solid. 1H NMR (500 MHz, CDCl3) δ 8.56 (d, J = 4.6 Hz, 1H), 8.20 (d, J = 7.8 Hz, 1H), 7.89 (s, 1H), 7.84 (td, J = 7.7, 1.8 Hz, 1H), 7.43 (dd, J = 7.6, 4.8 Hz, 1H), 6.23 (s, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.99, 145.59, 148.32, 137.31, 126.47, 122.44. HRMS (DART) Calc. for C6H6N2O (M+H+): 123.04746; found: 123.05493. General Procedure B: amidine 7. Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 1.5 mL of THF at 25 °C. 1.5 mL 50 of the NaHMDS solution was added to a dry 5 mL Kimble vial equipped with a magnetic stir bar. Methyl picolinate (3, 36 µl, 0.30 mmol) was then added to the reaction solution. The reaction was stirred at 50 °C for 0.3 h. DI water (1 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 h. Saturated NaOH solution was then added until pH =12. The mixture was partitioned between water (1 mL) and chloroform (4 mL). The aqueous layer was separated and extracted further with three 4 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford amidine 7 as a yellow oil. 1H NMR (500 MHz, CDCl3) δ 8.56 (m, 1H), 8.11 (d, J = 7.9 Hz, 1H), 7.78 (td, J = 7.7, 1.8 Hz, 1H), 7.35 (dd, J = 7.5, 4.9 Hz, 1H), 5.94 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 161.06, 150.79, 148.35, 137.03, 125.21, 120.81. HRMS (DART) Calc. for C6H7N3 (M+H+): 122.06345; found: 122.07097. NMR spectroscopic analyses. An NMR tube fitted with a double-septum under vacuum was flame-dried on a Schlenk line and allowed to passively cool to room temperature, backfilled with argon, and placed in a dry ice/acetone cooling bath. Individual stock solutions of the substrate and NaHMDS or [15N]NaHMDS were prepared at room temperature. The appropriate amounts of the substrate, NaHMDS, solvent, and co-solvent were added sequentially to the tube cooled to – 78 °C via a gastight syringe. The tube was flame-sealed under a partial vacuum while cold to minimize evaporation in some cases and left unsealed for incremental additions. The tubes were mixed with a vortex mixer for approximately 10 secs to minimize warming. Standard 1H, 13C, and 29Si direct detection spectra were recorded at 500, 125.79, and 99.36 MHz, respectively, and referenced to Me4Si (0.0 ppm). Integration of the NMR signals was determined using the line-fitting method included in MNova (Mestrelab research S.L.). 51 Rate Studies. IR spectra were recorded with an in situ IR spectrometer fitted with a 30-bounce, silicon-tipped probe. The spectra were acquired at a gain of 1 and a resolution of 4 cm−1. All tracked reactions were conducted under a positive flow of argon from a Schlenk line. A representative reaction was carried out as follows: The IR probe was inserted through a Teflon adapter and O-ring seal into an oven-dried, cylindrical flask fitted with a magnetic stir bar and a T-joint. The T- joint was capped with a septum for injections and an argon line. After evacuation under full vacuum, heating, and flushing with argon, the flask was charged with the solvent mixtures of our choice (toluene, DMEA, THF, 2,5-Me2THF, and 2,2,5,5- Me4THF) and cooled to −78 °C in a dry ice−acetone bath. A set of 256 baseline scans were collected and IR spectra were recorded every 15 seconds from 30 scans. The reaction vessel was charged stock solutions of NaHMDS and additional cosolvent through the septum. One set of scans was collected before the addition of substrate through the septum, and the baseline is zeroed. The substrate was added neat or in highly concentrated solutions and was tracked to completion (1731 cm-1 for 7, for example). The spectrometer was configured to collect spectra every 5 seconds from 16 scans. The reaction was tracked over 3–5 half-lives monitoring the disappearance of the starting material and the appearance of the product. The former was used for the rate studies. Density functional theory (DFT) computations. All DFT calculations were carried out using Gaussian 16.29 Prompted by a recent benchmarking of modern density functionals, all calculations were conducted at the M06-2X level of theory.30a-c A pruned (99, 590) integration grid (equivalent to Gaussian’s “UltraFine” option) was used for all calculations. The Ahlrichs basis set def2-svp was used for geometry optimizations and the expanded def2-tsvp basis set for single-point energy calculations.30d Ball-and-stick models were rendered using CYLview 1.0b.30e 52 CHAPTER 1 APPENDIX 53 Chapter 1 Appendix Table of Contents Contents Synthesis General Procedure A 57 General Procedure B 57 Synthesis of cinnamamide 2 from methyl cinnamate 1. 59 Figure A.1.1. 1H NMR spectrum of cinnamamide 2. 68 Figure A.1.2. 13C NMR spectrum of cinnamamide 2. 69 Synthesis of picolinamide 4 from methyl picolinate 3. 70 Synthesis of picolinamide 4 from ethyl picolinate 5. 71 Figure A.1.3. 1H NMR spectrum of picolinamide 4. 72 Figure A.1.4. 13C NMR spectrum of picolinamide 4. 73 Synthesis of picolinonitrile 6 from methyl picolinate 3. 74 Figure A.1.5. 1H NMR spectrum of picolinonitrile 6. 75 Figure A.1.6. 13C NMR spectrum of picolinonitrile 6. 76 Synthesis of picolinimidamide 7 from methyl picolinate 6. 77 Figure A.1.7. 1H NMR spectrum of picolinimidamide 7. 78 Figure A.1.8. 13C NMR spectrum of picolinimidamide 7. 79 Synthesis of isonicotinamide 9 from methyl isonicotinate 8. 80 Figure A.1.9. 1H NMR spectrum of isonicotinamide 9. 81 Figure A.1.10. 13C NMR spectrum of isonicotinamide 9. 82 Synthesis of isonicotinimidamide 10 from methyl isonicotinate 8. 83 Figure A.1.11. 1H NMR spectrum of isonicotinimidamide 10. 84 Figure A.1.12. 13C NMR spectrum of isonicotinimidamide 10. 85 54 Synthesis of nicotinamide 12 from methyl nicotinate 11. 86 Figure A.1.13. 1H NMR spectrum of nicotinamide 12. 87 Figure A.1.14. 13C NMR spectrum of nicotinamide 12. 88 Synthesis of nicotinimidamide 13 from methyl nicotinate 11. 89 Figure A.1.15. 1H NMR spectrum of nicotinimidamide 13. 90 Figure A.1.16. 13C NMR spectrum of nicotinimidamide 13. 91 Synthesis of benzamide 15 from methyl benzoate 14. 92 Figure A.1.17. 1H NMR spectrum of benzamide 15. 93 Figure A.1.18. 13C NMR spectrum of benzamide 15. 94 Synthesis of benzimidamide 16 from methyl benzoate 14. 95 Synthesis of benzimidamide 16 from benzonitrile 17. 96 Figure A.1.19. 1H NMR spectrum of benzimidamide 16. 97 Figure A.1.20. 13C NMR spectrum of benzimidamide 16. 98 Synthesis of 2-nitroaniline 19 from 2-fluoronitrobenzene 18. 99 Figure A.1.21. 1H NMR spectrum of 2-nitroaniline 19. 100 Figure A.1.22. 13C NMR spectrum of 2-nitroaniline 19. 101 Synthesis of 3-chloro-2-nitroaniline 21 from 1-chloro-3-fluoro-2- Nitrobenzene 20. 102 Figure A.1.23. 1H NMR spectrum of 3-chloro-2-nitroaniline 21. 103 Figure A.1.24. 13C NMR spectrum of 3-chloro-2-nitroaniline 21. 104 Synthesis of 3-fluoro-2-nitroaniline 23 from 2,6-difluoronitrobenzene 22. 105 Figure A.1.25. 1H NMR spectrum of 3-fluoro-2-nitroaniline 23. 106 Figure A.1.26. 13C NMR spectrum of 3-fluoro-2-nitroaniline 23. 107 Synthesis of pyridin-2-amine 25 from 2-fluoropyridine 24. 108 Figure A.1.27. 1H NMR spectrum of pyridin-2-amine 25. 109 55 Figure A.1.28. 13C NMR spectrum of pyridin-2-amine 25. 110 Synthesis of 6-fluoropyridin-2-amine 27 from 2,6-difluoropyridine 26. 111 Figure A.1.29. 1H NMR spectrum of 6-fluoropyridin-2-amine 27. 112 Figure A.1.30. 13C NMR spectrum of 6-fluoropyridin-2-amine 27. 113 Synthesis of (R)-2-amino-1-phenylethan-1-ol 29 from (R)-2- Phenyloxirane 28. 114 Figure A.1.31. 1H NMR spectrum of (R)-2-amino-1-phenylethan-1-ol 29. 115 Figure A.1.32. 13C NMR spectrum of (R)-2-amino-1-phenylethan-1-ol 29. 116 Synthesis of 1-aminooctan-2-ol 31 from 2-hexyloxirane 30. 117 Figure A.1.33. 1H NMR spectrum of 1-aminooctan-2-ol 31. 118 Figure A.1.34. 13C NMR spectrum of 1-aminooctan-2-ol 31. 119 Structural Elucidation and Reaction Mechanism General procedure for sealed tube NMR spectroscopy 120 Figure A.1.35. 1H NMR spectra of methyl picolinate 3 and [15N]NaHMDS in DMEA. 121 Figure A.1.36. 29Si NMR spectra of methyl picolinate 3 and [15N]NaHMDS in DMEA. 122 Figure A.1.37. (a) 29Si NMR spectra of methyl picolinate 3 and [15N]NaHMDS in DMEA. (b) 29Si NMR spectra of additional [15N]NaHMDS to (a). 123 Figure A.1.38. (a) 29Si NMR spectra of methyl picolinate 3 and [15N]NaHMDS in DMEA. (b) 29Si NMR spectra of addition o [14N]NaHMDS to (a). 124 Figure A.1.39. 1H and 29Si NMR spectra of mixed aggregate 43. 125 56 Figure A.1.40. 29Si NMR spectra of [15N]NaHMDS in DMEA with incremental additions of methyl picolinate 3 (0-0.5 equiv). 127 Figure A.1.41. 29Si NMR spectra of [15N]NaHMDS in DMEA with incremental additions of methyl picolinate 3 (0-0.5 equiv). 130 Figure A.1.42. 1H NMR spectra of methyl picolinate 3 and [15N]NaHMDS in THF. 131 Figure A.1.43. 29Si NMR spectra of methyl picolinate 3 and [15N]NaHMDS in THF. 132 Figure A.1.44. 29Si NMR spectra of methyl picolinate 3 and [15N]NaHMDS in THF. 133 Figure A.1.45. 1H NMR spectra of crude imino-ether 56 in CDCl3. 134 Figure A.1.46. 1H NMR spectra of methyl picolinate 3 and [15N]NaHMDS in THF (imino-ether 56 to amidine 57). 135 Figure A.1.47. (a) 1H NMR spectra of methyl picolinate 3 in THF. (b) 1H NMR spectra of reactant methyl picolinate 3 and [15N]NaHMDS in THF. 136 Figure A.1.48. (a) 13C NMR spectra of methyl picolinate 3 in THF. (b) 13C NMR spectra of methyl picolinate 3 and [15N]NaHMDS in THF. 137 Figure A.1.49. 29Si NMR spectra of [15N]NaHMDS in DMEA with incremental additions of THF and methyl picolinate 3. 138 Figure A.1.50. 1H NMR spectra of 0.050 M methyl picolinate 3 and 0.060 M [15N]NaHMDS in THF. 139 Figure A.1.51. 29Si NMR spectra of 0.050 M methyl picolinate 3 and 0.060 M [15N]NaHMDS in THF. 140 Figure A.1.52. 1H spectra of isolated crude O-methyl-imino ether 56 reacting with NaOMe, NaOTMS, NaHMDS in THF. 141 Figure A.1.53. 29Si NMR spectra of [15N2]57 and [15N1]57 in DMEA. 142 57 Figure A.1.54. 29Si NMR spectra of picolinonitrile 6 and [15N]NaHMDS in THF. 143 Figure A.1.55. (a) 1H NMR spectra of picolinonitrile 6 in THF. (b) 1H NMR spectra of reactant methyl picolinate 3 and [15N]NaHMDS in THF. 144 Figure A.1.56. (a) 1H NMR spectra of picolinonitrile 6 in DMEA. (b) 1H NMR spectra of reactant methyl picolinate 3 and [15N]NaHMDS in DMEA. 145 Figure A.1.57. (a) 29Si NMR spectra of picolinonitrile 6 in DMEA. (b) 29Si NMR spectra of reactant methyl picolinate 3 and [15N]NaHMDS in DMEA. 146 Figure A.1.58. 1H NMR spectra of benzonitrile 17 and [15N]NaHMDS in THF. 147 Figure A.1.59. 1H NMR spectra of benzonitrile 17 and [15N]NaHMDS in THF. 148 Figure A.1.60. 1H NMR spectra of methyl benzoate and [15N]NaHMDS in THF. 149 Figure A.1.61. NaHMDS monomer/dimer ratio in THF/cosolvent mixture of choice pentane, 2,5-Me2THF, 2,2,5,5-Me4THF. 151 Figure A.1.62. 29Si NMR spectra of [15N]NaHMDS in pentane. 152 Figure A.1.63. 29Si NMR spectra of [15N]NaHMDS in 2,5- Me2THF. 153 Figure A.1.64. 29Si NMR spectra of [15N]NaHMDS in 2,2,5,5-Me4THF. 154 Rate Studies General procedure for in situ IR analyses 155 Figure A.1.65. Emblematic addition of NaHMDS to methyl-2-picolinate 3 form mixed aggregate 46. 157 58 Figure A.1.66. Plot of [methyl-2-picolinate 3] vs time (s) for amminolysis of methyl-2-picolinate 3 by NaHMDS monitored by IR spectroscopy. 157 Figure A.1.67. Plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS to methyl-2-picolinate 3. 158 Table A.1.1. Average pseudo-first-order rate constants (kobsd) at various DMEA (pentane cosolvent) concentrations. 158 Figure A.1.68. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate 3 in DMEA. 159 Table A.1.2. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations. 159 Figure A.1.69. Emblematic addition of NaHMDS to methyl-2-picolinate 3 to form imino-ether 56 in DMEA. 160 Figure A.1.70. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate 3 in THF. 161 Table A.1.3. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations. 162 Figure A.1.71. Plot of kobsd vs [THF] (M) in pentane/2,5- Me2THF/2,2,5,5,-Me4THF for the addition of NaHMDS to methyl-2- picolinate 3. 163 Table A.1.4. Average pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations. 164 Table A.1.5. Average pseudo-first-order rate constants (kobsd) at various THF (2,5- Me2THF cosolvent) concentrations. 164 Table A.1.6. Average pseudo-first-order rate constants (kobsd) at various THF (2,2,5,5-Me4THF cosolvent) concentrations. 165 59 Figure A.1.72. Emblematic addition of NaHMDS to picolinonitrile (6) to form silyated amidine 57 in THF. 166 Figure A.1.73. Plot of kobsd vs [THF] (M) in pentane for the addition of NaHMDS to picolinonitrile 6. 167 Table A.1.7. Average pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations. 167 Figure A.1.74. Plot of kobsd vs [THF] (M) in 2,5- Me2THF for the addition of NaHMDS to picolinonitrile 6. 168 Figure A.1.75. Overlap plot of Figure A.1.73 and Figure A.1.74 169 Figure A.1.76. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to picolinonitrile (6) in pentane cosovent and 29Si chemical shift (green) plotted versus [THF]. 170 Figure A.1.77. Plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS (0.10 M) to picolinonitrile 6. 171 Table A.1.8. Average pseudo-first-order rate constants (kobsd) at various DMEA (pentane cosolvent) concentrations. 171 Figure A.1.78. Plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS to picolinonitrile 6. 172 Table A.1.9. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations. 172 Figure A.1.79. Plot of kobsd vs [NaHMDS] (M) in DMEA for the addition of NaHMDS to picolinonitrile 6. 173 Table A.1.10. Average pseudo-first-order rate constants (kobsd) at various DMEA (pentane cosolvent) concentrations. 173 Computational Data General computational methods 174 60 Scheme A.1.1. DFT-computed free energies for the methyl picolinate 3 and NaHMDS complexed ground state structures in DMEA. 175 Scheme A.1.2. DFT-computed free energies for the mixed aggregate 46 and serial solvation of mixed aggregate 46 with DMEA. 176 Firgure S80. DFT-computed reaction coordinate aminolysis of methyl-2- picolinate 3 by NaHMDS in DMEA. 177 Figure A.1.81. DFT-computed alternative pathway reaction coordinate aminolysis of methyl-2-picolinate 3 by NaHMDS in DMEA 178 Scheme A.1.3. DFT-computed free energies for the methyl picolinate 3 and NaHMDS complexed ground state structures in THF. 179 Figure A.1.82. DFT-computed reaction coordinate aminolysis of methyl- 2-picolinate 3 by NaHMDS in THF. 180 Figure A.1.83. DFT-computed reaction coordinate aminolysis of methyl- 2-picolinate 3 by NaHMDS in THF with an alternative pathway. 181 Figure A.1.84. DFT-computed reaction coordinate 1,2-addition of picolinonitrile 6 by NaHMDS in THF. 182 Scheme A.1.4. DFT-computed energy profile of 1,2-addition of picolinonitrile 6 by NaHMDS in THF via a monomer pathway. 183 Scheme A.1.5. DFT-computed energy profile of amidine 76 formation in THF via a monomer pathway. 183 Scheme A.1.6. DFT-computed energy profile of 1,2-addition of picolinonitrile 6 by NaHMDS in THF via a dimer pathway. 184 Scheme A.1.7. DFT-computed energy profile of amidine 71 formation via a monomer pathway starting from pre-silyl transfer amidine 82. 184 Figure A.1.85. DFT-computed reaction coordinate 1,2-addition of 2- pyridinecarbonitrile 6 by NaHMDS in DMEA. 185 61 Scheme A.1.8. DFT-computed free energies for the mixed aggregate 66 and serial solvation of mixed aggregate 66 with DMEA. 186 Scheme A.1.9. DFT-computed energy profile of 1,2-addition of picolinonitrile 6 by NaHMDS in DMEA via a dimer pathway. 187 Atomic Coordinates and Single Point Energies Table A.1.11. Atomic coordinates and single point energies for THF. 193 Table A.1.12. Atomic coordinates and single point energies for 2,5- Me2THF. 194 Table A.1.13. Atomic coordinates and single point energies for 2,2,5,5- Me4THF. 195 Table A.1.14. Atomic coordinates and single point energies for DMEA. 196 Table A.1.15. Atomic coordinates and single point energies for Me3N. 197 Table A.1.16. Atomic coordinates and single point energies for 3. 198 Table A.1.17. Atomic coordinates and single point energies for TMSOMe. 199 Table A.1.18. Atomic coordinates and single point energies for +Na(THF)6. 200 Table A.1.19. Atomic coordinates and single point energies for 39. 203 Table A.1.20. Atomic coordinates and single point energies for 40. 206 Table A.1.21. Atomic coordinates and single point energies for 44b. 209 Table A.1.22. Atomic coordinates and single point energies for 41. 212 Table A.1.23. Atomic coordinates and single point energies for 42. 215 Table A.1.24. Atomic coordinates and single point energies for 42a. 217 Table A.1.25. Atomic coordinates and single point energies for 42b. 219 Table A.1.26. Atomic coordinates and single point energies for 42c. 221 62 Table A.1.27. Atomic coordinates and single point energies for 46. 224 Table A.1.28. Atomic coordinates and single point energies for 46a. 227 Table A.1.29. Atomic coordinates and single point energies for 46b. 229 Table A.1.30. Atomic coordinates and single point energies for 46d. 232 Table A.1.31. Atomic coordinates and single point energies for 46e. 234 Table A.1.32. Atomic coordinates and single point energies for 46f. 237 Table A.1.33. Atomic coordinates and single point energies for TS-1. 240 Table A.1.34. Atomic coordinates and single point energies for 45. 243 Table A.1.35. Atomic coordinates and single point energies for 46i. 246 Table A.1.36. Atomic coordinates and single point energies for 46m. 249 Table A.1.37. Atomic coordinates and single point energies for TS-22. 252 Table A.1.38. Atomic coordinates and single point energies for 46n. 255 Table A.1.39. Atomic coordinates and single point energies for TS-2. 258 Table A.1.40. Atomic coordinates and single point energies for 47. 261 Table A.1.41. Atomic coordinates and single point energies for TS-3. 264 Table A.1.42. Atomic coordinates and single point energies for 48. 267 Table A.1.43. Atomic coordinates and single point energies for TS-4. 270 Table A.1.44. Atomic coordinates and single point energies for 49. 272 Table A.1.45. Atomic coordinates and single point energies for 52. 275 Table A.1.46. Atomic coordinates and single point energies for 53. 278 Table A.1.47. Atomic coordinates and single point energies for 53a. 281 Table A.1.48. Atomic coordinates and single point energies for 53b. 284 Table A.1.49. Atomic coordinates and single point energies for 54. 287 Table A.1.50. Atomic coordinates and single point energies for 55. 290 Table A.1.51. Atomic coordinates and single point energies for 55a. 293 Table A.1.52. Atomic coordinates and single point energies for 56. 294 63 Table A.1.53. Atomic coordinates and single point energies for 7. 296 Table A.1.54. Atomic coordinates and single point energies for TS-5. 297 Table A.1.55. Atomic coordinates and single point energies for TS-23. 299 Table A.1.56. Atomic coordinates and single point energies for 60c. 301 Table A.1.57. Atomic coordinates and single point energies for TS-12. 303 Table A.1.58. Atomic coordinates and single point energies for 60d. 306 Table A.1.59. Atomic coordinates and single point energies for 59. 309 Table A.1.60. Atomic coordinates and single point energies for 60. 311 Table A.1.61. Atomic coordinates and single point energies for 61. 313 Table A.1.62. Atomic coordinates and single point energies for 62. 315 Table A.1.63. Atomic coordinates and single point energies for TS-6. 317 Table A.1.64. Atomic coordinates and single point energies for 63. 319 Table A.1.65. Atomic coordinates and single point energies for TS-7. 321 Table A.1.66. Atomic coordinates and single point energies for 64. 323 Table A.1.67. Atomic coordinates and single point energies for 65. 325 Table A.1.68. Atomic coordinates and single point energies for 66. 327 Table A.1.69. Atomic coordinates and single point energies for 66a. 330 Table A.1.70. Atomic coordinates and single point energies for 66b. 332 Table A.1.71. Atomic coordinates and single point energies for 88. 335 Table A.1.72. Atomic coordinates and single point energies for 69. 338 Table A.1.73. Atomic coordinates and single point energies for 90. 341 Table A.1.74. Atomic coordinates and single point energies for 89. 344 Table A.1.75. Atomic coordinates and single point energies for TS-19. 347 Table A.1.76. Atomic coordinates and single point energies for TS-20. 350 Table A.1.77. Atomic coordinates and single point energies for TS-21. 353 Table A.1.78. Atomic coordinates and single point energies for 70. 356 64 Table A.1.79. Atomic coordinates and single point energies for 87. 359 Table A.1.80. Atomic coordinates and single point energies for 93. 362 Table A.1.81. Atomic coordinates and single point energies for 92. 364 Table A.1.82. Atomic coordinates and single point energies for TS-9. 367 Table A.1.83. Atomic coordinates and single point energies for 71. 370 Table A.1.84. Atomic coordinates and single point energies for TS-14. 373 Table A.1.85. Atomic coordinates and single point energies for TS-13. 375 Table A.1.86. Atomic coordinates and single point energies for 72. 378 Table A.1.87. Atomic coordinates and single point energies for 73. 381 Table A.1.88. Atomic coordinates and single point energies for 74. 383 Table A.1.89. Atomic coordinates and single point energies for 76. 386 Table A.1.90. Atomic coordinates and single point energies for 75. 388 Table A.1.91. Atomic coordinates and single point energies for TS-16. 391 Table A.1.92. Atomic coordinates and single point energies for 77. 393 Table A.1.93. Atomic coordinates and single point energies for 78. 395 Table A.1.94. Atomic coordinates and single point energies for 79. 398 Table A.1.95. Atomic coordinates and single point energies for 80. 401 Table A.1.96. Atomic coordinates and single point energies for TS-10. 404 Table A.1.97. Atomic coordinates and single point energies for TS-15. 407 Table A.1.98. Atomic coordinates and single point energies for 82. 410 Table A.1.99. Atomic coordinates and single point energies for 81. 413 Table A.1.100. Atomic coordinates and single point energies for 83. 416 Table A.1.101. Atomic coordinates and single point energies for 84. 419 Table A.1.102. Atomic coordinates and single point energies for 85. 422 Table A.1.103. Atomic coordinates and single point energies for TS-18. 425 Table A.1.104. Atomic coordinates and single point energies for 86. 428 65 General Experimental Procedure Reagents and solvents. NaHMDS and [15N]NaHMDS were prepared as white crystalline solids. Toluene, hexanes, THF, MTBE, cyclopentane, 2,5- Me2THF, and HMPA were distilled from blue or purple solutions containing sodium benzophenone ketyl. Substrates in Table 1 are all commercially available, and all products are either commercially available or available by literature procedures. Synthesis of picolinamide : picolinamide (4). Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2.0 mL of DMEA at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36 μL of methyl picolinate (3) (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.3 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80% ethyl acetate in hexanes) afforded picolinamide (4) as a white solid. Synthesis of picolinimidamide : picolinimidamide (7). Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 1.5 mL of THF at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36 μL methyl picolinate (3) (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 50 °C for 0.3 hr. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further 66 with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford picolinimidamide (7) as a yellow oil. 67 Synthesis of cinnamamide 2 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar, containing 50 mg of methyl cinnamate 1(0.30 mmol). The reaction was stirred at 25 °C for 5 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (50% ethyl acetate in hexanes) afforded 35 mg (73%) of product 2 as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.7 (d, J = 15.7 Hz, 1H), 7.5 (dd, J = 6.6, 3.0 Hz, 2H), 7.4 (q, J = 3.1 Hz, 3H), 6.5 (d, J = 15.7 Hz, 1H), 5.8 (s, 1H), 5.73 (s, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 167.9, 142.6, 134.6, 130.1, 129.0, 128.0, 119.6. NH2 O OMe O NaHMDS toluene, 25 oC, 5 hr 68 Figure A.1.1. 1H NMR spectrum of cinnamamide 2 in CDCl3 w/ 0.05% TMS at 25 °C. NH2 O 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (d) 7.65 B (dd) 7.51 C (q) 7.37 D (d) 6.47 E (s) 5.80 F (s) 5.73 1 .0 0 0 .9 8 0 .9 7 3 .0 1 2 .0 2 1 .0 2 5 .7 3 5 .8 0 6 .4 5 6 .4 8 7 .1 3 7 .2 1 7 .2 6 C D C l3 7 .3 6 7 .3 7 7 .3 8 7 .3 9 7 .4 0 7 .5 0 7 .5 0 7 .5 1 7 .5 1 7 .5 2 7 .6 3 7 .6 6 69 Figure A.1.2. 13C NMR spectrum of cinnamamide 2 in CDCl3 w/ 0.05% TMS at 25 °C. NH2 O 020406080100120140160180 13C (ppm) 1 1 9 .6 1 1 2 8 .0 8 1 2 9 .0 1 1 3 0 .1 3 1 3 4 .6 3 1 4 2 .6 9 1 6 7 .9 7 70 Synthesis of picolinamide 4 (a) Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2.0 mL of DMEA at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36 μL of methyl picolinate 3 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.3 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80% ethyl acetate in hexanes) afforded 39 mg (95%) of product picolinamide 4 as a white solid. NaHMDS DMEA, 25 oC, 0.3 hr N O NH2 N O OMe 71 Synthesis of picolinamide 4 (b) Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.90 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 34 μL of ethyl picolinate 5 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.3 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80% ethyl acetate in hexanes) afforded 37 mg (90%) of product picolinamide 4 as a white solid. 1H NMR (500 MHz, CDCl3) δ 8.6 (d, J = 4.6 Hz, 1H), 8.2 (d, J = 7.8 Hz, 1H), 7.9 (s, 1H), 7.8 (td, J = 7.7, 1.8 Hz, 1H), 7.4 (dd, J = 7.6, 4.8 Hz, 1H), 6.2 (s, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.9, 145.6, 148.3, 137.3, 126.5, 122.4. NaHMDS toluene, 25 oC, 0.3 hr N O NH2 N O OEt 72 Figure A.1.3. 1H NMR spectrum of picolinamide 4 in CDCl3 at 25 °C. N O NH2 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (d) 8.56 B (d) 8.20 C (s) 7.89 D (td) 7.84 E (dd) 7.43 F (s) 6.23 1 .0 7 1 .0 0 1 .0 9 0 .9 3 0 .9 3 0 .9 7 0 .0 6 2 .1 1 H 2 O 6 .2 3 7 .2 6 C D C l3 7 .4 2 7 .4 3 7 .4 4 7 .4 5 7 .8 3 7 .8 3 7 .8 4 7 .8 4 7 .8 6 7 .8 6 7 .8 9 8 .1 9 8 .2 0 8 .5 6 8 .5 7 73 Figure A.1.4. 13C NMR spectrum of picolinamide 4 in CDCl3 at 25 °C. N O NH2 020406080100120140160180 13C (ppm) 7 6 .8 1 7 7 .0 6 7 7 .3 2 1 2 2 .4 4 1 2 6 .4 7 1 3 7 .3 1 1 4 8 .3 2 1 4 9 .5 9 1 6 6 .9 9 74 Synthesis of picolinonitrile 6 Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 0.60 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36.5 μL of methyl picolinate 3 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.3 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (20% ethyl acetate in hexanes) afforded 37 mg (90%) of product picolinonitrile 6 as a yellow solid. 1H NMR (500 MHz, CDCl3) δ 8.7 (dt, J = 4.9, 1.4 Hz, 1H), 7.8 (td, J = 7.8, 1.7 Hz, 1H), 7.7 (dt, J = 7.8, 1.2 Hz, 1H), 7.5 (ddd, J = 7.8, 4.8, 1.2 Hz, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 151.2, 137.1, 134.0, 128.6, 127.0, 117.2. 1.1 equiv NaHMDS THF, 50 oC, 1 hr N CN N O OMe 75 Figure A.1.5. 1H NMR spectrum of picolinonitrile 6 in CDCl3 at 25 °C. N CN 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) A (dt) 8.71 B (td) 7.84 C (dt) 7.69 D (ddd) 7.53 1 .0 0 1 .0 0 0 .9 8 0 .9 2 1 .8 4 H 2 O 7 .2 6 C D C l3 7 .5 1 7 .5 2 7 .5 2 7 .5 3 7 .5 3 7 .5 3 7 .5 4 7 .5 4 7 .6 8 7 .6 9 7 .6 9 7 .7 0 7 .7 0 7 .7 0 7 .8 3 7 .8 3 7 .8 4 7 .8 5 7 .8 6 7 .8 6 8 .7 0 8 .7 0 8 .7 0 8 .7 1 8 .7 1 8 .7 1 76 Figure A.1.6. 13C NMR spectrum of picolinonitrile 6 in CDCl3 at 25 °C. N CN 020406080100120140160180 13C (ppm) 7 6 .9 1 7 7 .1 6 7 7 .4 2 1 1 7 .2 7 1 2 7 .0 5 1 2 8 .6 2 1 3 4 .0 2 1 3 7 .1 5 1 5 1 .2 0 77 Synthesis of picolinimidamide 7 Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36.5 μL of methyl picolinate 3 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 50 °C for 0.3 hr. Rotavap THF. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford product 33.4 mg (92%) of product picolinimidamide 7 as an off-white solid. 1H NMR (500 MHz, CDCl3) δ 8.6 (m, 1H), 8.1 (d, J = 7.9 Hz, 1H), 7.8 (td, J = 7.7, 1.8 Hz, 1H), 7.4 (dd, J = 7.5, 4.9 Hz, 1H), 5.9 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 161.1, 150.8, 148.4, 137.0, 125.2, 120.8. N NH NH2 3.0 equiv NaHMDS THF, 50 oC, 1 hrN O OMe 78 Figure A.1.7. 1H NMR spectrum of picolinimidamide 7 in CDCl3 at 25 °C. N NH NH2 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) 2 .7 1 1 .0 0 0 .9 8 0 .9 9 1 .0 0 2 .0 4 H 2 O 5 .9 4 7 .2 6 C D C l3 7 .3 4 7 .3 5 7 .3 6 7 .3 7 7 .7 6 7 .7 6 7 .7 8 7 .7 8 7 .7 9 7 .7 9 7 .8 3 8 .1 0 8 .1 2 8 .5 5 8 .5 6 8 .5 6 8 .6 3 8 .6 4 79 Figure A.1.8. 13C NMR spectrum of picolinimidamide 7 in CDCl3 at 25 °C. N NH NH2 102030405060708090100110120130140150160170180 13C (ppm) 7 6 .9 1 7 7 .1 6 7 7 .4 1 1 2 0 .8 1 1 2 5 .2 1 1 3 7 .0 3 1 4 8 .3 5 1 5 0 .7 8 1 6 1 .0 6 80 Synthesis of isonicotinamide 9 Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar, containing 42 mg of methyl isonicotinate (8) (0.30 mmol). The reaction was stirred at 70 °C for 0.3 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80% ethyl acetate in hexanes) afforded 31 mg (85%) of product isonicotinamide 9 as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.9 (s, 2H), 7.1 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 167.5, 148.9, 140.7, 121.1. 3.0 equiv NaHMDS toluene, 70 oC, 0.3 hr N O NH2 N O OMe 81 Figure A.1.9. 1H NMR spectrum of isonicotinamide 9 in CDCl3:DMSO-d6 = 1:1 at 25 °C. N OH2N 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 1H (ppm) A (s) 7.93 B (s) 7.05 1 .0 2 0 .9 8 82 Figure A.1.10. 13C NMR spectrum of isonicotinamide 9 in CDCl3:DMSO-d6 = 1:1 at 25 °C. N OH2N 0102030405060708090100110120130140150160170180 13C (ppm) 4 7 .3 4 4 7 .5 2 4 7 .6 9 4 7 .8 6 4 8 .0 3 4 8 .2 0 4 8 .3 7 7 6 .3 6 7 6 .6 2 7 6 .8 7 1 2 1 .1 3 1 4 0 .8 9 1 4 8 .9 9 1 6 7 .5 1 83 Synthesis of isonicotinimidamide 10 Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar, containing 42 mg of methyl isonicotinate 8 (0.30 mmol). The reaction was stirred at 70 °C for 1.0 hr. Rotavap THF. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford product 34.8 mg (96%) of product isonicotinimidamide 10 as an off-white solid. 1H NMR (500 MHz, CDCl3) δ 8.4 (m, 2H), 7.3 (m, 2H), 5.7 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 162.7, 150.2, 143.6, 120.6. 3.0 equiv NaHMDS THF, 70 oC, 1.0 hr N NH NH2 N O OMe 84 Figure A.1.11. 1H NMR spectrum of isonicotinimidamide 10 in CDCl3:DMSO-d6 = 7:1 at 25 °C. N NHH2N 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 1H (ppm) A (dd) 8.41 B (dd) 7.31 C (s) 5.74 1 .4 0 0 .9 8 1 .0 0 5 .7 4 7 .3 0 7 .3 0 7 .3 1 7 .3 2 7 .3 2 7 .3 3 8 .3 9 8 .3 9 8 .4 0 8 .4 1 8 .4 2 8 .4 3 85 Figure A.1.12. 13C NMR spectrum of isonicotinimidamide 10 in CDCl3:DMSO-d6 = 7:1 at 25 °C. N NHH2N 0102030405060708090100110120130140150160170180 13C (ppm) 7 7 .0 8 7 7 .2 9 7 7 .5 0 1 2 0 .6 2 1 4 3 .6 4 1 5 0 .1 8 1 6 2 .7 4 86 Synthesis of nicotinamide 12 Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar, containing 42 mg of methyl nicotinate 11 (0.30 mmol). The reaction was stirred at 70 °C for 1.0 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (80% ethyl acetate in hexanes) afforded 27.8 mg (76%) of product nicotinamide 12 as a off white solid. 1H NMR (500 MHz, CDCl3) δ 8.5 (m, 1H), 8.1 (m, 1H), 7.6 (m, 1H), 7.5 (s, 1H), 6.8 (d, J = 7.9 Hz, 1H), 6.6 (s, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.1, 150.7, 147.9, 134.2, 128.6, 121.9, 121.9. 2.0 equiv NaHMDS toluene, 70 oC, 1.0 hr N O NH2 N O OMe 87 Figure A.1.13. 1H NMR spectrum of nicotinamide 12 in CDCl3:DMSO-d6 = 1:1 at 25 °C. N O NH2 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (s) 8.51 B (m) 8.09 C (m) 7.64 D (s) 7.46 E (dd) 6.81 F (m) 6.58 0 .9 0 0 .7 6 0 .9 5 0 .9 6 0 .9 6 1 .0 0 6 .5 7 6 .5 7 6 .6 0 6 .8 0 6 .8 0 6 .8 1 6 .8 2 7 .4 6 7 .6 3 7 .6 3 7 .6 4 7 .6 5 7 .6 5 7 .6 5 8 .0 8 8 .0 8 8 .0 9 8 .0 9 8 .5 1 8 .5 1 88 Figure A.1.14. 13C NMR spectrum of nicotinamide 12 in CDCl3:DMSO-d6 = 1:1 at 25 °C. N O NH2 020406080100120140160180 13C (ppm) 3 8 .3 5 3 8 .5 1 3 8 .6 8 3 8 .8 5 3 9 .0 2 3 9 .1 8 3 9 .3 5 7 6 .9 1 C D C l3 7 6 .9 7 7 7 .1 7 C D C l3 7 7 .2 3 7 7 .4 3 C D C l3 7 7 .5 0 1 2 1 .9 7 1 2 8 .5 9 1 3 4 .1 6 1 4 7 .9 6 1 5 0 .6 7 1 6 6 .0 9 89 Synthesis of nicotinimidamide 13 Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar, containing 42 mg of methyl nicotinate 11 (0.30 mmol). The reaction was stirred at 70 °C for 1.0 hr. Rotavap THF. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford product 34.4 mg (95%) of product nicotinimidamide 13 as a red oil. 1H NMR (500 MHz, CDCl3) δ 8.8 (d, J = 2.4 Hz, 1H), 8.7 (dt, J = 4.9, 1.5 Hz, 1H), 7.9 (dt, J = 8.1, 2.1 Hz, 1H), 7.3 (dd, J = 7.9, 4.9 Hz, 1H), 5.7 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 163.2, 151.4, 147.4, 133.8, 132.2, 123.5. 3.0 equiv NaHMDS THF, 70 oC, 1.0 hr N NH NH2 N O OMe 90 Figure A.1.15. 1H NMR spectrum of nicotinimidamide 13 in CDCl3 at 25 °C. N NH NH2 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (d) 8.85 B (dt) 8.65 C (dt) 7.91 D (dd) 7.33 E (s) 5.68 2 .7 0 1 .1 0 1 .1 0 1 .0 7 1 .0 4 5 .6 8 7 .2 6 C D C l3 7 .3 2 7 .3 3 7 .3 3 7 .3 4 7 .9 0 7 .9 0 7 .9 1 7 .9 1 7 .9 2 7 .9 2 8 .6 4 8 .6 5 8 .6 5 8 .6 5 8 .6 6 8 .6 6 8 .8 5 8 .8 5 91 Figure A.1.16. 13C NMR spectrum of nicotinimidamide 13 in CDCl3 at 25 °C. N NH NH2 102030405060708090100110120130140150160170180 13C (ppm) 7 6 .8 1 7 7 .0 7 7 7 .3 2 1 2 3 .4 8 1 3 2 .2 5 1 3 3 .8 3 1 4 7 .3 7 1 5 1 .4 5 1 6 3 .2 2 92 Synthesis of benzamide 15 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 38 μL of methyl benzoate 14 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 50 °C for 1.0 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (40% ethyl acetate in hexanes) afforded 28.3 mg (78%) of product benzamide 15 as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.8 (dt, J = 7.0, 1.4 Hz, 2H), 7.5 (m, 1H), 7.4 (dd, J = 8.5, 7.0 Hz, 2H), 6.2 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 169.6, 133.4, 132.0, 128.6, 127.4. 3.0 equiv NaHMDS toluene, 50 oC, 1.0 hr O NH2 O OMe 93 Figure A.1.17. 1H NMR spectrum of benzamide 15 in CDCl3 at 25 °C. O NH2 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (dt) 7.82 B (m) 7.52 C (dd) 7.44 D (s) 6.17 2 .0 5 1 .9 8 0 .9 7 2 .0 1 1 .7 8 H 2 O 6 .1 7 7 .2 6 C D C l3 7 .4 3 7 .4 3 7 .4 4 7 .4 5 7 .4 6 7 .4 6 7 .5 1 7 .5 1 7 .5 2 7 .5 2 7 .5 3 7 .5 3 7 .5 4 7 .5 4 7 .5 4 7 .8 1 7 .8 1 7 .8 1 7 .8 2 7 .8 2 7 .8 3 94 Figure A.1.18. 13C NMR spectrum of benzamide 15 in CDCl3 at 25 °C. O NH2 020406080100120140160180 13C (ppm) 7 6 .7 9 7 7 .0 5 7 7 .3 0 1 2 7 .3 5 1 2 8 .6 4 1 3 2 .0 1 1 3 3 .4 1 1 6 9 .6 0 95 Synthesis of benzimidamide 16 (a) Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 38 μL of methyl benzoate 14 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 80 °C for 2.0 hr, then left at 25 °C for 24 hr. Rotavap THF. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford product 34.4 mg (92%) of product benzimidamide 16 as a yellow solid. 1) 3.0 equiv NaHMDS THF, 80 oC, 2.0 hr NH NH2 O OMe 2) 25 oC, 24 hr 96 Synthesis of benzimidamide 16 (b) Solid sodium hexamethyldisilazide (NaHMDS, 330 mg, 1.8 mmol) was dissolved in 3.0 mL of THF at 25 °C. 1.5 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 31 μL of benzonitrile 17 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 24 hr. Rotavap THF. DI water (1.0 mL) was then added. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 1 hr. Saturated NaOH solution was then added until pH = 12. Mixture was partitioned between water (1.0 mL) and chloroform (4.0 mL). The aqueous layer was separated and extracted further with three 4.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated to afford product 34.2 mg (95%) of product benzimidamide 16 as a yellow solid. 1H NMR (500 MHz, CDCl3) δ 7.6 (m 2H), 7.5 (m, 1H), 7.4 (qd, J = 7.8, 3.6 Hz, 3H), 5.6 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.1, 136.5, 130.5, 128.8, 126.0. 3.0 equiv NaHMDS THF, 25 oC, 24 hr NH NH2CN 97 Figure A.1.19. 1H NMR spectrum of benzimidamide 16 in CDCl3 at 25 °C. NH NH2 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (m) 7.59 B (qd) 7.41 C (s) 5.64 0 .9 7 1 .7 7 1 .2 6 5 .6 4 7 .3 9 7 .3 9 7 .3 9 7 .4 0 7 .4 1 7 .4 2 7 .4 3 C D C l3 7 .4 3 7 .4 3 7 .4 4 7 .4 4 7 .5 8 7 .5 8 7 .5 9 7 .6 0 7 .6 0 98 Figure A.1.20. 13C NMR spectrum of benzimidamide 16 in CDCl3 at 25 °C. NH NH2 020406080100120140160180 13C (ppm) 7 6 .8 1 7 7 .0 7 7 7 .3 2 1 2 6 .0 1 1 2 8 .7 6 1 3 0 .5 1 1 3 6 .5 0 1 6 6 .1 0 99 Synthesis of 2-nitroaniline 19 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36 μL of 2- fluoronitrobenzene 18 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 2.0 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (10% ethyl acetate in hexanes) afforded 35.2 mg (85%) of product 2-nitroaniline 19 as a yellow oil. 1H NMR (500 MHz, CDCl3) δ 8.1 (dd, J = 8.7, 1.5 Hz, 1H), 7.4 (ddd, J = 8.4, 7.0, 1.5 Hz, 1H), 6.8 (dd, J = 8.4, 1.3 Hz, 1H), 6.7 (ddd, J = 8.4, 7.0, 1.3 Hz, 1H), 6.1 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 144.6, 135.6, 132.3, 126.2, 118.7, 117.0. NO2 F NO2 NH2 2.0 equiv NaHMDS THF, 25 oC, 2.0 hr 100 Figure A.1.21. 1H NMR spectrum of 2-nitroaniline 19 in CDCl3 at 25 °C. NO2 NH2 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (dd) 8.12 B (dd) 6.80 C (ddd) 6.71 D (ddd) 7.36 E (s) 6.05 2 .6 8 1 .0 8 1 .0 6 1 .1 2 1 .0 0 6 .0 5 6 .6 8 6 .6 8 6 .6 9 6 .6 9 6 .7 0 6 .7 1 6 .7 1 6 .7 2 6 .7 2 6 .7 3 6 .7 3 6 .7 8 6 .7 9 6 .8 0 6 .8 0 6 .8 1 6 .8 1 6 .8 3 6 .8 3 7 .3 4 7 .3 4 7 .3 5 7 .3 6 7 .3 6 7 .3 7 7 .3 7 7 .3 8 8 .1 0 8 .1 1 8 .1 1 8 .1 2 8 .1 3 8 .1 3 8 .1 4 101 Figure A.1.22. 13C NMR spectrum of 2-nitroaniline 19 in CDCl3 at 25 °C. NO2 NH2 020406080100120140160180 13C (ppm) 7 6 .7 8 7 7 .0 4 7 7 .2 9 1 1 7 .0 0 1 1 8 .7 4 1 2 6 .2 5 1 4 4 .6 3 102 Synthesis of 3-chloro-2-nitroaniline 21 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toleune at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 36 μL of 1-chloro-3-fluoro- 2-nitrobenzene 20 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 2.0 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (10% ethyl acetate in hexanes) afforded 39.8 mg (77%) of product 3-chloro-2-nitroaniline 21 as a “red-brown” solid. 1H NMR (500 MHz, CDCl3) δ 7.2 (t, J = 8.1 Hz, 1H), 6.8 (d, J = 7.9 Hz, 1H), 6.7 (d, J = 8.4 Hz, 1H), 4.9 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 143.0, 135.2, 132.6, 128.3, 120.1, 116.6. NO2 F NO2 NH2 1) 2.0 equiv NaHMDS toluene, 25 oC, 2.0 hr ClCl 2) 2M HCl 103 Figure A.1.23. 1H NMR spectrum of 3-chloro-2-nitroaniline 21 in CDCl3 at 25 °C. NO2 NH2 Cl 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (t) 7.15 B (d) 6.81 C (d) 6.71 D (s) 4.92 2 .0 7 0 .9 7 0 .9 8 0 .9 8 4 .9 2 6 .7 0 6 .7 2 6 .8 0 6 .8 1 7 .1 3 7 .1 5 7 .1 6 7 .2 6 C D C l3 104 Figure A.1.24. 13C NMR spectrum of 3-chloro-2-nitroaniline 21 in CDCl3 at 25 °C. NO2 NH2 Cl 020406080100120140160180 13C (ppm) 7 6 .9 0 7 7 .1 6 7 7 .4 1 1 1 6 .6 0 1 2 0 .0 7 1 2 8 .3 5 1 3 2 .6 1 1 3 5 .1 4 1 4 3 .0 1 105 Synthesis of 3-fluoro-2-nitroaniline 23 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toleune at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 35 μL of 2,6- difluoronitrobenzene 22 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 2.0 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (10% ethyl acetate in hexanes) afforded 40.2 mg (85%) of product 3-fluoro-2-nitroaniline 23 as a brown solid. 1H NMR (500 MHz, CDCl3) δ 7.2 (td, J = 8.3, 5.4 Hz, 1H), 6.6 (d, J = 8.5, 1.5 Hz, 1H), 6.7 (ddd, J = 11.4, 8.1, 1.3 Hz, 1H), 5.7 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 158.5, 156.4, 145.1, 135.6, 134.3, 134.3, 124.9, 113.5, 113.5, 104.8, 104.6, 104.6. NO2 F NO2 NH2 1) 2.0 equiv NaHMDS toluene, 25 oC, 2.0 hr FF 2) 2M HCl 106 Figure A.1.25. 1H NMR spectrum of 3-fluoro-2-nitroaniline 23 in CDCl3 at 25 °C. NO2 NH2 F 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (td) 7.22 B (dt) 6.58 C (ddd) 6.46 D (s) 5.67 1 .9 5 1 .0 1 1 .0 1 1 .0 4 1 .6 3 H 2 O 5 .6 7 6 .4 4 6 .4 4 6 .4 6 6 .4 6 6 .4 7 6 .4 7 6 .4 8 6 .4 8 6 .5 7 6 .5 7 6 .5 7 6 .5 9 6 .5 9 6 .5 9 7 .1 9 7 .2 0 7 .2 1 7 .2 2 7 .2 3 7 .2 4 7 .2 6 C D C l3 107 Figure A.1.26. 13C NMR spectrum of 3-fluoro-2-nitroaniline 23 in CDCl3 at 25 °C. NO2 NH2 F 020406080100120140160180 13C (ppm) 7 6 .8 1 7 7 .0 7 7 7 .3 2 1 0 4 .6 1 1 0 4 .7 9 1 1 3 .4 9 1 1 3 .5 2 1 3 4 .2 5 1 3 4 .3 4 1 4 5 .0 8 1 5 6 .4 2 1 5 8 .5 0 108 Synthesis of pyridin-2-amine 25 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toleune at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 31 μL of 2-fluoropyridine 24 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 110 °C for 2.0 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (20% ethyl acetate in hexanes) afforded 15.6 mg (55%) of product pyridin-2-amine 25 as an off-white solid. 1H NMR (500 MHz, CDCl3) δ 8.1 (d, J = 5.4, 2.0 Hz, 1H), 7.4 (ddd, J = 8.6, 7.1, 1.9 Hz, 1H), 6.6 (ddd, J = 7.2, 5.1, 1.0 Hz, 1H), 6.5 (m, 1H), 4.5 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 158.6, 148.2, 137.8, 114.4, 108.7. N F N NH2 1) 2.0 equiv NaHMDS toluene, 110 oC, 2.0 hr 2) 2M HCl 109 Figure A.1.27. 1H NMR spectrum of pyridin-2-amine 25 in CDCl3 at 25 °C. N NH2 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (dd) 8.05 B (ddd) 7.39 C (ddd) 6.61 D (m) 6.47 E (s) 4.51 2 .0 0 1 .0 5 1 .0 5 1 .0 2 0 .9 6 4 .5 1 6 .4 6 6 .4 6 6 .4 6 6 .4 7 6 .4 8 6 .4 8 6 .6 0 6 .6 0 6 .6 1 6 .6 1 6 .6 1 6 .6 1 6 .6 2 6 .6 2 7 .2 6 C D C l3 7 .3 8 7 .3 8 7 .3 9 7 .3 9 7 .4 0 7 .4 1 7 .4 1 8 .0 4 8 .0 4 8 .0 5 8 .0 6 110 Figure A.1.28. 13C NMR spectrum of pyridin-2-amine 25 in CDCl3 at 25 °C. N NH2 020406080100120140160180 13C (ppm) 7 6 .9 1 7 7 .1 6 7 7 .4 1 1 0 8 .6 7 1 1 4 .0 4 1 3 7 .7 9 1 4 8 .2 2 1 5 8 .5 6 111 Synthesis of 6-fluoropyridin-2-amine 27 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toleune at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 28 μL of 2,6- difluoropyridine 26 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 110 °C for 2.0 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (20% ethyl acetate in hexanes) afforded 25.6 mg (76%) of product 6-fluoropyridin-2-amine 27 as an off-white solid. 1H NMR (500 MHz, CDCl3) δ 7.5 (q, J = 8.0 Hz, 1H), 6.3 (dd, J = 7.9, 2.3 Hz, 1H), 6.2 (dd, J = 7.8, 2.2 Hz, 1H), 4.7 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 164.2, 162.3, 157.9, 157.7, 142.2, 142.2, 104.6, 104.6, 97.1, 96.8. N F N NH2 1) 2.0 equiv NaHMDS toluene, 110 oC, 2.0 hr 2) 2M HCl F F 112 Figure A.1.29. 1H NMR spectrum of 6-fluoropyridin-2-amine 27 in CDCl3 at 25 °C. NF NH2 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (q) 7.46 B (dd) 6.29 C (dd) 6.18 D (s) 4.66 1 .9 8 1 .0 0 0 .9 9 1 .0 2 4 .6 6 6 .1 7 6 .1 8 6 .1 9 6 .2 0 6 .2 8 6 .2 9 6 .3 0 6 .3 0 7 .2 6 C D C l3 7 .4 3 7 .4 5 7 .4 7 7 .4 8 113 Figure A.1.30. 13C NMR spectrum of 6-fluoropyridin-2-amine 27 in CDCl3 at 25 °C. NF NH2 020406080100120140160180 13C (ppm) 7 6 .9 1 7 7 .1 6 7 7 .3 6 7 7 .4 1 9 6 .8 1 9 7 .1 0 1 0 4 .5 8 1 0 4 .6 1 1 4 2 .1 6 1 4 2 .2 3 1 5 7 .7 5 1 5 7 .8 8 1 6 2 .3 1 1 6 4 .1 9 114 Synthesis of (R)-2-amino-1-phenylethan-1-ol 29 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of toleune at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 35 μL of (R)-2- phenyloxirane 28 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 60 °C for 24 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (20% ethyl acetate in hexanes) afforded 35.4 mg (86%) of product (R)-2-amino-1-phenylethan-1-ol 29 as an off- white solid. 1H NMR (500 MHz, CDCl3) δ 7.4 (m, 4H), 7.3 (m, 1H), 4.7 (dd, J = 7.9, 3.9 Hz, 1H), 3.0 (m, 1H), 2.8 (dd, J = 12.7, 7.8j Hz, 1H), 2.1 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 142.6, 128.6, 127.7, 126.0, 74.4, 49.3. 1) 2.0 equiv NaHMDS toluene, 60 oC, 24 hr 2) 2M HClPh O Ph NH2 OH 115 Figure A.1.31. 1H NMR spectrum of (R)-2-amino-1-phenylethan-1-ol 29 in CDCl3 at 25 °C. Ph NH2 OH 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (dd) 4.65 B (dd) 3.03 C (dd) 2.82 D (s) 2.06 E (m) 7.35 F (dt) 7.28 3 .2 3 0 .9 8 0 .8 8 1 .0 0 1 .2 4 4 .3 8 2 .0 6 2 .8 0 2 .8 2 2 .8 3 2 .8 4 3 .0 1 3 .0 2 3 .0 3 3 .0 4 4 .6 3 4 .6 4 4 .6 5 4 .6 6 7 .2 6 7 .2 7 7 .2 8 7 .2 8 7 .2 9 7 .3 0 7 .3 3 7 .3 5 7 .3 5 7 .3 6 116 Figure A.1.32. 13C NMR spectrum of (R)-2-amino-1-phenylethan-1-ol 29 in CDCl3 at 25 °C. Ph NH2 OH 020406080100120140160180 13C (ppm) 4 9 .3 4 7 4 .3 5 7 6 .9 1 7 7 .1 6 7 7 .3 6 7 7 .4 1 1 2 6 .0 1 1 2 7 .7 1 1 2 8 .5 7 1 4 2 .5 6 117 Synthesis of 1-aminooctan-2-ol 31 Solid sodium hexamethyldisilazide (NaHMDS, 110 mg, 0.6 mmol) was dissolved in 2.0 mL of THF at 25 °C. 2.0 mL of the NaHMDS solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 46 μL of 2-hexyloxirane 30 (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 24 hr. 2M HCl aqueous solution was added to adjust pH = 1, which then was stirred at 25 °C for 24 hr. Saturated NaOH solution was then added until pH = 12. Biphasic mixture was partitioned between water (1.0 mL) and chloroform (5.0 mL). The aqueous layer was separated and extracted further with three 5.0 mL portions of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash column chromatography (30% methanol in dichloromethane) afforded 33 mg (76%) of product 1-aminooctan-2-ol 31 as white solid. 1H NMR (500 MHz, CDCl3) δ 3.5 (dp, J = 7.9, 3.9 Hz, 1H), 2.8 (d, J =12.5 Hz, 1H), 2.5 (dd, J = 12.6, 8.4 Hz, 1H), 2.2 (s, 3H), 1.42 (m, 2H), 1.3 (m, 8H), 0.9 (t, J = 6.2 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 71.9, 47.3, 34.8, 31.8, 29.4, 25.7, 22.6, 14.1. 1) 2.0 equiv NaHMDS THF, 25 oC, 24 hr 2) 2M HCln-C6H13 O NH2 OH n-C6H13 118 Figure A.1.33. 1H NMR spectrum of 1-aminooctan-2-ol 31 in CDCl3 at 25 °C. NH2 OH n-C6H13 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (dp) 3.50 B (d) 2.83 C (dd) 2.50 D (m) 1.42 E (m) 1.28 F (t) 0.87 G (s) 2.16 3 .0 7 8 .0 2 3 .0 9 3 .1 6 0 .9 4 0 .9 0 0 .9 9 0 .8 6 0 .8 7 0 .8 8 1 .2 4 1 .2 7 1 .2 8 1 .3 0 1 .3 1 1 .3 7 1 .3 9 1 .4 0 1 .4 1 1 .4 2 1 .4 2 1 .4 3 1 .4 5 2 .1 6 2 .4 8 2 .5 0 2 .5 1 2 .5 3 2 .8 2 2 .8 4 3 .4 8 3 .4 8 3 .4 9 3 .5 0 3 .5 1 3 .5 1 3 .5 2 7 .2 6 C D C l3 7 .2 6 119 Figure A.1.34. 13C NMR spectrum of 1-aminooctan-2-ol 31 in CDCl3 at 25 °C. NH2 OH n-C6H13 020406080100120140160180 13C (ppm) 1 4 .0 9 2 2 .6 2 2 5 .6 8 2 9 .4 1 3 1 .8 1 3 4 .8 2 4 7 .3 5 7 1 .9 5 7 6 .7 8 7 7 .0 4 7 7 .2 4 7 7 .2 9 120 Structural Elucidation and Reaction Mechanism General procedure for sealed tube NMR spectroscopy A double-stoppered NMR tube under vacuum was flame-dried on a Schlenk line and allowed to passively cool to room temperature. It was then backfilled with argon and placed in a dry ice/acetone cooling bath. Individual stock solutions of methyl picolinate (3) and [15N]NaHMDS were prepared at room temperature. The appropriate amounts of methyl picolinate (3), picolinonitrile (6), [15N]NaHMDS, solvent, and (when applicable) co-solvent were added sequentially via gastight syringe. Some tubes were flame-sealed under partial vacuum while cold to minimize evaporation and some did not. The tubes were mixed on a vortex mixer and stored at –80 °C. Standard 1H, 13C, and 29Si direct detection spectra were recorded on a 11.8 T spectrometer at 500.1, 125.8, and 99.3 MHz, respectively. 1H, 13C, and 29Si resonances are referenced to standard TMS. 1H spectra recorded in protonated DMEA and THF solvents were acquired using a WET solvent suppression sequence, whereas the 29Si spectra were acquired utilizing the INEPT sequence. Integration of the NMR signals were determined using the line-fitting method included in MNova (Mestrelab research S.L.). 121 Figure A.1.35. 1H NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 7 and 0.10 M [15N]NaHMDS in DMEA reacting at 25 ºC, observed at a low temperature of –80 ºC. The reaction time for each sample is labeled as (a)–(h) and was varied as follows: 0, 60, 120, 180, 240, 300, 600, and 1200 seconds, respectively. Orange ( ) represents methyl picolinate 3, red ( )represents mixed aggregate 46. NaHMDS DMEA N OMe O N Na NaMe3Si Me3Si Me2NEt N SiMe3 O N 46 EtMe2N 7.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.0 1H (ppm) (a) (b) (c) (d) (e) (f) (g) (h) 122 Figure A.1.36. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in DMEA at 25 ºC, observed at a low temperature of –80 ºC. The reaction time for each sample is labeled as (a)–(h) and was varied as follows: 0, 60, 120, 180, 240, 300, 600, and 1200 seconds, respectively. Orange ( ) represents the O-sodium-imino TMS (δ = –9.70 ppm, JN-Si = 11.2 Hz), red ( )represents the [15N]NaHMDS TMS (δ = –16.04 ppm, JN-Si = 9.7 Hz and δ = –16.55 ppm, JN-Si = 10.3 Hz) in mixed aggregate 46. -17-16-15-11-101718 29Si (ppm) (a) (b) (c) (d) (e) (f) (g) (h) TMSOMe [15N]NaHMDS N Na NaMe3Si Me3Si Me2NEt N SiMe3 O NEtMe2N 123 Figure A.1.37. (a) 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in DMEA, within a sealed NMR tube for a period of 30 minutes at 25 ºC, observed at –110 ºC. (b) 29Si NMR spectra of an additional 1 equiv of [15N]NaHMDS added to the reaction mixture (a), observed at –110 ºC. -17.0-16.0-15.0-10.5-9.5 29Si (ppm) (a) (b) 124 Figure A.1.38. (a) 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in DMEA, within a sealed NMR tube for a period of 30 minutes at 25 ºC, observed at –110 ºC. (b) 29Si NMR spectra of an additional 1.0 equiv of [14N]NaHMDS added to the reaction mixture (a), observed at –110 ºC. -17.0-16.5-16.0-15.5-15.0-10.0-9.5-9.0 29Si (ppm) (a) (b) 125 Figure A.1.39. 1H and 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in DMEA within a sealed NMR tube for a period of 30 minutes at 25 ºC. The spectra were recorded at different temperatures, as follows: –110 ºC, –80 ºC, –60 ºC, –40 ºC, –20 ºC and 10 ºC, labeled as (a)–(f), respectively. The orange color ( ) represents the O-sodium-imino TMS signals at δ –9.70 ppm, JN-Si = 11.2 Hz, while the red color ( ) corresponds to the two [15N]NaHMDS TMS signals at δ –16.04 ppm, JN-Si = 9.7 Hz and δ –16.55 -18.5-17.0-15.5-11.5-10.0 29Si (ppm) -0.60-0.50-0.40-0.30-0.20-0.100.00 1H (ppm) (a) (b) (c) (d) (e) (f) –110 ºC –80 ºC –60 ºC –40 ºC –20 ºC 10 ºC TMSOMe HMDS N Na NaMe3Si Me3Si Me2NEt N SiMe3 O NEtMe2N N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt 126 ppm, JN-Si = 10.3 Hz in mixed aggregate 43. The purple color ( ) indicates the free [15N]NaHMDS. 127 Figure A.1.40. 29Si NMR spectra of 0.10 M [15N]NaHMDS in DMEA at –110 °C with incremental additions of methyl picolinate 3 in DMEA:pentane = 1:2 at – 78 °C. The equiv of total added substrate for (a) to (f) are as follows: 0.0, 0.1, 0.2, 39 N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt N OMe O 40 -17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0 29Si (ppm) (a) (b) (c) (d) (e) (f) 0 equiv 0.1 equiv 0.2 equiv 0.3 equiv 0.4 equiv 0.5 equiv 128 0.3, 0.4 and 0.5 respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). 129 39 N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt Me2NEt N Na N Na SiMe3Me3Si SiMe3Me3Si Me2NEt N OMe O 40 N Na N Na SiMe3Me3Si SiMe3Me3Si N OMe O N MeO O 41 N Me3Si Me3Si N O Na O N OMe OMe 42 130 Figure A.1.41. 29Si NMR spectra of 0.10 M [15N]NaHMDS in DMEA at –110 °C with incremental additions of methyl picolinate 3 in DMEA:pentane = 2:1 at – 78 °C. The equiv of total added substrate for (a) to (e) are as follows: 0.0, 0.5, 1.0, 1.5 and 2.0 respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). -21.6-21.2-20.8-17.0-16.6-16.2-15.8-15.4 29Si (ppm) (a) (b) (c) (d) (e) 0 equiv 0.5 equiv 1.0 equiv 1.5 equiv 2.0 equiv 131 Figure A.1.42. 1H NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in THF reacting at 25 ºC, observed at –110 ºC. Reaction times for (a)–(h) are as follows: only susbtrate (without base), 0, 30, 60, 120, 180, 480 and 2280 s, respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Orange ( ) represents methyl picolinate 3, red ( ) represents imino ether 56. NaHMDSN OMe O N OMe N SiMe3 56 THF 6.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.0 1H (ppm) (a) (b) (c) (d) (e) (f) (g) (h) substrate 0 s 30 s 60 s 120 s 180 s 480 s 2280 s 132 Figure A.1.43. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in THF reacting at 25 ºC, observed at –110 ºC. Reaction times for (a)–(h) are as follows: only [15N]NaHMDS, 0, 60, 120, 180, 480 and 2280 s, respectively. Orange ( )represents the TMS of O-methyl-imino ether 56 (δ –4.61 ppm, JN-Si = 10.0 Hz). N OMe N SiMe3 -30-26-22-18-14-10-6-2261014182226 29Si (ppm) (a) (b) (c) (d) (e) (f) (g) (h) [15N]NaHMDS 0 s 30 s 60 s 120 s 180 s 480 s 2280 s TMSOMe (TMS) 2 O HMDS NaOTMS 133 Figure A.1.44. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.10 M [15N]NaHMDS in THF reacting at 25 ºC, observed at –110 ºC. Reaction times for (a)–(h) are as follows: only [15N]NaHMDS, 0, 60, 120, 180, 480 and 2280 s, respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Orange ( )represents the TMS of O-methyl-imino ether 56 (δ –4.51 ppm, JN-Si = 10.0 Hz). -23.1-22.8-22.5-22.2-5.0-4.7-4.4-4.1 29Si (ppm) (a) (b) (c) (d) (e) (f) (g) (h) [15N]NaHMDS 0 s 30 s 60 s 120 s 180 s 480 s 2280 s 134 Crude mixture of imino ether 56 Solid sodium hexamethyldisilazide (NaHMDS, 165 mg, 0.9 mmol) was dissolved in 2.0 mL of tetrahydrofuran (THF) at room temperature. Subsequently, 2.0 mL of the resulting NaHMDS solution was introduced into a dry 5.0 mL Kimble vial fitted with a magnetic stir bar. To the reaction solution, 36 μL of methyl picolinate (0.30 mmol) was added, and the resulting mixture was stirred at 25 °C for 0.3 hours. The reaction was then quenched using 10 equiv of water, followed by removal of all solvent by rotary evaporation. The residue was dissolved in CDCl3, and the proton spectrum of the crude mixture was obtained. Figure A.1.45. 1H NMR spectra of crude mixture in CDCl3. Orange ( ) represents imino ether 28, red ( ) represents carboxamide 4 0.00.20.40.63.63.84.04.27.17.37.57.77.98.18.38.58.78.99.1 1H (ppm) 9 .4 5 3 .0 8 1 .0 1 2 .0 9 1 .0 0 N OMe N SiMe3 N NH2 O : = 85 : 15 135 Figure A.1.46. 1H NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 7 and 0.15 M [15N]NaHMDS in THF reacting at 25 ºC, observed at –110 ºC. Reaction times for (a)–(d) are as follows: 0 s, 2280 s, 6 h, 21 h, respectively. Orange ( ) represents the O-methyl-imino 56. 1H spectra are referenced to a TMS internal standard (0.00 ppm). Red ( ) represents silyated amidine 57. Blue ( ) represents benzene from Na / benzophenone still. NaHMDSN OMe N SiMe3 56 THF 57 N N N SiMe3 Me3Si Na 6.36.66.97.27.57.88.18.48.79.0 1H (ppm) (a) (b) (c) (d) 2280 s 6 h 21 h 0 h 136 Figure A.1.47. (a)1H NMR spectra of 0.050 M methyl picolinate 3 in THF, observed at –110 ºC (b)1H NMR spectra of 0.050 M methyl picolinate 3 and 0.15 M [15N]NaHMDS in THF before reaction, observed at –110 ºC. 1H spectra are referenced to a TMS internal standard (0.00 ppm). 7.57.77.98.18.38.58.78.99.1 1H (ppm) (a) (b) 137 Figure A.1.48. (a) 13C NMR spectra of 0.050 M methyl picolinate 3 in THF, observed at –110 ºC (b) 13C NMR spectra of 0.050 M methyl picolinate 3 and 0.15 M [15N]NaHMDS in THF before reaction, observed at –110 ºC. 13C spectra are referenced to a TMS internal standard (0.00 ppm). 137140143146149152155158161164167 13C (ppm) (a) (b) 138 Figure A.1.49. (a)–(c) 29Si NMR spectra of 0.10 M [15N]NaHMDS in DMEA at – 110 °C with incremental additions of THF. The equiv of THF for (a) to (c) are as follows: 0.0, 2.0, and 4.0 respectively. (d)–(h) 29Si NMR spectra are followed incremental additions of methyl picolinate 3 in DMEA:pentane = 1:2 solvent. The equiv of methyl picolinate 3 for (d) to (h) are as follows: 0.1, 0.2, 0.3, 0.4 and 0.5 respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). -22.2-22.0-16.8-16.4-16.0-15.6 29Si (ppm) (a) (b) (c) (d) (e) (f) (g) (h) 139 Figure A.1.50. 1H NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.06 M [15N]NaHMDS in THF reacting at 25 ºC, observed at –110 ºC. Reaction times for spectra (a)–(c) are as follows: 38 m, 16 h, 24 h, respectively. Spectrum (d) corresponds to picolinonitrile 6 sample dissolved in THF. 1H spectra are referenced to a TMS internal standard (0.00 ppm). Orange ( ) represents the O- methyl-imino ether 56. Red ( ) represents an authentic sample of picolinonitrile 6. N OMe N SiMe3 56 6 N CN 1.2 equiv NaHMDS THF N OMe O 3 24 h 7.27.47.67.88.08.28.48.68.89.0 1H (ppm) (a) (b) (c) (d) 38 m 16 h 24 h picolinonitrile 29 140 Figure A.1.51. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl picolinate 3 and 0.060 M [15N]NaHMDS in THF at 25 ºC, observed at a low temperature of –110 ºC. Reaction times for spectra (a)–(c) are as follows: 38 m, 16 h, 24 h, respectively. -22-18-14-10-6-22610141822 29Si (ppm) (a) (b) (c) 38 m 16 h 24 h TMSOMe (TMS)2O HMDS 56 NaOTMS [15N]NaHMDS 141 Figure A.1.52. (a) 1H NMR spectrum of crude O-methyl-imino ether 56 in CDCl3, observed at 25 ºC. (b) 1H NMR spectrum obtained after the reaction between O- methyl-imino ether 56 (from (a)) and 1 equiv of NaOMe in THF at 50 ºC for 30 minutes, followed by the evaporation of THF and subsequent dissolution of the resulting product in CDCl3. (c) 1H NMR spectrum obtained after the reaction between O-methyl-imino ether 56 (from (b)) and 1 equiv of NaOTMS in THF at 50 ºC for 30 minutes, followed by the evaporation of THF and subsequent dissolution of the resulting product in CDCl3. (d) 1H NMR spectrum obtained after the reaction between O-methyl-imino ether 55 (from (c)) and 0.20 equiv of NaHMDS in THF at 50 ºC for 30 minutes, followed by the evaporation of THF and subsequent dissolution of the resulting product in CDCl3. 1H spectra are referenced to CDCl3 (7.16 ppm). N OMe N SiMe3 56 7.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.6 1H (ppm) (a) (b) (c) (d) 142 Virtual coupling of amidine Figure A.1.53. 29Si NMR spectra of [15N2]56 showing virtual coupling (JN–Si = 8.8 Hz) and standard coupling in [15N1]56 (1JN–Si = 8.9 Hz and 3JN–Si = 2.8 Hz). N 15N 15N SiMe3 Me3Si Na [15N2]57 (3) [14N]NaHMDS N 15N N SiMe3 Me3Si Na [15N1]57 -15.7-15.5-15.3-15.1-14.9-14.7-14.5 29Si (ppm) [15N2]57 1JN-Si = 8.8 Hz [15N1]57 1JN-Si = 8.9 Hz 3JN-Si = 2.8 Hz 143 Figure A.1.54. 29Si NMR spectra of a reaction mixture containing 0.050 M picolinonitrile 6 and 0.10 M [15N]NaHMDS in THF, observed at –110 ºC. The reaction progress was monitored by analyzing the status of the sealed NMR tube at various reaction times and temperatures. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Spectra (a)–(c) represent the status of the sealed NMR tube at different reaction times and temperatures. (a) 0 m at 25 ºC. (b) 10 m at 25 ºC. (c) 10 m at 25 ºC, followed by 30 m at 50 ºC. [15N]NaHMDS N 15N N SiMe3 Me3Si Na [15N]57 N N 6 -23.4-23.0-22.6-22.2-16.0-15.6-15.2 29Si (ppm) (a) (b) (c) NaHMDS [15N]56 0 s 10 m, 25 ºC 10 m, 25 ºC then 30 m, 50 ºC 144 Figure A.1.55. (a) 1H NMR spectrum of 0.050 M picolinonitrile 6 in THF, observed at –110 ºC. (b) 1H NMR spectrum of 0.050 M methyl picolinate 3 and 0.15 M [15N]NaHMDS in THF before reaction, observed at –110 ºC. 1H spectra are referenced to a TMS internal standard (0.00 ppm). 7.37.57.77.98.18.38.58.78.9 1H (ppm) (a) (b) 145 Figure A.1.56. (a) 1H NMR spectra of 0.050 M picolinonitrile 6 in DMEA, observed at –110 ºC. (b) 1H NMR spectra of 0.050 M methyl picolinate 7 and 0.15 M [15N]NaHMDS in DMEA before reaction, observed at –110 ºC. 1H spectra are referenced to a TMS internal standard (0.00 ppm). 7.47.67.88.08.28.48.68.89.0 1H (ppm) (a) (b) 146 Figure A.1.57. (a) 29Si NMR spectra of 0.050 M picolinonitrile 6 in DMEA, observed at –110 ºC. (b) 29Si NMR spectra of 0.050 M methyl picolinate 3 and 0.15 M [15N]NaHMDS in DMEA before reaction, observed at –110 ºC. 1H spectra are referenced to a TMS internal standard (0.00 ppm). -16.1-15.8-15.5-15.2-14.9-14.6-14.3 29Si (ppm) δ = –15.20 ppm 1JN-Si = 8.5 Hz δ = –15.20 ppm 1JN-Si = 8.5 Hz (a) (b) 147 Figure A.1.58. 1H NMR spectra of a reaction mixture containing 0.050 M benzonitrile 17 and 0.10 M [15N]NaHMDS in THF reacting at 25 ºC, observed at – 110 ºC. Reaction times for spectra (b)–(e) are as follows: 0 s, 20 m, 140 m and 12 h respectively. Spectrum (a) corresponds to authentic benzonitrile 17 sample dissolved in THF. 1H spectra are referenced to a TMS internal standard (0.00 ppm). C N NaHMDS (2.0 equiv) N N SiMe3 Me3Si Na 5817 6.46.56.76.87.07.37.47.57.67.77.8 1H (ppm) (a) (b) (c) (d) (e) only 17 0 s 20 m 140 m 12 h 148 Figure A.1.59. 1H NMR spectra of a reaction mixture containing 0.050 M benzonitrile 17 and 0.10 M [15N]NaHMDS in THF reacting at 25 ºC and 80 ºC, observed at –110 ºC. The reaction mixture is the same as of Figure A.1.58. Spectrum (e) is the same spectrum in Figure A.1.58. After reacting at 80 ºC for 30 min, the NMR tube containing the reaction mixture was immediately put into a dry ice acetone bath, and spectrum (f) was taken. Spectra (e) and (f) represent the status of the sealed NMR tube at different reaction times and temperatures. (e) 12 h at 25 ºC, (f) 12 h at 25 ºC, followed by 30 m at 80 ºC.1H spectra are referenced to a TMS internal standard (0.00 ppm). 6.26.46.56.76.87.07.37.47.57.67.7 1H (ppm) (e) (f) 12 h, 25 ºC 12 h, 25 ºC then 30 m, 80 ºC 149 Figure A.1.60. 1H NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.15 M [15N]NaHMDS in THF reacting at 80 ºC, observed at –110 ºC. Reaction times for (a)–(f) are as follows: 0 m, 70 m, 140 m, 260 m, 380 m and C N NaHMDS (2.0 equiv) N N SiMe3 Me3Si Na 80 °C: 1:1.5 25 °C: 1:22 5817 (4)PhCO2Me NaHMDS THF 80 °C OMe O C N 17 N N SiMe3 Me3Si Na 58 6.56.66.76.86.97.07.27.37.47.57.67.77.87.9 1H (ppm) 0 s 70 m 140 m 260 m 380 m 500 m (a) (b) (c) (d) (e) (f) 150 500 m respectively. Orange ( ) represents methyl benzoate. Red ( ) represents benzonitrile 17. Blue ( ) represents amidine 58. 1H spectra are referenced to a TMS internal standard (0.00 ppm). 151 Figure A.1.61. NaHMDS monomer/dimer ratio in THF/cosolvent mixture of choice pentane, 2,5-Me2THF, 2,2,5,5-Me4THF at 50 °C and DFT-computed solvation effect of 2,5-Me2THF and 2,2,5,5-Me4THF. N Na N Na SiMe3Me3Si SiMe3Me3Si S S NNa(S)n Me3Si Me3Si 2.0 M THF 50 °C cosolvent pentane Me2THF Me4THF monomer/ dimer 1 : 23 1.3 : 1 1 : 3 N Me3Si Me3Si THF THF Na THF THF NNa(THF)3(Me2THF)Me3Si Me3Si NNa(THF)3(Me4THF)Me3Si Me3SiN Me3Si Me3Si THF THF Na THF THF ∆G° = 1.9 kcal/mol ∆G° = 7.9 kcal/mol – THF + Me2THF – THF + Me4THF 53 53 53a 53b 152 pentane cosolvent Figure A.1.62. 29Si NMR spectra of 0.10 M [15N]NaHMDS in pentane varying the concentration of THF at 50 °C. THF concentration for (a)–(c) are as follows: 0.41, 2.00, and 12.31 M (neat), respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Concentrations for THF and coupling constants of the [15N]NaHMDS 29Si peaks are listed below. -21.6-20.6-19.6-18.6-17.6-16.6-15.6 29Si (ppm) (a) (b) (c) 1JN–Si coupling constant (Hz)[THF] (M) (pentane cosolvent) 0.41 2.00 12.31 (neat) 8.62 8.81 13.03 153 2,5-Me2THF cosolvent Figure A.1.63. 29Si NMR spectra of 0.10 M [15N]NaHMDS in 2,5-Me2THF varying the concentration of THF at 50 °C. THF concentration for (a)–(c) are as follows: 0.00, 2.00, and 12.31 M (neat), respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Concentrations for THF and coupling constants of the [15N]NaHMDS 29Si peaks are listed below. -23.0-21.5-20.0-18.5-17.0-15.5-14.0 29Si (ppm) (a) (b) (c) 1JN–Si coupling constant (Hz) [THF] (M) (2,5-dimethylTHF cosolvent) 0.00 2.00 12.31 (neat) 8.81 11.23 13.03 154 2,2,5,5-Me4THF cosolvent Figure A.1.64. 29Si NMR spectra of 0.10 M [15N]NaHMDS in 2,2,5,5-Me4THF varying the concentration of THF at 50 °C. THF concentration for (a)–(c) are as follows: 0.00, 2.00, and 12.31 M (neat), respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Concentrations for THF and coupling constants of the [15N]NaHMDS 29Si peaks are listed below. -21.8-20.8-19.8-18.8-17.8-16.8-15.8 29Si (ppm) (a) (b) (c) 1JN–Si coupling constant (Hz)[THF] (M) (2,2,5,5-tetramethylTHF cosolvent) 0.00 2.00 12.31 (neat) 8.02 9.23 13.03 155 Rate Studies General procedure for in situ IR analyses IR spectra were recorded with an in situ IR spectrometer fitted with a 30-bounce, silicon-tipped probe. The spectra were acquired at a gain of 1 and a resolution of 4 cm−1. All tracked reactions were conducted under positive flow of argon from a Schlenk line. A representative reaction was carried out as follows: The IR probe was inserted through a teflon adapter and O-ring seal into an oven-dried, cylindrical flask fitted with a magnetic stir bar and a T-joint. The T-joint was capped with a septum for injections and an argon line. After evacuation under full vacuum, heating, and flushing with argon, the flask was charged with the 0.1 M NaHMDS in THF/cosolvent mixture of choice 2,2,5,5-Me4THF, 2,5-Me2THF, pentane and cooled to 0 °C in the ice bath chiller and left to stir for 15 min. A set of 256 baseline scans were collected and IR spectra were recorded every 15 seconds from 30 scans. At this point spectral collection was halted and an additional 256 baseline scans were collected. The spectrometer was configured to collect spectra ever 5 seconds from 16 scans. 1 set of scans was collected before addition of 0.12 M methyl picolinate in THF through the septum. The reaction was tracked over the disappearance of methyl picolinate complex (1733 cm–1) and appearance of the imino-ether (1706 cm–1). 156 Figure A.1.65. Emblematic addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M; 1737 cm–1) to form mixed aggregate 46 (1584 cm–1) at 25 °C in DMEA. (a) Plot of [methyl-2-picolinate 3] (M) and [mixed aggregate 46] (M) vs time (s). (b) IR spectra of methyl-2-picolinate 3 (first recorded spectrum) and mixed aggregate 46 (last recorded spectrum). 5 4 3 2 1 0 [c on ce nt ra tio n] x 1 03 / (M ) 120010008006004002000 time (s) 35 30 25 20 15 10 5 0 ab so rb an ce x 1 03 1750 1700 1650 1600 1550 1500 wavenumber (cm -1) 5 4 3 2 1 0 [m et hy l p ic ol in at e] x 1 03 (M ) 160012008004000 time (s) methyl-2-picolinate 3 mixed aggregate 46 – methyl-2-picolinate 3 – mixed aggregate 46 (b) (a) 157 Figure A.1.66. Addition of 0.0050 M NaHMDS to methyl-2-picolinate (3, 0.10 M) at 25 °C monitored by IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ae–bx (a = 8.1 x 10–3 ± 0.1 x 10–3; b = 1.5 x 10–3 ± 0.1 x 10–3). Figure A.1.67. Plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M) at 25 °C monitored by IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b (a = 2.4 x 10–3 ± 0.2 x 10–3; b = 8.3 x 10–6 ± 0.3 x 10–6). Table A.1.1. Average pseudo-first-order rate constants (kobsd) at various DMEA (pentane cosolvent) concentrations for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M) at 25 °C. 5 4 3 2 1 0 k o bs d x 10 3 / se c-1 43210 [DMEA] (M) 158 [DMEA] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.77 2.28 0.21 1.54 2.60 0.16 2.31 2.83 0.21 3.08 2.72 0.26 3.85 (neat) 2.39 0.09 4 3 2 1 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaHMDS] (M) 159 Figure A.1.68. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate (3, 0.050 M) in 3.8 M (neat) DMEA at 25 °C monitored by IR spectroscopy (1737 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b (a = 2.7 x 10–3 ± 0.2 x 10–3; b = –1.3 x 10–3 ± 0.1 x 10–3). Table A.1.2. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations for the addition of NaHMDS to methyl-2-picolinate (3, 0.0050 M) in 3.85 M (neat) DMEA at 25 °C. [NaHMDS] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.1 2.38 0.41 0.2 2.62 0.13 0.3 2.52 0.38 0.4 1.99 0.05 0.5 2.05 0.08 160 Figure A.1.69. Emblematic addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M; 1734 cm–1) to form imino ether 56 (1713 cm–1) at 25 °C in DMEA. (a) Plot of [methyl-2-picolinate 3] (M) and [imino ether 56] (M) vs time (s). (b) IR spectra of methyl-2-picolinate 3 (first recorded spectrum) and imino ether 56 (last recorded spectrum). 5 4 3 2 1 0 co nc en tra tio n x 10 3 (M ) 6005004003002001000 time (s) 5 4 3 2 1 0 -1 ab so rb an ce x 1 03 1780 1760 1740 1720 1700 1680 wavenunmber (cm–1) 56 3 3 56 (b) (a) 161 Figure A.1.70. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to methyl-2-picolinate (3, 0.0050 M) in 12.8 M (neat) THF at 0 °C monitored by IR spectroscopy (1731 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 2.4 x 10–3 ± 0.1 x 10–3; n = 0.44 ± 0.01). Table A.1.3. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations for for the addition of NaHMDS to methyl-2-picolinate (3, 0.0050 M) in 12.8 M (neat) THF at 0 °C. [NaHMDS] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.05 4.64 0.61 0.1 7.75 0.95 15 10 5 0 k o bs d x 1 03 / se c-1 0.50.40.30.20.10.0 [NaHMDS] (M) 162 0.2 13.40 2.62 0.3 15.94 1.11 0.4 15.14 0.42 0.5 17.59 1.67 Figure A.1.71. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to methyl- 2-picolinate (3, 0.0050 M) in 0.10 M NaHMDS at 0 °C monitored by IR spectroscopy (1732 cm–1). Curve A (Red) derives from pentane cosolvent and depicts an unweighted least-squares fit to axn/(1+ bxn)(1/1+cx2) (a = 2.4 × 10–3 ± 0.1 × 10–3; b = 1.3 × 10–1 ± 0.1 × 10–1; c = 0.6 × 10–3 ± 0.1 × 10–4; n = 5). Curve B (Blue) derives from 2,5-Me2THF cosolvent and depicts an unweighted least- 20 15 10 5 0 k o bs d x 1 03 / se c-1 121086420 [THF] (M) A B C 163 squares fit to y = axn/(1+ bxn) (a = 1.6 × 10–1 ± 0.1 × 10–1; b = 1.6 × 10–1 ± 0.1 × 10–1; n = 5). Curve C (Green) derives from 2,2,5,5-Me4THF cosolvent and depicts an unweighted least-squares fit to y = axn/(1+ bxn) (a = 8.2 × 10–4 ± 0.1 × 10–1; b = 7.9 × 10–2 ± 0.1 × 10–2; n = 2.2 ± 0.2). 164 Table A.1.4. Average pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M) at 0 °C. Red Cosolve nt: pentane [THF] / M kobsd x 103 / sec–1 Standard Deviation x 103 / sec–1 1.28 7.90 0.61 1.59 9.83 0.09 1.89 14.59 0.37 2.51 16.32 0.10 3.12 19.79 1.18 3.74 18.74 0.11 6.2 15.06 0.71 8.66 13.53 0.64 11.13 11.37 0.56 12.31 10.11 1.61 Table A.1.5. Average pseudo-first-order rate constants (kobsd) at various THF (2,5- Me2THF cosolvent) concentrations for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M) at 0 °C. Blue Cosolve nt: 2,5-Me2THF 165 [THF] / M kobsd x 103 / sec–1 Standard Deviation x 103 / sec–1 1.28 3.62 0.81 3.54 8.96 0.89 5.81 9.74 0.90 8.08 9.93 0.15 10.34 11.20 0.97 12.31 9.71 0.37 166 Table A.1.6. Average pseudo-first-order rate constants (kobsd) at various THF (2,2,5,5-Me4THF cosolvent) concentrations for the addition of NaHMDS (0.10 M) to methyl-2-picolinate (3, 0.0050 M) at 0 °C. Green Cosolve nt: 2,2,5,5-Me4THF [THF] / M kobsd x 103 / sec–1 Standard Deviation x 103 / sec–1 1.28 1.67 0.18 3.54 5.79 0.63 5.81 9.06 0.05 8.08 10.46 0.46 10.34 10.26 0.18 12.31 10.25 0.11 167 Figure A.1.72. Emblematic addition of NaHMDS (0.10 M) to picolinonitrile (6, 0.0050 M; 1584 cm–1) to form silyated amidine 57 (1486 cm–1) at –20 °C in THF. (a) Plot of [picolinonitrile 6] (M) and [silyated amidine 57] (M) vs time (s). (b) IR spectra of picolinonitrile 6 (first recorded spectrum) and silyated amidine 57 (last recorded spectrum). 5 4 3 2 1 0 -1 co nc en tra tio n x 10 3 (M ) 2000150010005000 time (s) 2.5 2.0 1.5 1.0 0.5 0.0 ab so rb an ce x 1 03 1600 1560 1520 1480 wavenumber (cm–1) 20 15 10 5 0 absorbance x 10 3 57 6 6 57 (b) (a) 168 Figure A.1.73. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 0.10 M NaHMDS at –20 °C monitored by IR spectroscopy (1584 cm–1). Curve A (red) derives from pentane cosolvent and depicts an unweighted least-squares fit to axn/(1 + bxn) (a = 2.5 × 101 ± 0.5 × 10–1; b = 1.7 × 102 ± 0.8 × 10–2; n = –5.8 ± 0.2). Table A.1.7. Average pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations for the addition of NaHMDS (0.10 M) to picolinonitrile (6, 0.0050 M) at –20 °C. Cosolve nt: pentane 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 k o bs d x / s ec -1 121086420 [THF] (M) 169 [THF] / M kobsd / sec-1 Standard Deviation / sec- 1 1.28 0.141 0.006 1.95 0.143 not replicated 2.62 0.119 not replicated 3.29 0.0813 not replicated 4.03 0.0439 0.0008 5.15 0.0239 not replicated 5.81 0.0134 not replicated 6.79 0.00730 0.001 9.55 0.00188 0.0007 12.31 0.00119 0.0004 2.5 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 121086420 [THF] (M) 170 Figure A.1.74. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 0.10 M NaHMDS at –20 °C monitored by IR spectroscopy (1584 cm–1), utilizing 2,5-Me2THF as cosolvent. 171 Figure A.1.75. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 0.10 M NaHMDS at –20 °C monitored by IR spectroscopy (1584 cm–1). Curve A (red) derives from pentane cosolvent. Curve B (blue) derives from 2,5-Me2THF cosolvent. The large rate difference between the two curves might be attributed to the difference in the NaHMDS ground state monomer/dimer ratio of the pentane cosolvent and 2,5-Me2THF cosolvent at low THF concentration. 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 k o bs d x / s ec -1 121086420 [THF] (M) 172 Figure A.1.76. Plot of kobsd vs [THF] (M) for the addition of NaHMDS to picolinonitrile (6) in pentane cosovent (red) and 29Si chemical shift (green) plotted versus [THF] in 2:1 pentane/toluene as cosolvent measured at −20 °C. The latter plot fits to a model based on an A2S2−AS4 equilibrium. 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 k o bs d x / s ec -1 121086420 [THF] (M) -21 -20 -19 -18 -17 -16 δ 29S i chem ical shift (ppm ) 173 Figure A.1.77. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 12.8 M (neat) THF at –20 °C monitored by IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 4.3 x 10–2 ± 0.1 x 10–2; n = 2.0 ± 0.1). Table A.1.8. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 3.8 M (neat) DMEA at 25 °C. [NaHMDS] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.1 0.67 0.02 10 8 6 4 2 0 k o bs d x 1 03 / se c-1 0.50.40.30.20.10.0 [NaHMDS] (M) 174 0.2 3.13 0.05 0.3 5.78 0.22 0.4 7.56 0.13 0.5 11.77 0.76 Figure A.1.78. Plot of kobsd vs [DMEA] (M) in pentane for the addition of NaHMDS (0.10 M) to picolinonitrile (6, 0.0050 M) at –40 °C monitored by IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn/(1+ bxn) (n = –1.9 ± 0.1; a = 2.7 × 10–2 ± 0.1 × 10–2; b = 7.1 × 10–3 ± 0.1 × 10– 2). 7 6 5 4 3 2 1 0 k o bs d x 1 03 / se c-1 43210 [DMEA] (M) 175 Table A.1.9. Average pseudo-first-order rate constants (kobsd) at various DMEA (pentane cosolvent) concentrations for the addition of NaHMDS (0.10 M) to picolinonitrile (6, 0.0050 M) at –40 °C. [DMEA] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.77 6.54 0.63 1.02 4.80 0.41 1.28 2.63 0.02 1.54 1.54 0.04 2.31 0.91 0.04 3.08 0.57 0.04 3.85 (neat) 0.38 0.03 176 Figure A.1.79. Plot of kobsd vs [NaHMDS] (M) for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 3.85 M (neat) DMEA at –40 °C monitored by IR spectroscopy (1584 cm–1). The curve depicts an unweighted least-squares fit to y = axn (a = 2.1 x 10–2 ± 0.1 x 10–2; n = 1.1 ± 0.1). Table A.1.10. Average pseudo-first-order rate constants (kobsd) at various NaHMDS concentrations for the addition of NaHMDS to picolinonitrile (6, 0.0050 M) in 3.85 M (neat) DMEA at –40 °C. [NaHMDS] / M kobsd x 103 / sec–1 Standard Deviation x 103/ sec–1 0.1 1.23 0.13 0.2 2.66 1.05 0.3 5.35 0.94 10 8 6 4 2 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaHMDS] (M) 177 0.4 6.65 0.98 0.5 9.09 1.36 178 Computational Data General computational methods DFT calculations were performed with the Gaussian 16 program package. Geometry optimizations and single point energies were computed at the M06- 2X/def2-SVP level of theory and M06-2X/def2-TZVP level of theory respectively. A pruned (99,590) integration grid was used for all computations as well. CYLview Visualization Software was used for all ball-and- stick structures. Energies are defined as follows: G is the sum of electronic and thermal free energies calculated at the M06-2X level of theory (Hartrees; T = 298.15 K). GSP is derived from a single point calculation corresponding to the DFT-optimized geometry with the larger basis set (def2-TZVP) and includes a thermal correction from the optimization. Hydrogens have been removed from ball-and-stick models to improve clarity. A vibrational frequency analysis was conducted at the same level of theory as the geometry optimizations (M06-2X/def2-SVP). The optimized geometries characterized as local minima on the potential energy surface have no imaginary frequencies, while each transition state possesses exactly one. Transition structures were verified with bi-directional IRC calculations. 179 DFT-computed ground state structures of methyl picolinate 3 and NaHMDS in DMEA N Na N Na SiMe3Me3Si SiMe3Me3Si Me3N N OMe O 44 N Na N Na SiMe3Me3Si SiMe3Me3Si Me3N Me3N 39 N Na N Na SiMe3Me3Si SiMe3Me3Si N OMe O N MeO O 41 N O OMe ∆G° = –5.0 kcal/mol + N O OMe ∆G° = –7.9 kcal/mol + 1/2 1/2 1/2 N Na N Na SiMe3Me3Si SiMe3Me3Si N OMe O N MeO O 41 N Me3Si Me3Si N O Na O N OMe OMe 42 N O OMe ∆G° = 2.7 kcal/mol + 1/2 – Me3N – Me3N N Me3Si Me3Si N O Na O N OMe OMe 42 N Me3Si Me3Si O N Na O N OMe OMe 42a ∆G° = 10.4 kcal/mol N Me3Si Me3Si Na O N OMe 42b ∆G° = –8.4 kcal/mol N Na N Na SiMe3Me3Si SiMe3Me3Si Me3N N OMe O 44 ∆G° = 5.4 kcal/mol N Na N Na SiMe3Me3Si SiMe3Me3Si Me3N N OMe O 44b NMe3+ Me3N N Me3Si Me3Si N O Na O N OMe OMe 42 N Me3Si Me3Si NO Na O N MeO MeO 42c NMe3 ∆G° = 4.5 kcal/mol + Me3N N O OMe + 180 Scheme A.1.1. DFT-computed free energies for the methyl picolinate 3 and NaHMDS complexed ground state structures in DMEA using Me3N as a DMEA surrogate. 181 DFT-computed ground state structures of mixed aggregate 46 Scheme A.1.2. DFT-computed free energies for the mixed aggregate 46 and serial solvation of mixed aggregate 46 with Me3N. N Na NaMe3Si Me3Si Me2NEt N SiMe3 O NEtMe2N N Na NaMe3Si Me3Si Me2NEt N SiMe3 O N N Na NaMe3Si Me3Si N SiMe3 O N ∆G° = 0.7 kcal/mol ∆G° = –1.0 kcal/mol N Na NaMe3Si Me3Si Me3N N SiMe3 O NMe3N N Na NaMe3Si Me3Si Me3N N SiMe3 O N N Na NaMe3Si Me3Si N SiMe3 O N ∆G° = 0.02 kcal/mol ∆G° = 2.2 kcal/mol + Me3N + Me3N + DMEA + DMEA 46 46e 46b46a 46d46a N Na NaMe3Si Me3Si Me3N N SiMe3 O NMe3N 46e N Na O NaMe3Si Me3Si Me3N N NMe3N SiMe3 46f ∆G° = 2.3 kcal/mol 182 Reaction coordinate aminolysis of methyl-2-picolinate (3) by NaHMDS in DMEA using Me3N as a DMEA surrogate. Figure A.1.80. DFT-computed reaction coordinate aminolysis of methyl-2- picolinate (3) by NaHMDS in DMEA using Me3N as a DMEA surrogate. N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 N OMe O N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me3N O OMe N N Na NaMe3Si Me3Si Me3N O OMe N(SiMe3)2 N N Na N Na SiMe3 Me3Si SiMe3 Me3Si Me3N O OMe N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N ∆G° = +13.8 kcal/mol ∆G° = +9.2 kcal/mol ∆G° = –20.9 kcal/mol ∆G° = +12.3 kcal/mol ∆G° = –7.4 kcal/mol ∆G° = +7.5 kcal/mol ∆G° = –0.6 kcal/mol ∆G° = +8.0 kcal/mol ∆G° = –41.2 kcal/mol N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N 44 45 TS-1 46 TS-2 47 TS-3 48 TS-4 N Me3Si Me3Si Na Na O N SiMe3 Me3N N MeOSiMe3 + 50 49 ∆G° = –3.2 kcal/mol 183 Figure A.1.81. DFT-computed other pathway (carbonyl oxygen attacking TMS instead of methoxide group leaving) reaction coordinate aminolysis of methyl-2- picolinate (3) by NaHMDS using Me3N as a DMEA surrogate, starting from 46. N Na NaMe3Si Me3Si Me3N O OMe N(SiMe3)2 N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N N Me3Si Me3Si Na Na O O Me N SiMe3 SiMe3 Me3N N ∆G° = +21.0 kcal/mol ∆G° = –7.4 kcal/mol 46 TS-2 47 N Na NaMe3Si Me3Si Me3N O OMe N N Me3Si SiMe3 ∆G° = +12.3 kcal/mol N Na NaMe3Si Me3Si Me3N O OMe N N Me3 Si SiMe3 ∆G° = +3.6 kcal/mol ∆G° = –12.0 kcal/mol N Na NaMe3Si Me3Si Me3N O OMe N N SiMe3 SiMe3 46m TS-22 46n 184 DFT-computed ground state structures of methyl picolinate 3 and NaHMDS in THF Scheme A.1.3. DFT-computed free energies for the methyl picolinate 3 and NaHMDS complexed ground state structures in THF. N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N Me3Si Me3Si N O Na THF THF OMe NNa(THF)4 Me3Si Me3Si 52 53 1/2 N Na N Na SiMe3Me3Si SiMe3Me3Si THF N OMe O 54 N Na N Na SiMe3Me3Si SiMe3Me3Si N OMe O N MeO O 42 N O OMe ∆G° = –7.9 kcal/mol + N O OMe ∆G° = –4.8 kcal/mol + – THF – THF N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF 52 N Me3Si Me3Si N O Na OMe N Me3Si Me3Si Na O N OMe THF ∆G° = –5.0 kcal/mol + THF ∆G° = 0.2 kcal/mol + THF 5543b 55a ∆G° = 3.8 kcal/mol + 3THF 185 Reaction coordinate aminolysis of methyl-2-picolinate (3) by NaHMDS in THF Figure A.1.82. DFT-computed reaction coordinate aminolysis of methyl-2- picolinate (3) by NaHMDS in THF. N O OMeNaN N Me3Si Me3Si N O OMe Na N NMe3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe N SiMe3 SiMe3 ONaN Me3Si Me3Si SiMe3 N MeO N SiMe3 OSiMe3NaN Me3Si Me3Si N + OMe N SiMe3 ∆G° = +4.7 kcal/mol ∆G° = +10.7 kcal/mol ∆G° = +2.8 kcal/mol ∆G° = –11.7 kcal/mol ∆G° = –3.6 kcal/mol ∆G° = +6.0 kcal/mol ∆G° = +7.7 kcal/mol ∆G° = –16.1 kcal/mol ∆G° = –5.5 kcal/mol TS-5 61 60 59 3 62 TS-6 63 TS-7 64 5665 SiMe3 SiMe3 N Me3Si SiMe3 Na N Me3Si SiMe3 Na N Me3Si SiMe3 Na N Me3Si SiMe3 Na 186 Figure A.1.83. DFT-computed reaction coordinate aminolysis of methyl-2- picolinate (3) by NaHMDS in THF, containing an alternative pathway (methoxide group leaving instead of carbonyl oxygen attacking the TMS). N O OMeNaN NMe3Si Me3Si SiMe3 SiMe3 N O OMe Na N NMe3Si Me3Si SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe NaN N Me3Si Me3Si SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 ONaN Me3Si Me3Si SiMe3 N MeO N SiMe3 OSiMe3NaN Me3Si Me3Si + N + OMe N SiMe3 ∆G° = +4.7 kcal/mol ∆G° = +10.7 kcal/mol ∆G° = +2.8 kcal/mol ∆G° = –11.7 kcal/mol ∆G° = –3.6 kcal/mol ∆G° = +6.0 kcal/mol ∆G° = +7.7 kcal/mol ∆G° = –16.1 kcal/mol ∆G° = –5.5 kcal/mol TS-5 61 60 59 3 62 TS-6 63 TS-7 64 5665 N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 60b N O OMe NaN N Me3Si Me3Si SiMe3 SiMe3 60c difference between 62 and 60c: complexation between O and Si 60c : no, 62 : yes N O OMe Na N N Me3Si Me3Si SiMe3 SiMe3 TS-12 N O N Na N Me3Si Me3Si SiMe3 SiMe3 OMe 60d ∆G° = +15.4 kcal/mol ∆G° = –6.4 kcal/mol ∆G° = 22.8 kcal/mol ∆G° = 14.2 kcal/mol 187 DFT-computed reaction coordinate of 1,2-addition by picolinonitrile (6) and NaHMDS, and subsequent amidine (56) formation in THF Figure A.1.84. DFT-computed reaction coordinate 1,2-addition of 2- pyridinecarbonitrile (6) by NaHMDS in THF. Me3Si N C N Na N NaN Me3Si Me3Si THF THF SiMe3 SiMe3 N C N NaN Me3Si Me3Si THF THF N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N C N N C N Na N Me3Si Me3Si THF THF N N N Na Na NMe3Si Me3Si SiMe3 SiMe3 THF THF N N N NaMe3Si Me3Si THF THF N C N Na N Me3Si Me3Si THF THF THF +THF –0.5 A2S2 +THF N C N Na N NaN Me3Si Me3Si THF THF SiMe3 SiMe3 THF +THF N N N Na Na NMe3Si Me3Si SiMe3 SiMe3 THF THF THF N C N NaN Me3Si Me3Si THF THF THF N N N NaMe3Si Me3Si THF THFTHF ∆G° = 6.9 kcal/mol ∆G° = 1.5 kcal/mol ∆G° = 3.6 kcal/mol ∆G° = 5.0 kcal/mol ∆G° = –9.5 kcal/mol ∆G° = –9.1 kcal/mol ∆G° = 8.1 kcal/mol ∆G° = 3.5 kcal/mol ∆G° = 1.8 kcal/mol ∆G° = 11.2 kcal/mol ∆G° = 10.5 kcal/mol ∆G° = –2.1 kcal/mol ∆G° = –2.6 kcal/mol C N SiMe3 N NaMe3Si N THF THF N N N Me3Si SiMe3 Na THF THF ∆G° = 16.1 kcal/mol ∆G° = –30.7 kcal/mol N N N Me3Si SiMe3 Na THF THF ∆G° = –10.2 kcal/mol ∆G° = 11.5 kcal/mol ∆G° = –18.3 kcal/mol C N SiMe3N Na N Na THF THF C N SiMe3N NaMe3Si N Na THF THF N Me3Si SiMe3 Me3Si N SiMe3 SiMe3 N N N SiMe3 SiMe3 Na N Na N Me3Si SiMe3 THFTHF C N SiMe3NNaN Na N SiMe3 SiMe3 Me3Si THF ∆G° = 3.7 kcal/mol ∆G° = –2.8 kcal/mol C N Me3Si N NaN Na N Me3Si SiMe3THF THF Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 THF THF 51 72 73 74 TS-13 TS-14 79 80 81 82 75 76 83 TS-16 TS-17 77 84 85 86 71 Me3Si C N SiMe3 N NaN Na N Me3Si SiMe3THF THF TS-18 76 N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 TS-10 N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 TS-15 THF N C N 6 + 188 DFT-computed energy profile of 1,2-addition by picolinonitrile (6) and NaHMDS, and subsequent amidine formation in THF via a monomer or dimer pathway Scheme A.1.4. DFT-computed energy profile of 1,2-addition of picolinonitirile (6) by NaHMDS in THF via a monomer pathway. Scheme A.1.5. DFT-computed energy profile of amidine (57) formation via a monomer pathway starting from disolvated monomer pre-silyl-transfer amidinate 76. N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N C N N C N Na N Me3Si Me3Si THF THF ∆G° = 3.5 kcal/mol +THF, –0.5 A2S2 N C N NaN Me3Si Me3Si THF THF N N N NaMe3Si Me3Si THF THF ∆G° = 10.5 kcal/mol ∆G° = –2.1 kcal/mol ∆G° = 1.8 kcal/mol ∆G° = 2.7 kcal/mol N C N NaN Me3Si Me3Si THF THF THF ∆G° = 11.2 kcal/mol +THF +THF 72 73 TS-14 76 ∆G° = –2.6 kcal/mol N N N NaMe3Si Me3Si THF THFTHF ∆G° = 2.2 kcal/mol+THF 74 TS-13 75 N C N Na N Me3Si Me3Si THF THF THF C N SiMe3 N NaMe3Si N THF THF N N N NaMe3Si Me3Si THF THF N N N Me3Si SiMe3 Na THF THF ∆G° = 16.1 kcal/mol ∆G° = –30.7 kcal/mol N N N Me3Si SiMe3 Na THF THF∆G° = –10.1 kcal/mol 76 TS-16 77 57 189 Scheme A.1.6. DFT-computed energy profile of 1,2-addition of picolinonitrile (6) by NaHMDS in THF via a dimer pathway. Scheme A.1.7. DFT-computed energy profile of amidine (71) formation via a dimer pathway starting from disolvated monomer pre-silyl-transfer amidinate 82. N Na N Na SiMe3Me3Si SiMe3Me3Si THF THF N C N N C N Na N NaN Me3Si Me3Si THF THF SiMe3 SiMe3 N N N Na Na NMe3Si Me3Si SiMe3 SiMe3 THF THF ∆G° = 1.5 kcal/mol ∆G° = 8.1 kcal/mol ∆G° = –9.1 kcal/mol N C N Na N NaN Me3Si Me3Si THF THF SiMe3 SiMe3 THF N N N Na Na NMe3Si Me3Si SiMe3 SiMe3 THF THF THF ∆G° = 3.6 kcal/mol ∆G° = 0.7 kcal/mol ∆G° = 5.0 kcal/mol +THF +THF ∆G° = –9.5 kcal/mol ∆G° = 0.6 kcal/mol+THF 80 81 79 TS-10 8272 N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 N C N Na NNaN Me3Si Me3Si THF THF SiMe3 SiMe3 TS-15 THF N N N SiMe3 SiMe3 Na N Na N Me3Si SiMe3 THFTHFN N N Na Na NMe3Si Me3Si SiMe3 SiMe3 THF THF ∆G° = –4.7 kcal/mol C N SiMe3N Na N Na THF THF N Me3Si SiMe3 Me3Si ∆G° = 11.5 kcal/mol ∆G° = –2.9 kcal/mol C N SiMe3NNaN Na N SiMe3 SiMe3 Me3Si THF C N SiMe3N NaMe3Si N Na THF THF N SiMe3 SiMe3 ∆G° = 3.7 kcal/mol Me3Si C N Me3Si N NaN Na N Me3Si SiMe3THF THF Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 THF THF ∆G° = –0.8 kcal/mol Me3Si C N SiMe3 N NaN Na N Me3Si SiMe3THF THF ∆G° = –18.3 kcal/mol ∆G° = 2.8 kcal/mol 83 TS-17 8482 86 TS-18 8571 190 DFT-computed reaction coordinate 1,2-Addition of 2-pyridinecarbonitrile (6) by NaHMDS in DMEA using Me3N as a DMEA surrogate. Figure A.1.85. DFT-computed reaction coordinate 1,2-addition of 2- pyridinecarbonitrile (6) by NaHMDS in DMEA using Me3N as a DMEA surrogate. + N CN + Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 NMe3 NMe3 ∆G° = 7.1 kcal/mol + NMe3 ∆G° = –15.1 kcal/mol ∆G° = 4.2 kcal/mol + NMe3 ∆G° = –17.0 kcal/mol– 2NMe3 ∆G° = 7.2 kcal/mol 67 6 68 69 TS-8 70 66 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3N CN N Na N Na SiMe3 SiMe3 NMe3Si Me3Si N Na N Na SiMe3 SiMe3 N Me3Si Me3Si N Na N Na SiMe3 Me3Si SiMe3 SiMe3 NC N NMe3 N N 191 DFT-computed ground state structures of mixed aggregate Scheme A.1.8. DFT-computed free energies for the mixed aggregate 66 and serial solvation of mixed aggregate 66 with DMEA using Me3N as a surrogate. C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N Me3N NMe3 Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 NMe3 NMe3 ∆G° = –16.4 kcal/mol Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 NMe3 Me3Si C N Me3Si N NaN Na N SiMe3 SiMe3 NMe3 NMe3 ∆G° = –5.4 kcal/mol ∆G° = –1.4 kcal/mol +NMe3 +NMe3 66a 66b 66 87 66 192 DFT-computed energy profile of 1,2-addition by picolinonitrile (6) and NaHMDS in DMEA Scheme A.1.9. DFT-computed energy profile of 1,2-addition of picolinonitrile (6) by NaHMDS in DMEA via a dimer pathway using Me3N as a DMEA surrogate. N C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N∆G° = 4.2 kcal/mol ∆G° = –14.5 kcal/mol N C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 Me3N NMe3 C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N Me3N NMe3 C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N Me3N NMe3 ∆G° = 8.3 kcal/mol ∆G° = –24.3 kcal/mol ∆G° = 13.0 kcal/mol N C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N C N Na N Na N Me3Si SiMe3 SiMe3 SiMe3 N ∆G° = 9.2 kcal/mol ∆G° = –19.6 kcal/mol Me3N Me3N Me3N ∆G° = 4.7 kcal/mol ∆G° = 3.6 kcal/mol ∆G° = 0.7 kcal/mol ∆G° = –0.2 kcal/mol ∆G° = 5.1 kcal/mol ∆G° = –1.4 kcal/mol +NMe3 +NMe3 +NMe3 +NMe3 +NMe3 +NMe3 ∆G° = 7.1 kcal/mol 88 89 TS-21 87 90 TS-20 92 91 TS-19 93 N CN + 39 6 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3 N Na N Na SiMe3Me3Si SiMe3Me3Si NMe3 NMe3N CN 193 Table A.1.11. Atomic coordinates and single point energies for THF. G = –232.078328 GSP = –232.348175 C -1.13117800 -0.46076700 0.13845600 O -0.01005700 -1.18800400 -0.29984600 C 1.11055700 -0.48578900 0.17603900 C 0.78898700 0.99574800 -0.07428100 C -0.75601300 1.02638800 -0.02478700 H -2.00050600 -0.76807500 -0.45672800 H -1.34061400 -0.68810200 1.20168600 H 1.24953400 -0.67214400 1.25943200 H 2.00145600 -0.84580900 -0.35409600 H 1.25610000 1.65352600 0.67003800 H 1.15027000 1.30071600 -1.06523800 H -1.14029100 1.63287200 0.80571300 H -1.16961500 1.43756200 -0.95460100 194 Table A.1.12. Atomic coordinates and single point energies for 2,5-Me2THF. G = –310.558747 GSP = –310.914859 C -1.13141200 -0.11493300 -0.38014700 O 0.00003300 -0.89724700 -0.06597800 C 1.13142900 -0.11481800 -0.38010000 C 0.77083900 1.30399600 0.10522300 C -0.77095200 1.30401100 0.10497000 H -1.25515500 -0.09384400 -1.48258100 H 1.25513000 -0.09361800 -1.48252800 H 1.16387100 1.46046200 1.12012200 H 1.20434700 2.07725100 -0.54279600 H -1.16436400 1.46087400 1.11965800 H -1.20420300 2.07704100 -0.54348900 C -2.35884400 -0.72520000 0.25839300 H -3.25066300 -0.12255400 0.03669100 H -2.52126000 -1.74497100 -0.11514200 H -2.22283100 -0.77138700 1.34849200 C 2.35892000 -0.72513300 0.25829500 H 2.52119500 -1.74490900 -0.11530100 H 3.25076000 -0.12255500 0.03649900 H 2.22303400 -0.77135300 1.34840200 195 Table A.1.13. Atomic coordinates and single point energies for 2,2,5,5-Me4THF. G = –389.044351 GSP = –389.4868685 C -1.18822700 -0.01098900 -0.08042100 O -0.00004200 -0.00018800 -0.87272400 C 1.18827500 0.01091700 -0.08046100 C 0.70144700 0.30012400 1.35094300 C -0.70140700 -0.30028100 1.35095100 H 1.36619000 -0.13181800 2.11172900 H 0.65759400 1.38694700 1.52013200 H -0.65756200 -1.38711000 1.52011800 H -1.36611500 0.13166700 2.11176000 C -2.11057500 -1.09371000 -0.62332000 H -3.02897400 -1.16298200 -0.02215900 H -2.38717500 -0.86911000 -1.66315500 H -1.59853300 -2.06607800 -0.60515100 C 1.84749500 -1.36436600 -0.18178500 H 2.01717200 -1.61172100 -1.23894400 H 2.81187700 -1.38242100 0.34674000 H 1.19750600 -2.14046300 0.24851200 C -1.84724900 1.36446600 -0.18165800 H -2.01697500 1.61182800 -1.23880700 H -2.81152500 1.38268700 0.34703000 H -1.19704300 2.14044000 0.24854500 C 2.11028300 1.09393100 -0.62330000 H 3.02858300 1.16352100 -0.02199900 H 2.38719500 0.86946400 -1.66307800 H 1.59787800 2.06610100 -0.60516500 196 Table A.1.14. Atomic coordinates and single point energies for DMEA. G = –213.385949 GSP = –213.632267 N -0.45720800 -0.00327800 -0.31588300 C -1.66546400 -0.75259200 -0.06018300 C 0.69850700 -0.65063500 0.27782000 C 2.02409400 -0.03226900 -0.14249600 C -0.60214100 1.37503500 0.09391400 H -2.51572500 -0.28597700 -0.57818000 H -1.91612100 -0.81051900 1.02298700 H -1.55962600 -1.77996100 -0.43743900 H 0.68127900 -1.70499400 -0.03975600 H 0.62391500 -0.65864400 1.39094800 H 2.06820700 0.04904100 -1.23791100 H 2.86040800 -0.65862100 0.19692600 H 2.17020900 0.96941000 0.28492100 H -1.48654000 1.81399300 -0.38940500 H 0.26992500 1.96809000 -0.21178100 H -0.72545000 1.48389400 1.19554700 197 Table A.1.15. Atomic coordinates and single point energies for Me3N. G = –174.146930 GSP = –174.349420 N 0.00000000 0.00000000 0.36503400 C 0.00000000 1.38014100 -0.05831500 H -0.88959600 1.89515600 0.33235600 H 0.88959600 1.89515600 0.33235600 H 0.00000000 1.49077800 -1.16656600 C 1.19523800 -0.69007100 -0.05831500 H 2.08605200 -0.17716500 0.33235600 H 1.19645600 -1.71799100 0.33235600 H 1.29105200 -0.74538900 -1.16656600 C -1.19523800 -0.69007100 -0.05831500 H -1.19645600 -1.71799100 0.33235600 H -2.08605200 -0.17716500 0.33235600 H -1.29105200 -0.74538900 -1.16656600 198 Table A.1.16. Atomic coordinates and single point energies for 3. G = –475.508936 GSP = –476.048857 N 1.04291200 1.21578000 -0.00025800 C 2.35664500 1.03245700 -0.00026000 C 0.26139800 0.13834000 0.00003000 C 2.95563200 -0.23074100 -0.00000400 C 0.75301000 -1.17036800 0.00017000 C 2.13370900 -1.35300900 0.00018500 H 2.97497600 1.93514500 -0.00049500 H 4.04204400 -0.32324700 0.00007800 H 2.55948700 -2.35756500 0.00039100 H 0.06052000 -2.01018000 0.00021600 C -1.22181700 0.41340100 0.00014200 O -1.71973100 1.50034100 0.00049600 O -1.93269500 -0.72487600 -0.00028800 C -3.34168700 -0.56051200 -0.00021900 H -3.66395700 -0.00500700 0.89080400 H -3.77102100 -1.56700400 -0.00079000 H -3.66437100 -0.00372900 -0.89032700 199 Table A.1.17. Atomic coordinates and single point energies for TMSOMe. G = –523.905424 GSP = –524.287985 Si -0.38203600 -0.00008400 -0.00686000 C -0.46829600 1.53438700 -1.08719900 C -1.73483400 0.00367700 1.27950600 C -0.46881600 -1.54012500 -1.07912000 H -1.65619500 0.89482600 1.91894100 H -1.65676500 -0.88408100 1.92371400 H -2.73001200 0.00274000 0.81062800 H -0.35880200 2.44501100 -0.47954200 H -1.43583000 1.58833800 -1.60924600 H 0.32164900 1.53837100 -1.85342200 H -0.36307500 -2.44784800 -0.46648100 H 0.32304000 -1.54997100 -1.84329600 H -1.43517600 -1.59452900 -1.60332200 O 1.05456700 0.00211100 0.85532000 C 2.31637000 0.00055700 0.25060300 H 2.47416600 -0.89457000 -0.37761500 H 3.08842000 0.00278900 1.03292800 H 2.47399600 0.89223400 -0.38254800 200 Table A.1.18. Atomic coordinates and single point energies for +Na(THF)6. G = –1554.573195 GSP = –1556.202536 Na -0.01521300 -0.00921800 -0.00300000 O 1.73780200 0.63700600 1.29003100 O 1.43561400 -1.05223900 -1.39587100 O 0.17673800 1.87362300 -1.26688300 O -1.76768100 -0.64501600 -1.29761100 O -1.46913100 0.98253800 1.42031400 O -0.19534100 -1.89084700 1.25887100 C -0.67003300 2.21755900 -2.36165900 C 0.98722000 2.98613200 -0.88942500 C -0.70786100 3.73992800 -2.36997800 C 0.71805300 4.07273000 -1.92984400 H -1.64560800 1.73546100 -2.20539100 H -0.23761900 1.82721500 -3.30050000 H -1.43477400 4.10866800 -1.62984100 H -0.97413500 4.15614600 -3.34939600 H 0.83023000 5.08541600 -1.52348600 H 1.40879400 3.96825700 -2.77960400 H 0.69560900 3.30947600 0.12478300 H 2.04170800 2.67214900 -0.85888200 C 1.92540600 -0.48661400 -2.61192800 C 2.28517100 -2.10482600 -0.94637100 C 3.56931400 -1.96250100 -1.75565200 C 3.03119800 -1.42656400 -3.08328200 H 1.09096200 -0.39906300 -3.32336500 H 2.30607800 0.52962100 -2.40806800 H 3.78878700 -0.91902300 -3.69298500 H 2.60693400 -2.24803700 -3.67953100 H 4.23735900 -1.22392700 -1.28649400 201 H 4.11884400 -2.90700700 -1.85231900 H 2.42577100 -1.99846900 0.13983900 H 1.79892100 -3.07773600 -1.14067400 C 1.52663000 1.32701500 2.52468600 C 3.10698500 0.70378400 0.90633900 C 2.91354400 1.75079500 3.00646300 C 3.68184400 1.87587000 1.68993400 H 3.15402700 0.81730100 -0.18720800 H 3.61888000 -0.23821400 1.17781700 H 3.43648500 2.82567700 1.19040100 H 4.77094800 1.81977300 1.80842400 H 2.89216500 2.67681100 3.59397000 H 3.36101500 0.96274100 3.63009700 H 1.01131300 0.65414500 3.22684400 H 0.86934900 2.19200400 2.33677100 C 0.63252000 -2.27855000 2.35187400 C -0.89807500 -3.01753700 0.73466400 C 0.79957100 -3.78544000 2.20752900 C -0.57507500 -4.18379800 1.66838800 H 1.56930500 -1.70528600 2.29035400 H 0.13165800 -2.02827800 3.30470100 H -1.97290200 -2.78452600 0.68976600 H -0.54489600 -3.20526800 -0.29424000 H 1.06170000 -4.27969300 3.15115200 H 1.58351200 -4.01341100 1.46918400 H -0.58330800 -5.15275200 1.15416400 H -1.30384400 -4.22903200 2.49099400 C -2.09722300 2.23365200 1.15846000 C -2.06005100 0.34697300 2.55493000 C -3.41734900 2.18384100 1.91665600 C -3.01708600 1.37609600 3.15189200 H -1.26437800 0.03684900 3.24766900 H -2.58904000 -0.56153000 2.22063200 H -2.48816700 2.02096400 3.86942100 H -3.86594200 0.91437500 3.67104800 H -3.81552100 3.17906900 2.14984000 H -4.17310100 1.63840100 1.33057300 H -2.20464700 2.34747200 0.06935600 H -1.45807400 3.05534100 1.53013600 C -3.14139000 -0.50472900 -0.93660400 C -1.63839200 -1.44688300 -2.46924700 C -3.93917500 -1.25392200 -2.00703100 C -2.91719000 -2.26996800 -2.52010100 H -3.39942500 0.56516800 -0.88355400 H -3.28619500 -0.93828100 0.06710500 H -4.22798300 -0.56985500 -2.81839400 202 H -4.85364900 -1.71054800 -1.60898100 H -3.14399000 -2.65002600 -3.52389100 H -2.84391400 -3.12776700 -1.83414100 H -1.55388200 -0.79489000 -3.35830100 H -0.71335500 -2.03326300 -2.37774800 203 Table A.1.19. Atomic coordinates and single point energies for 39. G = –2417.956178 GSP = –2419.545983 Na -1.26548900 -0.77739100 -0.01634900 Na 1.33486000 0.67616800 0.00877400 N -0.84573600 1.52384000 -0.00253900 N 0.91718400 -1.61484600 -0.00711300 Si -0.83863900 2.46738700 -1.43034500 C 0.63414700 1.96176400 -2.52729700 C -0.62009100 4.32955700 -1.13174800 C -2.38827400 2.24408300 -2.49917300 Si -1.63439700 2.00811600 1.43686000 C -1.93684600 0.49014200 2.54582200 C -3.34657700 2.78065100 1.15945300 C -0.62680400 3.22290900 2.48698900 Si 1.25216600 -2.22042200 -1.56346100 C 2.77179100 -1.38155100 -2.34007900 C -0.23072100 -1.87698900 -2.71567100 C 1.56127600 -4.08466100 -1.68752000 Si 1.22889600 -2.26684600 1.53529800 C 1.73530300 -0.87467500 2.73923700 C 2.62218300 -3.54561300 1.63715800 C -0.31364500 -3.10815500 2.26451900 H -2.47424600 1.20060200 -2.84350500 H -2.36774100 2.88963000 -3.39108300 H -3.29548500 2.48713400 -1.92371000 H 1.59947400 2.19692300 -2.04940600 H 0.61561100 2.51082600 -3.48145400 204 H 0.62706700 0.88771200 -2.77165300 H 0.32350700 4.52428700 -0.59611100 H -1.43630400 4.74551600 -0.52059600 H -0.59294000 4.88902400 -2.07992100 H -4.00159400 2.08092000 0.61480000 H -3.28586600 3.70360300 0.56176700 H -3.83676500 3.03113700 2.11326400 H 0.31877700 2.75783200 2.81053500 H -1.17247200 3.53459200 3.39129400 H -0.37937100 4.12737700 1.90950700 H -2.63352900 -0.22741500 2.08290000 H -2.38970900 0.79166800 3.50305700 H -1.00466400 -0.04648900 2.78293200 H 0.75740900 -4.65086600 -1.18959000 H 2.51382700 -4.36642800 -1.21439500 H 1.60044500 -4.40543300 -2.74052600 H -0.62351700 -0.85012800 -2.61715100 H -1.04985200 -2.57995000 -2.49060400 H 0.03073900 -2.02019500 -3.77567800 H 2.69058100 -0.28085800 -2.33882700 H 2.93449800 -1.69690000 -3.38256600 H 3.66869400 -1.65530000 -1.76071800 H -1.18773900 -2.43444300 2.28653000 H -0.15011500 -3.46549700 3.29322800 H -0.57352800 -3.97956500 1.64125900 H 3.53457900 -3.17191700 1.14459200 H 2.33887000 -4.48987400 1.14867700 H 2.87073000 -3.77067300 2.68636700 H 2.79081200 -0.60030100 2.57813700 H 1.64454600 -1.19221100 3.78985700 H 1.12373300 0.03714800 2.62616000 N -3.44270400 -1.85905400 -0.18735000 N 3.44329800 1.87068600 0.21917900 C -3.87068300 -1.27181500 -1.45132900 C -4.43863300 -1.61110200 0.84505700 C -3.20446400 -3.28973600 -0.32614000 H -4.83484800 -1.69694900 -1.79752300 H -3.11625500 -1.45624200 -2.23003100 H -3.98939900 -0.18438000 -1.33651300 H -5.41037200 -2.08255500 0.59254100 H -4.59807200 -0.53023000 0.96320200 H -4.09465500 -2.01866600 1.80606300 H -4.11748300 -3.82768100 -0.65375200 H -2.87889100 -3.70666300 0.63649400 H -2.41068200 -3.47493700 -1.06396100 C 3.23589600 2.51911100 1.50794100 205 C 3.80079500 2.85580700 -0.79061500 C 4.46901100 0.83969600 0.30911600 H 4.75209100 3.36829200 -0.53997700 H 3.01006400 3.61469100 -0.87304300 H 3.91714000 2.36758100 -1.76841600 H 2.42365200 3.25636900 1.42901600 H 4.15042900 3.03954000 1.85879100 H 2.95437600 1.77385000 2.26609900 H 4.16458100 0.06100800 1.02316900 H 5.44227000 1.25670300 0.63956300 H 4.60585800 0.36603200 -0.67225600 206 Table A.1.20. Atomic coordinates and single point energies for 40. G = –2719.329639 GSP = –2721.253393 N -0.41817600 -1.83088300 -0.11746100 N -0.82145000 1.79253900 0.10244300 Na 0.88303200 0.15069400 0.02203900 Na -2.05787800 -0.13299000 -0.11278100 Si -0.14015000 -2.32844400 -1.72915800 C -1.73961800 -2.42958300 -2.75587300 C 0.69434400 -4.02310900 -1.92375200 C 0.99747600 -1.07610700 -2.60494400 Si -1.01089200 -2.85134700 1.11529000 C -2.51996400 -3.87194300 0.55869200 C -1.56313900 -1.83346500 2.62848600 C 0.22490200 -4.11730600 1.81018100 Si -0.41813400 2.47655800 1.61378000 C 0.70302100 1.27804400 2.58702900 C -1.93875800 2.79762000 2.70309700 C 0.57579800 4.09035100 1.51490700 Si -1.16932300 2.68350800 -1.30946000 C -2.31658000 4.17530000 -1.04850900 C -2.05969000 1.54851600 -2.56044500 C 0.36903200 3.33616900 -2.20696500 H 0.61922200 -0.04098600 -2.54437600 H 1.09397400 -1.31509900 -3.67512400 H 2.01091300 -1.09435700 -2.17141600 H 0.07093400 -4.82210000 -1.49128300 H 1.67423000 -4.05282400 -1.42120900 H 0.85506300 -4.26389900 -2.98639600 207 H -2.39491300 -3.22145900 -2.35967500 H -1.53485600 -2.65906400 -3.81362000 H -2.30670900 -1.48389800 -2.73068500 H -0.27721600 -4.80494000 2.50903600 H 1.03509300 -3.61840100 2.36524700 H 0.67518900 -4.72374800 1.00829100 H -3.28995000 -3.22465200 0.10688100 H -2.98197800 -4.42166200 1.39408600 H -2.23126800 -4.60885500 -0.20850300 H -2.27514600 -2.39957700 3.24971800 H -2.04140700 -0.87262800 2.37241500 H -0.69564800 -1.59344200 3.26247800 H 1.50161000 3.89787000 0.94968400 H 0.84878000 4.45787000 2.51674500 H 0.02476000 4.89208300 0.99971300 H -2.48305900 1.85606000 2.88781500 H -2.62755400 3.49363300 2.19752300 H -1.67462300 3.22973800 3.68089500 H 0.30074700 0.25184400 2.59465100 H 0.80409300 1.59499800 3.63626800 H 1.72020900 1.25158300 2.16021800 H 0.91843200 4.03096500 -1.55242500 H 0.10931800 3.86803400 -3.13584500 H 1.05479700 2.51155200 -2.45837600 H -3.02474800 1.17293900 -2.17709800 H -1.44056300 0.67684100 -2.82800500 H -2.28171500 2.08515000 -3.49574200 H -3.25893300 3.87242800 -0.56593100 H -2.56402500 4.66681200 -2.00269000 H -1.84404200 4.92848300 -0.39884900 N 3.00720800 -0.94863400 0.30968900 C 3.14237600 -2.24935100 0.53800300 C 4.10058200 -0.19843900 0.17601800 C 4.39657800 -2.85784700 0.65471800 C 5.39412300 -0.70602800 0.27620100 C 5.53692300 -2.07161800 0.52405400 H 2.21150800 -2.81739100 0.62404200 H 4.46494700 -3.92926500 0.84323100 H 6.53004400 -2.51474500 0.60992600 H 6.25070200 -0.04398200 0.15865200 O 2.69902600 1.68515600 -0.24354200 C 3.81624200 1.24989000 -0.11314600 O 4.90987000 1.98750400 -0.21448700 C 4.70350100 3.37092200 -0.49654700 H 5.69893200 3.81336600 -0.59002900 H 4.14466700 3.84309500 0.32186000 208 H 4.13412100 3.48662400 -1.42772200 N -4.45243100 -0.10413200 0.20875600 C -5.12942500 -0.76050200 -0.90097600 H -4.83134500 -0.29918100 -1.85354000 H -4.85570500 -1.82473900 -0.93368400 H -6.23251200 -0.68638700 -0.80937500 C -4.81152900 -0.73585600 1.47158600 H -4.49162800 -1.78783300 1.47648600 H -4.31354800 -0.21954300 2.30411000 H -5.90637500 -0.69805700 1.64672700 C -4.77003700 1.31857300 0.24609800 H -4.17916300 1.81533000 1.02930800 H -4.51810600 1.78668300 -0.71551400 H -5.84744300 1.49123500 0.44571400 209 Table A.1.21. Atomic coordinates and single point energies for 44b. G = –2893.468015 GSP = –2895.592055 N 0.17973200 1.71913500 -0.50238400 N 1.78504100 -1.45521600 0.38613800 Na 2.28428400 0.73073300 -0.13827600 Na -0.38540500 -0.48266300 0.15093300 Si 0.02966000 1.84444100 -2.20172200 Si 0.11057900 3.05599500 0.55748400 C -0.50081900 0.18000900 -2.96816000 C 1.67718900 2.34460200 -3.01982800 C -1.21894600 3.12788500 -2.83891500 C -1.62484300 3.78009000 0.81596500 C 1.20606800 4.51009100 -0.00174900 C 0.72767800 2.57374000 2.29310200 Si 1.60763000 -2.08768700 1.96504800 Si 2.49989900 -2.34480600 -0.88341000 C 3.12877700 -1.77871500 3.05787400 C 1.20887000 -3.94200600 2.04224100 C 0.13826900 -1.24669900 2.83667100 C 1.33470000 -3.61918300 -1.67531700 C 4.07570300 -3.29419600 -0.40505600 C 3.02302100 -1.16657700 -2.28842000 H -2.24169000 2.92015700 -2.48824500 H -1.23721300 3.12835200 -3.94046100 H -0.95092300 4.14440800 -2.50984800 H 2.50388700 1.66029900 -2.76743900 H 1.96387200 3.35357200 -2.68180800 H 1.60055400 2.36597400 -4.11859100 210 H -0.07664900 -0.69005300 -2.43746400 H -0.16957300 0.10692400 -4.01609700 H -1.59729800 0.07619800 -2.96139600 H -2.02997300 4.17563400 -0.12942500 H -1.60706000 4.60713700 1.54406400 H -2.32535800 3.01374800 1.18650200 H 0.85055100 4.92914500 -0.95682700 H 2.24666600 4.18128700 -0.16187000 H 1.21785700 5.32603900 0.73805500 H -0.04715700 2.02575300 2.85153200 H 0.98010600 3.46932300 2.88252200 H 1.62325900 1.92963700 2.27365600 H 4.83726800 -2.61329700 0.00616400 H 4.51377500 -3.80734900 -1.27579100 H 3.86988600 -4.05656300 0.36230400 H 1.03469100 -4.35815800 -0.91565300 H 1.81223600 -4.15398400 -2.51131600 H 0.42102800 -3.13177500 -2.05199200 H 2.16281700 -0.62561600 -2.71310900 H 3.49065100 -1.72802200 -3.11206000 H 3.76603900 -0.41935600 -1.95684600 H 0.18781900 -0.14825900 2.75947900 H 0.11727600 -1.49504100 3.90888500 H -0.81602600 -1.59642400 2.40822800 H 2.00104600 -4.56465300 1.59889100 H 0.27672100 -4.12576200 1.48471800 H 1.06215000 -4.27436700 3.08210800 H 4.02351900 -2.24152500 2.61137700 H 3.00522000 -2.18664500 4.07324800 H 3.31775700 -0.69613100 3.15170600 N 4.50769500 1.56097600 0.25796300 C 5.32237200 0.37072000 0.46812700 C 4.44844000 2.35720800 1.47606400 C 5.01429400 2.35395500 -0.85249400 H 5.44872300 2.74324800 1.76099500 H 4.07117200 1.74296000 2.30623000 H 3.77043200 3.21236500 1.34061800 H 6.04534200 2.71617000 -0.66120300 H 4.36551300 3.22537900 -1.02102400 H 5.02509200 1.75158700 -1.77230800 H 4.86980300 -0.26159900 1.24591000 H 6.35594100 0.63195700 0.77484700 H 5.37596700 -0.21701700 -0.45880200 N -2.71062400 -0.27486800 -0.51692200 C -3.30745200 0.87636600 -0.79930700 C -3.28574100 -1.41350000 -0.90669900 211 C -4.52178100 0.93261400 -1.49358600 C -4.48999000 -1.46643100 -1.60393600 C -5.11857700 -0.25527100 -1.89995300 H -2.79120800 1.78086600 -0.47224000 H -4.97797800 1.89918200 -1.70803500 H -6.06272500 -0.24455100 -2.44646000 H -4.90669100 -2.42704400 -1.90265900 C -2.50538200 -2.64591100 -0.54356300 C -2.34935600 -4.96737400 -0.68185800 O -1.46717100 -2.60595600 0.07088500 O -3.06428400 -3.76593100 -0.96964300 H -2.27238600 -5.10961300 0.40407100 H -1.33889300 -4.91381100 -1.10737500 H -2.92371400 -5.77840700 -1.13768200 N -4.13740400 1.30400000 2.12323900 C -5.27596000 0.45552800 1.85804500 C -4.49806500 2.44507400 2.93554500 C -3.03814100 0.56072800 2.69705100 H -4.98152200 -0.37418800 1.19629600 H -6.06690700 1.03012700 1.35282000 H -5.70840300 0.01717500 2.78461800 H -3.62504400 3.09885200 3.07319100 H -4.87149300 2.14914200 3.94054700 H -5.28530900 3.02909500 2.43702900 H -2.14836900 1.20414400 2.77578500 H -2.78526000 -0.28966000 2.04732900 H -3.26764400 0.16346300 3.71024000 212 Table A.1.22. Atomic coordinates and single point energies for 41. G = –3020.706276 GSP = –3022.964298 N -0.00114400 1.78388100 0.00070500 N 0.00021400 -1.83840200 0.00122600 Na 1.50615300 0.00919000 -0.00372900 Na -1.50705500 0.00826500 0.00798600 Si -0.47843500 2.55769300 -1.43498400 C 0.96634000 3.10032800 -2.54011300 C -1.58611100 4.08048300 -1.17204500 C -1.53867100 1.35622100 -2.47856800 Si 0.47790300 2.56017100 1.43452300 C 1.53707500 1.35965500 2.48032900 C -0.96562800 3.10681700 2.53915600 C 1.58772100 4.08064800 1.16744400 Si -0.56682500 -2.61552900 1.40804400 C -1.64959400 -4.14715900 1.09383100 C -1.65709300 -1.42322200 2.42121700 C 0.80232100 -3.19551500 2.59198800 Si 0.56822500 -2.61396200 -1.40604300 C 1.65740600 -1.41970500 -2.41815400 C -0.79987600 -3.19480000 -2.59080300 C 1.65243100 -4.14483300 -1.09295200 H -1.06182000 4.86936100 -0.60963800 H -2.46818400 3.78064000 -0.58376600 H -1.93083400 4.51518300 -2.12362900 H 1.60772300 3.80729100 -1.98979800 H 0.62247500 3.58892400 -3.46550900 213 H 1.59012200 2.23336400 -2.80890600 H -1.04741300 0.37633400 -2.61166000 H -1.72901900 1.76222200 -3.48389300 H -2.52416500 1.18395400 -2.01150600 H -1.59016600 2.24101400 2.80989800 H -1.60652600 3.81346100 1.98788000 H -0.62074900 3.59681300 3.46343400 H 2.46841700 3.77758100 0.57877100 H 1.93431100 4.51658700 2.11777900 H 1.06427600 4.86934900 0.60400600 H 1.04479300 0.38057800 2.61556900 H 1.72784800 1.76757700 3.48479600 H 2.52239400 1.18543200 2.01363600 H 1.44405600 -3.94439600 2.09916400 H 0.38278800 -3.65999500 3.49819800 H 1.43186100 -2.34830200 2.90897700 H -2.62695200 -1.24406400 1.92678500 H -1.17079700 -0.44654900 2.58745000 H -1.87825400 -1.84763200 3.41244100 H -2.55107200 -3.87861500 0.52055000 H -1.97899500 -4.60652000 2.03932200 H -1.10521200 -4.91450200 0.52051300 H 2.55372900 -3.87606200 -0.51950300 H 1.98212300 -4.60318900 -2.03883100 H 1.10868700 -4.91306600 -0.52021400 H -1.43011500 -2.34822800 -2.90807900 H -1.44114300 -3.94444500 -2.09852900 H -0.37928800 -3.65872700 -3.49681000 H 1.17027600 -0.44323100 -2.58309400 H 1.87868800 -1.84279200 -3.40991400 H 2.62723700 -1.24042000 -1.92371300 N -3.76040300 -0.93589500 -0.53396200 C -4.01651400 -2.08178300 -1.15495800 C -4.78921400 -0.19434700 -0.11844500 C -5.31819200 -2.53801800 -1.38621000 C -6.12217800 -0.55696800 -0.30125000 C -6.38663800 -1.76170200 -0.95159900 H -3.14913000 -2.65883600 -1.48374000 H -5.47697300 -3.48642300 -1.89916000 H -7.41488800 -2.08691800 -1.11555500 H -6.91597600 0.09436700 0.06096800 C -4.39606600 1.08011100 0.57625700 O -3.24979400 1.39444700 0.76984600 O -5.43323200 1.81280100 0.95124000 C -5.11767400 3.03683900 1.61392200 H -6.07464000 3.48525200 1.89441700 214 H -4.56182900 3.69877500 0.93707500 H -4.50017200 2.84090000 2.49980500 H 4.56208000 3.70173800 -0.93322800 C 4.78874900 -0.19305000 0.11727800 C 5.32045900 -2.53864400 1.38031400 C 6.38794600 -1.76265000 0.94278400 C 6.12208300 -0.55692900 0.29483900 C 4.39413700 1.08266400 -0.57425700 C 5.11331300 3.03941100 -1.61346800 C 4.01831200 -2.08113300 1.15427000 N 3.76084000 -0.93432400 0.53553300 O 3.24738900 1.39867900 -0.76228400 O 5.43047300 1.81442600 -0.95325300 H 5.48033300 -3.48780900 1.89151600 H 6.91508100 0.09423100 -0.06943800 H 7.41652400 -2.08888400 1.10261300 H 6.06948200 3.48655700 -1.89866900 H 3.15169800 -2.65806100 1.48529600 H 4.49080900 2.84499800 -2.49619000 215 Table A.1.23. Atomic coordinates and single point energies for 42. G = –1985.854875 GSP = –1987.520377 N -0.02441400 -0.92801400 -0.60080000 Si -0.04312700 -0.10999900 -2.08065600 Si 0.12499900 -2.59751700 -0.37716200 C -0.98080200 1.54831400 -1.96533300 C -0.87476400 -1.04690400 -3.51343700 C 1.68225400 0.37865700 -2.72398800 C 1.71518900 -3.32438600 -1.14029600 C -1.29931000 -3.64603100 -1.08535600 C 0.19717300 -3.06097800 1.47972400 Na -0.02671100 0.15605500 1.39346400 H -1.90158800 -1.34084100 -3.24322300 H -0.32017400 -1.96657200 -3.76190700 H -0.92147800 -0.42872300 -4.42433000 H 2.13076100 1.15085000 -2.07864500 H 1.64066300 0.78285800 -3.74843100 H 2.35883700 -0.49103600 -2.72462500 H -2.04883600 1.38874900 -1.74376000 H -0.91205500 2.11150100 -2.90990000 H -0.54606700 2.16873000 -1.16551200 H 1.64429400 -3.32091800 -2.24047500 H 1.91980200 -4.35919300 -0.82014200 H 2.58079100 -2.69428900 -0.87596400 H 1.20718400 -2.93616700 1.89422000 H -0.10539500 -4.10983100 1.62967500 H -0.46647000 -2.43582000 2.10025900 H -1.34311000 -3.56055000 -2.18165100 216 H -2.26995500 -3.30318300 -0.69219600 H -1.18127100 -4.71212500 -0.83191800 N 1.76502100 1.75423000 0.81131700 C 1.65250800 2.96167200 0.27302200 C 2.90680200 1.08827600 0.64435600 C 2.68597900 3.56412700 -0.45064900 C 3.99653800 1.59421900 -0.06231700 C 3.87760400 2.86636700 -0.61846500 H 0.69479900 3.46559700 0.43072500 H 2.54868000 4.55885200 -0.87456700 H 4.70312300 3.30196400 -1.18281800 H 4.89890600 0.99505700 -0.17088100 C 2.94753600 -0.25774100 1.31157600 O 2.09393000 -0.64671700 2.06928200 O 4.03486400 -0.94910400 1.00801000 C 4.15311300 -2.23566600 1.61015100 H 4.07365100 -2.15200400 2.70177500 H 5.13580400 -2.61730700 1.31915100 H 3.36032000 -2.89639500 1.23618300 N -2.50560600 -0.35949500 1.54568300 C -3.10962800 0.61671400 0.86645500 C -3.07549700 -1.55881300 1.54669100 C -4.29823400 0.44499200 0.15767400 C -4.26583600 -1.83845000 0.86989800 C -4.88518600 -0.81823300 0.15879800 H -4.73314200 1.28380900 -0.38284500 H -5.80924500 -1.00035300 -0.39119900 H -2.56151100 -2.34894900 2.09887500 H -4.68117100 -2.84585000 0.89720900 C -2.40407500 1.94300600 0.87955900 O -1.30717900 2.11876200 1.35323400 O -3.11655500 2.90325600 0.30980300 C -2.48943800 4.17297300 0.18790500 H -1.65183200 4.10222800 -0.51998000 H -2.12110700 4.51419100 1.16393800 H -3.25263000 4.85504900 -0.19754200 217 Table A.1.24. Atomic coordinates and single point energies for 42a. G = –1985.835865 GSP = –1987.50386 N -2.21117200 0.36116900 -0.29013600 Si -2.64174700 1.68691100 0.66450800 Si -3.21444100 -0.62354300 -1.23270100 C -1.20191800 2.16590800 1.82007700 C -4.12951100 1.36799200 1.81113100 C -3.05495500 3.26436400 -0.31136500 C -4.10133200 -1.99804400 -0.25491700 C -2.16146400 -1.54132000 -2.53536500 C -4.57496000 0.28912500 -2.19529300 Na -0.10719400 -0.07792500 -1.04412200 H -3.93774100 0.50343200 2.46780400 H -5.03059600 1.13675300 1.21976800 H -4.36050800 2.23618500 2.44898900 H -2.20680300 3.54315200 -0.95711800 H -3.28313800 4.11738900 0.34785900 H -3.92453800 3.09607500 -0.96583200 H -0.92222300 1.31351600 2.46157800 H -1.46173400 3.01362700 2.47413000 H -0.31402000 2.45615500 1.23206400 H -3.37569800 -2.69425000 0.19670700 H -4.77476400 -2.58839400 -0.89684800 H -4.70274000 -1.56471600 0.56031500 H -5.27370200 0.78666300 -1.50295900 H -5.16096700 -0.39325700 -2.83139200 H -4.13498800 1.06795700 -2.83781800 H -1.39651600 -2.17592700 -2.05501500 H -1.65208700 -0.83408000 -3.21298900 H -2.77962100 -2.20063000 -3.16425400 218 N 1.81649900 0.69692100 0.59340500 C 1.81778700 0.48450900 1.90429900 C 2.22609900 1.88576000 0.14675300 C 2.20349300 1.45522100 2.83257700 C 2.61478700 2.92680800 0.98937000 C 2.59241600 2.70417400 2.36517800 H 1.47738300 -0.49964100 2.24181800 H 2.16878700 1.23448900 3.89916100 H 2.86644200 3.50015800 3.05865700 H 2.89655600 3.89687700 0.58001800 C 2.10961200 2.07616900 -1.34989800 O 1.20020200 1.59122200 -1.96371700 O 3.00402300 2.84360300 -1.97288600 C 4.33657500 3.01483500 -1.51675400 H 4.46469100 4.01096900 -1.07230300 H 4.98411000 2.93419600 -2.39775200 H 4.62189300 2.24622900 -0.78607200 N -0.00986500 -1.89541600 0.50894600 C 1.09964000 -2.62847700 0.50374700 C -0.82392300 -1.94645700 1.55714500 C 1.46782100 -3.46766700 1.55461700 C -0.54403100 -2.75788600 2.66432200 C 0.61703700 -3.52592900 2.66015900 H 2.38783800 -4.04765700 1.49801300 H 0.86077000 -4.16790100 3.50816000 H -1.70792000 -1.30113400 1.48334900 H -1.23192200 -2.77952600 3.50974800 C 1.93665200 -2.45353300 -0.73321000 O 1.65834000 -1.69228000 -1.62375400 O 3.01764700 -3.22653800 -0.73805500 C 3.84932700 -3.12236600 -1.88735300 H 4.22937700 -2.09751500 -1.99083500 H 3.28253600 -3.37926000 -2.79159400 H 4.67276100 -3.82580500 -1.73483500 219 Table A.1.25. Atomic coordinates and single point energies for 42b. G = –1510.332815 GSP = –1511.466763 N -2.01408600 0.01250100 -0.02175300 Na 0.16186400 0.27866300 -0.09609500 Si -2.87623400 1.45634400 0.19178000 C -1.67339100 2.92321300 -0.00753100 C -3.65051100 1.65608700 1.91509900 C -4.28317200 1.72834100 -1.05403900 Si -2.58589900 -1.57013400 -0.18674700 C -1.09145600 -2.75804500 -0.07029500 C -3.40508800 -1.95014700 -1.85733600 C -3.81816400 -2.12363200 1.14706500 H -3.91405600 1.63434200 -2.08726900 H -4.75038900 2.71946500 -0.94067000 H -5.07033400 0.96969700 -0.91308000 H -2.87802700 1.57840700 2.69643300 H -4.38902900 0.86101600 2.10279000 H -4.15948200 2.62652500 2.02966200 H -0.87282600 2.88988100 0.75220700 H -2.18404400 3.89201000 0.10765300 H -1.20017500 2.91533200 -1.00390600 H -2.71701500 -1.72055300 -2.68615500 H -4.30418400 -1.32966000 -1.99618200 H -3.70567800 -3.00687700 -1.94069200 H -3.41038500 -1.94404700 2.15407300 H -4.07282600 -3.19181000 1.05940600 H -4.75490800 -1.54898900 1.06249900 H -0.37467000 -2.54209600 -0.88286000 H -1.37930900 -3.81708400 -0.15952700 H -0.58249600 -2.62532300 0.90006400 N 2.30262700 -1.00573800 0.06558100 C 2.48692300 -2.31560000 0.20390200 C 3.38016400 -0.21618600 0.02837400 C 3.75734000 -2.89047700 0.31135800 C 4.68655300 -0.68971300 0.12676500 220 C 4.87379200 -2.06386700 0.27210400 H 1.58593900 -2.93380700 0.22857700 H 3.85449800 -3.97019700 0.42334700 H 5.87910200 -2.47918400 0.35311000 H 5.52122300 0.00839900 0.08923300 O 1.96116800 1.68977100 -0.21714300 O 4.16613800 2.00012800 -0.16453400 C 3.08228800 1.24892100 -0.13028900 C 3.95488200 3.40465000 -0.31300900 H 3.35285100 3.78492800 0.52172500 H 3.42836600 3.60838600 -1.25381500 H 4.94801000 3.86118100 -0.31642700 221 Table A.1.26. Atomic coordinates and single point energies for 42c. G = –2160.001577 GSP = –2161.864042 N -0.14901600 -1.39693000 0.07350500 Si -0.33681400 -1.91310800 1.67768000 Si 0.62218800 -2.30724500 -1.13024300 C -1.27500900 -0.65565100 2.75298300 C 1.30841100 -2.20408800 2.60745000 C -1.32041400 -3.53011900 1.87017100 C -0.18139800 -3.99310700 -1.53477600 C 2.43785900 -2.76598100 -0.73941500 C 0.65866100 -1.36499700 -2.79508300 Na -0.07711900 0.82819200 -0.58104500 H 1.96151000 -1.31604600 2.57360600 H 1.87342100 -3.03392400 2.15534600 H 1.13371900 -2.45533000 3.66683600 H -2.29059800 -3.43795200 1.35496400 H -1.51391500 -3.77048500 2.92804700 H -0.78813800 -4.38291000 1.42087800 H -0.85750900 0.35596400 2.64125300 H -1.22228300 -0.94529700 3.81578300 H -2.33993400 -0.61465000 2.47500600 H 0.13504200 -4.75348800 -0.80365300 H 0.10794500 -4.35576400 -2.53491300 H -1.28000600 -3.94312400 -1.48571700 H -0.32052600 -1.38101800 -3.29511800 H 1.39792600 -1.81426000 -3.47832600 H 0.91882800 -0.30160300 -2.67216900 H 2.46831100 -3.64884600 -0.08081600 222 H 2.95407600 -1.95162600 -0.20773800 H 3.01382300 -3.01204500 -1.64699400 N -2.26996300 1.44327300 0.41182300 C -2.56688800 2.14159400 1.50025100 C -3.12370300 0.50451100 0.00843000 C -3.74708900 1.95401000 2.22323700 C -4.31613300 0.21565700 0.67311900 C -4.63442900 0.96918100 1.80100900 H -1.82500400 2.88016800 1.81868000 H -3.95153500 2.56082100 3.10522200 H -5.56073000 0.78311500 2.34640600 H -4.96507200 -0.57544400 0.30130400 C -2.74755200 -0.19270200 -1.27109900 O -1.93117000 0.24135300 -2.04582400 O -3.47414600 -1.27694200 -1.48566000 C -3.20024600 -1.98517600 -2.68895500 H -3.89710700 -2.82799800 -2.71211900 H -2.16463100 -2.34577600 -2.68052700 H -3.35154300 -1.33072700 -3.55798900 N 2.53580400 0.80986600 -0.71307700 C 2.98315900 0.77438300 0.54384000 C 3.36338500 0.42150200 -1.67737600 C 4.26521200 0.34708400 0.89264900 C 4.67175100 -0.00644000 -1.43827200 C 5.12833000 -0.04784600 -0.12691600 H 4.56176700 0.32741300 1.93953500 H 6.13779800 -0.39009300 0.10399200 H 2.97122700 0.43629300 -2.69779900 H 5.30395500 -0.31305700 -2.27133000 C 2.01733700 1.24600200 1.59741600 O 0.91465600 1.67514300 1.36499000 O 2.52748400 1.15182300 2.81787400 C 1.65789200 1.46278600 3.90110700 H 0.86068800 0.70971600 3.96020000 H 1.21317400 2.45642500 3.76100300 H 2.27570400 1.43837800 4.80327500 N -0.00358900 2.95385300 -1.79726400 C 0.43955200 2.53590300 -3.11384000 C 0.94375200 3.86117600 -1.17995800 C -1.33152500 3.53481800 -1.86126600 H -0.25612200 1.78638400 -3.51826600 H 1.43833800 2.08152400 -3.03907300 H 0.50058900 3.38773800 -3.82519000 H 1.05998200 4.80269600 -1.75881700 H 1.92507500 3.37208000 -1.10115600 H 0.60790500 4.11361000 -0.16411400 223 H -2.03985100 2.78714900 -2.24357000 H -1.35757100 4.43094700 -2.51801500 H -1.65838100 3.82942600 -0.85473800 224 Table A.1.27. Atomic coordinates and single point energies for 46. G = –2448.082940 GSP = –2449.915069 C 0.74970700 4.26774500 -0.45014900 C 1.92166200 4.96381700 -0.74114000 C 3.04992100 4.23073500 -1.10255300 C 2.97044800 2.84167900 -1.12424900 C 1.75647400 2.23267700 -0.80016600 N 0.66026400 2.93952900 -0.49662000 H -0.16029100 4.80784100 -0.17304400 H 3.98156900 4.73622900 -1.36286200 H 1.93957200 6.05250800 -0.69579500 H 3.82467600 2.22405300 -1.39761400 C 1.57431600 0.72061000 -0.77852000 N 2.32243400 -0.05497800 -0.04025800 O 0.58705100 0.32208700 -1.46535000 Si 3.57195000 0.27039300 1.12749300 C 3.96659900 -1.35486600 1.99537500 C 3.02469800 1.53253600 2.41985300 C 5.21738600 0.84123500 0.37745200 H 2.16765600 1.15245200 2.99650900 H 2.72375600 2.48513600 1.95499500 H 3.84320800 1.74298900 3.12592700 H 5.39470400 0.36366600 -0.59898500 H 6.04120700 0.54721600 1.04634600 H 5.27247000 1.93153900 0.24838700 H 3.07109100 -1.83555600 2.41599800 H 4.67491000 -1.18150400 2.82041800 H 4.44031700 -2.06006300 1.29455700 225 Na -1.18531400 1.27293600 -0.42972500 Na 0.35530100 -1.50186800 -0.14815400 N -1.71106800 -0.67039100 0.73095500 Si -2.68630700 -1.94721700 0.16522400 C -2.21483000 -3.61297000 0.96258700 C -2.42367100 -2.15835100 -1.70675200 C -4.55430200 -1.75742800 0.44365400 Si -1.37936900 -0.27279300 2.35566200 C -0.79972900 1.53603600 2.46131600 C 0.07535800 -1.29358800 3.03736300 C -2.82950900 -0.47806600 3.55807600 H -1.35732300 -2.28587500 -1.95848100 H -2.77351000 -1.27418700 -2.26302300 H -2.96537100 -3.03479600 -2.09617600 H -1.13067000 -3.79948800 0.87064100 H -2.74267700 -4.46546900 0.50617800 H -2.44976500 -3.60804200 2.03947800 H -4.77183700 -1.58883400 1.50981700 H -5.08866900 -2.66795400 0.12931900 H -4.97942900 -0.91281300 -0.12055200 H -3.68812200 0.13873400 3.24850200 H -2.54925600 -0.18147500 4.58084900 H -3.16767200 -1.52604400 3.59313600 H 0.97999600 -1.09039000 2.43778100 H -0.13831200 -2.37376400 2.98274800 H 0.31943000 -1.04893200 4.08323100 H 0.11072700 1.69192800 1.85797300 H -0.55041900 1.81802400 3.49629700 H -1.56885500 2.24315500 2.10612700 N -3.28735100 2.38648900 -0.74766500 C -4.06576500 2.14180600 0.45982000 C -3.27905800 3.79881600 -1.08796400 C -3.79058700 1.55155700 -1.83901500 C -2.92470500 1.56635100 -3.09114400 H -4.82994600 1.85066400 -2.09697800 H -3.84772100 0.52282200 -1.45005600 H -2.90092700 2.55463900 -3.57056700 H -3.33056600 0.85661800 -3.82501100 H -1.88643100 1.26012500 -2.88346100 H -4.29118600 4.16803900 -1.35626400 H -2.60330700 3.99226400 -1.93191400 H -2.92054100 4.38042900 -0.22689600 H -3.94459500 1.09235700 0.76759500 H -5.14396100 2.35314600 0.30442200 H -3.70498800 2.78468600 1.27505900 N 1.17301800 -3.50297900 -1.20638800 226 C 0.35824400 -4.60831000 -1.68216500 C 2.03977200 -3.91226200 -0.11148800 C 1.89706700 -2.81409700 -2.28322300 C 2.89996900 -3.66118800 -3.06522600 H -0.31140300 -4.95232100 -0.88058000 H 0.96524700 -5.47366300 -2.01402200 H -0.26398700 -4.27720400 -2.52577500 H 2.63381000 -3.05089400 0.22898600 H 2.73434000 -4.73058500 -0.38622100 H 1.42771500 -4.26807200 0.73251600 H 3.68982200 -4.06556700 -2.41544100 H 3.38813600 -3.04026600 -3.82902400 H 2.41658300 -4.50257100 -3.58244100 H 2.40731000 -1.94851100 -1.83032700 H 1.14152500 -2.40077300 -2.97075200 227 Table A.1.28. Atomic coordinates and single point energies for 46a. G = –2021.299996 GSP = –2022.650064 C 2.12475100 3.21723500 0.84763100 C 3.50703200 3.37711500 0.78207400 C 4.23991400 2.46789000 0.02236200 C 3.56852600 1.42720200 -0.61101300 C 2.18047600 1.34579500 -0.48777100 N 1.47219000 2.24230200 0.21362700 H 1.51619700 3.91210200 1.43356300 H 3.98947600 4.20019300 1.30858500 H 5.32281400 2.56643100 -0.07015800 H 4.09709800 0.68263600 -1.20564500 C 1.36351800 0.24241500 -1.14700600 O 0.33566900 0.66509500 -1.75858700 N 1.65861700 -1.01661300 -0.99784500 Si 2.86851600 -1.94371900 -0.16487600 C 2.13460500 -3.66204600 0.06948500 C 3.33348500 -1.26893500 1.53822700 C 4.42718600 -2.15352700 -1.21122600 H 2.43458400 -1.12988100 2.15863200 H 3.86212200 -0.30629800 1.48753500 H 3.98821700 -1.98771500 2.05573000 H 4.15648400 -2.42808500 -2.24178900 H 5.04899600 -2.96236500 -0.79721000 H 5.05221500 -1.24969400 -1.25338900 H 1.22864200 -3.62512300 0.69323400 H 2.85092300 -4.34109200 0.55654600 H 1.86565900 -4.09581200 -0.90621300 228 Na -0.87890700 1.76774900 -0.28057400 Na -0.68952400 -1.29707900 -1.23596200 N -2.22204900 -0.11999300 0.06690400 Si -2.04441900 -0.45880700 1.72460000 C -1.32729800 1.05497100 2.64044900 C -0.75577600 -1.83451100 1.94703300 C -3.60584700 -0.97678000 2.65608300 Si -3.52576000 0.18805600 -0.97698000 C -3.47468600 1.99922000 -1.58628600 C -5.26194600 -0.10442200 -0.29132600 C -3.35186500 -0.86091800 -2.55761000 H -4.36290500 -0.17817600 2.65411000 H -3.36914200 -1.21674200 3.70450600 H -4.05982500 -1.86928900 2.19868100 H -0.31614200 1.30578900 2.27257000 H -1.23283200 0.87605500 3.72275100 H -1.97752600 1.93787900 2.51188700 H 0.17936100 -1.55295600 1.43278500 H -1.11348700 -2.78422100 1.51408900 H -0.50745600 -2.02510000 3.00263200 H -5.47642500 0.57171700 0.55035400 H -5.37847500 -1.13661800 0.07201400 H -6.02173400 0.07189300 -1.06868000 H -3.51219000 2.70524600 -0.73785000 H -4.32878700 2.23964900 -2.23782700 H -2.56661700 2.20031000 -2.18258000 H -2.42637300 -0.60819300 -3.10459400 H -4.18332800 -0.69404300 -3.25934100 H -3.34263100 -1.93813800 -2.31821100 229 Table A.1.29. Atomic coordinates and single point energies for 46b. G = –2234.690219 GSP = –2236.281216 C 2.20629400 3.03500100 1.08351600 C 3.54403700 3.40893700 0.96712700 C 4.34797600 2.70983500 0.06918500 C 3.79419600 1.65358800 -0.64797600 C 2.44606300 1.34643300 -0.45474300 N 1.66389800 2.04321000 0.37909300 H 1.54128100 3.56301700 1.77324100 H 5.39542000 2.98375900 -0.06849500 H 3.93722700 4.23408200 1.56056000 H 4.38100200 1.07320000 -1.35890100 C 1.75114700 0.19883900 -1.17127300 N 2.19358100 -1.02591300 -1.10255900 O 0.66622300 0.53279300 -1.73839100 Si 3.48954500 -1.79462300 -0.23115600 C 3.20194600 -3.64729400 -0.39919000 C 3.48911400 -1.32608000 1.59759100 C 5.20688400 -1.45668700 -0.95363800 H 2.55327200 -1.64406000 2.08245600 H 3.59072200 -0.23789600 1.73694400 H 4.32458000 -1.81412200 2.12345900 H 5.16222600 -1.36927000 -2.05023300 H 5.87837400 -2.29511400 -0.71197100 H 5.66491300 -0.54285900 -0.54864000 H 2.22166900 -3.94859400 -0.00049000 H 3.97264000 -4.22016700 0.13874500 H 3.24146500 -3.93827800 -1.46035000 230 Na -0.62345900 1.13162700 0.00518900 Na -0.06800700 -1.58162500 -1.48214600 N -1.72137700 -0.95428700 0.07051600 Si -3.09770800 -1.44319500 -0.81403600 C -3.35159700 -3.32832200 -0.81355900 C -2.85141700 -0.96545800 -2.64352900 C -4.76087900 -0.70959800 -0.26670500 Si -1.34344600 -1.44904100 1.66329400 C -0.20305600 -0.15817600 2.47669000 C -0.35656000 -3.06997000 1.69201700 C -2.83337900 -1.66514500 2.81472200 H -2.12050000 -1.61596600 -3.15723100 H -2.49455600 0.07202300 -2.74939900 H -3.79049400 -1.06130800 -3.21019800 H -2.45161400 -3.85058700 -1.18014700 H -4.19529800 -3.62968800 -1.45421200 H -3.55196000 -3.70356200 0.20289700 H -4.92744100 -0.88836700 0.80706100 H -5.58509000 -1.18838900 -0.81868900 H -4.83351100 0.37455600 -0.44065700 H -3.39436900 -0.72221800 2.91390600 H -2.51689500 -1.97793900 3.82195600 H -3.52876300 -2.42810700 2.43020200 H 0.57323600 -2.94962500 1.10995000 H -0.93430800 -3.89350000 1.24292000 H -0.06850200 -3.37302000 2.71089800 H 0.72589400 -0.01777800 1.89752900 H 0.09696500 -0.48310200 3.48505500 H -0.69033800 0.82665700 2.59037300 N -2.23848400 2.83901900 0.32303600 C -3.14250200 2.32755700 1.34406900 C -1.81544200 4.19545500 0.62504700 C -2.85409400 2.72332100 -1.00082500 C -1.92087700 3.05615900 -2.15732200 H -3.76421400 3.36001200 -1.05206900 H -3.19571300 1.68076400 -1.10183800 H -1.62886400 4.11539100 -2.16397400 H -2.43505700 2.85492000 -3.10723800 H -1.00429900 2.44332700 -2.14393100 H -2.66115600 4.91352800 0.58495200 H -1.04238200 4.52703900 -0.08064000 H -1.38642200 4.22831200 1.63651100 H -3.34706600 1.26271100 1.15630700 H -4.10572100 2.87834800 1.35957200 H -2.67792800 2.42097300 2.33620200 231 Table A.1.30. Atomic coordinates and single point energies for 46d. G = –2195.455306 GSP = –2197.002290 N 1.93907500 -0.85240600 0.01271900 N -3.39490200 0.88025800 -0.00206400 Na -0.11873500 -1.90794800 -0.31606100 Na 0.55912600 1.01956500 0.04320000 Si 2.26843200 -1.06203200 1.67668000 C 1.24307800 0.20030900 2.66986100 C 4.08241400 -0.87103500 2.18384300 C 1.69884700 -2.76467100 2.30859300 Si 2.91832900 -1.34086200 -1.29783900 C 4.51074300 -0.33916600 -1.54538500 C 1.91238000 -1.18981500 -2.90473900 C 3.45910000 -3.15907800 -1.18073900 Si -2.84688300 2.52687500 0.01293100 C -4.35861000 3.64073200 0.05627200 C -1.86337600 2.94427400 -1.55290900 C -1.80637200 2.93347000 1.54430500 H 0.60673700 -2.89288100 2.20478800 H 1.93187900 -2.90628100 3.37548000 H 2.19240600 -3.57359500 1.74657100 H 4.47068800 0.12519200 1.92100700 H 4.71160600 -1.61874800 1.67507900 H 4.20944400 -1.00912600 3.26879400 H 1.52696600 1.24402600 2.44833600 H 1.37465700 0.06135600 3.75362300 H 0.16549800 0.08150900 2.45903500 H 4.03780300 -3.47512300 -2.06273100 H 2.58630700 -3.82829200 -1.09666900 232 H 4.08662400 -3.32754900 -0.29059000 H 4.31023100 0.70628400 -1.82632200 H 5.12771700 -0.78252400 -2.34270700 H 5.11112300 -0.32777100 -0.62223700 H 2.52617800 -1.41388100 -3.79078500 H 1.50246200 -0.17414200 -3.03101700 H 1.05844600 -1.88943600 -2.92603300 H -2.36691400 2.65332700 2.44925800 H -1.59717500 4.01337100 1.59995300 H -0.84392500 2.40062200 1.59326200 H -2.49021900 2.75654800 -2.43792800 H -0.96823100 2.31236000 -1.66174400 H -1.55751800 4.00227300 -1.57734000 H -5.00095400 3.44626200 -0.81552500 H -4.08436800 4.70654000 0.05328300 H -4.95419200 3.44028800 0.95949100 N -2.39182300 -2.57087000 -0.21915000 C -2.93643300 -3.79064500 -0.24886400 C -3.19979100 -1.50632600 -0.11227100 C -4.30639800 -4.01684500 -0.17484600 C -4.59083000 -1.64074700 -0.03416000 C -5.14995800 -2.91120200 -0.06528000 H -2.24508000 -4.63431100 -0.33562400 H -4.69646000 -5.03415200 -0.20275500 H -6.23174100 -3.04277300 -0.00488400 H -5.17823200 -0.72748200 0.04843300 O -1.29160800 -0.07999200 -0.12641100 C -2.57393100 -0.10966000 -0.07664600 N 1.90225900 2.98458400 -0.19118900 C 3.15795900 2.65762700 0.47301000 C 2.08075500 2.97025800 -1.63705600 H 2.41256100 1.97210000 -1.96145500 H 1.13128900 3.20763800 -2.13785100 H 2.84126900 3.70774300 -1.96583500 C 1.38364100 4.26727100 0.25790600 H 0.41743200 4.46887900 -0.22608700 H 1.22486200 4.24645100 1.34533200 H 2.07834800 5.09856800 0.01979800 H 3.02871700 2.69754600 1.56371500 H 3.96357100 3.36720400 0.19385500 H 3.46889200 1.63893500 0.19738300 233 Table A.1.31. Atomic coordinates and single point energies for 46e. G = –2369.611915 GSP = –2371.356254 N 2.39763900 -0.43764000 -0.60717500 N -3.21263600 0.15434400 -0.00306200 Na 0.60050900 -1.41915600 0.44382000 Na 0.75564800 1.21213900 -0.55004400 Si 3.57269100 0.04678800 0.50949700 C 3.35560200 1.89966800 0.93091700 C 5.38022400 -0.15884200 -0.00663100 C 3.35911700 -0.91317100 2.14167800 Si 2.34160900 -0.91377400 -2.23727800 C 1.62451400 0.49439600 -3.31049100 C 1.12134800 -2.35741900 -2.42930900 C 3.98662700 -1.42681500 -3.01470200 Si -3.88368200 -0.43860200 -1.50472400 C -3.45390500 -2.25761100 -1.76732600 C -3.26635600 0.56113500 -2.98054300 C -5.75295300 -0.26631500 -1.38352600 H 2.31876900 -0.86739100 2.50844000 H 4.00897500 -0.53874900 2.94823000 H 3.60630700 -1.97521800 1.97918400 H 5.61556700 0.46922600 -0.87967900 H 5.59688300 -1.20311600 -0.27884600 H 6.06002700 0.12946000 0.81054300 H 3.52861500 2.50047800 0.02151500 H 4.06179300 2.25148800 1.69924900 H 2.33834300 2.12425800 1.29793500 H 3.84451500 -1.74681500 -4.05873100 H 4.43590300 -2.26520000 -2.46022400 H 4.70926100 -0.59675300 -3.00858700 234 H 0.57215300 0.69909600 -3.04140500 H 1.62775300 0.24908600 -4.38365200 H 2.21331500 1.41841500 -3.17914200 H 1.02926400 -2.69804000 -3.47196900 H 0.11748200 -2.03775900 -2.09885400 H 1.44208100 -3.22369000 -1.82582300 H -6.13978600 -0.84750400 -0.53289700 H -6.25299000 -0.62016300 -2.29784600 H -6.03324900 0.78582400 -1.22392200 H -2.17082000 0.48032700 -3.04360000 H -3.53788900 1.62304700 -2.87683700 H -3.69921400 0.19214400 -3.92309500 H -2.36659200 -2.36615000 -1.89576700 H -3.95048900 -2.66459600 -2.66156100 H -3.77104700 -2.86007500 -0.90152200 N -0.15066300 0.66789000 1.79964900 C 0.28563200 1.12701100 2.97789600 C -1.46532700 0.70316700 1.54139400 C -0.56318700 1.64168700 3.95310300 C -2.39246400 1.20344100 2.46374400 C -1.93353100 1.67902100 3.68542600 H 1.36557800 1.08209200 3.14844400 H -0.15584800 2.00335000 4.89710600 H -2.63156500 2.07545400 4.42504200 H -3.44302800 1.18953700 2.17522700 O -0.99581000 -0.21893200 -0.59744200 C -1.93698100 0.16126300 0.18563400 N -0.11224400 3.43071500 -0.50825800 C 0.77871200 4.22250500 -1.34430000 C -1.42309800 3.29046000 -1.13252200 H -1.32335300 2.79237000 -2.10805900 H -2.08365500 2.67267100 -0.50624200 H -1.90722600 4.27590000 -1.29119300 C -0.22513500 4.01284800 0.82052500 H -0.89065700 3.39970500 1.44515900 H 0.76479000 4.05367900 1.29844500 H -0.63655700 5.04259200 0.78177200 H 1.77331400 4.28431700 -0.87942900 H 0.39789800 5.25403300 -1.49094600 H 0.88372700 3.75331300 -2.33362100 N -0.50550800 -3.08020000 1.75924700 C -0.93380200 -4.01883800 0.73012300 H -1.55431900 -3.49941600 -0.01402700 H -0.05824000 -4.44341000 0.21765100 H -1.52473000 -4.85551000 1.15569800 C 0.37568800 -3.72285600 2.72168100 235 H 1.26199100 -4.12744300 2.21181800 H 0.71265900 -2.99072200 3.46921200 H -0.13064200 -4.55531400 3.25210900 C -1.65886200 -2.48758400 2.42420100 H -1.32562600 -1.73588300 3.15548700 H -2.30963500 -1.99059700 1.68896700 H -2.25699800 -3.25415500 2.95867100 236 Table A.1.32. Atomic coordinates and single point energies for 46f. G = –2369.607022 GSP = –2371.352467 C 2.03885700 3.75907900 -0.50989800 C 3.37882500 4.05693300 -0.75168700 C 4.23029900 3.01420500 -1.11018600 C 3.71869300 1.72192200 -1.17600000 C 2.36545000 1.51880300 -0.89809200 N 1.53736700 2.52823500 -0.59974600 H 1.33681900 4.55259600 -0.23791400 H 5.28120000 3.20609000 -1.33381500 H 3.73634100 5.08332100 -0.67193600 H 4.34353000 0.87286700 -1.44892100 C 1.72060200 0.13880000 -0.92610600 N 2.18299600 -0.85519000 -0.21479200 O 0.66744200 0.08817700 -1.62730700 Si 3.45078400 -0.97288000 0.97230000 C 3.29026000 -2.65496400 1.80711800 C 3.31680200 0.36812500 2.29437200 C 5.20445600 -0.94616600 0.25108200 H 2.37687100 0.26595900 2.85806800 H 3.33967800 1.37837700 1.85541100 H 4.15122100 0.28946600 3.00882900 H 5.23199200 -1.42466000 -0.74047300 H 5.87694400 -1.51347700 0.91322200 H 5.61405100 0.06996200 0.16030300 H 2.27426600 -2.84285100 2.18458400 H 3.98379300 -2.71912800 2.66006800 H 3.55293500 -3.46274600 1.10641500 237 Na -0.75054000 1.53115100 -0.62417700 Na -0.14046000 -1.59919300 -0.35081400 N -1.87498200 -0.17512600 0.48304900 Si -3.18231300 -1.06178000 -0.15281400 C -3.27865000 -2.82053000 0.57384400 C -2.94611700 -1.27477600 -2.02823500 C -4.90214000 -0.30030200 0.10319600 Si -1.46461400 0.04528700 2.12261200 C -0.33057300 1.56275900 2.29476600 C -0.42160600 -1.40740100 2.77821200 C -2.92526500 0.26850200 3.30920500 H -1.95373000 -1.69331400 -2.26633800 H -3.01372200 -0.31112000 -2.55758600 H -3.70634400 -1.94524400 -2.45926600 H -2.31107100 -3.34204700 0.47197600 H -4.04592900 -3.43888400 0.08147500 H -3.51405300 -2.78310700 1.64998800 H -5.08336100 -0.10110000 1.17102900 H -5.68955400 -0.98355600 -0.25227600 H -5.02073700 0.65133800 -0.43822700 H -3.54088600 1.13614500 3.02402800 H -2.58271800 0.42068300 4.34459900 H -3.57701300 -0.61988700 3.29842900 H 0.52374600 -1.46922500 2.21076500 H -0.95569000 -2.36528800 2.66466100 H -0.15082400 -1.29515400 3.83994400 H 0.59640200 1.41871600 1.71375800 H -0.03121000 1.72594800 3.34197900 H -0.80951500 2.49150000 1.94110400 N -2.39071200 3.30598100 -0.70192900 C -3.24033700 3.19288800 0.47562500 C -1.92362700 4.66685800 -0.89458500 H -2.76075400 5.37519500 -1.06569500 H -1.24935900 4.71521000 -1.76225700 H -1.37013800 4.99919300 -0.00460600 H -3.46979800 2.13330900 0.66029900 H -4.18832200 3.75654700 0.35179600 H -2.71658800 3.59053400 1.35613900 N 0.05198100 -3.68743900 -1.51456500 C -1.03269600 -4.52153700 -2.00266000 C 0.86993800 -4.40259500 -0.54663200 H -1.65852700 -4.85964300 -1.16496700 H -0.65016800 -5.41638100 -2.53645300 H -1.66608200 -3.94918400 -2.69453000 H 1.66562200 -3.73928400 -0.17792300 H 1.34232800 -5.30506900 -0.98748600 238 H 0.25260000 -4.72016900 0.30742800 C -3.09117500 2.81555300 -1.87871800 H -2.42853300 2.84131100 -2.75710600 H -3.40837300 1.77622200 -1.70930500 H -3.99385200 3.41887800 -2.10788700 C 0.87095800 -3.19322900 -2.61545200 H 0.25242400 -2.59756000 -3.30162400 H 1.66503500 -2.54304000 -2.22014300 H 1.33225300 -4.02677200 -3.18469400 239 Table A.1.33. Atomic coordinates and single point energies for TS-1. G = –2719.294899 GSP = –2721.216825 N 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 4.48057353 Na 2.14401756 0.00000000 0.93273590 Na -0.71140134 -0.54582211 2.21231036 Si 0.04243108 1.54102079 -0.73719134 C -1.06152961 2.82233728 0.11319903 C -0.41714102 1.59690030 -2.57505765 C 1.82788345 2.25379549 -0.66579898 Si -0.05178624 -1.50113790 -0.81863387 C -1.41219125 -1.69830636 -2.12766600 C -0.24614625 -2.94663854 0.40443691 C 1.58674194 -1.87650422 -1.72562117 Si -0.76218825 -0.89130381 5.75247173 C -1.43361621 -2.57857278 5.16109701 C -2.27758192 -0.03668484 6.52858248 C 0.35769455 -1.22342853 7.25048011 Si -0.06112568 1.72648751 4.53117226 C 0.46653038 2.51520899 6.17593504 C -1.78704277 2.42234839 4.14293008 C 1.04475666 2.51763665 3.20544512 H 2.17865353 2.46045152 0.36165606 H 1.88385247 3.21466483 -1.20029145 H 2.54661109 1.57828722 -1.16544391 H -1.46054712 1.28059362 -2.72844004 H 0.22581027 0.93948879 -3.18164573 H -0.31570065 2.62195633 -2.96495543 H -2.11754470 2.65785536 -0.15126873 H -0.79606193 3.84246573 -0.20632818 H -0.97384822 2.78106500 1.20967976 240 H 1.54314593 -2.82861902 -2.27758912 H 2.43497620 -1.96222594 -1.02210354 H 1.82841766 -1.08140044 -2.44971106 H -2.40073765 -1.39269945 -1.75062544 H -1.48377500 -2.74982703 -2.44798078 H -1.19888726 -1.09107143 -3.01941929 H -0.42430293 -3.88410122 -0.14545887 H -1.08855333 -2.82106592 1.10398395 H 0.66658403 -3.06674162 1.00556110 H 1.23889701 -1.82330949 6.98231958 H -0.20040475 -1.76321693 8.03189808 H 0.69960917 -0.27161794 7.68950189 H -3.10617292 0.08819978 5.81687864 H -2.04380074 0.95213027 6.95060859 H -2.64151008 -0.66997973 7.35378285 H -2.43128063 -2.75082270 5.59506459 H -0.79853292 -3.41770226 5.47786697 H -1.53851448 -2.62980829 4.06373977 H 2.09164293 2.60900560 3.52712053 H 0.67624002 3.53064873 2.98016384 H 1.01324057 1.94832461 2.26180312 H -2.54604388 2.10655449 4.87245138 H -2.12408395 2.10431701 3.14264513 H -1.75847243 3.52378020 4.13846856 H -0.17587003 2.19914662 7.01167966 H 0.40779757 3.61306208 6.10621742 H 1.50355099 2.25161929 6.43279841 N 3.41922232 0.44961959 2.94116740 C 4.38962373 1.34565801 3.14216974 C 2.79218612 -0.05600800 4.00510973 C 4.77676628 1.77025475 4.40847345 C 3.11393887 0.29788302 5.31641003 C 4.12109377 1.23218642 5.51746732 H 4.87723172 1.74764203 2.24967381 H 5.57289328 2.50592494 4.52003983 H 4.39251096 1.54293687 6.52761360 H 2.55510463 -0.15016921 6.13784755 O 1.43548737 -1.35686666 2.53158064 C 1.76893712 -1.12677648 3.69586519 O 1.81237082 -2.11608883 4.60314193 C 1.51490295 -3.41673593 4.11734181 H 1.50825373 -4.07384202 4.99344514 H 2.29313882 -3.73813686 3.40956774 H 0.54336570 -3.44904551 3.61176516 N -3.15962684 -0.90301882 1.90094817 C -3.40340783 0.19039451 0.96930638 241 C -3.62245431 -2.15908559 1.33221866 H -3.13290336 -2.33810974 0.36508338 H -3.37920468 -2.99327539 2.00659734 H -4.72049951 -2.15053526 1.17066895 C -3.82436655 -0.64727509 3.17022010 H -3.61852661 -1.46396472 3.87568085 H -3.44823096 0.28799840 3.60669305 H -4.92391017 -0.55902938 3.04562002 H -3.07790858 1.14093599 1.41523081 H -4.48010906 0.27854122 0.71485312 H -2.81928013 0.03699836 0.05112881 242 Table A.1.34. Atomic coordinates and single point energies for 45. G = –2719.305439 GSP = –2721.231429 N 2.43456200 -0.48324500 0.00681000 N -1.70902300 0.93845200 0.29081600 Na 1.09641300 -2.27730500 -0.60743700 Na 0.55258300 0.96561300 -0.19610500 Si 3.10433200 -1.19278100 1.41086300 C 2.57785900 -0.38316300 3.03846100 C 4.99545100 -1.29392600 1.46470700 C 2.52982100 -3.02588900 1.55960500 Si 3.25062700 -0.09033800 -1.44406800 C 4.93011000 0.77078900 -1.26922500 C 2.17866400 1.04524600 -2.53289800 C 3.55114100 -1.64146700 -2.51674900 Si -2.72538200 2.15386700 -0.33990100 C -1.86270700 3.19127900 -1.70810400 C -3.34695600 3.44556500 0.91738400 C -4.33630600 1.48091700 -1.10398600 Si -1.94906700 0.31164300 1.85755300 C -3.74608400 -0.13792600 2.29881000 C -1.37715700 1.46008200 3.26546900 C -0.94282300 -1.28862400 2.10662500 H 1.43932500 -3.13062900 1.70720600 H 2.99790300 -3.49750800 2.43718400 H 2.84199100 -3.62890800 0.68641100 H 5.44576500 -0.28946600 1.46585700 H 5.40242900 -1.84408700 0.60134100 H 5.32345000 -1.81075300 2.38035000 H 3.12996100 0.55366000 3.20831100 H 2.79704200 -1.05272800 3.88521100 243 H 1.50108100 -0.15568200 3.06065600 H 4.13386100 -1.41501600 -3.42327700 H 2.59942900 -2.08545000 -2.86089800 H 4.10507400 -2.40820700 -1.94962200 H 4.87904600 1.61952300 -0.56870800 H 5.26081300 1.15854100 -2.24574400 H 5.70563400 0.08397100 -0.90093400 H 2.71460600 1.28985000 -3.46306800 H 1.93592500 2.00222200 -2.04427700 H 1.24023200 0.54246200 -2.81256600 H -4.14830600 0.74752600 -1.90261100 H -4.95512300 2.29215500 -1.52007800 H -4.92843000 0.97861500 -0.32100300 H -2.52120400 4.01158400 1.37530200 H -3.91980700 2.97679100 1.73301200 H -4.01255000 4.16871100 0.41877900 H -1.94106500 4.26516800 -1.47558100 H -2.32638900 3.05024200 -2.69633700 H -0.78774100 2.95625100 -1.80243900 H -1.50476300 -2.17019000 1.76630300 H -0.68968100 -1.44729300 3.16677700 H 0.00875200 -1.23685700 1.54937400 H -1.88022400 2.43827000 3.21487600 H -0.29026500 1.64015100 3.22249500 H -1.59684900 1.01675600 4.25003200 H -4.38276800 0.75967300 2.34438900 H -3.79674100 -0.63263300 3.28217300 H -4.18777800 -0.81720200 1.55366500 N -1.11629700 -3.29083300 -0.56163200 C -1.55833800 -4.28663700 0.20280600 C -1.99416300 -2.36330300 -0.95583300 C -2.88706100 -4.38718400 0.61872100 C -3.33790000 -2.36590700 -0.59168300 C -3.78757200 -3.40177500 0.22422500 H -0.82179500 -5.03293900 0.51215200 H -3.19774100 -5.21790800 1.25194200 H -4.82752600 -3.43467900 0.55177900 H -3.98664400 -1.55661200 -0.92780500 O -0.24275100 -1.07501100 -1.94025200 C -1.43271200 -1.29776400 -1.85016900 O -2.34131900 -0.71967800 -2.59535500 C -1.87062600 0.28034400 -3.49599600 H -2.76056800 0.71556600 -3.95966400 H -1.21910200 -0.17864100 -4.25187100 H -1.31228500 1.04473700 -2.94357900 N 1.46722700 3.22039800 0.40103600 244 C 2.30826200 2.72607600 1.47994800 C 2.23914900 4.05252000 -0.50526300 H 3.10136000 3.49021600 -0.89115400 H 1.61574700 4.36314600 -1.35648400 H 2.61931100 4.96492800 -0.00001100 C 0.33600100 3.96047100 0.94117100 H -0.28883600 4.33923500 0.12194000 H -0.28332400 3.29728000 1.56069200 H 0.66887800 4.82147100 1.55819600 H 1.70890900 2.10835900 2.16359300 H 2.75596400 3.55518700 2.06740300 H 3.10987400 2.09204400 1.07448400 245 Table A.1.35. Atomic coordinates and single point energies for 46i. G = –2719.333755 GSP = –2721.250152 N -2.73196700 0.56054700 -0.00713500 N 2.76794900 -0.44160600 0.03779900 Na -0.85444200 1.91812200 -0.36169700 Na -1.04829600 -1.06546500 0.01317500 Si -3.09708600 0.81151600 1.64340000 C -1.93080100 -0.24376700 2.71261100 C -4.87577400 0.41589500 2.15923600 C -2.75368300 2.60894300 2.17539500 Si -3.78711600 0.83172600 -1.32161800 C -5.20334800 -0.41972700 -1.49860100 C -2.80158800 0.76385900 -2.94596800 C -4.60226000 2.54855300 -1.27795400 Si 3.21873700 -1.84665400 -0.94250300 C 1.64720500 -2.75348600 -1.48442600 C 4.21673800 -3.05349300 0.12179200 C 4.35500800 -1.48956700 -2.39997500 Si 2.61341000 -0.53929700 1.79523500 C 4.29821700 -0.77901400 2.60530100 C 1.47696400 -1.95916400 2.32806900 C 1.91979200 1.05567100 2.52342200 H -1.68260500 2.86377800 2.07858500 H -3.02101600 2.78586100 3.22888600 H -3.33087600 3.31659500 1.55887900 H -5.12156200 -0.63970500 1.96425200 H -5.59640300 1.03424500 1.60078900 H -5.03044200 0.60676100 3.23252700 H -2.03792500 -1.32284100 2.50931600 H -2.12134700 -0.09686400 3.78683000 246 H -0.87882800 0.03587700 2.53194700 H -5.24182200 2.72453000 -2.15696700 H -3.84054700 3.34603800 -1.25438800 H -5.22814900 2.66803900 -0.37886700 H -4.83713700 -1.43117500 -1.73453000 H -5.88801600 -0.11935300 -2.30729300 H -5.78880500 -0.48499700 -0.56825400 H -3.46066100 0.87449300 -3.82107300 H -2.26341100 -0.19262200 -3.05273900 H -2.05070500 1.57089300 -3.00638400 H 3.79843900 -1.11251200 -3.26633600 H 4.90494100 -2.39847500 -2.68884300 H 5.09422500 -0.72404700 -2.11745200 H 3.72861600 -3.38055900 1.04990300 H 5.19998600 -2.63217200 0.37997800 H 4.39707300 -3.95110600 -0.49117300 H 1.06121400 -3.00562900 -0.58426300 H 1.85890200 -3.68659800 -2.02918200 H 1.04219400 -2.09373600 -2.12377600 H 2.62917300 1.89147700 2.42554800 H 1.73427600 0.89252000 3.59711500 H 0.97558100 1.34881900 2.04509100 H 1.83650000 -2.93634300 1.97414300 H 0.45697700 -1.81579600 1.94102600 H 1.40302300 -2.00420800 3.42605200 H 4.73364700 -1.77216500 2.43839500 H 4.20065800 -0.63109500 3.69230900 H 5.00510400 -0.02517300 2.22544700 N 1.32473600 2.89391700 -0.24394400 C 1.69331000 4.16655800 -0.05208500 C 2.27233200 1.95975300 -0.36980500 C 3.01868100 4.57513800 0.01320900 C 3.63430300 2.28645600 -0.34703700 C 4.01175100 3.60657900 -0.14899300 H 0.88657700 4.89782700 0.05614900 H 3.26343700 5.62388700 0.18006200 H 5.06695400 3.88389600 -0.11686000 H 4.36080700 1.48392300 -0.47024200 O 0.55959400 0.28131800 -0.33185600 C 1.82780200 0.48636900 -0.62224700 O 2.12346400 0.28164000 -2.03078300 C 1.18396100 0.79444900 -2.92594400 H 1.55809200 0.59841000 -3.93981900 H 1.06011500 1.88899400 -2.81265800 H 0.19730100 0.31671000 -2.81008700 N -2.08941100 -3.23004500 0.03512200 247 C -3.39778700 -3.02794200 0.64530900 C -2.21419000 -3.30640500 -1.41443600 H -2.68298400 -2.38567000 -1.79582800 H -1.22036300 -3.41423200 -1.87368900 H -2.84242200 -4.16344200 -1.73244900 C -1.43991400 -4.41747100 0.56760200 H -0.45739100 -4.55315300 0.09425200 H -1.29112800 -4.30859400 1.65119100 H -2.04208800 -5.33121200 0.38583000 H -3.30322500 -3.01476800 1.74007600 H -4.10512400 -3.83670600 0.36904300 H -3.81387800 -2.06240300 0.32147900 248 Table A.1.36. Atomic coordinates and single point energies for 46m. G = –2719.298927 GSP = –2721.216761 N 2.21501700 0.62666300 0.23513000 N -1.80056800 -0.64326000 0.00536000 Na 0.35809300 1.18116800 1.64148100 Na 0.65398400 -0.99921100 -0.58449000 Si 2.25533500 1.63799100 -1.15937800 C 0.75974000 1.21806300 -2.26660100 C 3.76621400 1.45258000 -2.29969300 C 2.24879300 3.50654900 -0.77845900 Si 3.63146900 0.57431600 1.22132700 C 5.07985100 -0.44696200 0.53046600 C 3.29938400 -0.13205500 2.95292900 C 4.37615900 2.29409900 1.54341700 Si -1.46918100 -1.62182500 1.55791500 C 0.18111900 -1.48445100 2.50974800 C -1.06507800 -3.33770900 0.72527300 C -2.91074400 -2.13120300 2.66237100 Si -2.59630900 -1.27375700 -1.45348000 C -4.10013800 -2.34181200 -1.09013400 C -1.31157000 -2.24895800 -2.44699100 C -3.15215600 0.08312700 -2.63908800 H 1.62550400 4.07308500 -1.48739500 H 3.27365100 3.90121900 -0.85012200 H 1.89818500 3.71445300 0.24317700 H 3.90826200 0.43231500 -2.68505500 H 4.69175500 1.75124000 -1.78233800 H 3.64659000 2.12411900 -3.16557300 H 0.92710800 0.26580000 -2.80274500 249 H 0.62005000 1.98346600 -3.04509400 H -0.18639600 1.14924100 -1.70323000 H 5.22089700 2.21936600 2.24616900 H 3.63686900 2.98573000 1.97824700 H 4.75545100 2.75625200 0.61864700 H 4.87525300 -1.52722500 0.50066900 H 5.96544500 -0.29810400 1.16862700 H 5.34661400 -0.12828700 -0.48867900 H 4.21944300 -0.02940200 3.54975000 H 3.02631000 -1.19764200 2.94785800 H 2.50504700 0.40817100 3.49562500 H -3.05217300 -1.41686900 3.48445100 H -2.74535500 -3.13535700 3.08044500 H -3.83729700 -2.15443400 2.06887000 H -0.16204600 -3.32551900 0.09357000 H -1.87790300 -3.76217200 0.11607600 H -0.86429900 -4.05361900 1.53939200 H 0.47041800 -2.46678700 2.91298100 H 0.09047600 -0.78843800 3.35907700 H 1.03508200 -1.15618100 1.89164600 H -4.10772200 0.53479400 -2.34325300 H -3.30274600 -0.39072600 -3.62253000 H -2.40656400 0.88224000 -2.76132000 H -0.83290100 -3.05957200 -1.88476800 H -0.53152000 -1.58182800 -2.85333200 H -1.81340000 -2.70172000 -3.31645900 H -3.87116000 -3.20250600 -0.44712900 H -4.54654200 -2.71626000 -2.02431000 H -4.84066700 -1.71818800 -0.56867000 N -1.09506400 2.56465700 0.38126000 C -0.97894700 3.81218800 -0.08061600 C -2.22791300 1.89322000 0.15155800 C -1.97202500 4.45484700 -0.81259100 C -3.28746700 2.47266700 -0.55688100 C -3.15379900 3.76204600 -1.05656600 H -0.04965100 4.33471600 0.14709600 H -1.81965700 5.47499500 -1.16420700 H -3.96909500 4.22526400 -1.61488600 H -4.20457600 1.90444100 -0.68863500 O -1.73849700 0.36283800 1.95258400 C -2.36588500 0.47968700 0.76565900 O -3.77675700 0.22054700 0.85837300 C -4.43651500 0.85905200 1.92313800 H -5.43914500 0.41778000 1.99444400 H -4.53988200 1.94676600 1.75285300 H -3.89492800 0.70357300 2.86639000 250 N 2.05869300 -2.93032100 -1.13096100 C 3.03868700 -2.18998700 -1.91513400 C 2.59275900 -3.24000000 0.18933700 H 2.82663700 -2.30755100 0.72415000 H 1.84956400 -3.80082900 0.77345500 H 3.52090600 -3.84452700 0.12507500 C 1.66229500 -4.14691700 -1.82284400 H 0.89012600 -4.67629500 -1.24603600 H 1.24944500 -3.89945900 -2.81069700 H 2.52350600 -4.83127400 -1.96413400 H 3.31913700 -1.27204400 -1.38039600 H 2.60784300 -1.91664800 -2.89090100 H 3.95773100 -2.78490200 -2.09607600 251 Table A.1.37. Atomic coordinates and single point energies for TS-22. G = –2719.291865 GSP = –2721.211208 N 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 4.18709508 Na 1.90928846 0.00000000 1.41499763 Na -1.27469290 -0.08203529 2.02208990 Si -0.12870466 1.67554845 -0.37347836 C -0.87811992 2.59342026 1.11990539 C -1.23056015 2.16849545 -1.83974159 C 1.54908107 2.44904589 -0.85174097 Si 0.17577438 -1.12468074 -1.29877855 C -1.34016048 -1.33204223 -2.43176042 C 0.62827371 -2.86962828 -0.71451054 C 1.57806335 -0.64511142 -2.49398934 Si 0.92279208 -1.92524074 3.79544402 C 2.10942020 -3.01232834 2.73424492 C -0.70666342 -2.52223172 2.98295926 C 1.12173492 -2.65513142 5.51900916 Si -1.30019641 0.36673151 5.29729481 C -1.77116694 -1.05833529 6.44455725 C -2.83794212 0.70223103 4.23715488 C -1.08139967 1.88422305 6.39524087 H 1.54323713 3.54609127 -0.75353578 H 1.75212716 2.21409055 -1.90734475 H 2.40161607 2.05826463 -0.27332938 H -2.27134910 1.82728550 -1.73645409 H -0.83652005 1.77297820 -2.78872887 H -1.24553799 3.26738083 -1.92239538 252 H -1.96465469 2.39998492 1.16626155 H -0.76043437 3.68328018 1.01694537 H -0.42915575 2.31214874 2.08697007 H 1.77740876 -1.46281529 -3.20460640 H 2.51848124 -0.43086658 -1.95928222 H 1.32192007 0.24911223 -3.08413341 H -2.18233646 -1.85195969 -1.95295586 H -1.04295856 -1.93137167 -3.30740161 H -1.71149529 -0.36542651 -2.80251200 H 0.52249495 -3.56536842 -1.56206739 H 0.00384767 -3.25008274 0.10786882 H 1.67776255 -2.92584085 -0.38634858 H 2.19726898 -2.72240392 5.74453758 H 0.71375247 -3.67814868 5.53776240 H 0.64722646 -2.06298097 6.30706090 H -0.71270227 -2.30350469 1.90205149 H -1.62490081 -2.12007791 3.44264566 H -0.74108167 -3.62110338 3.05521228 H 1.79181912 -4.06693933 2.71802784 H 3.13462076 -2.96689574 3.13336401 H 2.15335849 -2.69776965 1.67671372 H -0.21820503 1.75908998 7.06463852 H -1.98460582 1.98957479 7.01698311 H -0.95922048 2.81177025 5.81751816 H -3.12386698 -0.17964927 3.64503638 H -2.68013182 1.55387629 3.55253376 H -3.70223515 0.94990975 4.87203963 H -1.80666904 -2.02493851 5.91976843 H -2.76542033 -0.86600604 6.87796497 H -1.05563966 -1.15242843 7.27457548 N 2.07546378 2.04766377 2.64653194 C 2.37852826 3.29216428 2.26065521 C 1.71172669 1.84243180 3.91591472 C 2.32427144 4.39398312 3.10580660 C 1.65275725 2.89183909 4.84244093 C 1.94988631 4.18371157 4.43059581 H 2.68295811 3.42224483 1.22171172 H 2.58218898 5.38416747 2.73110904 H 1.90467253 5.01361702 5.13790131 H 1.39024031 2.66855812 5.87328094 O 2.04619459 -0.53503867 3.61176771 C 1.34766253 0.41172788 4.36335360 O 1.69734411 0.30492080 5.74213737 C 3.07340754 0.25620163 6.02585973 H 3.17331261 0.13437364 7.11174584 H 3.59075628 1.18541976 5.72493235 253 H 3.55555279 -0.59066737 5.51535351 N -3.50852766 -0.99867095 1.18748798 C -3.63275492 -0.03975264 0.09849521 C -3.16904714 -2.31450375 0.66595050 H -2.19897301 -2.27499859 0.15196824 H -3.09357698 -3.03751997 1.48927753 H -3.93116997 -2.67593309 -0.05597878 C -4.74619691 -1.06765594 1.94798649 H -4.62966834 -1.75837862 2.79566095 H -5.00285321 -0.07574523 2.34436241 H -5.58925387 -1.42438401 1.32136920 H -2.68386590 0.01516734 -0.45277966 H -3.86940607 0.95695722 0.50171997 H -4.43628277 -0.32360929 -0.61309475 254 Table A.1.38. Atomic coordinates and single point energies for 46n. G = –2719.309158 GSP = –2721.230323 N 2.20839300 0.62972300 0.16392700 N -1.60518900 -0.54374400 -0.47834500 Na 0.26987700 1.29532000 1.26790800 Na 0.68514200 -0.94764100 -0.83557300 Si 2.28762100 1.79487300 -1.10246500 C 0.94695100 1.41167800 -2.39413900 C 3.92724400 1.88742000 -2.05224500 C 2.00713200 3.57810600 -0.48391700 Si 3.50387800 0.50120100 1.28802800 C 5.08672600 -0.32128400 0.63299800 C 3.00340000 -0.48653500 2.83378000 C 4.07720000 2.18936200 1.95261700 Si -1.39756000 -1.24298200 2.54887200 C -0.91790300 -0.63323500 4.25980600 C 0.03572900 -2.19804800 1.79176400 C -2.89684400 -2.35161300 2.65696200 Si -2.38651900 -1.48097700 -1.68806900 C -3.32136500 -3.00960100 -1.07139800 C -0.98535500 -2.15528300 -2.77894500 C -3.58128200 -0.58520700 -2.85727100 H 1.62346100 4.23056600 -1.28420800 H 2.95531800 4.00729000 -0.12678900 H 1.29880900 3.62866000 0.35863000 H 4.20528300 0.92477700 -2.50772500 H 4.75234800 2.20027900 -1.39313700 H 3.84960400 2.63193700 -2.86059000 H 1.20878300 0.50755200 -2.97273300 255 H 0.86719700 2.23246900 -3.12322000 H -0.05299600 1.26052600 -1.95052700 H 4.82042600 2.06308900 2.75551500 H 3.23808100 2.77698400 2.36050400 H 4.54617000 2.79432100 1.16035600 H 4.95602000 -1.38851100 0.40135100 H 5.88458500 -0.24260500 1.38859000 H 5.44240100 0.17725700 -0.28154800 H 3.79754800 -0.40346800 3.59215500 H 2.85308600 -1.55796000 2.63293000 H 2.07571500 -0.10723000 3.29480700 H -3.73517900 -1.85618400 3.16639400 H -2.63311500 -3.25328200 3.23195800 H -3.22712200 -2.65004100 1.65372500 H 0.87640000 -1.53217200 1.53916400 H -0.30465700 -2.71829800 0.88392700 H 0.42201100 -2.94222200 2.50664900 H -0.63763700 -1.47377000 4.91243700 H -1.76289700 -0.10504800 4.72624000 H -0.06408100 0.06123000 4.23434400 H -4.54468800 -0.38094300 -2.36590500 H -3.78782300 -1.22430000 -3.73062200 H -3.16512200 0.36711000 -3.22045200 H -0.31904000 -2.81212700 -2.19873300 H -0.38348300 -1.34977800 -3.23366400 H -1.39130100 -2.76231600 -3.60212900 H -2.67294200 -3.64954800 -0.45141500 H -3.69247700 -3.61717500 -1.91220300 H -4.18254600 -2.70138500 -0.46021300 N -1.41302300 2.54188200 0.24033600 C -1.45075700 3.77948400 -0.26701200 C -2.41030700 1.69797700 -0.03647200 C -2.47692500 4.24180200 -1.07986700 C -3.48756300 2.08176800 -0.84910800 C -3.51859200 3.36296300 -1.37792400 H -0.61649500 4.43740300 -0.01360700 H -2.45644100 5.26074800 -1.46519300 H -4.34847000 3.67720000 -2.01341300 H -4.27816200 1.36235200 -1.05165300 O -1.67595900 0.22669400 1.72744900 C -2.31009500 0.22462500 0.43211800 O -3.63898200 -0.27050500 0.61078500 C -4.44779600 0.35494400 1.57547700 H -5.33154600 -0.28168300 1.71476200 H -4.78151300 1.35688800 1.25552500 H -3.92525600 0.46086300 2.53904000 256 N 2.26813600 -2.78694700 -1.44631300 C 3.22731800 -1.92729100 -2.12753900 C 2.77847000 -3.18709400 -0.14427300 H 2.93991700 -2.29776700 0.48040000 H 2.05203900 -3.83941000 0.36025500 H 3.74191800 -3.73253900 -0.22930100 C 1.96660600 -3.95705700 -2.25480500 H 1.20934500 -4.57705700 -1.75386700 H 1.56719100 -3.64866600 -3.23047300 H 2.87024100 -4.57810200 -2.42396700 H 3.42946600 -1.04063500 -1.51009600 H 2.81500000 -1.60098200 -3.09471900 H 4.18691200 -2.45158000 -2.31911400 257 Table A.1.39. Atomic coordinates and single point energies for TS-2. G = –2719.31406 GSP = –2721.230503 N 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 5.24999085 Na 1.74654089 0.00000000 1.54385881 Na -0.94616518 -0.57626896 2.09671826 Si -0.48835251 1.62097636 -0.27019453 C -1.64171256 2.21026029 1.11954573 C -1.41436382 1.91433315 -1.90203162 C 0.98526454 2.82173680 -0.24728830 Si 0.51040372 -1.04731524 -1.24846160 C -0.86813023 -1.72681188 -2.36583442 C 1.38732021 -2.56016153 -0.49805118 C 1.79153411 -0.26683962 -2.41832478 Si -0.37816914 -1.62689861 5.86278838 C -1.41432459 -2.61443167 4.63583211 C -1.48794755 -1.49776169 7.38274261 C 1.14037436 -2.55612380 6.47322418 Si -1.01069415 1.44606556 5.60577517 C -1.23649605 1.65401424 7.46941499 C -2.69712106 1.25440434 4.79101496 C -0.14388177 3.01856714 5.05433151 H 1.48966909 2.79443106 0.73413406 H 0.67464198 3.86361804 -0.42300412 H 1.72171242 2.55296424 -1.02125380 H -2.34658941 1.32853913 -1.94098979 H -0.80551603 1.62954354 -2.77450929 H -1.68124282 2.97710876 -2.01262907 258 H -2.53033399 1.56463616 1.21674821 H -2.00162073 3.23338604 0.93004681 H -1.10112931 2.21177839 2.07823033 H 2.13655068 -0.98252846 -3.18119163 H 2.67576583 0.07424083 -1.85436526 H 1.38096888 0.61045596 -2.94276977 H -1.57812387 -2.36482326 -1.81716077 H -0.43946933 -2.33145698 -3.18068861 H -1.44219828 -0.90553815 -2.82230328 H 1.62490357 -3.30613546 -1.27245215 H 0.76933969 -3.05356847 0.26927822 H 2.34509181 -2.28367197 -0.02226436 H 0.86698626 -3.61069473 6.63718633 H 1.45359837 -2.14044262 7.44363033 H 1.99995982 -2.52979592 5.79496618 H -2.46631198 -1.04013382 7.17465117 H -1.02216641 -0.96506489 8.22244562 H -1.67521433 -2.53417446 7.70754218 H -2.14137992 -1.92855746 4.16969373 H -1.98670777 -3.39771705 5.15683834 H -0.80828831 -3.06765563 3.84356922 H 0.92051243 2.98912770 5.33681969 H -0.60438271 3.87827903 5.56442308 H -0.19573722 3.17031375 3.97030164 H -3.19031440 0.32480133 5.11713093 H -2.59761867 1.23363432 3.69448867 H -3.35968630 2.09512770 5.04780963 H -2.03363007 1.03942882 7.90337565 H -1.49169954 2.70903475 7.65401562 H -0.30176795 1.44237401 8.01174474 N 3.20868658 0.21662898 3.43115865 C 4.51903028 0.24688191 3.65061731 C 2.37658982 0.16927496 4.48018715 C 5.07998625 0.23871934 4.92892436 C 2.84431214 0.16792944 5.79386743 C 4.21983583 0.20102383 6.01990345 H 5.16330318 0.28006387 2.76734850 H 6.16217237 0.26487411 5.05382997 H 4.61156052 0.20135520 7.03832933 H 2.12793452 0.14832325 6.61348696 O 0.51957395 0.93681811 3.22015027 C 0.88645641 0.20220279 4.15887944 O 0.87203255 -1.48156521 3.16250793 C 1.71094314 -2.57963727 3.25442141 H 2.67332580 -2.34406917 3.75840314 H 1.97850268 -2.97162046 2.25377052 259 H 1.26457194 -3.42769542 3.81593751 N -3.10653133 -1.55003737 1.39909120 C -3.47055277 -0.84179814 0.17691956 C -2.48325805 -2.82360743 1.06453406 H -1.58070114 -2.64578501 0.46054383 H -2.19625054 -3.35643337 1.98214165 H -3.16433124 -3.47491598 0.47840785 C -4.27660032 -1.74931381 2.23904263 H -4.00419652 -2.31049491 3.14360185 H -4.69065648 -0.77701711 2.54174052 H -5.06885453 -2.31681051 1.70837809 H -3.97897407 0.10000340 0.42580125 H -4.15524274 -1.44938619 -0.45062189 H -2.56340351 -0.61220980 -0.40012954 260 Table A.1.40. Atomic coordinates and single point energies for 47. G = –2719.323886 GSP = –2721.242376 N -2.63315600 0.42584800 0.43351800 N 2.58055200 -0.45623900 0.40202700 Na -0.82130800 1.83856000 -0.10273000 Na -0.84039400 -0.88096400 -0.41751100 Si -2.80487200 -0.34803300 1.94600300 C -1.62053200 -1.84629700 2.05121500 C -4.53256000 -1.06154300 2.28653800 C -2.34606800 0.76113600 3.41196400 Si -3.85794700 1.34301800 -0.31847800 C -5.19971000 0.34063400 -1.21341100 C -3.06972100 2.47516600 -1.64133600 C -4.77380600 2.52981100 0.84959500 Si 3.12422000 -0.90672000 -1.25995700 C 1.85079700 -2.03894300 -2.04455100 C 4.72434700 -1.88869800 -1.10128100 C 3.50122400 0.57400600 -2.34344000 Si 2.75514300 -1.58574700 1.80234900 C 4.58739800 -1.78702900 2.19010000 C 2.00379100 -3.26343600 1.41762300 C 1.99946800 -0.80918500 3.33215400 H -1.31342900 1.12627800 3.28973100 H -2.41374100 0.23446200 4.37691800 H -3.01182200 1.63752600 3.45460400 H -4.80022300 -1.81985100 1.53335300 H -5.30810800 -0.28022400 2.26032900 H -4.57513300 -1.54118200 3.27715600 261 H -1.82158900 -2.59214400 1.26288800 H -1.72849800 -2.36242100 3.01764100 H -0.57171700 -1.51753300 1.97745700 H -5.50849800 3.14632500 0.30769500 H -4.05880500 3.20871500 1.34196400 H -5.31207200 1.98855800 1.64330300 H -4.78973600 -0.24608800 -2.05019500 H -5.97854000 1.00527400 -1.61944600 H -5.68523000 -0.36173600 -0.51723800 H -3.84212000 2.90926700 -2.29433400 H -2.36125200 1.92800400 -2.28579100 H -2.53871800 3.33543300 -1.19280600 H 3.61155200 0.20543400 -3.37597000 H 4.44462200 1.05954200 -2.05514600 H 2.69169300 1.31411000 -2.33462900 H 4.58813900 -2.86701600 -0.61804100 H 5.50908900 -1.33784100 -0.56238000 H 5.08882500 -2.07840000 -2.12354500 H 1.58514900 -2.86564700 -1.36854400 H 2.24570000 -2.47471000 -2.97559800 H 0.95340700 -1.44596100 -2.26945500 H 2.39866300 0.20612200 3.48313900 H 2.29288500 -1.41618600 4.20257000 H 0.90595800 -0.73747300 3.30147300 H 2.53480700 -3.76715100 0.59604400 H 0.93963400 -3.18204200 1.14859300 H 2.07495800 -3.90879500 2.30679600 H 5.12715100 -2.43891600 1.49321700 H 4.67842300 -2.22363800 3.19699200 H 5.09015700 -0.80766200 2.20846800 N 1.31037400 2.94596000 0.05726200 C 1.72413400 4.18606400 -0.17537500 C 2.22620600 1.99435000 0.26599500 C 3.07230800 4.55389500 -0.17931500 C 3.59377800 2.26805400 0.30622300 C 4.02303700 3.57456200 0.08038600 H 0.94893200 4.93469100 -0.36132100 H 3.35649600 5.58820000 -0.37200500 H 5.08548100 3.82104600 0.10702000 H 4.29622500 1.46073200 0.51273000 O 0.62402500 0.49356600 1.13363200 C 1.71217500 0.60425100 0.59083100 O 0.22694300 0.59687600 -1.62811600 C 0.26717200 0.97121700 -2.94210100 H 0.72104500 1.97980500 -3.10614100 H -0.73306300 1.02441000 -3.43583600 262 H 0.86704700 0.27855700 -3.58744200 N -1.94642300 -2.55089000 -1.78045800 C -3.23166700 -2.79311200 -1.13905800 C -2.09204100 -1.57554400 -2.85354000 H -2.46034100 -0.62198000 -2.44351900 H -1.11778100 -1.38622600 -3.32590500 H -2.80476000 -1.92313500 -3.63012100 C -1.36937600 -3.78785000 -2.27657400 H -0.40248400 -3.58411200 -2.75671700 H -1.20441700 -4.48583400 -1.44279800 H -2.03073500 -4.28275200 -3.01805800 H -3.12130500 -3.54962100 -0.34876300 H -3.98650400 -3.15974400 -1.86577000 H -3.59762300 -1.86062300 -0.68517700 263 Table A.1.41. Atomic coordinates and single point energies for TS-3. G = –2719.312343 GSP = –2721.230445 N 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 4.95295113 Na 1.83340062 0.00000000 1.49532365 Na -0.91899147 -0.64216855 2.03971965 Si 0.01632305 1.68473289 -0.31785453 C -1.25150553 2.63361455 0.72884022 C -0.31090467 2.18659739 -2.11692352 C 1.71913762 2.44444756 0.11542013 Si 0.31494273 -1.22121011 -1.15410414 C -0.81308782 -1.21659530 -2.68035607 C 0.13140441 -2.97115190 -0.39772671 C 2.10039388 -1.13315291 -1.81823216 Si -0.01691598 -1.81455709 5.15185335 C -1.23604583 -2.78930618 4.06502749 C -0.95602154 -1.97605537 6.81752943 C 1.61039165 -2.62717845 5.65719646 Si -1.27926577 1.12769579 5.51714297 C -1.40649068 1.15892051 7.39470718 C -2.92153674 0.64578186 4.74493562 C -0.81397419 2.87604636 5.01295383 H 1.90148077 2.46091895 1.20327858 H 1.77831951 3.48883004 -0.22808219 H 2.53972913 1.89824071 -0.38290052 H -1.29510255 1.82747187 -2.45586331 H 0.45014091 1.78044040 -2.80199425 H -0.29911303 3.28384475 -2.21320760 H -2.25772423 2.58652515 0.28617236 264 H -0.97156562 3.69639637 0.80359373 H -1.29524396 2.23222598 1.75381609 H 2.30303698 -1.92356354 -2.55814304 H 2.84020115 -1.25484464 -1.00649454 H 2.29434099 -0.16152940 -2.30077036 H -1.87533267 -1.22118557 -2.38541748 H -0.63080492 -2.11443940 -3.29239309 H -0.64790056 -0.33469961 -3.31547211 H 1.05570873 -3.55507445 -0.53093904 H -0.67765423 -3.53475694 -0.88841154 H -0.08390244 -2.94751613 0.68259642 H 1.47831695 -3.72000566 5.59791921 H 1.82171675 -2.38309978 6.70915729 H 2.48221656 -2.35930951 5.05158040 H -2.01520317 -1.67476639 6.77367085 H -0.47675229 -1.43214023 7.64553938 H -0.94534139 -3.04733340 7.08036410 H -1.98977054 -2.09776572 3.64878014 H -1.79407477 -3.51791200 4.67256553 H -0.74528375 -3.30780470 3.23077417 H 0.20600086 3.12411717 5.34696830 H -1.50589811 3.57657335 5.50518986 H -0.85780840 3.03400717 3.92832321 H -3.19681012 -0.39103696 4.99071049 H -2.86065336 0.73439666 3.64735199 H -3.73216291 1.30560830 5.09039415 H -1.95500610 0.31101149 7.82055508 H -1.92929839 2.08458140 7.68182100 H -0.40662136 1.18690234 7.85462313 N 3.24751419 0.38732487 3.39667384 C 4.54796070 0.33013901 3.66710403 C 2.38324789 0.40721876 4.41726305 C 5.05582735 0.31065363 4.96775029 C 2.79246265 0.38629190 5.75032909 C 4.15705613 0.34314802 6.02834072 H 5.22579685 0.29960135 2.80953952 H 6.13206971 0.26915368 5.13365512 H 4.51183531 0.33066252 7.05994618 H 2.04093621 0.39696835 6.53996855 O 0.60090725 1.20331281 3.08925154 C 0.91432878 0.53615974 4.06601385 O 0.94724584 -1.54363430 3.01440347 C 1.83279267 -2.52102303 2.61395309 H 2.85613222 -2.37759054 3.02929632 H 1.95677566 -2.56447269 1.50836035 H 1.52215063 -3.54768582 2.91120674 265 N -3.34144251 -1.10322483 1.49769444 C -3.66579550 0.03783025 0.65073476 C -3.04570239 -2.26510972 0.67100286 H -2.24908717 -2.01651162 -0.04168475 H -2.70878477 -3.10349481 1.29927399 H -3.93556199 -2.59336346 0.09484554 C -4.44318742 -1.40415449 2.39789687 H -4.16953122 -2.23217285 3.06833251 H -4.68775461 -0.52584841 3.00908744 H -5.35228319 -1.70123878 1.83535246 H -3.86055324 0.92410763 1.27219671 H -4.56403766 -0.15800380 0.02923037 H -2.81360700 0.25404678 -0.01070058 266 Table A.1.42. Atomic coordinates and single point energies for 48. G = –2719.312695 GSP = –2721.231277 N 2.44842800 0.59637400 -0.16532600 N -2.25723100 -0.61361800 -0.28879600 Na 0.55237300 1.99259600 -0.01029200 Na 0.73540800 -0.92183000 0.24937800 Si 2.75696500 0.90698600 -1.82589500 C 2.05183400 -0.43885200 -2.96322800 C 4.58116900 1.08900600 -2.30879000 C 1.93042600 2.54266600 -2.37877500 Si 3.51148300 1.00037800 1.11322100 C 5.27192300 0.30414800 0.97368800 C 2.86344500 0.37533900 2.80440300 C 3.70866000 2.88684800 1.30504700 Si -2.31982200 -0.82020300 1.55316000 C -1.00690600 -1.93401900 2.39898900 C -3.70719000 -2.17676200 1.57814800 C -3.29837900 0.46782600 2.55155700 Si -2.54008600 -1.87427200 -1.53006900 C -4.32690200 -2.46198000 -1.56998700 C -1.37097600 -3.31593700 -1.24156000 C -2.21779600 -1.12767500 -3.22510500 H 0.83109900 2.46278500 -2.41987400 H 2.26145900 2.81888700 -3.39180300 H 2.21127600 3.37892500 -1.71400000 H 5.15213900 0.18011600 -2.06369000 H 5.06122900 1.93792800 -1.79673400 H 4.66570300 1.25950400 -3.39378200 H 2.72834600 -1.30346700 -3.03442700 H 1.91168100 -0.04352900 -3.98180900 267 H 1.06750900 -0.78403700 -2.60937800 H 4.38606200 3.14776100 2.13347600 H 2.74012300 3.37586300 1.51439200 H 4.11436400 3.33542300 0.38378300 H 5.25738400 -0.78393400 0.79703100 H 5.82387900 0.48420400 1.91010200 H 5.83902000 0.76658100 0.15374300 H 2.71490700 1.21269400 3.50428800 H 3.58539500 -0.31115200 3.27385100 H 1.90245100 -0.15724000 2.72664200 H -3.19037100 0.23314000 3.62365400 H -4.36734100 0.37143600 2.31086800 H -3.00222900 1.51356300 2.40568800 H -3.41001500 -3.15241100 1.15736100 H -4.63928400 -1.86083500 1.08367500 H -3.94942000 -2.35868200 2.63939700 H -0.49971300 -2.53005500 1.61750700 H -1.47970100 -2.66577000 3.07042500 H -0.23711200 -1.38066500 2.95594500 H -2.81511400 -0.21416400 -3.37450800 H -2.52476600 -1.85546500 -3.99186700 H -1.16409800 -0.86627400 -3.38375700 H -1.48656700 -3.73647000 -0.23144300 H -0.32607500 -2.98300800 -1.36005500 H -1.54762300 -4.12234200 -1.96989800 H -4.57753500 -3.17459500 -0.77592600 H -4.50037000 -2.95066900 -2.54149900 H -5.02142500 -1.61090000 -1.49769900 N -1.64446400 2.93294100 -0.22226200 C -2.24423000 4.09267900 0.03186000 C -2.40566800 1.84811900 -0.40328900 C -3.63169400 4.23399800 0.09675300 C -3.79824100 1.88485400 -0.34497400 C -4.42179700 3.10605000 -0.09912100 H -1.59319100 4.95659600 0.19169200 H -4.07224100 5.20951200 0.30132700 H -5.50970900 3.17323500 -0.05331400 H -4.36234600 0.96180000 -0.48095300 O -0.67941500 0.61111700 -1.43251700 C -1.68521900 0.55504300 -0.73675300 O -0.72103500 0.51157000 1.39348300 C -0.43929400 1.32119800 2.48333200 H -1.06731100 2.23585400 2.50735200 H 0.61783800 1.65695800 2.48494000 H -0.58920900 0.80816900 3.45599200 N 1.92037900 -3.14929900 0.42624500 268 C 2.80346800 -3.09195100 -0.73172000 C 2.66857900 -2.82844600 1.63380100 H 3.15476100 -1.85164200 1.51773600 H 1.99184000 -2.78600200 2.50027300 H 3.45466300 -3.58464400 1.83848700 C 1.32590300 -4.47098800 0.55271800 H 0.61798400 -4.48852000 1.39445500 H 0.78460600 -4.73627400 -0.36437300 H 2.10086200 -5.24356600 0.73614000 H 2.23632000 -3.30880900 -1.64875600 H 3.63121200 -3.82656300 -0.65051400 H 3.23060800 -2.08140200 -0.81464200 269 Table A.1.43. Atomic coordinates and single point energies for TS-4. G = –2719.299499 GSP = –2721.218382 N 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 5.22433636 Na 1.50749994 0.00000000 1.79329724 Na -1.57410094 0.22976535 1.68149310 Si 0.05076149 1.61185494 -0.58504426 C -1.14617865 2.70474325 0.41822436 C -0.40920513 1.83429359 -2.41027552 C 1.76068122 2.40689292 -0.34002316 Si 0.46103724 -1.35794075 -0.93891857 C -0.72483086 -1.80591070 -2.35169973 C 0.61835630 -2.91276137 0.14016778 C 2.17190795 -1.12600046 -1.74058150 Si 0.15665767 -1.91611295 4.73007930 C -1.07412329 -2.07785097 3.28959753 C -0.94724324 -2.35956882 6.26669193 C 1.13342742 -3.58079130 4.87587129 Si -1.33511772 0.79909449 6.07276788 C -1.33214502 0.44204808 7.91964698 C -3.03374353 0.47085185 5.30786556 C -1.06095483 2.66382498 5.90602867 H 1.99965639 2.48073285 0.73477942 H 1.80422475 3.42572255 -0.75565925 H 2.54390985 1.80803283 -0.83232487 H -1.43023627 1.47522096 -2.61412495 H 0.27692005 1.27978058 -3.06958747 H -0.36176978 2.89690102 -2.69545676 H -2.19579874 2.37488362 0.33268368 H -1.11409109 3.74277078 0.05373260 H -0.85837062 2.72542697 1.48222855 H 2.47731558 -2.01333673 -2.31675961 270 H 2.94626280 -0.94641909 -0.97488638 H 2.18272105 -0.26180349 -2.42406735 H -1.71935722 -2.09933724 -1.98101697 H -0.32701332 -2.65188728 -2.93427207 H -0.86102033 -0.95743792 -3.03932408 H 1.07426133 -3.72915582 -0.44169532 H -0.35917141 -3.27109539 0.49866332 H 1.24652526 -2.75285556 1.03368639 H 1.66098207 -3.83676534 3.94507888 H 0.42748730 -4.39149750 5.10695272 H 1.87686643 -3.57170455 5.69039713 H -1.88657444 -1.79687970 6.35651696 H -0.38871816 -2.23085114 7.20901246 H -1.21879824 -3.42349954 6.19912550 H -1.95350911 -1.43676072 3.47090811 H -1.43532101 -3.11680130 3.23037142 H -0.61725729 -1.84734868 2.31425451 H -0.12700660 2.98990750 6.38883574 H -1.88990458 3.19467961 6.39941703 H -1.03311437 2.98859672 4.85519269 H -3.32169621 -0.58938272 5.30893971 H -3.03917937 0.83216870 4.26594664 H -3.80572113 1.03478174 5.85468113 H -1.77232480 -0.52684194 8.18430375 H -1.89976438 1.23350934 8.43333076 H -0.30123083 0.46218477 8.30517371 N 2.54247331 1.68229113 3.26475797 C 3.74008068 2.25196321 3.36038857 C 1.87741815 1.39196986 4.38814385 C 4.33542731 2.56576237 4.58380183 C 2.40426891 1.63047050 5.65641525 C 3.65408396 2.23957293 5.75249087 H 4.25556309 2.46615781 2.41938039 H 5.31610727 3.04046216 4.61016022 H 4.09290863 2.45097731 6.72882106 H 1.83298416 1.32606912 6.53309914 O -0.10451769 1.05351013 3.17568817 C 0.50052381 0.77435632 4.21592186 O 1.59154294 -1.25039168 3.70607256 C 2.90188835 -1.42302869 4.16182316 H 2.99849065 -1.24244236 5.25001934 H 3.57716571 -0.70335623 3.66209690 H 3.28913847 -2.43540292 3.95903738 N -3.66709698 -0.51616104 0.76938158 C -3.68821336 0.08212032 -0.56035885 C -3.38835652 -1.94317364 0.66238949 271 H -2.40006952 -2.09297777 0.20235022 H -3.37898175 -2.40403332 1.65907306 H -4.14628311 -2.46050257 0.03922677 C -4.91803931 -0.28269991 1.47415182 H -4.86703625 -0.71713458 2.48280609 H -5.09929723 0.79724139 1.57068187 H -5.78109182 -0.73399260 0.94350632 H -3.92589454 1.15304851 -0.49060123 H -4.44778674 -0.39877253 -1.21004397 H -2.69849891 -0.03021541 -1.02898025 272 Table A.1.44. Atomic coordinates and single point energies for 49. G = –2719.361990 GSP = –2721.284031 N 2.22480700 0.72195300 -0.37715400 N -2.91048800 -1.57120500 -0.55561400 Na 0.00239100 1.53153900 -0.44570400 Na 1.06724100 -1.28736000 -0.14159800 Si 2.55441100 0.60269200 -2.05807500 C 1.81945100 -1.00786200 -2.76196100 C 4.38869400 0.61512100 -2.53560700 C 1.70039800 1.98685100 -3.04757200 Si 3.16359100 1.69617500 0.67213100 C 4.87382800 0.98689900 1.09700300 C 2.30329300 1.98622300 2.34354300 C 3.45995900 3.44393600 -0.01980100 Si -1.62229500 1.10675200 2.63822700 C -0.44026100 -0.32007000 2.40877800 C -3.39901800 0.53451900 2.51542900 C -1.30554100 2.02436000 4.24217300 Si -2.35897000 -3.20300800 -0.33796800 C -3.88537200 -4.29939100 -0.31552000 C -1.42037900 -3.53378000 1.28066200 C -1.22977000 -3.75472100 -1.75005400 H 0.60129500 1.90074600 -2.98094600 H 1.95755700 1.94239000 -4.11738200 H 1.99609700 2.97930900 -2.67141700 H 4.92010100 -0.23451200 -2.07842400 H 4.89092200 1.53805800 -2.20676100 H 4.50710500 0.53861200 -3.62769100 H 2.25599600 -1.91539100 -2.30895000 H 2.01373400 -1.07389900 -3.84316400 273 H 0.72505800 -1.02842500 -2.62439500 H 4.05789000 4.05924600 0.67059900 H 2.49950600 3.96203800 -0.18173300 H 3.98599400 3.41838800 -0.98724900 H 4.79350200 0.04661500 1.66570600 H 5.44847000 1.69685100 1.71264200 H 5.45770800 0.77905800 0.18716400 H 2.86559200 2.73773600 2.92011000 H 2.25286800 1.07409500 2.95935400 H 1.27617600 2.36622000 2.21123000 H -0.26175800 2.36838600 4.29142000 H -1.48595700 1.35815700 5.09966700 H -1.96485200 2.89719500 4.35866100 H -3.63124800 -0.13632400 3.35752300 H -3.55510200 -0.03138600 1.58266100 H -4.11294800 1.37099900 2.55197800 H -0.85999000 -0.99521200 1.65190900 H -0.30321600 -0.87398500 3.35010400 H 0.54143200 0.04913800 2.07433300 H -1.72106500 -3.59441400 -2.72150700 H -0.98737100 -4.82556300 -1.66314400 H -0.28474400 -3.18934400 -1.76744000 H -1.95111800 -3.12293500 2.15301500 H -0.40353700 -3.10937500 1.27677400 H -1.32260500 -4.62197800 1.42465200 H -4.54631900 -4.01753100 0.51812200 H -3.62701600 -5.36356400 -0.20719200 H -4.45574600 -4.17405700 -1.24786600 N -2.06805600 1.75655200 -1.63588000 C -2.65906400 2.85125100 -2.11660800 C -2.82986400 0.71964700 -1.26614900 C -4.03984900 2.98738000 -2.22812500 C -4.22768600 0.76999800 -1.33350800 C -4.83934100 1.92242200 -1.81231900 H -1.99731800 3.66715000 -2.42507800 H -4.47156600 3.90458600 -2.62870900 H -5.92710200 1.98765800 -1.87457200 H -4.78005700 -0.11483600 -1.01957400 O -0.86186300 -0.50780900 -0.72967700 C -2.13536700 -0.56782000 -0.80554400 O -1.29616800 2.17558600 1.34962700 C -2.14774800 3.28044800 1.13568600 H -3.11939600 2.96181800 0.72022700 H -1.67546100 3.96472600 0.41622000 H -2.32494500 3.84162000 2.06907300 N 2.62460400 -2.88795500 0.70762100 274 C 3.86758000 -2.55130900 0.02303700 C 2.65075200 -2.38085200 2.07285200 H 2.79439500 -1.28869500 2.05822700 H 1.69856500 -2.60345800 2.57759100 H 3.47409100 -2.82956700 2.66560100 C 2.38270900 -4.32213000 0.68221900 H 1.43584200 -4.55423700 1.18933700 H 2.31130500 -4.67003800 -0.35792600 H 3.19604600 -4.88451100 1.18482700 H 3.85419400 -2.95498400 -0.99919400 H 4.74839800 -2.97180700 0.55028200 H 3.97408800 -1.45760800 -0.03287600 275 Table A.1.45. Atomic coordinates and single point energies for 52. G = –2533.804958 GSP = –2535.52468 N 1.26875900 1.18450700 -0.50175800 Si 1.17413400 2.58397100 0.47104200 C 0.21988700 2.16678500 2.06560300 C 0.22254400 3.99273400 -0.38997600 C 2.82179800 3.35373500 1.00633700 Si 2.31542300 0.96118000 -1.83433300 C 4.16191800 1.02056800 -1.39996000 C 2.03108300 2.18012100 -3.25665100 C 2.06022100 -0.79319300 -2.54396500 Na -1.06091500 0.88146300 -0.69115500 Na 0.95858300 -1.07095700 0.01796200 N -1.34893500 -1.39655000 -0.22787800 Si -1.66059900 -2.10873400 1.29452700 C -3.18902600 -1.40556700 2.17144900 C -0.19065000 -1.76861700 2.46305900 C -1.84683400 -3.99591900 1.26548800 Si -2.06660500 -1.89061900 -1.69983600 C -2.02462400 -0.42978300 -2.93334200 C -3.89989200 -2.37455600 -1.58122200 C -1.18507100 -3.34960000 -2.52406800 O -2.84681600 2.05754400 -0.01622800 C -3.05038100 3.17292900 0.84215300 C -4.03162700 1.25241200 -0.02842200 C -3.91811100 2.61555200 1.95996700 C -4.86810100 1.69091600 1.18801700 H -2.06790500 3.53793800 1.16697400 276 H -3.56743900 3.98124600 0.29376000 H -3.71030800 0.20156400 0.02745100 H -4.57203500 1.40828400 -0.97619300 H -5.20231500 0.83353000 1.78618500 H -5.75941300 2.24508200 0.86241600 H -4.44063500 3.39510000 2.52885200 H -3.29010800 2.04067100 2.65749800 O 2.97219000 -1.62975300 0.85373600 C 3.34501100 -0.68002300 1.86245600 C 4.06283300 -2.49478300 0.54314100 C 4.84917800 -0.85426000 2.05217700 C 5.04349100 -2.32990400 1.69806500 H 5.17429000 -0.60082000 3.06903000 H 5.40086100 -0.21626800 1.34563400 H 4.74689700 -2.96941200 2.54293600 H 6.07381900 -2.58261900 1.41739200 H 3.67934300 -3.51839900 0.43121000 H 4.51664500 -2.18080900 -0.41299400 H 3.05325100 0.32166700 1.51223500 H 2.78834500 -0.91375500 2.78575000 H -0.72857300 1.63523700 1.86673800 H -0.01969200 3.06921300 2.65082700 H 0.82774100 1.50912200 2.70811900 H -0.74631600 3.65925300 -0.79859300 H 0.81127400 4.37233200 -1.23968000 H 0.02725400 4.84061800 0.28658700 H 3.49465100 2.61731200 1.47288700 H 2.65385200 4.16632800 1.73063100 H 3.34802100 3.78401800 0.13975900 H 4.46893900 1.99873700 -1.00111500 H 4.78716100 0.79978200 -2.27965100 H 4.37658700 0.25973500 -0.63231700 H 2.28386300 3.20535900 -2.94247600 H 0.97462100 2.18110100 -3.56987500 H 2.64851500 1.93805300 -4.13564600 H 2.48091200 -1.56960800 -1.88031700 H 2.58053400 -0.89900600 -3.50794900 H 0.99820200 -1.02886000 -2.72289500 H -2.67569000 0.39974400 -2.60283100 H -2.40294100 -0.74426300 -3.91768700 H -1.00881300 -0.03110800 -3.10168800 H -0.11783400 -3.13415800 -2.68972100 H -1.63436200 -3.60926500 -3.49525200 H -1.24893800 -4.23627100 -1.87358900 H -4.51930200 -1.53803700 -1.22159600 H -4.05036700 -3.21956600 -0.89167000 277 H -4.28844600 -2.67760000 -2.56629700 H -3.07750800 -0.31801000 2.31513000 H -3.33998800 -1.86530400 3.16047700 H -4.09811400 -1.58058100 1.57320600 H -2.69859300 -4.31768600 0.64673600 H -1.99953000 -4.39850400 2.27922400 H -0.93982000 -4.46225300 0.84883100 H 0.05790200 -0.69408300 2.49941100 H 0.71541800 -2.33008400 2.17410400 H -0.43486300 -2.07673300 3.49110500 278 Table A.1.46. Atomic coordinates and single point energies for 53. G = –1963.108437 GSP = –1964.762125 N 1.94890500 0.03967200 0.03812200 Si 2.49726700 0.32520600 1.60668400 Si 2.80587600 -0.45095100 -1.33235600 C 0.98941800 0.38265000 2.77600500 C 3.43564400 1.96757600 1.83082100 C 3.65316200 -1.00808000 2.31990900 C 3.13590800 -2.32555000 -1.42094600 C 4.49249000 0.39920600 -1.55239900 C 1.79863600 -0.07890700 -2.90434700 H 2.86442900 2.81672100 1.42270900 H 4.39005000 1.92775200 1.28186200 H 3.66195300 2.18221600 2.88769100 H 0.25185400 1.11966400 2.41478100 H 1.25070800 0.64463000 3.81329700 H 0.49444400 -0.60337200 2.78396500 H 5.16376000 0.15327500 -0.71326800 H 4.37353600 1.49461300 -1.56844800 H 4.99467900 0.09482500 -2.48446000 H 0.82473600 -0.59529500 -2.85060600 H 2.30898800 -0.42340700 -3.81757700 H 1.61041600 1.00234700 -3.00894800 H 3.61218600 -2.69324700 -0.49747300 H 3.78121500 -2.59494800 -2.27212800 H 2.17680400 -2.85450400 -1.54293900 H 3.16655300 -1.99694500 2.31699200 H 3.95792200 -0.78312900 3.35454600 H 4.56806400 -1.08914300 1.71050500 279 Na -0.34256500 -0.00178100 -0.12267900 O -2.17350200 0.30553600 -1.60304500 O -0.35113900 -2.25451300 -0.52779400 O -2.05773700 -0.63598400 1.35037500 O -0.57372800 2.34077800 -0.07653300 C -1.76214500 0.82152900 -2.86924500 C -3.18951400 1.13101600 -1.03806800 C -2.82641600 1.83924700 -3.26291800 C -3.22448900 2.39198000 -1.89449000 H -2.94257400 1.32313400 0.01624400 H -4.15453500 0.59354000 -1.08027500 H -2.45806200 3.09582200 -1.53811700 H -4.20320200 2.88876300 -1.88320300 H -1.66211100 -0.01375600 -3.57656200 H -0.77499400 1.30143000 -2.76193800 H -2.44590600 2.60229300 -3.95392600 H -3.68271700 1.33759200 -3.73895700 C -0.81369000 -3.17749400 -1.49976500 C 0.30529900 -2.92560600 0.55105500 C -0.82026300 -4.53273600 -0.79799200 C 0.38335300 -4.39480200 0.13761100 H -0.30303300 -2.78803100 1.46403500 H 1.28306100 -2.44632600 0.70553000 H 0.34943300 -5.07610100 0.99748700 H 1.31654600 -4.58416800 -0.41276900 H -1.74779000 -4.65802800 -0.21744700 H -0.73964800 -5.37446800 -1.49805000 H -1.80544100 -2.85173700 -1.84911700 H -0.12578500 -3.18250500 -2.36415000 C -1.08075400 3.08613900 1.01910300 C 0.54577600 3.02328700 -0.66891100 C 0.73289200 4.30926600 0.14182100 C 0.08115700 3.95467500 1.47946300 H -1.43468100 2.38099800 1.78576300 H -1.93910800 3.70576300 0.69250600 H 0.76957600 3.35540800 2.09441400 H -0.23954700 4.82967300 2.05945000 H 1.79044700 4.58809800 0.23631400 H 0.19922700 5.15020900 -0.32649800 H 1.40955700 2.34216400 -0.60438000 H 0.31864800 3.22599700 -1.72837900 C -2.92811700 -1.63600300 0.81414700 C -2.57791700 -0.13047000 2.57791600 C -3.68856700 -1.09419600 2.98051200 C -4.22165300 -1.51465500 1.61126700 H -4.79928300 -2.44777300 1.62616700 280 H -4.85889200 -0.72009100 1.19236000 H -3.26804400 -1.96300600 3.50906800 H -4.44125700 -0.62732600 3.62850500 H -1.75956800 -0.05522000 3.30668600 H -2.99049300 0.88157500 2.40954400 H -3.03502200 -1.46048000 -0.26486100 H -2.46763600 -2.62816400 0.95875800 281 Table A.1.47. Atomic coordinates and single point energies for 53a. G = –2041.594084 GSP = –2043.334788 N 2.09724700 -0.09198700 0.03624500 Si 2.72716700 -0.36797900 -1.50673200 Si 2.95000400 0.32367600 1.43763200 C 1.29290100 -0.39285100 -2.76516500 C 3.64812100 -2.02331000 -1.70235600 C 3.93495600 0.95760400 -2.14735700 C 3.13940000 2.20448100 1.68195900 C 4.69975400 -0.41359500 1.55540900 C 2.03059200 -0.25919000 2.99794400 H 3.03991400 -2.86445400 -1.33266600 H 4.57531900 -2.00844000 -1.10787500 H 3.92086600 -2.23048900 -2.74973800 H 0.52654600 -1.12014400 -2.45053900 H 1.61997800 -0.65986100 -3.78234600 H 0.81110400 0.59864600 -2.80861100 H 5.33019300 -0.08443500 0.71361300 H 4.65669800 -1.51425000 1.52564900 H 5.20517800 -0.11801000 2.48856900 H 1.04672000 0.23274800 3.05300600 H 2.58061200 -0.00808500 3.91851600 H 1.86743300 -1.34936500 2.98381000 H 3.64593900 2.67057100 0.82060200 H 3.70963900 2.45371200 2.59084400 H 2.13711600 2.65536300 1.77274600 H 3.45368800 1.94865900 -2.17903400 H 4.29803200 0.72675600 -3.16173300 H 4.81315900 1.03893000 -1.48702800 282 Na -0.21644800 0.03976200 -0.04069700 O -2.19158000 -0.23252800 1.31327600 O -0.18725200 2.30960400 0.37776200 O -1.79276700 0.64582700 -1.65635300 O -0.45482900 -2.28224400 -0.20722500 C -1.67264200 -0.70956300 2.56311400 C -3.17352300 -1.12594100 0.78088100 C -2.58182900 -1.87129300 2.96176700 C -3.03341500 -2.41053200 1.60569700 H -2.91871600 -1.28951400 -0.27941000 H -2.24728100 -3.04347000 1.17370600 H -3.96977300 -2.98318500 1.64952600 H -0.65000700 -1.09119500 2.38267600 H -2.05638600 -2.61448500 3.57596100 H -3.43823500 -1.49609300 3.54440700 C -0.75773200 3.30267100 1.21588400 C 0.64518200 2.90367200 -0.62451800 C -0.57445500 4.62154200 0.47028800 C 0.75572000 4.37766400 -0.24507600 H 0.15464600 2.77260400 -1.60729500 H 1.60105200 2.36216300 -0.63342400 H 0.91215400 5.02670900 -1.11617600 H 1.59503900 4.52470800 0.45068500 H -1.38506200 4.76493300 -0.26143600 H -0.56310300 5.48968700 1.14201400 H -1.80932200 3.04104100 1.41041300 H -0.22152700 3.32350100 2.18170400 C -0.92373500 -3.04427900 -1.30632100 C 0.54446200 -3.02146900 0.51524300 C 0.77206800 -4.31567600 -0.27656300 C 0.23645200 -3.96106500 -1.66551800 H -1.20964000 -2.35148000 -2.11050200 H -1.81891500 -3.62859000 -1.01353800 H 0.98954600 -3.39567900 -2.23536800 H -0.07013700 -4.83498900 -2.25472700 H 1.82836900 -4.61415400 -0.28517400 H 0.18854500 -5.14468300 0.15136100 H 1.43597700 -2.37762700 0.57098200 H 0.17549300 -3.21983100 1.53627400 C -2.61539300 1.74290200 -1.25294500 C -2.24534600 0.11671900 -2.90007200 C -3.20129500 1.16132600 -3.46375600 C -3.82594200 1.70576700 -2.17932300 H -4.29954800 2.68896500 -2.29638400 H -4.58255700 1.00061100 -1.80082500 H -2.63945900 1.95328400 -3.98164700 283 H -3.92819800 0.73624500 -4.16752000 H -1.37323200 -0.08607100 -3.53660900 H -2.77927900 -0.83445100 -2.71913700 H -2.84662700 1.62387600 -0.18511100 H -2.05135100 2.68202500 -1.38102700 C -1.61617100 0.43231100 3.55514400 H -1.18295800 0.09191300 4.50636400 H -0.99054900 1.24840200 3.16879100 H -2.62859800 0.82195500 3.73911000 C -4.55960000 -0.50623800 0.89707800 H -4.57987900 0.49329300 0.44300100 H -5.30720300 -1.13391600 0.39056100 H -4.85137600 -0.40278900 1.95305800 284 Table A.1.48. Atomic coordinates and single point energies for 53b. G = –2120.06819 GSP = –2121.897238 N -2.15573300 -0.06849400 0.23084300 Si -2.91318600 0.25668400 -1.25247200 Si -2.95960200 -0.77190000 1.55356400 C -1.60622600 0.63148200 -2.59030200 C -4.09405900 1.74992700 -1.23979400 C -3.92938500 -1.16739100 -2.01602300 C -2.68976400 -2.65808800 1.65553600 C -4.84635500 -0.50326100 1.58950500 C -2.40984400 -0.11488900 3.25471400 H -3.59468200 2.65312600 -0.85550400 H -4.95533900 1.54842600 -0.58404800 H -4.48068600 1.97479400 -2.24690400 H -0.88639800 1.38998900 -2.24602400 H -2.07300500 1.00127400 -3.51736500 H -1.03464800 -0.27832400 -2.83533200 H -5.34361300 -0.83191800 0.66432000 H -5.07600300 0.56561000 1.72840700 H -5.30105200 -1.05398300 2.42851800 H -1.40960300 -0.46480000 3.54642400 H -3.11798500 -0.46479800 4.02290600 H -2.40626600 0.98695400 3.27589500 H -3.14955400 -3.16718000 0.79194600 H -3.11864500 -3.09165000 2.57275900 H -1.60865800 -2.88023900 1.64161500 H -3.29411400 -2.04111500 -2.23360300 H -4.39205800 -0.85041800 -2.96482000 H -4.73688400 -1.50418700 -1.34831900 285 Na 0.17126900 0.12217900 -0.13332800 O 2.23165400 0.10738200 1.29593200 O 0.37934000 -2.24998100 -0.12605500 O 1.50572600 -0.15194500 -2.10637100 O 0.00905000 2.55501200 -0.07531100 C 1.75782500 0.15181700 2.66054600 C 3.48484200 0.80320900 1.14391900 C 3.00085100 0.54102900 3.47082600 C 3.73871300 1.46590200 2.51036600 H 3.30360200 2.47570900 2.53105600 H 4.81188400 1.55869600 2.72522800 H 2.73822500 1.01421200 4.42630800 H 3.60258100 -0.35466100 3.68876300 C 1.16347800 -3.30911200 0.40271500 C -0.59085900 -2.75706500 -1.04991800 C 0.95046200 -4.48727900 -0.54134400 C -0.51096400 -4.27684700 -0.94044100 H -0.32240800 -2.40833600 -2.06448900 H -1.56615000 -2.33262100 -0.78161500 H -0.79310900 -4.78313300 -1.87241500 H -1.17661700 -4.63021300 -0.13864900 H 1.60788600 -4.40283300 -1.42085300 H 1.14399600 -5.45483000 -0.06018100 H 2.20887400 -2.97166900 0.48182700 H 0.80987800 -3.56255800 1.41757900 C 0.32523700 3.41871300 -1.15510800 C -1.07806200 3.10979700 0.68716500 C -1.52909500 4.36983500 -0.06280400 C -0.97577500 4.14328300 -1.47020900 H 0.70904900 2.80724000 -1.98423900 H 1.11435500 4.13602600 -0.85799300 H -1.64205300 3.47944200 -2.04187400 H -0.82622300 5.06994600 -2.03955400 H -2.61916700 4.49766700 -0.04246600 H -1.07570400 5.26954800 0.37947200 H -1.85302900 2.33011600 0.75030300 H -0.72642700 3.34540600 1.70296800 C 2.38721400 -1.27010900 -2.02041600 C 1.77348800 0.59807500 -3.29148300 C 2.77210800 -0.23199700 -4.09510100 C 3.52620000 -0.95898000 -2.98126100 H 4.05683000 -1.85885700 -3.31823000 H 4.25609600 -0.28246600 -2.50802500 H 2.24455300 -0.95816400 -4.73141500 H 3.41278000 0.38573200 -4.73710000 H 0.82716200 0.78695600 -3.81670700 286 H 2.21752000 1.56824900 -3.00649300 H 2.68138100 -1.38711200 -0.96981900 H 1.85325600 -2.18498800 -2.33037300 C 1.21026500 -1.21966700 3.01312800 H 0.84967800 -1.23196700 4.05201900 H 0.36930900 -1.47786400 2.35066500 H 1.99683200 -1.97961500 2.90133100 C 4.57989000 -0.21848700 0.84062700 H 4.35763800 -0.76644600 -0.08433100 H 5.54996900 0.28420700 0.71619400 H 4.66702000 -0.94829700 1.65885800 C 0.67816900 1.22465000 2.76587500 H -0.18855800 0.97976300 2.13283500 H 0.31135100 1.30766200 3.79920700 H 1.07182400 2.19847000 2.44184800 C 3.33623400 1.81186500 0.01553200 H 4.26592900 2.38320800 -0.12303100 H 3.08872400 1.29168400 -0.92152600 H 2.51196200 2.50142800 0.24642000 287 Table A.1.49. Atomic coordinates and single point energies for 54. G = –2777.259118 GSP = –2779.246949 Na 1.85743800 0.61162900 0.02403500 Na -0.98998300 -0.15573400 0.00101000 N -0.01809200 2.00314800 0.09863200 N 0.95926400 -1.49765700 -0.23040400 Si -0.48157400 2.50625300 1.66160800 C -1.26720200 1.03815700 2.59220100 C -1.76798300 3.90290000 1.71673800 C 0.98428100 3.08653700 2.72111300 Si 0.39086300 3.00652700 -1.21999400 C 1.65255500 2.11146800 -2.34030000 C 1.23657500 4.63669000 -0.73595400 C -1.07092800 3.47528900 -2.33665500 Si 1.50818600 -2.33872400 1.14704700 C 0.13723100 -3.18897200 2.14392800 C 2.34932200 -1.09777200 2.32900800 C 2.81900800 -3.67234100 0.79825800 Si 0.54612100 -2.20679900 -1.72662900 C -0.79293000 -1.16049800 -2.60124900 C -0.22020700 -3.93912900 -1.59474200 C 2.01133000 -2.32610500 -2.92620800 H 1.76059600 2.30523300 2.78247600 H 0.68120400 3.33744400 3.74976900 H 1.44699900 3.98115500 2.27560100 H -2.22886500 0.74349300 2.13879700 H -1.47205900 1.30166500 3.64109200 H -0.60901500 0.15188600 2.60861400 288 H -2.71826500 3.58702400 1.25804100 H -1.41290600 4.79298100 1.17372800 H -1.98292900 4.20692600 2.75332500 H 2.17261700 4.43384100 -0.19095000 H 0.59817500 5.25097400 -0.08143500 H 1.48643700 5.23982000 -1.62309600 H -1.58509500 2.57882700 -2.71903700 H -0.73702700 4.06823200 -3.20241800 H -1.80250500 4.08465700 -1.78049800 H 2.65100200 2.05270500 -1.87240400 H 1.78351100 2.65440500 -3.28882500 H 1.33257700 1.08685800 -2.59579800 H 3.68899500 -3.25257500 0.26810300 H 2.40942500 -4.47712700 0.16797200 H 3.18175300 -4.13229300 1.73127000 H 1.67400600 -0.26986900 2.60703200 H 3.25251000 -0.66253200 1.86822500 H 2.66293100 -1.58318300 3.26576300 H -0.62405000 -2.46010300 2.46371800 H 0.53590100 -3.69387900 3.03797700 H -0.37104500 -3.93887600 1.51737200 H 2.43598800 -1.32947800 -3.12896200 H 1.72133100 -2.77341000 -3.88982800 H 2.80868600 -2.95003100 -2.49029000 H -1.11302200 -3.88150600 -0.95215100 H 0.47332200 -4.66714600 -1.14613800 H -0.52316800 -4.32479900 -2.58104200 H -1.77661300 -1.28990200 -2.11776900 H -0.91085300 -1.47754800 -3.64874100 H -0.55709500 -0.08260700 -2.61347700 O 4.09823300 0.68505200 -0.11750300 C 5.13831800 1.22557100 0.69917000 C 4.54794900 -0.48771500 -0.80464300 C 6.37601000 0.37484200 0.41148700 C 5.75524600 -0.95957300 -0.00753800 H 5.27459300 2.28808600 0.45267000 H 4.83087400 1.14892100 1.75552100 H 4.82588400 -0.22179000 -1.83923500 H 3.71382900 -1.20593500 -0.83846600 H 6.43067400 -1.59465000 -0.59457800 H 5.42486800 -1.52745600 0.87610200 H 7.04174300 0.29728500 1.28026600 H 6.95032000 0.80275000 -0.42352400 N -3.32889000 0.45919600 -0.30292600 C -3.76141400 1.66781000 -0.64080600 C -4.22394200 -0.49316800 -0.03811700 289 C -5.12312900 1.97482700 -0.73355900 C -5.60077900 -0.29151800 -0.10307100 C -6.05425300 0.97821700 -0.46125900 H -2.98884700 2.41421500 -0.84250300 H -5.43499600 2.98074400 -1.01429700 H -7.12363400 1.18412000 -0.52448800 H -6.28253600 -1.10975400 0.12388200 O -2.42726900 -1.98512100 0.44081100 O -4.51620300 -2.75404500 0.58714900 C -3.61747800 -1.81259200 0.35121000 C -3.99613500 -4.02767300 0.96714700 H -3.39244400 -4.44631400 0.15129800 H -4.86376600 -4.66129200 1.17003000 H -3.36508800 -3.92805300 1.85963400 290 Table A.1.50. Atomic coordinates and single point energies for 55. G = –1974.486739 GSP = –1976.146934 N 1.52540300 -1.18038300 0.03595300 Si 1.87938800 -2.09243500 -1.34003300 Si 2.22994400 -1.08678100 1.56381700 C 0.78148100 -1.48275200 -2.77724300 C 1.51882400 -3.95476100 -1.17217200 C 3.68015800 -1.98250000 -1.94674400 C 3.58191400 0.25075300 1.69152100 C 3.04568300 -2.69004800 2.18228200 C 0.89852400 -0.64440400 2.86223400 H 0.45204600 -4.13537700 -0.96156800 H 2.10249900 -4.38655400 -0.34349300 H 1.77642200 -4.50536100 -2.09113800 H -0.28608000 -1.60788800 -2.52293800 H 0.96338500 -2.04203600 -3.70795100 H 0.95860400 -0.41449500 -2.98891000 H 3.85785500 -3.00112600 1.50524300 H 2.31162200 -3.51137300 2.21652000 H 3.47277400 -2.57439900 3.19132300 H 0.19556500 0.08742900 2.43172700 H 1.32022600 -0.22407000 3.78978200 H 0.31288600 -1.53714900 3.13670000 H 4.40363100 0.01574600 0.99503100 H 4.00743400 0.32852600 2.70482500 H 3.18988500 1.24162200 1.40949800 H 3.96330300 -0.94296200 -2.17578900 H 3.84842700 -2.58663100 -2.85257900 H 4.36777600 -2.34762700 -1.16651700 291 Na -0.14906700 0.29960200 -0.53853400 O 1.09055900 1.89731000 -1.52980400 O -0.63368800 1.96172100 0.97121200 C 0.73165200 3.21965300 -1.88711400 C 2.49948200 1.75689400 -1.63729400 C 1.98505400 4.09153900 -1.63919100 C 3.03226600 3.08879700 -1.12141800 H 2.78362800 1.59387700 -2.69446700 H 2.78559400 0.87760100 -1.04311800 H 4.04817000 3.30776800 -1.47397000 H 3.05277800 3.07248500 -0.02200700 H 2.31890000 4.55897300 -2.57556800 H 1.79451400 4.90096200 -0.92132800 H 0.42754900 3.25217900 -2.94702200 H -0.13546300 3.50092300 -1.27135400 C 0.37330000 2.75575900 1.59452400 C -1.80984300 1.91166700 1.77015500 C -1.41140100 2.49218700 3.12486400 C -0.33662700 3.50231000 2.72070600 H -0.80160900 4.42360900 2.33757500 H 0.34137700 3.77287100 3.53998700 H -2.25834100 2.93850700 3.66172100 H -0.97157100 1.70546900 3.75541500 H -2.60140500 2.51251800 1.28810700 H -2.15098200 0.86626600 1.83217900 N -1.78799300 -1.35411000 0.08592500 C -1.44396000 -2.47965200 0.70095600 C -3.06789000 -1.14237300 -0.21465600 C -2.39289600 -3.44772800 1.05182100 C -4.08765200 -2.04024800 0.09351100 C -3.73078800 -3.22154100 0.74566800 H -0.37112100 -2.59248100 0.89299700 H -2.07481200 -4.36183600 1.55329500 H -4.49247500 -3.95797800 1.00603200 H -5.11799900 -1.81447500 -0.17717300 C -3.31465500 0.15241500 -0.93655400 O -2.43398200 0.90842800 -1.26259300 H 1.16481700 2.09364600 1.98434700 O -4.60099500 0.37455800 -1.17903200 C -4.90551400 1.57555400 -1.87841100 H -5.99317000 1.59725800 -1.99014400 H -4.41555500 1.57835600 -2.86076500 H -4.55783200 2.44682300 -1.30790700 H 0.81614200 3.41999600 0.83823100 292 Table A.1.51. Atomic coordinates and single point energies for 55a. G = –1742.417049 GSP = –1743.813947 N -1.31944500 -1.00140300 0.05406400 Si -1.73347100 -1.73082500 1.51521900 Si -1.86197700 -0.98087500 -1.53959600 C -0.75937500 -0.86276400 2.90965200 C -1.28337700 -3.57588000 1.63912200 C -3.57017300 -1.61140500 1.98900100 C -3.72404000 -0.66130000 -1.75909000 C -1.48879500 -2.55809500 -2.53555900 C -0.95921300 0.43487200 -2.45365200 H -0.19598600 -3.72833700 1.54400400 H -1.77243000 -4.14578500 0.83290800 H -1.59786000 -4.01185600 2.60073500 H 0.32719100 -0.94364000 2.72839500 H -0.95654400 -1.29685200 3.90208500 H -1.02137500 0.20858400 2.96324900 H -1.95288700 -3.43429600 -2.05519400 H -0.40395100 -2.74395200 -2.59203500 H -1.87164700 -2.49480400 -3.56665500 H -1.15739600 1.40113300 -1.95774700 H -1.26500500 0.53170500 -3.50682700 H 0.13204200 0.26374100 -2.44198000 H -4.30809400 -1.49930800 -1.34677000 H -3.99984000 -0.54862300 -2.81984100 H -4.04053300 0.24935000 -1.22528700 H -3.91058500 -0.56351900 1.99165900 H -3.76369400 -2.03369600 2.98796900 293 H -4.19395200 -2.15873200 1.26470300 Na 0.20603400 0.66485300 0.36723100 O -1.07675500 2.51590300 0.51052100 C -0.88452300 3.77325600 -0.13493200 C -2.47145300 2.24883900 0.69443900 C -2.28096300 4.37542200 -0.30877000 C -3.16662600 3.12803200 -0.33433400 H -2.76486500 2.52878900 1.72172200 H -2.62413900 1.16858200 0.55419900 H -4.21607100 3.32932800 -0.08392500 H -3.13278100 2.64654300 -1.32385900 H -2.53867500 5.00265300 0.55768100 H -2.36154400 4.99274800 -1.21263400 H -0.21848200 4.39929300 0.47683800 H -0.39682300 3.59820200 -1.10875900 N 1.99111500 -0.85360800 -0.10426100 C 1.77938500 -2.13786700 -0.36827500 C 3.23688300 -0.38368400 -0.10679300 C 2.83512500 -3.01439700 -0.64697900 C 4.35412400 -1.17236400 -0.37078600 C 4.13681600 -2.52334300 -0.64671900 H 0.72840500 -2.44822600 -0.35287600 H 2.62686200 -4.06304100 -0.85963800 H 4.97904800 -3.18314900 -0.86006400 H 5.35122000 -0.73460400 -0.35909000 C 3.32526100 1.08480900 0.19728200 O 2.35660000 1.77478000 0.41057800 O 4.56677500 1.54346200 0.20599400 C 4.72252200 2.93071200 0.48816900 H 5.79732000 3.12921200 0.45793300 H 4.31270300 3.16404700 1.47926300 H 4.19615300 3.53178200 -0.26444100 294 Table A.1.52. Atomic coordinates and single point energies for 56. G = –863.964501 GSP = –864.7163518 N -2.45182000 0.80149200 0.45261800 C -3.73676000 0.46222800 0.51392000 C -1.58202900 -0.09735800 -0.00553200 C -4.21819800 -0.78334600 0.11323600 C -1.96063000 -1.37850300 -0.42498200 C -3.30593000 -1.72108300 -0.36853400 H -4.42272200 1.22082000 0.90246100 H -5.28280100 -1.00859400 0.18016200 H -3.64031400 -2.70839300 -0.69117900 H -1.18886600 -2.06727500 -0.76570700 O 0.23523800 1.55866700 0.03020400 N 0.75226400 -0.66245000 0.02587900 Si 2.49647800 -0.37412700 0.06973600 C -0.54521600 2.58939800 -0.55275500 C -0.11556400 0.25093000 -0.00512600 H -1.22253200 3.03331300 0.18481100 H -1.13899800 2.21594100 -1.39864700 H 0.16649600 3.34066800 -0.91911800 C 2.94255000 0.47663700 1.68379200 C 3.02294800 0.66573100 -1.40754200 C 3.31175700 -2.06099200 -0.02162400 H 2.44336300 1.45418700 1.74389900 H 4.02931900 0.63024300 1.76451200 H 2.61818700 -0.12936900 2.54270100 H 2.58666600 1.67241900 -1.34253100 H 2.68875100 0.20285000 -2.34825200 H 4.11873300 0.76176700 -1.44771100 H 2.98757500 -2.69124100 0.81964900 295 H 4.40849000 -1.97810800 0.01222400 H 3.03538900 -2.57593600 -0.95381000 296 Table A.1.53. Atomic coordinates and single point energies for 6. G = –340.070939 GSP = –340.452349 N 0.04404400 -1.20408100 0.00000000 C 1.37134500 -1.21011800 0.00000000 C -0.56677600 -0.01948600 0.00000000 C 2.14598200 -0.04658100 0.00000000 C 0.10617700 1.20722000 0.00000000 C 1.49782800 1.18457700 0.00000000 H 1.85118100 -2.19276300 0.00000000 H 3.23401000 -0.11308700 0.00000000 H 2.06521300 2.11610000 0.00000000 H -0.45606900 2.14063600 0.00000000 C -2.01976800 -0.02998800 0.00000000 N -3.17305200 -0.00515200 0.00000000 297 Table A.1.54. Atomic coordinates and single point energies for TS-5. G = –2382.922559 GSP = –2384.607027 Na -1.24528800 0.49086100 0.95187300 N -3.41479200 0.41094400 0.36614800 N 2.86682100 0.36109600 -0.05873300 Si -4.08414500 -1.08210700 0.78166900 C -5.62031300 -0.97994400 1.90460200 C -2.81120100 -2.11952000 1.74896200 C -4.62035000 -2.16611200 -0.69480300 Si -4.03610700 1.61721400 -0.64009500 C -3.32046600 3.31891700 -0.19128800 C -5.93257800 1.80754600 -0.58312100 C -3.60557500 1.35484700 -2.48003400 Si 2.47013100 1.97360800 0.28164000 C 0.62518700 2.40119200 -0.00787600 C 3.40175000 3.26269300 -0.77580000 C 2.80389100 2.47774600 2.08982400 Si 4.39203300 -0.13117000 -0.60673500 C 4.64775900 -2.01914100 -0.66362600 C 5.84104400 0.49021900 0.48052900 C 4.82437500 0.41736200 -2.38149400 H -5.37662500 -1.64325400 -1.30331400 H -5.05405300 -3.12514700 -0.36724000 H -3.76068100 -2.38677700 -1.34791300 H -2.46851600 -1.58573700 2.65201200 H -1.92606300 -2.34286500 1.13012000 H -3.23587300 -3.08083900 2.07931300 H -5.38837800 -0.40422400 2.81454600 H -5.97753200 -1.97783300 2.20759900 H -6.44459000 -0.46388600 1.38740500 H -2.51166300 1.37683300 -2.61727700 H -4.04218900 2.12823800 -3.13286000 H -3.96892700 0.37195300 -2.82331500 298 H -3.57352800 3.57860300 0.84901400 H -3.70498700 4.11575800 -0.84799600 H -2.22129600 3.31588200 -0.27933400 H -6.26791100 2.01979500 0.44458800 H -6.42968500 0.87906500 -0.90973300 H -6.28175200 2.62457700 -1.23527400 H 3.16265900 3.13298400 -1.84338400 H 4.49453600 3.17759400 -0.66479500 H 3.11042300 4.28474900 -0.48238400 H 0.15503700 1.66162700 -0.67512000 H 0.51947600 3.39041000 -0.47921300 H 0.08664600 2.45508100 0.95321600 H 2.20071100 1.84330100 2.75835500 H 2.54388400 3.53166600 2.28283700 H 3.86675800 2.33392300 2.34528900 H 4.02707100 0.09752300 -3.07137700 H 5.77397200 -0.02894900 -2.72064000 H 4.91345600 1.51130700 -2.45985600 H 4.35377400 -2.50878800 0.27693500 H 5.71440800 -2.22785000 -0.84750000 H 4.07593000 -2.47349500 -1.48751900 H 5.75574000 0.09087200 1.50476600 H 5.83800400 1.58969000 0.55571600 H 6.81997200 0.18137200 0.07793200 N -0.28307800 -0.97059700 -0.61857500 C -0.87635900 -1.42010400 -1.72096000 C 0.81707300 -1.57238100 -0.17444900 C -0.39089400 -2.51412800 -2.43580900 C 1.36077200 -2.69686700 -0.79934100 C 0.74521800 -3.16485200 -1.95507400 H -1.78656000 -0.89198100 -2.02312400 H -0.90549200 -2.85363500 -3.33476900 H 1.14551300 -4.03745100 -2.47487700 H 2.24279600 -3.17099300 -0.37585800 O 0.74792500 -0.21266200 1.79268300 C 1.36637600 -1.02228200 1.11732700 O 2.33270200 -1.79195400 1.62296100 C 2.99470500 -1.25265800 2.74938400 H 3.78354100 -1.96437700 3.01837500 H 2.29545600 -1.11770400 3.58658200 H 3.42777500 -0.28050600 2.47002100 299 Table A.1.55. Atomic coordinates and single point energies for TS-23. G = –2382.921687 GSP = –2384.601813 Na 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 2.27789869 N 1.94096447 0.00000000 -1.51712643 Si 0.58670938 1.45858544 2.88402758 C -0.29712111 2.94450264 2.07518729 C 2.42246167 1.75094139 2.47909272 C 0.41873453 1.71286249 4.76526784 Si -0.63459594 -1.40116088 2.96549161 C -1.91938000 -2.19683206 1.80284034 C -1.56442197 -1.16831023 4.61603563 C 0.66726715 -2.74586102 3.32082540 Si 2.64416387 -1.45690012 -0.88859804 C 1.39694331 -2.87039905 -0.66613400 C 3.34002393 -1.25970095 0.86248909 C 4.06319684 -2.16875714 -1.95316308 Si 2.97367733 1.32822365 -1.90746130 C 2.23611789 3.03570790 -1.52132776 C 3.44723373 1.32559480 -3.74848237 C 4.63119516 1.37788211 -0.96791172 H -0.08281488 2.94398905 0.99324819 H 0.03883001 3.91248126 2.48109506 H -1.38868935 2.86563206 2.20449905 H -0.63541469 1.67204581 5.08114469 H 0.83309830 2.68817863 5.06899493 H 0.96306541 0.92674849 5.31352089 H -2.35040776 -0.40268767 4.51365898 H -0.88358314 -0.84336361 5.41810233 H -2.04159160 -2.10957394 4.93558001 300 H 1.19654730 -3.02973185 2.39757027 H 0.22231752 -3.65498921 3.75800073 H 1.42242959 -2.35807762 4.02416928 H -2.77385113 -1.51292084 1.67228312 H -2.30276341 -3.14847982 2.20548955 H -1.50952730 -2.40526238 0.80049483 H 2.55295792 1.34487653 -4.38738500 H 3.99685542 0.40008145 -3.98532463 H 4.08724128 2.18519108 -4.00518778 H 4.47398271 1.59607963 0.09954755 H 5.24122012 2.19300994 -1.39093804 H 5.21340008 0.44808727 -1.04122084 H 2.52471357 -0.95530121 1.54133472 H 4.14233855 -0.51228639 0.93684159 H 3.73459669 -2.22683356 1.21708831 H 0.61996825 -2.60240085 0.06760027 H 1.94560212 -3.73143353 -0.24923257 H 0.87852256 -3.17878143 -1.58179964 H 3.75899043 -2.36951102 -2.99163433 H 4.42393910 -3.11421888 -1.51634178 H 4.91614013 -1.47435720 -1.99425672 H 1.45542910 3.35221465 -2.22725895 H 3.04196762 3.78682175 -1.55930604 H 1.80979663 3.05309250 -0.50536221 N -0.70380934 1.70590829 -1.57800500 C -1.21660343 2.93159294 -1.56906299 C -0.21027227 1.21942969 -2.71746992 C -1.27758543 3.73830400 -2.70612529 C -0.22159310 1.95121787 -3.90850126 C -0.76721368 3.23198373 -3.89759751 H -1.59561801 3.29174593 -0.60831517 H -1.71249715 4.73609474 -2.64755417 H -0.79399938 3.82761004 -4.81223626 H 0.18157123 1.50028142 -4.81273159 O -0.44203088 -1.04409728 -2.03936063 O 0.77040109 -0.56294996 -3.89337357 C 0.23209014 -0.23843927 -2.68143357 C 0.93318218 -1.93620592 -4.13973822 H -0.00380314 -2.48248575 -3.95851409 H 1.71615499 -2.35779426 -3.49368737 H 1.23690323 -2.03452910 -5.18921332 H 2.74731855 2.77273287 2.73603408 H 2.58536021 1.59726648 1.39899181 H 3.06965077 1.03363491 3.00826728 301 Table A.1.56. Atomic coordinates and single point energies for 60c. G = –2382.93489 GSP = –2384.612083 Na -0.66054600 0.39741100 -0.95394700 N -2.79741100 0.38616300 -0.18788200 N 1.40835100 -0.73694100 0.33395400 Si -2.90353000 1.45040200 1.11103500 C -2.05420700 3.11031200 0.69985300 C -1.96053300 0.81532500 2.63672400 C -4.65942400 1.88803600 1.70375600 Si -3.86453900 -0.57352000 -1.06895200 C -3.25314100 -0.77269700 -2.86141400 C -5.64203500 0.10449500 -1.21173700 C -4.05632300 -2.34624400 -0.39724200 Si 0.79797400 -2.41222400 0.46617000 C 0.27601300 -3.22186500 -1.14744100 C -0.73526700 -2.43502400 1.56442400 C 2.15406100 -3.55053100 1.14970600 Si 2.24083400 -0.05714400 1.73993100 C 2.02455000 1.81018300 1.95023200 C 4.09339300 -0.43177400 1.70580300 C 1.57858500 -0.76116700 3.36863700 H -0.99748500 2.93219000 0.43404700 H -2.07066100 3.81731200 1.54517400 H -2.53970700 3.58816800 -0.16628800 H -5.25266900 2.33018300 0.88804600 H -4.63062500 2.60606900 2.53956100 H -5.18788900 0.98471700 2.04925100 H -5.63345600 1.12891500 -1.61764800 H -6.13460500 0.14007000 -0.22728800 302 H -6.25672000 -0.52379900 -1.87725800 H -3.09359000 -2.88027800 -0.44064700 H -4.79740700 -2.92933500 -0.96849800 H -4.37261600 -2.32364600 0.65840200 H -3.22998800 0.20682300 -3.36617800 H -3.90098600 -1.44360000 -3.44847800 H -2.23106700 -1.18658800 -2.89438300 H 4.56744900 0.00250300 0.81590700 H 4.25879500 -1.51836300 1.66602400 H 4.58646900 -0.02851700 2.60495900 H 0.55226300 -0.42085300 3.56850000 H 2.22486000 -0.35918800 4.16596200 H 1.60002800 -1.85626600 3.43947200 H -1.49061800 -1.74528900 1.14766000 H -0.55259300 -2.14273300 2.60664100 H -1.16776900 -3.44907200 1.56279600 H -0.56792600 -2.69576300 -1.61221100 H -0.02500400 -4.25876500 -0.91891600 H 1.09888900 -3.22642500 -1.87307400 H 3.00350800 -3.50288600 0.45031100 H 1.79376800 -4.59060600 1.19315700 H 2.52114700 -3.27539600 2.14844900 H 2.64766700 2.40472200 1.26682000 H 2.31158900 2.06934900 2.98239600 H 0.97397600 2.10574800 1.80530700 N 1.23929500 1.96626400 -1.05098100 C 1.46593900 3.27194700 -1.13841300 C 2.27197800 1.11471200 -1.10509900 C 2.74046100 3.81568500 -1.30423800 C 3.58471600 1.56895700 -1.26935400 C 3.81857900 2.93757600 -1.37568600 H 0.58868700 3.92358000 -1.06805200 H 2.87408700 4.89531500 -1.37534600 H 4.83466400 3.31608600 -1.50772400 H 4.39346400 0.84047500 -1.30364000 O 0.98751500 -0.62404400 -1.97960700 O 3.10657900 -1.16592800 -1.22509200 C 1.87397600 -0.39153200 -1.06584500 C 3.43292800 -1.43771600 -2.55768600 H 3.67058700 -0.51788100 -3.12771700 H 2.60699100 -1.93961700 -3.08232300 H 4.32342600 -2.08412500 -2.54992900 H -1.88518500 1.56413000 3.44220700 H -0.93975500 0.54090900 2.32207000 H -2.42823700 -0.09569100 3.04337200 303 Table A.1.57. Atomic coordinates and single point energies for TS-12. G = –2382.910172 GSP = –2384.589925 Na 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 2.23538149 N 1.83972044 0.00000000 -3.55115132 Si -0.47266897 1.41628291 3.02181287 C -1.27210078 2.60719041 1.76719615 C 0.95230654 2.40152978 3.81457769 C -1.75017304 1.17318036 4.41493181 Si 0.51800523 -1.46083515 2.91547075 C 1.33647352 -2.54402994 1.58455922 C -0.88610347 -2.51479397 3.65445457 C 1.79448167 -1.27167743 4.31817146 Si 2.76759431 -1.53482655 -3.82580862 C 2.03138848 -3.09252611 -3.10380462 C 4.45088196 -1.30711934 -2.98579305 C 2.98136180 -1.78484076 -5.67912270 Si 2.12549447 1.39872788 -4.61695222 C 1.56135709 3.00045128 -3.78764344 C 1.32458148 1.15434420 -6.30511024 C 3.99204473 1.60483946 -4.81044174 H -0.55330949 2.85351071 0.96675660 H -1.59477993 3.55352532 2.22970525 H -2.15455564 2.13545051 1.30373705 H -2.62852572 0.62292761 4.04223372 H -2.09276597 2.13223872 4.83649824 H -1.31276166 0.58159875 5.23620613 H -1.64407081 -2.73147093 2.88519066 304 H -1.38905615 -1.97285643 4.47112875 H -0.51802205 -3.47373696 4.05439701 H 2.65954418 -0.68094415 3.97764485 H 2.16041661 -2.24768297 4.67619335 H 1.34832282 -0.74375057 5.17737442 H 0.63820996 -2.77541200 0.76265385 H 1.68427057 -3.50481574 1.99634459 H 2.20860973 -2.03348969 1.14389137 H 0.56523253 1.92490697 -6.50771329 H 0.83323335 0.16580385 -6.28081836 H 2.06911751 1.17691906 -7.11523522 H 4.46608546 1.79588990 -3.83595045 H 4.16862059 2.48199135 -5.45351061 H 4.48895721 0.74224212 -5.27410860 H 4.29616604 -1.13307441 -1.90927454 H 5.04357203 -0.47304652 -3.38478038 H 5.04382200 -2.22976963 -3.09332885 H 2.08755803 -3.10471396 -2.00794817 H 2.59370131 -3.95094144 -3.50799492 H 0.98160220 -3.16028134 -3.41374916 H 1.96452439 -1.98250764 -6.05175518 H 3.62627388 -2.65939480 -5.86051251 H 3.40635146 -0.92940120 -6.22313996 H 0.48352505 3.19269109 -3.88228047 H 2.09814036 3.84007514 -4.25787033 H 1.81440114 2.99192722 -2.71645076 N -0.73107994 1.48377987 -1.85939028 C -1.68173429 2.41941731 -1.88388319 C -0.45973015 0.82136397 -2.99165876 C -2.42142205 2.71687930 -3.02649345 C -1.18334066 1.00627107 -4.17351016 C -2.17864732 1.97727844 -4.18340680 H -1.86781417 2.94605173 -0.94370635 H -3.18814613 3.49149848 -2.99233243 H -2.76796322 2.15014312 -5.08629645 H -0.92916578 0.33175589 -4.99823844 O 0.57620401 -0.97390525 -1.91312305 O -0.00858042 -1.40923378 -4.81649806 C 0.67277560 -0.18636840 -2.85575755 C -1.10572517 -2.18497108 -4.67370625 H -2.06653651 -1.60428241 -4.54259237 H -1.08097420 -2.86477960 -3.77870278 H -1.31629866 -2.86698147 -5.54003730 H 0.60186306 3.34156678 4.27156678 H 1.71265335 2.64852342 3.05681311 H 1.44803971 1.80484137 4.59650776 305 306 Table A.1.58. Atomic coordinates and single point energies for 60d. G = –2382.920174 GSP = –2384.598272 Na -1.61602000 0.12449400 -0.20279900 N -3.81837600 -0.19030800 -0.03554800 N 2.50662300 -0.58295600 0.44319900 Si -4.73691400 1.16225200 0.38665300 C -3.64602600 2.72239600 0.29462800 C -5.42862100 1.13264000 2.16085400 C -6.23995200 1.49356600 -0.73581000 Si -4.35638800 -1.76031500 -0.36959100 C -2.89078300 -2.97110600 -0.35117700 C -5.17056800 -1.95286300 -2.08061100 C -5.63159600 -2.43948200 0.87308900 Si 3.05864300 -2.18199700 -0.20929000 C 2.64333300 -2.25817300 -2.02722800 C 2.20578200 -3.54938200 0.76695800 C 4.92355800 -2.23282000 -0.04192100 Si 3.42881500 0.27698100 1.72524600 C 2.36612800 1.66505600 2.43986800 C 5.09825100 0.91058400 1.17454700 C 3.59044800 -0.98589300 3.12225800 H -2.79158000 2.63269900 0.98759900 H -4.19655200 3.63817600 0.56241900 H -3.24903000 2.85106500 -0.72626000 H -5.92935300 1.55308900 -1.79085100 H -6.75739800 2.43017700 -0.47177500 H -6.96922500 0.67091200 -0.65138100 H -4.47032200 -1.64459000 -2.87303400 307 H -6.06196500 -1.31034500 -2.15916100 H -5.47840100 -2.99244300 -2.27916100 H -5.24161000 -2.37841300 1.90140900 H -5.89204300 -3.48948200 0.66268100 H -6.56157100 -1.84822700 0.83422200 H -2.12987300 -2.69799400 -1.10142000 H -3.20975300 -4.00255700 -0.57014800 H -2.39846400 -2.97408400 0.63501600 H 5.26778400 1.92712000 1.56229200 H 5.11317000 0.91452200 0.06326700 H 5.90924500 0.26051100 1.53537900 H 2.59555200 -1.30685500 3.46719700 H 4.11792600 -0.52402500 3.97198500 H 4.15432900 -1.88134000 2.82510700 H 1.11651300 -3.44991200 0.64967800 H 2.44633900 -3.49682100 1.83915000 H 2.50741800 -4.54101700 0.39487200 H 1.56255800 -2.27142400 -2.21654000 H 3.10300100 -3.14994100 -2.48081200 H 3.10534300 -1.35329900 -2.45552500 H 5.27738300 -1.38017800 -0.64983600 H 5.29139700 -3.17372800 -0.48136300 H 5.31245800 -2.16244900 0.98343500 H 2.38275800 2.57755600 1.82810800 H 2.76977800 1.91344700 3.43479800 H 1.31694200 1.35725500 2.56810900 N 0.05461700 1.93210500 -0.14460600 C -0.06931300 3.23712300 -0.38201100 C 1.25083200 1.37170600 -0.36527300 C 0.97710100 4.01421400 -0.88282000 C 2.35745300 2.03582700 -0.90393100 C 2.19277300 3.39710900 -1.16973300 H -1.04818200 3.67948900 -0.17719200 H 0.81966300 5.07831800 -1.06418500 H 3.01624700 3.96975000 -1.60192900 H 3.29012900 1.42765500 -1.16598500 O 0.41106000 -0.83133600 -0.42969200 O 4.47091400 0.39231700 -1.72692800 C 1.35420500 -0.11165500 -0.09285100 C 4.78045600 0.83605300 -2.96758400 H 4.20839100 1.75884900 -3.28046800 H 4.56737800 0.10218800 -3.79184300 H 5.85616200 1.11915700 -3.11498600 H -5.97559100 2.05731800 2.40769600 H -4.60955600 1.01190200 2.88739900 H -6.11598600 0.28249700 2.29471800 308 309 Table A.1.59. Atomic coordinates and single point energies for 59. G = –1907.434448 GSP = –1908.586391 Na -0.00005400 0.02562500 -0.02609000 N -2.23849600 0.00466100 -0.00301600 N 2.23860100 0.02092800 -0.02002500 Si -2.97446200 1.06929100 -1.08559000 C -1.67241000 1.75552700 -2.29429800 C -3.77203700 2.59404700 -0.26826500 C -4.34803400 0.29628900 -2.15727300 Si -2.90541800 -1.08222700 1.10239300 C -1.54170800 -1.72903700 2.26403000 C -3.68412200 -2.62960900 0.30997000 C -4.26347900 -0.35127600 2.22212600 Si 2.93564900 -1.09821500 -1.07314700 C 3.76574600 -0.32606500 -2.60405300 C 1.58928200 -2.26349200 -1.74924500 C 4.26650400 -2.21399900 -0.28796600 Si 2.94419400 1.11358300 1.05505500 C 1.62424600 2.33147500 1.68884900 C 4.34252000 2.17485200 0.31283700 C 3.69344000 0.31034000 2.61144000 H -3.97064500 -0.59341800 -2.68562200 H -4.73990700 1.00499100 -2.90500000 H -5.19118000 -0.02636800 -1.52414200 H -3.02026300 3.14537000 0.31855400 H -4.57129300 2.28687000 0.42486300 H -4.20697600 3.28468000 -1.00927800 H -0.87876200 2.29854000 -1.75283400 H -2.10849900 2.45673600 -3.02353800 H -1.19497400 0.93754100 -2.85894100 H -3.89490800 0.54971900 2.73740500 H -4.60673600 -1.07131300 2.98280500 H -5.13804600 -0.05473400 1.61961300 310 H -0.75120500 -2.24924800 1.69611200 H -1.93123900 -2.44213100 3.00793400 H -1.06885000 -0.89735400 2.81247200 H -2.93634000 -3.15718300 -0.30320000 H -4.51554000 -2.34626800 -0.35491200 H -4.07219000 -3.33388800 1.06404700 H 0.81761300 -1.69873600 -2.30016000 H 1.08883100 -2.80130300 -0.92675800 H 1.99845500 -3.01665900 -2.44130700 H 3.03829900 0.28511800 -3.16142000 H 4.17181700 -1.08971400 -3.28754800 H 4.59145400 0.33757600 -2.30173500 H 5.13343200 -1.61106600 0.02942700 H 4.62954300 -2.98346300 -0.98872300 H 3.86810500 -2.71846500 0.60642900 H 2.92366900 -0.26890700 3.14573500 H 4.10939600 1.05726600 3.30738100 H 4.49956400 -0.38802100 2.33565500 H 1.17343700 2.88837500 0.85074600 H 2.04055900 3.06714500 2.39535500 H 0.81277800 1.79804200 2.21322100 H 3.99385700 2.69313600 -0.59433300 H 5.19466700 1.53733000 0.02428700 H 4.71277100 2.93045300 1.02480500 311 Table A.1.60. Atomic coordinates and single point energies for 60. G = –2382.94305 GSP = –2384.627751 Na -0.27354000 -0.29085500 -0.50793800 N -2.52497900 -0.51724300 -0.05604800 N 1.94552100 -0.83499700 0.04880400 Si -3.50370800 0.00548800 -1.32234800 C -4.98369200 -1.13158200 -1.71929400 C -2.49679200 0.15391500 -2.92794700 C -4.27773700 1.73251700 -1.04984200 Si -2.84733300 -1.31757100 1.38907000 C -1.23336300 -1.50562400 2.37316200 C -3.55944800 -3.07492200 1.19781900 C -4.07895800 -0.40958700 2.53579800 Si 2.17740400 -2.15592900 -0.98196900 C 0.63417300 -2.42664100 -2.06987700 C 2.50396800 -3.82046000 -0.11204200 C 3.60614600 -1.97944100 -2.23977200 Si 2.79028900 -0.49291300 1.47337700 C 2.35433200 1.22288100 2.16946000 C 4.69124300 -0.45957600 1.24882200 C 2.51434500 -1.70904400 2.91410700 H -4.82033700 1.76677200 -0.09055200 H -4.98561200 1.99650100 -1.85292800 H -3.49525800 2.50826200 -1.02313900 H -2.12462700 -0.83663500 -3.23644400 H -1.62231400 0.81059800 -2.77977300 H -3.09108200 0.56824200 -3.75848200 H -4.63488400 -2.15682700 -1.92136000 H -5.55335400 -0.78018400 -2.59528300 H -5.67572100 -1.17930600 -0.86192800 312 H -3.71573100 0.60223700 2.78045700 H -4.24189100 -0.94898400 3.48334700 H -5.05560300 -0.29905300 2.03581900 H -0.49728500 -2.09193200 1.79691800 H -1.37299300 -2.00499500 3.34551600 H -0.77659900 -0.51857000 2.56227700 H -2.87869100 -3.69000300 0.58786900 H -4.53311500 -3.04733300 0.68319700 H -3.69800900 -3.57526400 2.17035800 H 1.70315800 -4.03840400 0.61237400 H 3.45611000 -3.79109700 0.44326100 H 2.55721700 -4.65404400 -0.83127600 H -0.26927200 -2.65338800 -1.47647300 H 0.78375200 -3.26886300 -2.76366700 H 0.43077500 -1.53384600 -2.68647000 H 3.38073600 -1.18546300 -2.96966500 H 3.76111100 -2.91652000 -2.79922600 H 4.55222800 -1.72406900 -1.73473000 H 1.45312900 -1.73174800 3.20511000 H 3.10926500 -1.42141400 3.79700500 H 2.80306200 -2.73211600 2.62631100 H 2.72412100 2.01152900 1.49598600 H 2.81265600 1.37517500 3.16010700 H 1.26338700 1.34873300 2.27605700 H 4.98841000 0.27567500 0.48344100 H 5.05874100 -1.44678700 0.92180700 H 5.21090500 -0.20196400 2.18653300 N -0.47115300 2.03820900 -0.01460200 C -1.32361200 2.50336300 0.89193600 C 0.63870100 2.71716000 -0.27723600 C -1.10018600 3.70945900 1.56187100 C 0.96042800 3.92361700 0.34383400 C 0.05837200 4.42909400 1.27707100 H -2.20026900 1.86983900 1.06980500 H -1.82137500 4.06656500 2.29727700 H 0.26517600 5.37076600 1.78867300 H 1.89715700 4.42645500 0.10637900 O 1.13883800 1.28184000 -2.12077700 C 1.53568000 2.04992300 -1.28644800 O 2.80701000 2.40817100 -1.13595100 C 3.73992700 1.64135400 -1.89045000 H 4.73097800 2.03280800 -1.63960800 H 3.54136300 1.74294800 -2.96626500 H 3.64275000 0.58775800 -1.59418500 313 Table A.1.61. Atomic coordinates and single point energies for 61. G = –2382.924637 GSP = –2384.610658 Na 1.27275500 0.45142000 -0.94931600 N 3.43867800 0.42593800 -0.34222200 N -2.96980700 0.40218700 0.07879200 Si 4.15186600 -1.02948100 -0.81352900 C 5.69986000 -0.84717600 -1.90934100 C 2.91532000 -2.05020600 -1.84500600 C 4.69168600 -2.16534000 0.62181300 Si 4.03234400 1.63095600 0.68304200 C 3.28458000 3.32361500 0.25591700 C 5.92486200 1.85837400 0.63749400 C 3.60201500 1.33370900 2.51774500 Si -2.50955300 1.96964100 -0.32785800 C -0.64937600 2.32234000 -0.00181500 C -3.42035900 3.36116800 0.61354200 C -2.75083800 2.39564500 -2.17421800 Si -4.50176200 -0.07345600 0.58844900 C -4.70412000 -1.96261900 0.76834200 C -5.91847400 0.43030800 -0.60083400 C -5.04139500 0.59277300 2.29432500 H 5.42600900 -1.65088700 1.26346800 H 5.15352900 -3.09878600 0.26062900 H 3.82886300 -2.43438500 1.25219900 H 2.58349500 -1.48787600 -2.73476200 H 2.02182800 -2.30860800 -1.25246600 H 3.36083200 -2.99237800 -2.20177000 H 5.47038800 -0.23079700 -2.79287900 H 6.07474400 -1.82402900 -2.25639000 H 6.51092800 -0.34645400 -1.35757800 H 2.50782500 1.33228600 2.65392400 H 4.02198600 2.10735500 3.18104800 H 3.98543100 0.35438300 2.84948200 314 H 3.54260300 3.60682500 -0.77698000 H 3.64408500 4.11738100 0.93023000 H 2.18492500 3.29411200 0.33144900 H 6.26128600 2.09368800 -0.38479200 H 6.43879900 0.93504200 0.95258200 H 6.25404700 2.67189500 1.30423800 H -3.25295500 3.26785500 1.69861900 H -4.50804700 3.31612600 0.43963100 H -3.06730000 4.35630700 0.29598700 H -0.22095200 1.53136800 0.63457300 H -0.50457800 3.28149200 0.51866000 H -0.09822500 2.39866000 -0.95519500 H -2.14169600 1.71507400 -2.79073300 H -2.45158400 3.43134700 -2.40617500 H -3.80662600 2.27051700 -2.46706100 H -4.28147600 0.34006000 3.05110100 H -6.00498600 0.16270100 2.61489200 H -5.14382900 1.68891400 2.28053200 H -4.37054500 -2.49584900 -0.13579700 H -5.76308600 -2.21057600 0.94758500 H -4.12494200 -2.33897200 1.62661200 H -5.77038400 -0.01879700 -1.59704000 H -5.94054600 1.52448800 -0.73496600 H -6.90826700 0.11478000 -0.23087400 N 0.37839100 -1.08500000 0.58933900 C 0.94626500 -1.45823200 1.73218400 C -0.75097400 -1.66890200 0.19901000 C 0.39762700 -2.45165400 2.54347500 C -1.36646800 -2.68674900 0.92747300 C -0.77733400 -3.07555000 2.12648000 H 1.87913100 -0.94693400 1.99086900 H 0.89003400 -2.73032700 3.47520700 H -1.23274400 -3.86130400 2.73193200 H -2.28502000 -3.13439400 0.55519700 O -0.69089100 -0.37680000 -1.81054900 C -1.27467600 -1.19668300 -1.13039400 O -2.30110600 -1.91040500 -1.56063500 C -2.98828400 -1.37268400 -2.67924200 H -3.82117900 -2.05368400 -2.88485400 H -2.31925300 -1.30356000 -3.54806200 H -3.35775400 -0.37398200 -2.40484200 315 Table A.1.62. Atomic coordinates and single point energies for 62. G = –2382.945822 GSP = –2384.624228 Na -1.02570000 0.62779700 0.75492500 N -3.22785800 0.45699200 0.31984600 N 2.74307600 0.27276600 -0.05691700 Si -3.81581200 -1.02548600 0.87567700 C -5.22317100 -0.88878600 2.15350600 C -2.42690900 -1.99442300 1.74655200 C -4.49682300 -2.18026600 -0.48364600 Si -3.97241000 1.54423000 -0.73687100 C -3.31254700 3.31030200 -0.50280100 C -5.86692700 1.66781200 -0.54648500 C -3.66981500 1.13113900 -2.57526400 Si 2.25230700 1.91349100 0.48698100 C 0.62466600 2.69658300 -0.12857900 C 3.48604700 2.98180600 -0.56850000 C 2.72710000 2.56975500 2.21032400 Si 4.16240000 -0.32085800 -0.87895600 C 4.05291700 -2.18121300 -1.17558500 C 5.73664900 -0.03998100 0.13673200 C 4.40674600 0.47087000 -2.57683000 H -5.35593000 -1.71239700 -0.99231700 H -4.83099700 -3.14870500 -0.07657000 H -3.72543200 -2.37582000 -1.24528300 H -2.00298600 -1.41506200 2.58468600 H -1.60326400 -2.23822400 1.05443000 H -2.79529600 -2.94562300 2.16304800 H -4.90053200 -0.27549100 3.00965200 H -5.53633700 -1.87550500 2.53251300 H -6.10264600 -0.39827900 1.70697800 H -2.59107700 1.18441100 -2.79821400 H -4.18979300 1.82263400 -3.25835700 H -4.01018000 0.10654300 -2.79877600 316 H -3.48430100 3.64979600 0.53110500 H -3.80246100 4.02381400 -1.18496500 H -2.22802900 3.35484300 -0.69440600 H -6.12946700 1.97249700 0.47926000 H -6.34617100 0.69308200 -0.73598700 H -6.30272300 2.40026200 -1.24542300 H 3.25980600 2.91870600 -1.64554800 H 4.54940500 2.71981300 -0.43318100 H 3.37519100 4.03955300 -0.27519300 H 0.15990000 2.04361500 -0.88643600 H 0.78644000 3.67896600 -0.59583300 H -0.08171200 2.85100900 0.70474300 H 2.06928400 2.17796900 2.99771000 H 2.67374800 3.67086800 2.20929700 H 3.76759600 2.29989300 2.45606000 H 3.45235500 0.49025600 -3.12478700 H 5.12689000 -0.12686500 -3.15845200 H 4.78531400 1.49954500 -2.51399300 H 3.91101600 -2.71368700 -0.22479400 H 4.99514400 -2.52204100 -1.63443000 H 3.22555000 -2.44638400 -1.85023500 H 5.73236600 -0.68756800 1.02715200 H 5.81197700 1.00364400 0.47772400 H 6.63732000 -0.27533200 -0.45272600 N -0.00678700 -0.81759500 -0.87171800 C -0.84416800 -1.52894700 -1.62453900 C 0.91888100 -1.44511100 -0.14132500 C -0.79450400 -2.91960100 -1.70392700 C 1.01752600 -2.84144200 -0.12863700 C 0.15421500 -3.58282900 -0.92902400 H -1.61177500 -0.96321100 -2.16173800 H -1.50374600 -3.46040400 -2.33086200 H 0.21010100 -4.67345400 -0.93462800 H 1.75434900 -3.31203900 0.51744500 O 1.08328500 0.41251200 1.37133600 C 1.80827400 -0.52671000 0.72717500 O 2.48674700 -1.43190900 1.60177900 C 3.10384100 -0.82052400 2.69887900 H 3.61303800 -1.61170200 3.26675200 H 2.36724300 -0.31614400 3.34215500 H 3.85146300 -0.07339300 2.38106800 317 Table A.1.63. Atomic coordinates and single point energies for TS-6. G = –2382.935844 GSP = –2384.615248 Na 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 2.25727897 N 1.85971739 0.00000000 -3.44115119 Si 0.42054201 1.49547195 2.91781903 C -1.00845443 2.38271059 3.81434478 C 0.98790022 2.69737121 1.55217839 C 1.84636063 1.43879204 4.18402821 Si -0.31037039 -1.47254159 3.01934745 C -1.03697705 -2.71254086 1.77300952 C -1.53843589 -1.37939495 4.47442761 C 1.23510704 -2.33626028 3.73410354 Si 0.04033808 -0.54655478 -3.29322195 C -1.43296439 -1.06070627 -2.10433669 C 0.37505243 -2.36685256 -3.82762730 C -0.81671095 0.32472551 -4.75008734 Si 2.97238608 0.13769558 -4.76740958 C 4.69601025 0.66765880 -4.18719142 C 2.45885790 1.39085476 -6.09042977 C 3.19020244 -1.52008959 -5.65030839 H 1.55286735 0.85535197 5.07238953 H 2.13756091 2.44652895 4.52272078 H 2.73278189 0.95412837 3.74386064 H 0.24627165 2.75761406 0.73671407 H 1.94697717 2.37788381 1.11154692 H 1.12429240 3.71773923 1.94562853 H -1.85257637 2.53578033 3.12332780 H -0.70463058 3.36532585 4.21115350 H -1.37684065 1.77214624 4.65399439 H 1.93633044 -2.60740266 2.92805193 H 0.97518355 -3.26088401 4.27535094 H 1.76802842 -1.67002152 4.43110333 318 H -1.96843005 -2.32513094 1.32891473 H -1.26209516 -3.68630995 2.23656159 H -0.32332826 -2.89835069 0.95172481 H -2.47377592 -0.89086135 4.15879574 H -1.11317418 -0.78132699 5.29747341 H -1.78428354 -2.37654046 4.87458510 H 0.91841854 -2.88859821 -3.02099311 H 0.99134817 -2.44310551 -4.73322395 H -0.56678225 -2.91267504 -4.00012497 H -1.11888153 -1.76082110 -1.30669837 H -2.18844916 -1.61342221 -2.68488803 H -1.94430809 -0.19735075 -1.64238325 H -0.62990591 1.40826106 -4.69360502 H -1.90489167 0.15739303 -4.76263609 H -0.40763881 -0.03779064 -5.70705047 H 3.36590913 -2.33971943 -4.93842694 H 4.05796606 -1.45017461 -6.32585193 H 2.31266073 -1.77895881 -6.26055634 H 4.70571608 1.73209216 -3.91161789 H 5.41795282 0.52712412 -5.00777574 H 5.03668838 0.08257623 -3.31967766 H 2.34725054 2.37911294 -5.62191337 H 1.49233591 1.11962576 -6.54046614 H 3.21073950 1.45418458 -6.89401314 N 2.34974367 0.00631140 -0.33632097 C 3.14061108 -0.15116573 0.72400635 C 2.66649570 0.90799660 -1.26754159 C 4.31421938 0.57770116 0.90579201 C 3.81310338 1.70293969 -1.15514214 C 4.64875021 1.52763894 -0.05740134 H 2.79641286 -0.86256131 1.48046001 H 4.92743150 0.41930393 1.79302300 H 5.54642743 2.13930399 0.05462736 H 4.01647246 2.45145413 -1.91875930 O 0.39919479 0.81444546 -2.04947738 C 1.69264245 1.02765964 -2.46370150 O 1.87046339 2.31504089 -3.05100883 C 1.28735456 3.37186669 -2.33563274 H 1.52887567 4.30018468 -2.87139720 H 1.68073548 3.44373370 -1.30477612 H 0.19458346 3.25447692 -2.27675587 319 Table A.1.64. Atomic coordinates and single point energies for 63. G = –2382.938755 GSP = –2384.618939 Na -1.00743900 0.86854100 0.58104700 N -3.17332200 0.37344600 0.22515700 N 2.82052200 0.29787800 -0.15329900 Si -3.66893500 -1.07637700 0.93341500 C -4.96182200 -0.86384500 2.31700700 C -2.19302100 -1.96962700 1.74462300 C -4.43773000 -2.33592200 -0.27639000 Si -3.98974500 1.40225700 -0.83351400 C -3.09320000 3.07721200 -0.93842300 C -5.79397800 1.78202200 -0.35127600 C -4.07312900 0.76548800 -2.63109600 Si 2.02538400 1.97924100 0.53069600 C 0.74189200 3.14448700 1.46544700 C 1.71427800 2.65822800 -1.22040600 C 3.60647900 2.59597900 1.39138900 Si 4.37654600 -0.21326300 -0.67414800 C 4.35559600 -1.88539500 -1.56969000 C 5.65403200 -0.38984300 0.71473600 C 5.02831800 1.06155000 -1.90958200 H -5.35138500 -1.92253600 -0.73488700 H -4.70836000 -3.27885500 0.22629000 H -3.73271900 -2.57156300 -1.08983400 H -1.64739500 -1.29636800 2.42856500 H -1.47802400 -2.33353800 0.98783100 H -2.52442600 -2.83799300 2.33666400 H -4.56775700 -0.20515100 3.10707000 H -5.24296100 -1.82546700 2.77683400 H -5.87514800 -0.39265500 1.92018600 H -3.06212700 0.71592900 -3.06778200 H -4.68404500 1.41824000 -3.27600500 H -4.50340000 -0.24854500 -2.66410600 320 H -3.05220300 3.55969900 0.05157100 H -3.58964200 3.77265100 -1.63392300 H -2.05584500 2.94884200 -1.29404100 H -5.84235800 2.17511500 0.67652400 H -6.40198300 0.86263900 -0.38385600 H -6.25869600 2.51800600 -1.02735800 H 0.89691400 2.06616000 -1.66891400 H 2.59154200 2.51402200 -1.86704900 H 1.41590400 3.71807400 -1.22873800 H -0.28666200 3.14385700 1.05199100 H 1.07442800 4.19328000 1.38885700 H 0.66439200 2.89764500 2.53830600 H 3.80658600 1.92746300 2.24538800 H 3.52134200 3.62542500 1.77027300 H 4.47916400 2.53436700 0.72338700 H 4.39213100 1.08544700 -2.80760000 H 6.05566800 0.81189800 -2.21899700 H 5.03841200 2.07443400 -1.47944500 H 4.22267000 -2.71750200 -0.86206800 H 5.31462800 -2.04101000 -2.09028400 H 3.54449100 -1.93364800 -2.31216200 H 5.25775400 -1.08649600 1.46848400 H 5.83603700 0.57425500 1.21229800 H 6.61555700 -0.77617700 0.33918300 N -0.06849500 -0.79008800 -0.83556600 C -0.86646300 -1.51916300 -1.61521200 C 0.99000500 -1.36082700 -0.25846700 C -0.63785500 -2.86827000 -1.87621300 C 1.28335900 -2.71749600 -0.44319600 C 0.46071700 -3.47542000 -1.26860900 H -1.74746800 -1.00617500 -2.01306200 H -1.32044700 -3.42724500 -2.51652300 H 0.66577300 -4.53631600 -1.42679200 H 2.13848700 -3.14919100 0.07501800 O 1.12544300 0.55991000 1.18756500 C 1.89216300 -0.44674100 0.59980100 O 2.53658900 -1.24736500 1.58348700 C 1.70625300 -1.68827700 2.62485600 H 2.31466200 -2.32712500 3.27949200 H 0.84758800 -2.27798500 2.25374500 H 1.31269600 -0.83971800 3.20542100 321 Table A.1.65. Atomic coordinates and single point energies for TS-7. G = –2382.923189 GSP = –2384.608706 Na 0.00000000 0.00000000 0.00000000 N 0.00000000 0.00000000 2.25785438 N 2.04738534 0.00000000 -3.98618119 Si -0.77052281 1.36071838 2.87807755 C -2.40223692 1.01281356 3.79574723 C -1.21576812 2.52596710 1.43507905 C 0.27409849 2.39740985 4.09025339 Si 0.86344545 -1.29429335 2.90297355 C 1.47471410 -2.41007428 1.48596906 C -0.13516835 -2.41130986 4.07882419 C 2.42606521 -0.80997132 3.88516681 Si -1.07283141 -0.74132370 -3.04627947 C -2.24340732 -1.61347077 -1.82723079 C -0.54462315 -2.04266244 -4.30778913 C -2.07420585 0.61707401 -3.90263849 Si 2.06998562 0.39275829 -5.64879500 C 3.38065935 1.73014345 -5.95569222 C 0.48101467 1.03784997 -6.46054967 C 2.60341109 -1.15156868 -6.60078512 H 0.48443517 1.82093016 5.00573617 H -0.23967097 3.32641500 4.38681555 H 1.24253293 2.66936607 3.64063054 H -1.90711175 2.03138656 0.72952049 H -0.30597863 2.80597247 0.87695255 H -1.70517981 3.45384079 1.77091964 H -3.10076864 0.47070450 3.13906891 H -2.89483221 1.93825988 4.13629849 H -2.21911884 0.37806662 4.67749588 322 H 3.13588001 -0.26424131 3.24304765 H 2.94499575 -1.69674602 4.28468633 H 2.16991466 -0.15415756 4.73250197 H 0.62534202 -2.80768747 0.90481409 H 2.05514458 -3.27192457 1.85173099 H 2.12304044 -1.84682453 0.79197321 H -1.05371451 -2.76295394 3.58332218 H -0.43865516 -1.84720715 4.97584441 H 0.44032572 -3.29136752 4.40925833 H 0.18451569 -2.72504788 -3.84568656 H -0.05785777 -1.59091763 -5.18216095 H -1.41168291 -2.62836595 -4.65340846 H -1.72119379 -2.42781237 -1.29897524 H -3.11500019 -2.05238023 -2.33873932 H -2.62967761 -0.91084231 -1.06912749 H -2.61825620 1.21197850 -3.15125028 H -2.80791802 0.21649898 -4.62011923 H -1.39314456 1.29348813 -4.43903199 H 3.56635070 -1.51504475 -6.21067493 H 2.71809452 -0.94546531 -7.67671895 H 1.87126063 -1.96439228 -6.48035513 H 3.11257694 2.63455189 -5.38786981 H 3.46613824 1.99820818 -7.02093829 H 4.36776869 1.39098290 -5.60443575 H 0.19096488 1.99172905 -5.99494376 H -0.36340743 0.34030600 -6.35725383 H 0.65162048 1.21121020 -7.53584008 N 2.03276577 1.05033268 -0.53478335 C 2.85282924 1.09032188 0.51746409 C 2.51231958 0.71428824 -1.73478908 C 4.21296214 0.80622934 0.42789268 C 3.86676219 0.40212231 -1.91324542 C 4.72319921 0.45089325 -0.81971072 H 2.38048232 1.32506597 1.47757058 H 4.84211227 0.84554636 1.31763750 H 5.78068537 0.20479890 -0.93752672 H 4.19214751 0.10899297 -2.90984608 O 0.14596899 -0.10376623 -2.15814692 C 1.62478409 0.70281844 -2.98957295 O 1.06115954 1.93642171 -3.30086702 C 0.43336570 2.74578597 -2.33969306 H -0.02627137 3.57677299 -2.89281977 H 1.14447179 3.15573305 -1.60564107 H -0.34865511 2.18917807 -1.80490934 323 Table A.1.66. Atomic coordinates and single point energies for 64. G = –2382.943615 GSP = –2384.634413 Na -1.50201900 -0.75620600 -0.21497000 N -3.61482100 0.03959500 -0.16034100 N 3.72862300 0.88818000 0.92705400 Si -3.89327800 1.12478900 -1.42108100 C -5.20372600 0.56617700 -2.68556200 C -2.28701000 1.36740300 -2.41742600 C -4.45372600 2.86370300 -0.87273100 Si -4.59295000 -0.57339300 1.06576200 C -3.61970000 -1.86084400 2.07995400 C -6.16839000 -1.46702000 0.47504000 C -5.21816800 0.72196900 2.32092500 Si 1.57487300 -2.59050600 -0.68603600 C 0.87402300 -4.34689700 -0.90741800 C 2.77970500 -2.69897700 0.78574200 C 2.66111600 -2.25774400 -2.21330500 Si 5.37399400 0.91731900 0.32672300 C 5.80743100 2.67284200 -0.20504900 C 5.66187100 -0.27450800 -1.10013600 C 6.46601600 0.41124600 1.77345300 H -5.44716900 2.81162700 -0.39833700 H -4.52240700 3.55999900 -1.72438800 H -3.76112600 3.29561300 -0.13284000 H -1.95783000 0.41279300 -2.86315200 H -1.46318600 1.74162400 -1.78602300 H -2.42197900 2.08345300 -3.24378000 H -4.94746600 -0.42732200 -3.08600500 H -5.28846900 1.26876000 -3.53068800 H -6.19408700 0.48508100 -2.20972000 H -4.38710400 1.29632200 2.76052700 H -5.78399400 0.25562300 3.14404800 324 H -5.88230300 1.44537600 1.82130000 H -3.30525300 -2.70033800 1.43727100 H -4.21856900 -2.28049700 2.90390600 H -2.70933600 -1.42148500 2.52152800 H -5.91414200 -2.24657800 -0.26022300 H -6.85313100 -0.75820800 -0.01796500 H -6.71312400 -1.94005800 1.30845400 H 2.23662600 -2.94080400 1.71423900 H 3.29912800 -1.73862000 0.93986800 H 3.54243900 -3.47961300 0.62716700 H 0.27729200 -4.63730600 -0.02767000 H 1.66867800 -5.09865700 -1.04273600 H 0.21136200 -4.38853200 -1.78665200 H 2.04442100 -2.22233300 -3.12606900 H 3.43856300 -3.02684900 -2.35289400 H 3.16479900 -1.28359400 -2.11090800 H 6.30627500 1.08454500 2.62881800 H 7.53359600 0.43263100 1.50579200 H 6.21125000 -0.60934100 2.09758100 H 5.15052800 2.97776500 -1.03290200 H 6.85358400 2.74718600 -0.54001300 H 5.65945300 3.37720200 0.62712700 H 5.12000800 0.06236700 -1.99526100 H 5.29824200 -1.28188700 -0.84640500 H 6.73481700 -0.34296500 -1.33985600 N 0.37072600 1.79661200 0.37798600 C -0.80819600 1.81293500 1.00017000 C 1.33909600 1.03798200 0.88729200 C -1.07649100 1.07031300 2.14957300 C 1.18511600 0.28354700 2.05593200 C -0.04974300 0.29408300 2.68940600 H -1.59574800 2.42719200 0.55353600 H -2.07473400 1.09513300 2.58741600 H -0.21907300 -0.30610000 3.58531800 H 2.02893600 -0.30092100 2.41795900 O 0.43439400 -1.47388300 -0.50250000 C 2.68876700 1.04540000 0.22109500 O 2.77297400 1.28222400 -1.09954700 C 1.68447300 1.08593900 -2.00644700 H 2.15161700 0.85836200 -2.97375800 H 1.08312900 1.99936000 -2.08063700 H 1.06533200 0.23458500 -1.68301900 325 Table A.1.67. Atomic coordinates and single point energies for 65. G = –1518.978897 GSP = –1519.921239 Na -0.59574800 0.00011900 -0.00044700 N 1.65812400 0.00014500 -0.00055900 Si 2.38505400 1.52381900 -0.00437400 C 3.15464600 2.03322500 1.66358200 C 1.09218700 2.86352600 -0.39989100 C 3.78302100 1.73952100 -1.28345800 Si 2.38406300 -1.52395000 0.00433500 C 1.08846900 -2.86324600 0.39258800 C 3.77653100 -1.74217100 1.28897500 C 3.16013200 -2.03228300 -1.66096100 Si -4.25163600 -0.00007600 0.00020300 C -5.01075500 -0.85800700 1.52481500 C -5.00834700 -0.89093900 -1.50675500 C -5.00988800 1.74947500 -0.01933700 H 4.62664800 1.06974300 -1.04747800 H 4.16887700 2.77182700 -1.30569600 H 3.42616400 1.48020400 -2.29279200 H 0.28084200 2.86544300 0.34759200 H 0.63626700 2.68727200 -1.38780900 H 1.53271400 3.87332700 -0.40761800 H 2.39255700 2.00210000 2.45835800 H 3.57933600 3.05012100 1.63219000 H 3.95747400 1.33496400 1.94896700 H 2.40128900 -1.99975800 -2.45878600 H 3.58375500 -3.04959400 -1.62872700 H 3.96475700 -1.33452400 -1.94244500 H 0.62750100 -2.68758700 1.37827500 H 1.52839600 -3.87329400 0.40169700 H 0.28119600 -2.86389100 -0.35930200 H 3.41565100 -1.48358500 2.29706700 H 4.62159300 -1.07272500 1.05721200 326 H 4.16158200 -2.77476600 1.31181400 H -4.67991200 -1.94217700 -1.53785900 H -4.67653500 -0.41329000 -2.44255400 H -6.11068900 -0.87759100 -1.48838100 H -4.68153000 -1.90799500 1.57989800 H -6.11307700 -0.84586900 1.50404000 H -4.68113100 -0.35957100 2.45050100 H -4.68086000 2.32154500 0.86292000 H -6.11222700 1.72618000 -0.02001200 H -4.67919500 2.30234800 -0.91313200 O -2.65322200 0.00089100 0.00140500 327 Table A.1.68. Atomic coordinates and single point energies for 66. G = –2758.058575 GSP = –2760.017343 N 3.61642700 0.76188800 -0.66415300 C 4.94867400 0.75874800 -0.65356300 C 2.97814600 -0.13862500 0.08376400 C 5.70883900 -0.15200300 0.07909500 C 3.64919600 -1.08866600 0.86298300 C 5.03894700 -1.10132800 0.84982100 H 5.44087600 1.51890500 -1.26744700 H 6.79751100 -0.11572600 0.04160700 H 5.59434300 -1.83695200 1.43405500 H 3.07832800 -1.80146500 1.46103200 C 1.46435700 -0.10596300 0.05378900 N 0.83246700 -0.52773000 -1.03017700 N 0.81441200 0.34018000 1.12020900 Si 1.52094000 -1.10604500 -2.53233000 C 3.09681800 -2.14327800 -2.35728100 C 1.88879400 0.32985900 -3.69797500 C 0.25312200 -2.20946200 -3.38355300 Si 1.42674500 1.07090700 2.58187700 C 0.15364300 2.34204400 3.14355400 C 3.09288600 1.95613500 2.42248200 C 1.59122200 -0.19250500 3.97704800 H 3.13683700 2.59669500 1.52945100 H 3.93587900 1.25135000 2.36450300 H 3.24601100 2.59245200 3.30857800 H 0.63334500 -0.69826900 4.17187000 H 1.89872500 0.31369200 4.90553200 H 2.34882500 -0.95858300 3.74994300 H -0.00081500 3.13136500 2.39075100 328 H 0.47930100 2.83101300 4.07471600 H -0.82183400 1.86960000 3.33195500 H 3.97751700 -1.54822100 -2.07418600 H 3.30998900 -2.61576200 -3.32957600 H 2.97940900 -2.95028600 -1.61724800 H 2.53715600 1.06575800 -3.19910700 H 0.95702100 0.82593400 -4.01059300 H 2.39749200 -0.02642400 -4.60724900 H 0.07082700 -3.14069100 -2.82637600 H 0.62342000 -2.48854400 -4.38257000 H -0.71224300 -1.69868800 -3.50975700 Na -0.96226600 -1.23835000 0.46764400 N -2.71550300 0.19864300 -0.08446800 Na -0.74111100 1.34377100 -0.51038200 Si -3.29337600 -0.32861500 -1.59253800 C -2.32619800 0.56488400 -2.96996300 C -5.12506200 -0.02528400 -1.96123600 C -3.01417800 -2.20380400 -1.79571500 Si -3.47776100 0.50045700 1.40407800 C -2.55932100 -0.47012200 2.77314400 C -5.29114700 -0.03223600 1.53852500 C -3.42127200 2.33844700 1.86830700 H -2.56398800 1.64195400 -2.93546700 H -2.58200500 0.20096800 -3.97731700 H -1.23568400 0.44506900 -2.84870300 H -1.96050500 -2.47788400 -1.61307300 H -3.27495300 -2.58145100 -2.79691300 H -3.63760500 -2.73589300 -1.05735600 H -5.38445400 1.03497800 -1.81324700 H -5.77240600 -0.62496600 -1.30408200 H -5.36173000 -0.29127300 -3.00362100 H -5.41237300 -1.09679600 1.28081100 H -5.93055300 0.55232300 0.85975000 H -5.66557400 0.11327000 2.56421400 H -2.70773200 -1.55400800 2.61657500 H -2.92608200 -0.23420000 3.78411900 H -1.47514000 -0.26223400 2.75800900 H -2.39406700 2.73130600 1.80742300 H -3.79517100 2.53531500 2.88534200 H -4.04050600 2.91182100 1.15960900 N 0.02371900 3.50797300 -1.16567400 C 1.33116400 3.59530400 -0.52769700 H 1.97177300 2.75677200 -0.84542400 H 1.21437400 3.54354800 0.56403600 H 1.84399000 4.54830000 -0.77404900 C -0.88002200 4.53137600 -0.66300900 329 H -0.51191500 5.55335400 -0.88884000 H -0.98991600 4.43747000 0.42691500 H -1.87367100 4.41103000 -1.11826400 C 0.15530300 3.59834400 -2.61226600 H 0.82831000 2.80961500 -2.97350900 H 0.56942200 4.58000000 -2.92240000 H -0.82461700 3.46811000 -3.09254000 N -0.44184100 -3.44902400 1.18031500 C -1.54189500 -4.39800100 1.24709500 H -2.31617400 -4.02635400 1.93329900 H -1.20688100 -5.39323000 1.60490000 H -1.99167000 -4.51726000 0.25156000 C 0.14329800 -3.21777400 2.49182900 H 0.60974600 -4.13505500 2.90692600 H -0.62936500 -2.87101000 3.19303300 H 0.91012700 -2.43162800 2.42211800 C 0.57240500 -3.88299600 0.23216200 H 0.12037800 -4.02582200 -0.75954900 H 1.04793100 -4.83667500 0.54164800 H 1.35213800 -3.11219400 0.13865900 330 Table A.1.69. Atomic coordinates and single point energies for 66a. G = –2409.743596 GSP = –2411.307627 N -3.07289800 -0.25430100 1.40334600 C -4.31053200 -0.27207900 1.89715600 C -2.91694100 0.06613900 0.11707500 C -5.44380400 0.01467300 1.13653000 C -3.98516000 0.37831300 -0.72890400 C -5.27343500 0.34435800 -0.20733200 H -4.40809700 -0.53145500 2.95538100 H -6.43370100 -0.02155600 1.59115600 H -6.13486700 0.57189700 -0.83758600 H -3.79646400 0.63253400 -1.77324100 C -1.48536900 0.07566700 -0.36239900 N -0.90138900 -1.06704500 -0.66698600 N -0.81968700 1.22542600 -0.35475800 Si -1.52974500 -2.69553900 -0.75552500 C -3.40613900 -2.87383300 -0.88880000 C -0.96352900 -3.67599500 0.74924000 C -0.80956700 -3.45958000 -2.32155700 Si -1.34915900 2.85868600 -0.04244800 C 0.10556700 3.74875600 0.76076600 C -2.80024000 3.05566900 1.15304300 C -1.77093900 3.70447300 -1.67249000 H -2.60873400 2.51724900 2.09403800 H -3.75491100 2.69158800 0.74712200 H -2.91915500 4.12420800 1.39323800 H -0.91862400 3.65583100 -2.36715400 H -2.02596700 4.76414800 -1.51936100 H -2.63064200 3.21583600 -2.15624000 H 0.33493300 3.31185400 1.74739900 H -0.12982300 4.81144700 0.92588700 H 1.01757000 3.69547900 0.14874500 H -3.93674300 -2.52400700 0.00942600 H -3.64014600 -3.94202600 -1.02425200 331 H -3.80834900 -2.33077300 -1.75720600 H -1.33269300 -3.20179000 1.67228300 H 0.13341500 -3.73806200 0.80387100 H -1.35806500 -4.70322000 0.71442700 H -1.16830500 -2.91539100 -3.20935900 H -1.11653500 -4.51144400 -2.42634700 H 0.29028000 -3.43185200 -2.32579000 Na 0.95485900 0.02642700 -1.57968700 N 2.59544000 -0.06856300 0.05731000 Na 0.58331500 0.12203200 1.19814600 Si 3.10309100 -1.54135200 0.75756000 C 2.80493000 -3.00753500 -0.40093400 C 2.05801200 -1.88997900 2.32835200 C 4.90440200 -1.62406400 1.33000700 Si 3.54273600 1.28878700 -0.36454500 C 2.66531600 2.21323200 -1.79335300 C 5.27593700 0.90972100 -1.03125300 C 3.78033000 2.51990400 1.05568300 H 1.75634800 -3.00671000 -0.73911400 H 3.00601600 -3.97970600 0.07551200 H 3.44704100 -2.92558000 -1.29252000 H 5.59218700 -1.62203000 0.47124900 H 5.08564800 -2.54693500 1.90286800 H 5.16415500 -0.76825500 1.97323200 H 0.98400300 -2.05284600 2.12450700 H 2.16637400 -1.07313900 3.06416200 H 2.39879400 -2.80981100 2.82799200 H 5.24460700 0.11031900 -1.78875000 H 5.95654800 0.58775800 -0.22927400 H 5.71388500 1.80532700 -1.49991000 H 2.71370000 1.62603900 -2.72933600 H 3.16138600 3.17162000 -2.00994100 H 1.60906600 2.44340100 -1.57092700 H 2.81800900 2.85057900 1.47524100 H 4.33806400 3.41602100 0.74152200 H 4.34966300 2.03661400 1.86606200 332 Table A.1.70. Atomic coordinates and single point energies for 66b. G = –2583.904557 GSP = -2585.665658 N -3.51207000 -0.51215800 0.64891400 C -4.83927700 -0.55680100 0.76270100 C -2.99180300 0.07279500 -0.43106400 C -5.70939300 -0.04832700 -0.20055300 C -3.77887000 0.62563600 -1.44761400 C -5.16202500 0.55187200 -1.33386800 H -5.23319700 -1.03038300 1.66684100 H -6.78784300 -0.12526800 -0.06271500 H -5.80674300 0.95680900 -2.11574200 H -3.30055700 1.09106800 -2.31075100 C -1.48218500 0.08210800 -0.53065000 N -0.85114600 -1.06374700 -0.72880300 N -0.82104000 1.22289400 -0.40913000 Si -1.47548200 -2.65152200 -1.09952800 C -3.08623400 -2.64944700 -2.09018500 C -1.74383200 -3.72416500 0.42491200 C -0.14549700 -3.45268200 -2.17085300 Si -1.34647900 2.86207300 -0.13925300 C 0.03447200 3.71768000 0.81668400 C -2.95567800 3.08855400 0.82970600 C -1.54270700 3.75967900 -1.78973200 H -2.94642200 2.54988000 1.78827700 H -3.83814300 2.75526600 0.26499300 H -3.08336700 4.16034200 1.05086300 H -0.62794900 3.67722600 -2.39628600 H -1.74179100 4.83030400 -1.62674800 H -2.37954400 3.35136000 -2.37647000 H 0.23308800 3.21722200 1.77742700 H -0.22360800 4.76566900 1.03297400 H 0.97275100 3.71320200 0.24202500 333 H -3.95221300 -2.34393200 -1.48308900 H -3.28014700 -3.66709500 -2.46471300 H -3.02668200 -1.97691900 -2.96002800 H -2.55084500 -3.31246500 1.04931000 H -0.83237400 -3.80076200 1.03585000 H -2.03193300 -4.74140700 0.11669600 H -0.01392800 -2.89493100 -3.11269200 H -0.40239200 -4.49002600 -2.43376400 H 0.82340500 -3.46713200 -1.64774700 Na 0.89581600 0.11759600 -1.78837600 N 2.70675100 -0.01587800 -0.38135400 Na 0.76356200 -0.05458000 0.94482700 Si 3.45500400 -1.47271300 0.11008500 C 2.17634500 -2.51832900 1.06526900 C 4.90063600 -1.24493100 1.31789000 C 4.08525800 -2.52846600 -1.33018200 Si 3.54003200 1.42028600 -0.78567400 C 2.46326200 2.42248700 -2.00957700 C 5.18729600 1.16591800 -1.69018000 C 3.88799500 2.53174900 0.70750400 H 1.97742500 -2.07389600 2.05682000 H 2.53911700 -3.54153600 1.24646300 H 1.21963400 -2.59399000 0.52104100 H 3.27296700 -2.75470100 -2.03918700 H 4.51322500 -3.48328300 -0.98707600 H 4.86772100 -1.98525600 -1.88300900 H 4.56625500 -0.69792400 2.21423800 H 5.72572200 -0.67112600 0.86846100 H 5.30793800 -2.21479900 1.64447000 H 5.03476100 0.59571100 -2.62019100 H 5.91014400 0.60923200 -1.07401900 H 5.64865500 2.13023000 -1.95545100 H 2.40288000 1.91659300 -2.99127700 H 2.89381000 3.41659200 -2.20430600 H 1.44068300 2.58398500 -1.62868600 H 2.96144000 2.74912500 1.26206000 H 4.34828900 3.49031800 0.42149300 H 4.57602100 2.01709000 1.39697800 N -0.21931300 -0.27077200 3.12217600 C -1.22569700 0.77702200 3.21865500 H -1.93922800 0.66994900 2.38957700 H -0.75446000 1.76886700 3.16122500 H -1.78838600 0.71519200 4.17341400 C 0.74011700 -0.17901500 4.21084400 H 0.25190200 -0.29808100 5.19993000 H 1.24322000 0.79868200 4.18962800 334 H 1.50409200 -0.96344500 4.10934900 C -0.87182300 -1.57434800 3.09595300 H -1.58001600 -1.60691400 2.25535000 H -1.42934800 -1.76769600 4.03593200 H -0.12466000 -2.37017300 2.96590400 335 Table A.1.71. Atomic coordinates and single point energies for 88. G = –2758.020414 GSP = –2759.987621 N 4.07284600 -1.11203400 0.44533800 C 5.04449000 -0.90915500 1.32677100 C 4.14157200 -0.45904100 -0.71557000 C 6.12929000 -0.06189300 1.08466000 C 5.17920300 0.40864400 -1.06534500 C 6.19668000 0.60450100 -0.13481300 H 4.95733400 -1.44467500 2.27646900 H 6.89960500 0.06990500 1.84432200 H 7.02596100 1.27592700 -0.35968600 H 5.17058400 0.91625700 -2.02902600 C 3.05080100 -0.70712800 -1.64008800 N 2.17830000 -0.92213600 -2.36441900 Na 0.34254500 -1.05743100 -0.31628900 Na -1.64274100 1.14011500 0.13277400 N 0.70787000 1.28744500 -0.00834500 N -2.05435800 -1.15481100 0.01852400 Si 0.92529900 2.45058900 -1.24191500 Si 1.29689000 1.49253300 1.58404700 C -0.16945400 2.03324000 -2.73633400 C 2.67863400 2.64304100 -1.95300700 C 0.47902200 4.21322100 -0.66661200 C 0.24137900 2.68051600 2.63413500 C 3.05964900 2.19242600 1.70709400 C 1.30952800 -0.19530200 2.45312300 Si -2.88811500 -1.39179900 1.49178600 Si -2.58381000 -1.74335900 -1.49946000 C -2.60635200 0.09767100 2.65291400 336 C -2.33083800 -2.90034700 2.49854800 C -4.77485500 -1.56109000 1.33856600 C -3.88073000 -0.62613300 -2.33073500 C -3.36457800 -3.47637500 -1.49439800 C -1.13231300 -1.76375800 -2.72519500 H 0.25645100 1.16634600 -3.26622200 H -0.21576700 2.87154300 -3.44915700 H -1.20792000 1.77232400 -2.46848600 H 2.94783900 1.78708100 -2.59018700 H 3.42514900 2.74273900 -1.14941300 H 2.73073000 3.54979900 -2.57680000 H -0.48473800 4.23624600 -0.13443000 H 0.42410300 4.92156900 -1.50873800 H 1.24037300 4.58966900 0.03637000 H 0.32021500 3.70492400 2.23663500 H 0.57917900 2.70039500 3.68270900 H -0.82616500 2.40672600 2.64121600 H 3.08841800 3.23511200 1.35102200 H 3.76753100 1.61500300 1.09299200 H 3.42195200 2.18510500 2.74762400 H 0.33241500 -0.70339300 2.37776700 H 1.55496000 -0.11652000 3.52364900 H 2.06489100 -0.84231300 1.97982900 H -1.53994200 0.24433100 2.88496300 H -3.12643600 -0.06037200 3.61043500 H -2.99585000 1.04441400 2.23994700 H -1.24932700 -2.87077000 2.70640900 H -2.54855400 -3.83659900 1.96062200 H -2.85711600 -2.94121200 3.46517700 H -5.21053900 -0.73914400 0.75001800 H -5.24849300 -1.55491400 2.33325800 H -5.05285600 -2.50561600 0.84680500 H -4.38766800 -3.44152600 -1.09021900 H -2.79260000 -4.19493200 -0.88871000 H -3.43113100 -3.87376000 -2.51976300 H -4.81018300 -0.59847300 -1.73994000 H -4.13613700 -0.98355000 -3.34086300 H -3.50442500 0.40639300 -2.43100400 H -0.72132100 -0.75060100 -2.86049100 H -1.46986100 -2.10533000 -3.71600300 H -0.29504900 -2.41732500 -2.43190600 N -3.39232700 2.84927000 0.05701500 C -3.29329900 3.50603100 -1.24134000 H -2.30235900 3.96531700 -1.36400200 H -3.43672600 2.76967000 -2.04489800 H -4.06461100 4.29496000 -1.35638900 337 C -4.67513300 2.16608100 0.17434900 H -4.76186800 1.39714000 -0.60566500 H -4.75545200 1.67421500 1.15371800 H -5.52258900 2.87427400 0.07039200 C -3.23378500 3.81936300 1.13260500 H -3.29076400 3.31539200 2.10814000 H -2.25547600 4.31411500 1.05931100 H -4.02343300 4.59766900 1.09691500 N 1.19218500 -3.42163700 -0.00234500 C 1.69319200 -3.57350100 1.35681800 H 2.61630600 -2.99044900 1.47411500 H 0.94920900 -3.20635900 2.07739100 H 1.90700000 -4.63774000 1.59032100 C 2.19669300 -3.87599300 -0.95242600 H 1.85759600 -3.69330800 -1.98199600 H 3.13249100 -3.32368200 -0.78972400 H 2.40442800 -4.96004300 -0.83315400 C -0.03716500 -4.18747400 -0.16222300 H -0.82290300 -3.77243500 0.48270500 H -0.38579100 -4.13182200 -1.20195000 H 0.11636800 -5.25666500 0.09445900 338 Table A.1.72. Atomic coordinates and single point energies for 69. G = –2757.996898 GSP = –2759.966283 N -1.69362900 -2.44069400 0.07095600 C -1.93914600 -3.39184200 0.96527200 C -0.42502700 -2.28019400 -0.33652500 C -0.94187500 -4.22464100 1.47965400 C 0.64610300 -3.03894500 0.12497900 C 0.36825600 -4.04045100 1.05439900 H -2.97519300 -3.49288400 1.30082100 H -1.19765800 -4.98768700 2.21453900 H 1.17986000 -4.65017300 1.45339000 H 1.65610700 -2.80298200 -0.19872600 C -0.26804800 -1.19532200 -1.29129500 N -0.35675500 -0.30560400 -2.02364600 Na -2.69024300 -0.25778700 -0.52994000 Na 0.80251700 1.23623900 -0.06986000 N -1.50678600 1.22303500 0.87220700 Si -2.25062600 2.63942800 0.26740600 C -3.05102000 3.81694600 1.51395300 C -3.66220300 2.21507400 -0.96734900 C -1.03085600 3.65411000 -0.75162800 Si -1.90592100 0.51454800 2.38171900 C -0.69981700 -0.86282700 2.88240900 C -3.64516700 -0.30034800 2.29358100 H -4.40559200 0.43876500 1.98778800 H -3.95197400 -0.69694900 3.27435800 H -3.69220800 -1.15031700 1.58808500 H 0.03014700 -0.49832900 3.62103900 H -0.12225400 -1.23224000 2.02218800 339 H -1.23105400 -1.71262800 3.34062100 H -0.19354400 3.99534900 -0.12353600 H -1.50469800 4.54298800 -1.19629200 H -0.61101200 3.05405900 -1.57652500 H -4.45094700 1.58782600 -0.51214500 H -3.28538500 1.71078700 -1.87520400 H -4.15721100 3.13597000 -1.31180500 H -3.89637100 3.34516700 2.03884700 H -3.43465200 4.70765700 0.99183400 H -2.32805700 4.15101300 2.27306900 C -1.97453400 1.66760700 3.88221300 H -1.04731500 2.25917900 3.94714200 H -2.05229600 1.06629100 4.80219500 H -2.82266000 2.36543800 3.86038300 N 2.53251400 -0.41268000 -0.06912400 Si 3.06839500 -0.23940300 1.54366200 C 2.84739500 -1.78773600 2.62995300 C 2.13479600 1.19817500 2.38647700 C 4.90622000 0.21602100 1.76049700 Si 3.51729300 -1.17310800 -1.23823800 C 2.55365900 -1.72248400 -2.78668400 C 4.36704500 -2.77557400 -0.62694500 C 4.96376400 -0.13542600 -1.91424100 H 1.03798600 1.09933500 2.35180000 H 2.40955300 2.15790000 1.91501000 H 2.41190300 1.27323300 3.44951200 H 5.56937700 -0.56240400 1.35095700 H 5.15079300 0.33097900 2.82869200 H 5.15564800 1.16287200 1.25638600 H 1.79528000 -2.09815900 2.70947600 H 3.22207600 -1.60854100 3.65065400 H 3.42408400 -2.62631500 2.20592800 H 1.80165000 -2.49914100 -2.56843000 H 3.25973800 -2.15151600 -3.51552500 H 2.02731400 -0.88869800 -3.27527700 H 4.62197800 0.72970000 -2.50228000 H 5.59496100 -0.75520800 -2.57102300 H 5.59732500 0.24410000 -1.09756300 H 3.65894100 -3.54550200 -0.27823000 H 5.05284100 -2.56596300 0.20933700 H 4.96204000 -3.22467900 -1.43812700 N 2.26483700 3.04351700 -1.31609100 C 2.05112600 4.45407700 -1.58991000 H 1.08193600 4.60777000 -2.08142600 H 2.05710000 5.02623700 -0.65090500 H 2.84625900 4.86165500 -2.24895400 340 C 2.16909200 2.27014400 -2.54477100 H 2.31247000 1.20304200 -2.32431900 H 1.17543800 2.40290400 -2.99893600 H 2.93421100 2.57749400 -3.28935200 C 3.56818500 2.85335400 -0.69439900 H 3.62477900 3.43447100 0.23789000 H 3.71197600 1.79008900 -0.46440400 H 4.39019200 3.18945700 -1.36195600 N -4.06406000 -1.28381100 -2.22693300 C -3.20507500 -2.14249300 -3.03350900 H -2.51026800 -1.52918400 -3.62356200 H -2.61671100 -2.80085800 -2.37887300 H -3.79673800 -2.77465300 -3.72632600 C -4.83596400 -0.39240400 -3.08201000 H -5.45293900 0.28090900 -2.47123800 H -4.15802900 0.22096800 -3.69143100 H -5.50140200 -0.95988800 -3.76379600 C -4.94657000 -2.08249100 -1.38779100 H -4.34678400 -2.73537700 -0.73677000 H -5.56343500 -1.42616400 -0.75554500 H -5.62545800 -2.72097300 -1.98891900 341 Table A.1.73. Atomic coordinates and single point energies for 90. G = –2583.855497 GSP = –2585.62505 N -1.15322800 -1.81221500 1.51366000 C -1.08694500 -1.97568600 2.82958200 C -0.00754300 -1.89914900 0.82054200 C 0.11262600 -2.23211600 3.50116300 C 1.24582400 -2.11741500 1.38656900 C 1.29304400 -2.29299300 2.77030900 H -2.02656700 -1.88788000 3.38190400 H 0.11147600 -2.35657300 4.58393400 H 2.25167900 -2.45376200 3.26461900 H 2.13818400 -2.08100800 0.76268200 C -0.19806700 -1.70658400 -0.60622400 N -0.53305000 -1.50615000 -1.69417600 Na -2.57209400 -0.49899100 -0.12086600 Na 0.79146500 0.94537000 -0.85087100 N -1.35545000 1.49552300 -0.08900000 Si -1.94822700 2.22565700 -1.51413500 C -2.73254400 3.93585400 -1.35076900 C -3.26575800 1.10371700 -2.32768400 C -0.56990400 2.36284900 -2.81970400 Si -1.62420400 1.90419000 1.54814600 C -0.22586000 1.28287300 2.67551900 C -3.23769500 1.06583500 2.17508600 H -4.08784400 1.33135900 1.52161100 H -3.49526100 1.40313400 3.19114900 H -3.16864300 -0.03617400 2.22561700 H 0.50339300 2.08207700 2.87859900 H 0.33128800 0.44889300 2.21856700 H -0.61536300 0.94236400 3.64857700 H 0.27109300 2.98174100 -2.46229300 342 H -0.94691200 2.84215500 -3.73565000 H -0.18082300 1.37619400 -3.12779800 H -4.13264700 0.93733900 -1.66178600 H -2.82844600 0.12790200 -2.60159200 H -3.66061800 1.54519600 -3.25548300 H -3.63111900 3.90334600 -0.71500800 H -3.03344200 4.31447100 -2.34003700 H -2.03251900 4.65867600 -0.90589700 C -1.83307300 3.74085100 1.94337800 H -0.97407900 4.31304900 1.55848000 H -1.87189100 3.88750600 3.03447200 H -2.74787200 4.16925900 1.50953100 N 2.78846100 -0.03039200 -0.51613800 Si 3.50096700 1.09636600 0.54615000 C 3.62077900 0.47508900 2.34090200 C 2.45488300 2.69801800 0.58856800 C 5.24091000 1.69948000 0.08242000 Si 3.69120300 -1.15545400 -1.42550600 C 2.59567700 -2.48530900 -2.22806800 C 4.93552600 -2.14039500 -0.36449300 C 4.68662900 -0.39743200 -2.85068500 H 1.39997000 2.55000200 0.87574700 H 2.47761800 3.18879300 -0.40022000 H 2.87227000 3.41623600 1.31145600 H 5.96481900 0.87126700 0.03134700 H 5.61326500 2.42454500 0.82347100 H 5.23038700 2.19397800 -0.90143100 H 2.62083700 0.28143400 2.76095600 H 4.12460900 1.20389700 2.99542800 H 4.19713400 -0.46467000 2.37500900 H 2.06097400 -3.10110400 -1.48532100 H 3.22288000 -3.16779300 -2.82347500 H 1.84119700 -2.04629200 -2.89853900 H 4.01812400 0.15437800 -3.53041500 H 5.20849400 -1.17015700 -3.43714000 H 5.43952500 0.31169600 -2.47531100 H 4.42682300 -2.70649600 0.43430100 H 5.66419900 -1.47369800 0.12338100 H 5.50007900 -2.86497400 -0.97257100 N -4.04513000 -2.27321800 -0.76926200 C -5.38797900 -1.95465400 -0.30271200 H -5.37981100 -1.78224400 0.78357700 H -5.75088100 -1.04235500 -0.79754400 H -6.10455400 -2.77296000 -0.51757800 C -4.03179600 -2.46750500 -2.21521500 H -4.43849500 -1.57893700 -2.71639000 343 H -2.99933200 -2.61918800 -2.56180100 H -4.63953300 -3.34636100 -2.51066500 C -3.53544900 -3.46210200 -0.09750000 H -2.50769100 -3.66687200 -0.43073900 H -3.51701700 -3.30446300 0.98981300 H -4.15931000 -4.35189800 -0.31709700 344 Table A.1.74. Atomic coordinates and single point energies for 89. G = –2757.996823 GSP = –2759.966332 N -1.74700600 -2.41208400 -0.07447000 C -2.00983500 -3.39103000 0.78481000 C -0.47158300 -2.24256500 -0.45502200 C -1.02469400 -4.24465800 1.28756900 C 0.58876200 -3.02201100 -0.00224500 C 0.29250200 -4.05301700 0.88827200 H -3.05186800 -3.49931800 1.09913000 H -1.29534500 -5.02975000 1.99329800 H 1.09564400 -4.67901300 1.27918200 H 1.60490900 -2.77539400 -0.29779700 C -0.29078200 -1.12526000 -1.36708400 N -0.34463300 -0.20723300 -2.06699300 Na -2.74517200 -0.19887500 -0.51586500 Na 0.87778000 1.20802300 -0.05486200 N -1.45555500 1.21821700 0.86055200 Si -2.11607400 2.67574100 0.25850300 C -2.98206100 3.82206100 1.49114400 C -3.43874600 2.33617000 -1.09347400 C -0.80857800 3.70435900 -0.62927500 Si -1.90293000 0.49793400 2.34891100 C -0.75600300 -0.93104000 2.84305500 C -3.66242400 -0.27349500 2.20912700 H -4.39274600 0.46892300 1.84199100 H -4.02057900 -0.62287500 3.19026400 H -3.69949500 -1.15296000 1.53983100 H -0.00822300 -0.60389100 3.58132400 H -0.19877900 -1.32193500 1.97877600 H -1.32433400 -1.75876400 3.29758000 H 0.01163300 3.97390800 0.05396700 345 H -1.23165700 4.63679400 -1.03423200 H -0.37374600 3.14594600 -1.47505100 H -4.30934200 1.77710700 -0.70650800 H -3.01820100 1.79020100 -1.95840800 H -3.83019500 3.28582700 -1.48931800 H -3.85143400 3.33655800 1.96179200 H -3.34096100 4.72558000 0.97348700 H -2.29863600 4.13810400 2.29343600 C -1.97201000 1.62653400 3.86695800 H -1.03291000 2.19568000 3.95652300 H -2.08071600 1.01464000 4.77667200 H -2.80349600 2.34412900 3.83886900 N 2.56660900 -0.47233100 -0.09009300 Si 3.07844600 -0.37721900 1.53638800 C 2.78528600 -1.95560500 2.56089200 C 2.17055100 1.05368100 2.41755400 C 4.92614800 0.00571300 1.80154400 Si 3.53800400 -1.22247300 -1.27667900 C 2.56871600 -1.67257200 -2.85258500 C 4.31785400 -2.87762300 -0.71554300 C 5.03156500 -0.21600600 -1.89438900 H 1.07222000 0.97995300 2.36522100 H 2.47215900 2.02302100 1.98369500 H 2.43452500 1.08502100 3.48610000 H 5.56767700 -0.78294500 1.37711900 H 5.15515000 0.07554600 2.87704800 H 5.21906900 0.95871400 1.33408000 H 1.72020700 -2.22290300 2.62278200 H 3.15936500 -1.83087000 3.58986000 H 3.32892100 -2.80174700 2.10899900 H 1.78749000 -2.42898100 -2.66894600 H 3.26243400 -2.09715000 -3.59574900 H 2.07604200 -0.80054300 -3.30865400 H 4.73187300 0.68581000 -2.44927400 H 5.64527800 -0.83330800 -2.56981400 H 5.67020500 0.10364400 -1.05628200 H 3.57484900 -3.63103300 -0.40538300 H 4.99819400 -2.72450800 0.13741900 H 4.90749500 -3.31999900 -1.53426100 N 2.44540300 3.03315500 -1.19023900 C 2.28415500 4.46172600 -1.39756600 H 1.32739100 4.67335400 -1.89182900 H 2.29755800 4.98714200 -0.43169500 H 3.10131200 4.87287800 -2.02688800 C 2.33847700 2.32245200 -2.45489700 H 2.44060300 1.24174300 -2.28323300 346 H 1.35671500 2.51263500 -2.91475800 H 3.12391000 2.63568400 -3.17560100 C 3.73271000 2.76768900 -0.56377400 H 3.79758500 3.30117900 0.39605800 H 3.83564400 1.69043400 -0.38366400 H 4.57489300 3.10606600 -1.20471400 N -4.39476600 -1.11531900 -2.01560500 C -3.53412700 -1.57064300 -3.10105100 H -3.03983700 -0.71144300 -3.57731900 H -2.75661600 -2.23980600 -2.70417000 H -4.10524000 -2.12071800 -3.87606200 C -5.42490600 -0.21713900 -2.51874500 H -6.04604700 0.14534700 -1.68748000 H -4.96427900 0.65178500 -3.00750200 H -6.08421200 -0.72609500 -3.25083000 C -4.99984700 -2.24910600 -1.33068500 H -4.21197500 -2.91473900 -0.95233300 H -5.60392700 -1.89703700 -0.48183000 H -5.65623700 -2.83454200 -2.00622900 347 Table A.1.75. Atomic coordinates and single point energies for TS-19. G = –2757.98648 GSP = –2759.952416 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32929733 C 1.18252269 0.00000000 -0.63741814 C 1.16906681 -0.03344815 2.09060250 C 2.40213244 -0.02882108 0.03142272 C 2.38879725 -0.05851204 1.42394230 H -0.97801115 0.03705763 1.81861536 H 1.11318774 -0.03193513 3.17889018 H 3.32872029 -0.07782890 1.97736582 H 3.32410497 0.00692026 -0.53977109 C 1.03503957 0.03082790 -2.10327807 N 0.32334925 -0.18825670 -3.00928248 Na -1.66359807 0.42741993 -1.75378902 Na 0.71911092 2.15020445 -3.69207793 N -1.25620753 2.69893666 -2.34727630 Si -2.53636250 2.82613157 -3.47062255 C -3.67210592 4.33498454 -3.34877084 C -3.70992620 1.30981001 -3.37013632 C -1.86698868 2.76651455 -5.23839673 Si -1.28971545 3.41607357 -0.79161302 C 0.37409231 3.28171243 0.12004361 C -2.59070615 2.55428398 0.32308869 H -3.59610957 2.64129816 -0.12224344 H -2.63299080 3.01147102 1.32453973 H -2.38185387 1.47963265 0.47426170 H 0.94364769 4.22088695 0.04261332 H 1.00812364 2.48432124 -0.29176082 H 0.22067410 3.07875104 1.19251221 H -1.16464105 3.59483912 -5.42308664 348 H -2.67102113 2.83111832 -5.98780611 H -1.32975574 1.81920873 -5.41451940 H -4.11369282 1.15858603 -2.35247025 H -3.20504457 0.38156482 -3.69102814 H -4.57486470 1.43757810 -4.03931127 H -4.23653683 4.34203395 -2.40318887 H -4.40089565 4.32465771 -4.17450695 H -3.10156001 5.27404822 -3.40652805 C -1.71740968 5.26114395 -0.71979286 H -1.07244615 5.82513313 -1.41262683 H -1.53400153 5.64513709 0.29659053 H -2.76320060 5.47590429 -0.97960314 N 2.90652385 1.08277401 -2.77008480 Si 3.56424394 2.59758194 -2.26571543 C 4.02083188 2.73049666 -0.42529997 C 2.36746630 4.03343205 -2.64625596 C 5.16483086 3.10392125 -3.16450161 Si 3.96367448 -0.19737834 -3.25249540 C 3.07100690 -1.86726245 -3.35502611 C 5.41601495 -0.50073420 -2.04695678 C 4.81416936 0.01614403 -4.93938375 H 1.35922303 3.91998223 -2.21852264 H 2.27414456 4.19158599 -3.73482733 H 2.77916055 4.96631759 -2.23087675 H 5.97862438 2.37830209 -3.01382716 H 5.50829830 4.07343983 -2.76957097 H 5.01800890 3.22109066 -4.24864624 H 3.15685138 2.63588668 0.24737785 H 4.48338895 3.71271529 -0.23783819 H 4.76034827 1.96002524 -0.15125373 H 2.65586108 -2.17322575 -2.38092875 H 3.78877260 -2.64072930 -3.67056407 H 2.23917212 -1.85065472 -4.07468076 H 4.10002275 -0.00002313 -5.77551112 H 5.51662514 -0.81928570 -5.08882389 H 5.38918868 0.95187740 -5.00205361 H 5.09727663 -0.91844246 -1.07872342 H 5.98775934 0.41766980 -1.84191710 H 6.11279910 -1.22951609 -2.49057893 N 1.41224262 2.14449825 -6.13189015 C 0.76509632 2.73822773 -7.29046993 H -0.27092766 2.38635985 -7.37300485 H 0.75098174 3.83332106 -7.19380835 H 1.30041735 2.47830524 -8.22725308 C 1.35918804 0.69025535 -6.20563050 H 1.81862759 0.25239277 -5.30748426 349 H 0.31305593 0.35358518 -6.25243465 H 1.89117675 0.30437824 -7.10071618 C 2.79347092 2.59687315 -6.04952854 H 2.82590797 3.69484900 -5.99180740 H 3.26512815 2.17503500 -5.15292079 H 3.38160248 2.27938283 -6.93647628 N -2.62878149 -1.78094405 -1.52938873 C -1.49049920 -2.68956458 -1.59087224 H -1.03786775 -2.65399001 -2.59095445 H -0.72782258 -2.38076658 -0.86244048 H -1.79170572 -3.73352185 -1.36731859 C -3.63786242 -2.16317177 -2.50542991 H -4.47799338 -1.45538112 -2.48098730 H -3.20378932 -2.14883868 -3.51505409 H -4.02947986 -3.18250555 -2.30917733 C -3.19303910 -1.74831542 -0.18916470 H -2.41927505 -1.44162375 0.52982025 H -4.02046080 -1.02437267 -0.14428372 H -3.58206289 -2.73920671 0.12377654 350 Table A.1.76. Atomic coordinates and single point energies for TS-20. G = –2583.842873 GSP = –2585.608845 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32986753 C 1.18252246 0.00000000 -0.63328456 C 1.17030135 -0.03184668 2.08876914 C 2.40600991 -0.02657652 0.03082192 C 2.39216369 -0.05666229 1.42276595 H -0.97863113 0.03028478 1.81826049 H 1.11594972 -0.03218426 3.17716769 H 3.33024189 -0.07762588 1.97918326 H 3.32597761 0.00585917 -0.54842307 C 1.03752453 0.00401044 -2.09716826 N 0.33696181 -0.29227894 -2.99267632 Na -1.71095506 0.26251932 -1.82530949 Na 0.66430750 2.11366682 -3.49512863 N -1.41390487 2.52700443 -2.47400347 Si -2.34937853 2.59378066 -3.89683618 C -3.63226385 3.97380680 -4.03895314 C -3.28058605 0.94901034 -4.16715840 C -1.21441840 2.73958207 -5.42671260 Si -1.74527035 3.20692222 -0.94252777 C -0.19371517 3.36070671 0.14540857 C -2.96210713 2.08609643 0.03465785 H -3.86291521 1.87503507 -0.56771385 H -3.29753141 2.57335150 0.96353541 H -2.51431121 1.12181408 0.33537412 H 0.28907358 4.34183602 0.01652008 H 0.55569040 2.58984332 -0.09191743 H -0.45635251 3.26183863 1.21129369 H -0.55250351 3.62035369 -5.36067702 351 H -1.81166658 2.86116499 -6.34290036 H -0.59909557 1.83610300 -5.58898959 H -3.95074779 0.71946435 -3.31932671 H -2.55968831 0.12161152 -4.28299009 H -3.90146179 0.96348324 -5.07619671 H -4.42416549 3.85692916 -3.28277576 H -4.10981229 3.95299553 -5.03098415 H -3.17676394 4.96516621 -3.89663948 C -2.53701677 4.92617109 -0.93692743 H -1.93861853 5.62365144 -1.54416298 H -2.57327995 5.32082940 0.09098666 H -3.56151349 4.92421651 -1.33591031 N 2.73883588 1.25189252 -2.72436772 Si 3.31350540 2.78643064 -2.16721968 C 3.73135308 2.88345967 -0.31981605 C 2.03067903 4.16125887 -2.50600111 C 4.84430898 3.44095185 -3.08097380 Si 3.83116870 0.13972266 -3.48127511 C 3.09990092 -1.59320284 -3.69949538 C 5.40916312 -0.15771293 -2.45273581 C 4.37329158 0.68247485 -5.21298424 H 1.02330052 3.98868537 -2.09590397 H 1.94332774 4.35606280 -3.59063848 H 2.39109984 5.09992507 -2.05740588 H 5.71073755 2.76545453 -3.03620575 H 5.14535028 4.40260258 -2.63563999 H 4.61435501 3.62281303 -4.14188313 H 2.85396834 2.71898178 0.32274163 H 4.13230505 3.88307002 -0.08910396 H 4.50247507 2.14468458 -0.04743233 H 2.80249912 -2.04153510 -2.73792979 H 3.86901910 -2.24234536 -4.14743261 H 2.21641728 -1.59441233 -4.35327427 H 3.48852497 0.85825651 -5.84582188 H 4.98063814 -0.10024133 -5.69411983 H 4.96617846 1.60770152 -5.19604053 H 5.18960979 -0.75375160 -1.55147078 H 5.89432692 0.77409182 -2.12578235 H 6.14577965 -0.72884306 -3.03985675 N -2.61518088 -1.96653532 -1.78009814 C -1.65078307 -2.67015303 -0.94527537 H -0.63992895 -2.54045626 -1.35905658 H -1.66053043 -2.25744741 0.07321432 H -1.87575812 -3.75490365 -0.88942710 C -2.58250028 -2.49842149 -3.13694420 H -3.32965730 -1.98620602 -3.75805428 352 H -1.58789950 -2.33092632 -3.57532064 H -2.80165149 -3.58566589 -3.15135282 C -3.95362599 -2.05535459 -1.21707987 H -3.96777898 -1.62039467 -0.20715843 H -4.66228098 -1.49668041 -1.84504146 H -4.30480680 -3.10536480 -1.14787753 353 Table A.1.77. Atomic coordinates and single point energies for TS-21. G = –2757.98648 GSP = –2759.952416 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32929733 C 1.18252269 0.00000000 -0.63741814 C 1.16906681 -0.03344815 2.09060250 C 2.40213244 -0.02882108 0.03142272 C 2.38879725 -0.05851204 1.42394230 H -0.97801115 0.03705763 1.81861536 H 1.11318774 -0.03193513 3.17889018 H 3.32872029 -0.07782890 1.97736582 H 3.32410497 0.00692026 -0.53977109 C 1.03503957 0.03082790 -2.10327807 N 0.32334925 -0.18825670 -3.00928248 Na -1.66359807 0.42741993 -1.75378902 Na 0.71911092 2.15020445 -3.69207793 N -1.25620753 2.69893666 -2.34727630 Si -2.53636250 2.82613157 -3.47062255 C -3.67210592 4.33498454 -3.34877084 C -3.70992620 1.30981001 -3.37013632 C -1.86698868 2.76651455 -5.23839673 Si -1.28971545 3.41607357 -0.79161302 C 0.37409231 3.28171243 0.12004361 C -2.59070615 2.55428398 0.32308869 H -3.59610957 2.64129816 -0.12224344 H -2.63299080 3.01147102 1.32453973 H -2.38185387 1.47963265 0.47426170 H 0.94364769 4.22088695 0.04261332 H 1.00812364 2.48432124 -0.29176082 H 0.22067410 3.07875104 1.19251221 H -1.16464105 3.59483912 -5.42308664 354 H -2.67102113 2.83111832 -5.98780611 H -1.32975574 1.81920873 -5.41451940 H -4.11369282 1.15858603 -2.35247025 H -3.20504457 0.38156482 -3.69102814 H -4.57486470 1.43757810 -4.03931127 H -4.23653683 4.34203395 -2.40318887 H -4.40089565 4.32465771 -4.17450695 H -3.10156001 5.27404822 -3.40652805 C -1.71740968 5.26114395 -0.71979286 H -1.07244615 5.82513313 -1.41262683 H -1.53400153 5.64513709 0.29659053 H -2.76320060 5.47590429 -0.97960314 N 2.90652385 1.08277401 -2.77008480 Si 3.56424394 2.59758194 -2.26571543 C 4.02083188 2.73049666 -0.42529997 C 2.36746630 4.03343205 -2.64625596 C 5.16483086 3.10392125 -3.16450161 Si 3.96367448 -0.19737834 -3.25249540 C 3.07100690 -1.86726245 -3.35502611 C 5.41601495 -0.50073420 -2.04695678 C 4.81416936 0.01614403 -4.93938375 H 1.35922303 3.91998223 -2.21852264 H 2.27414456 4.19158599 -3.73482733 H 2.77916055 4.96631759 -2.23087675 H 5.97862438 2.37830209 -3.01382716 H 5.50829830 4.07343983 -2.76957097 H 5.01800890 3.22109066 -4.24864624 H 3.15685138 2.63588668 0.24737785 H 4.48338895 3.71271529 -0.23783819 H 4.76034827 1.96002524 -0.15125373 H 2.65586108 -2.17322575 -2.38092875 H 3.78877260 -2.64072930 -3.67056407 H 2.23917212 -1.85065472 -4.07468076 H 4.10002275 -0.00002313 -5.77551112 H 5.51662514 -0.81928570 -5.08882389 H 5.38918868 0.95187740 -5.00205361 H 5.09727663 -0.91844246 -1.07872342 H 5.98775934 0.41766980 -1.84191710 H 6.11279910 -1.22951609 -2.49057893 N 1.41224262 2.14449825 -6.13189015 C 0.76509632 2.73822773 -7.29046993 H -0.27092766 2.38635985 -7.37300485 H 0.75098174 3.83332106 -7.19380835 H 1.30041735 2.47830524 -8.22725308 C 1.35918804 0.69025535 -6.20563050 H 1.81862759 0.25239277 -5.30748426 355 H 0.31305593 0.35358518 -6.25243465 H 1.89117675 0.30437824 -7.10071618 C 2.79347092 2.59687315 -6.04952854 H 2.82590797 3.69484900 -5.99180740 H 3.26512815 2.17503500 -5.15292079 H 3.38160248 2.27938283 -6.93647628 N -2.62878149 -1.78094405 -1.52938873 C -1.49049920 -2.68956458 -1.59087224 H -1.03786775 -2.65399001 -2.59095445 H -0.72782258 -2.38076658 -0.86244048 H -1.79170572 -3.73352185 -1.36731859 C -3.63786242 -2.16317177 -2.50542991 H -4.47799338 -1.45538112 -2.48098730 H -3.20378932 -2.14883868 -3.51505409 H -4.02947986 -3.18250555 -2.30917733 C -3.19303910 -1.74831542 -0.18916470 H -2.41927505 -1.44162375 0.52982025 H -4.02046080 -1.02437267 -0.14428372 H -3.58206289 -2.73920671 0.12377654 356 Table A.1.78. Atomic coordinates and single point energies for 70. G = –2583.883064 GSP = –2585.643535 N 0.84726100 2.95020700 0.39062800 C 1.13431200 4.24843000 0.45749000 C 1.84411700 2.04743300 0.40701200 C 2.43122400 4.74576400 0.56473600 C 3.17909600 2.46785100 0.50468500 C 3.47382900 3.82516600 0.59436600 H 0.28550300 4.93895200 0.42579100 H 2.60824600 5.81939500 0.62242700 H 4.50945200 4.15890800 0.68137800 H 3.97137400 1.72196300 0.50338100 C 1.45468600 0.56095700 0.35058500 N 0.30305900 0.14794200 0.57820800 Na -1.25212200 1.88078700 0.45865000 Na -1.55662600 -1.08187000 0.22165600 N -3.13895200 0.64374700 0.01203400 Si -4.11613100 0.37678300 1.37515400 C -5.97811400 0.26360700 1.06764400 C -3.82698900 1.72218200 2.68346200 C -3.60748500 -1.26334100 2.22050500 Si -3.41298400 0.67022500 -1.66530900 C -3.02027500 -1.03081100 -2.44250100 C -2.19969500 1.89019800 -2.47420500 H -2.37381700 2.91908500 -2.11577700 H -2.29720300 1.90619900 -3.57068300 H -1.15345200 1.61605900 -2.25178300 H -3.60947300 -1.82132600 -1.94710300 H -1.94978200 -1.28837200 -2.34428800 357 H -3.25172300 -1.06418700 -3.51840300 H -3.70058600 -2.11191000 1.51880800 H -4.23669200 -1.49448200 3.09360000 H -2.56574900 -1.22105100 2.58696000 H -4.10331900 2.71195500 2.28588800 H -2.76600400 1.75788900 2.98639700 H -4.41609800 1.55110700 3.59765300 H -6.35784700 1.17886600 0.58868900 H -6.52501500 0.11996700 2.01255700 H -6.21717800 -0.58386600 0.40599400 C -5.15369100 1.14203700 -2.23172700 H -5.89913900 0.40019600 -1.90838300 H -5.20071900 1.21479900 -3.32955300 H -5.44814100 2.11685800 -1.81281500 N 2.61636500 -0.28032700 0.00286500 Si 3.04121700 -0.37603200 -1.69965900 C 4.46478000 0.77178600 -2.17483900 C 1.52546800 0.12139600 -2.69434100 C 3.57163600 -2.13030600 -2.14472500 Si 3.44877500 -1.11780400 1.30218600 C 2.87327900 -0.38656400 2.93401900 C 5.31387900 -0.86969100 1.11211100 C 3.16003000 -2.98161000 1.33869000 H 1.27121500 1.17521200 -2.50013200 H 0.65435000 -0.48732500 -2.40855800 H 1.70204300 0.00665800 -3.77434900 H 4.47165100 -2.44082800 -1.59214700 H 3.81017500 -2.18185600 -3.21827400 H 2.77571200 -2.86024900 -1.93616900 H 4.17395800 1.82891900 -2.08382700 H 4.76439100 0.59249000 -3.21943400 H 5.34719100 0.60386500 -1.53823900 H 3.06394100 0.69673100 2.97572000 H 3.39658600 -0.86203700 3.77719100 H 1.79112100 -0.53941400 3.05824300 H 2.11403600 -3.22265000 1.57147600 H 3.79216100 -3.43504500 2.11861700 H 3.41426300 -3.45616000 0.37972100 H 5.59198100 0.19497300 1.14720600 H 5.68498700 -1.28273000 0.16109600 H 5.85099100 -1.38242500 1.92502900 N -0.95005200 -3.35556900 0.02105100 C -1.81564200 -4.39443500 -0.50929100 H -2.74357800 -4.44672700 0.07825500 H -2.07846200 -4.16412700 -1.55128200 H -1.32976600 -5.39145900 -0.48258100 358 C -0.62935500 -3.59049900 1.42104700 H -0.04445400 -2.74269200 1.81228100 H -1.55448400 -3.67887400 2.00882600 H -0.03455200 -4.51679900 1.56150000 C 0.26532600 -3.21248000 -0.77128500 H 0.00162000 -3.02853900 -1.82404400 H 0.85417900 -2.35585600 -0.40134100 H 0.89378000 -4.12697900 -0.72621200 359 Table A.1.79. Atomic coordinates and single point energies for 87. G = –2758.027861 GSP = –2759.987108 N 0.21646300 -2.51114400 0.01800700 C 0.08663400 -3.80140800 0.31629400 C 1.39851800 -1.90270600 0.22616400 C 1.11873000 -4.58595600 0.82851100 C 2.49201700 -2.62451600 0.72786500 C 2.35161600 -3.97584500 1.03135400 H -0.90022300 -4.24576600 0.14797800 H 0.95010400 -5.63759900 1.05875200 H 3.19633900 -4.54220100 1.42768700 H 3.43732000 -2.11030100 0.88624800 C 1.46671900 -0.39478500 -0.05913800 N 0.49334400 0.27571700 -0.44477000 Na -1.49518000 -0.90997600 -0.73713400 Na -0.90455900 1.75494900 0.57163800 N -2.75942800 0.38162800 0.87626900 Si -4.05754100 1.14605700 0.07987600 C -5.77792900 0.96001300 0.84737100 C -4.19295600 0.51456900 -1.71139800 C -3.72360100 3.01280900 -0.06489600 Si -2.87047100 -0.84023600 2.06503900 C -1.19862200 -1.11256100 2.91514800 C -3.36853000 -2.51338900 1.28326100 H -4.36847100 -2.43191500 0.82576200 H -3.40304500 -3.32640800 2.02577100 H -2.66925100 -2.83170700 0.49011400 H -0.98698300 -0.28831200 3.61520100 H -0.37911200 -1.16359700 2.18132300 360 H -1.19385100 -2.04955400 3.49432700 H -3.61644800 3.46837100 0.93312000 H -4.52920600 3.54297700 -0.59590600 H -2.79180100 3.20030900 -0.62371600 H -4.35236500 -0.57784100 -1.71661500 H -3.25810700 0.71980800 -2.26056600 H -5.01654600 0.97809300 -2.27680400 H -6.08032500 -0.09768600 0.90517600 H -6.52696500 1.49111500 0.23912600 H -5.80896400 1.37456000 1.86628000 C -4.11250200 -0.54456600 3.46549600 H -3.96378400 0.45262300 3.90895700 H -3.97342900 -1.29331300 4.26157100 H -5.15450300 -0.60843800 3.12056900 N 2.81218300 0.15716500 0.23638200 Si 3.07134900 0.89209300 1.80715800 C 3.75170100 -0.35092500 3.05364300 C 1.45269500 1.56417700 2.50526500 C 4.28384300 2.33295600 1.68748300 Si 3.99310200 0.13792800 -1.06280900 C 3.41322500 -1.05019300 -2.40103100 C 5.66595400 -0.45546000 -0.41546100 C 4.20969200 1.82402700 -1.87799800 H 0.67650400 0.78627900 2.52002100 H 1.10804600 2.42671800 1.91576300 H 1.60638200 1.90612300 3.54035100 H 5.25918500 2.04554300 1.26892100 H 4.46291600 2.73679700 2.69610500 H 3.87436000 3.14388800 1.06698400 H 3.02648500 -1.15874700 3.23707600 H 3.96572600 0.13760300 4.01690600 H 4.68626000 -0.80672600 2.69012600 H 3.27752100 -2.07455700 -2.02327600 H 4.15149100 -1.07878600 -3.21709100 H 2.45512300 -0.70681200 -2.81708900 H 3.26180100 2.13995300 -2.34038300 H 4.97349100 1.77063800 -2.66963700 H 4.51558300 2.60055000 -1.16212500 H 5.59489800 -1.49171200 -0.04970100 H 6.05062400 0.16488800 0.40731300 H 6.41506000 -0.43772800 -1.22222700 N -0.03685100 3.67852000 -0.73522300 C -0.56724400 5.03029300 -0.64716600 H -1.64569000 5.03154900 -0.85720100 H -0.41297400 5.42946700 0.36542600 H -0.07046400 5.71182200 -1.36822100 361 C -0.26971400 3.11275300 -2.05961300 H 0.13721300 2.09128100 -2.08385700 H -1.34912600 3.07656200 -2.27322700 H 0.21636300 3.72137800 -2.85036400 C 1.39295300 3.66911100 -0.44978900 H 1.58131700 4.13203200 0.53043100 H 1.75606600 2.62878200 -0.43887800 H 1.96198700 4.24344600 -1.21105100 N -1.55096300 -1.75946500 -3.05204100 C -0.12551200 -1.62850400 -3.31984100 H 0.14051300 -0.56391000 -3.38863900 H 0.45340300 -2.06450400 -2.49424500 H 0.16411900 -2.13163000 -4.26608400 C -2.32693800 -1.16199700 -4.12570400 H -3.40017000 -1.22362400 -3.90143900 H -2.06074900 -0.10123000 -4.23529700 H -2.13718000 -1.66946400 -5.09457800 C -1.91940400 -3.15401800 -2.86887600 H -1.32358100 -3.59044100 -2.05482000 H -2.98483700 -3.23079700 -2.60611700 H -1.74236700 -3.75456900 -3.78550700 362 Table A.1.80. Atomic coordinates and single point energies for 93. G = –2409.727928 GSP = –2411.290157 N -0.57665800 2.63075200 0.56115200 C -0.81574300 3.94173600 0.54555600 C -1.60575900 1.78281400 0.71466100 C -2.08403600 4.49358900 0.71189600 C -2.91311000 2.25224300 0.90060200 C -3.15275100 3.62196800 0.90970400 H 0.04977500 4.59409400 0.39367200 H -2.22066400 5.57452500 0.69349600 H -4.16251600 4.00673100 1.06456000 H -3.71499300 1.52706300 1.03606000 C -1.28456000 0.29118700 0.73347100 N -0.21905100 -0.15894000 1.20707000 Na 1.44959800 1.36735700 0.80189200 Na 1.28474600 -1.71323800 0.69970600 N 2.89591100 -0.27531900 -0.08599100 Si 2.57454300 -0.15540200 -1.75200600 C 3.97012300 -0.67113800 -2.91732200 C 2.06354300 1.61134500 -2.24729800 C 1.06741300 -1.25620500 -2.14871100 Si 4.28586200 -0.20330200 0.88695000 C 4.34063500 -1.70310000 2.05448000 C 4.19958800 1.32345500 2.03147500 H 4.12600700 2.25435300 1.44234800 H 5.09102100 1.41765300 2.67051500 H 3.33228600 1.26731600 2.71366300 H 4.38968900 -2.64063800 1.47651800 H 3.43940900 -1.73613400 2.69231200 H 5.20830000 -1.68430700 2.73171200 H 1.30256900 -2.32838300 -2.01920700 363 H 0.72213300 -1.13018900 -3.18685200 H 0.21578400 -0.99773600 -1.49232200 H 2.88235100 2.31741500 -2.02972300 H 1.16305000 1.95842900 -1.70960700 H 1.83612700 1.68774300 -3.32220100 H 4.84041300 -0.00515100 -2.81732800 H 3.63813600 -0.64040600 -3.96683800 H 4.30597600 -1.69604200 -2.69530600 C 5.94230200 -0.11488900 -0.01869100 H 6.07761300 -0.98286100 -0.68186400 H 6.78267700 -0.09345000 0.69245600 H 6.00180900 0.79261800 -0.64004600 N -2.38723400 -0.52127900 0.23955900 Si -2.58015700 -2.01392300 1.16049100 C -2.50138200 -1.65806100 3.00146600 C -1.29479300 -3.34491400 0.71185600 C -4.29874900 -2.71332100 0.81010000 Si -2.99171600 -0.31849300 -1.41042700 C -2.05051800 1.06352100 -2.27870000 C -4.83286000 0.08136400 -1.44203600 C -2.70308000 -1.89697000 -2.40714800 H -0.50638000 -3.38310400 1.48156800 H -0.84686900 -3.13301400 -0.27247800 H -1.74165300 -4.34944700 0.66114000 H -5.07128200 -1.99963100 1.13491000 H -4.43511500 -3.63925300 1.39052500 H -4.48267700 -2.95508400 -0.24625200 H -1.51505300 -1.26756600 3.28464900 H -2.70355100 -2.57468700 3.57706700 H -3.26043000 -0.91003500 3.27740500 H -2.34920400 2.06399200 -1.93376100 H -2.25213500 1.00282800 -3.35978400 H -0.96364400 0.96198000 -2.13462400 H -1.62501600 -2.06838400 -2.54621800 H -3.15860200 -1.79502800 -3.40464900 H -3.13109100 -2.79371200 -1.93656700 H -5.03820100 1.04422800 -0.95089300 H -5.42624900 -0.69483100 -0.93777300 H -5.18539700 0.15425600 -2.48267500 364 Table A.1.81. Atomic coordinates and single point energies for 92. G = –2583.879458 GSP = –2585.640023 N 0.56352000 1.89641300 -1.46259700 C 0.69674700 2.90874100 -2.31794500 C 1.60951800 1.54410200 -0.70321300 C 1.86396500 3.66035100 -2.44167000 C 2.82182600 2.24589200 -0.75850700 C 2.94413600 3.32584300 -1.62624100 H -0.17578100 3.14029700 -2.93773100 H 1.91686700 4.48392900 -3.15341100 H 3.87347300 3.89664600 -1.67374000 H 3.64210700 1.92789200 -0.11459300 C 1.40002200 0.39959000 0.28143200 N 0.33057400 0.25265900 0.91296800 Na -1.44591700 1.08639200 -0.35118200 Na -1.02387100 -1.44713300 1.36569100 N -2.61672900 -1.01620700 -0.22998100 Si -4.13596800 -0.79285400 0.49356900 C -5.46807300 -2.07911400 0.10368800 C -4.88653000 0.89885600 0.05310600 C -3.90874100 -0.84248700 2.38883600 Si -2.06020700 -1.84022800 -1.61276000 C -0.45182300 -2.76458000 -1.15855500 C -1.59710400 -0.64752700 -3.01740900 H -2.48409400 -0.07223300 -3.33132000 H -1.21785200 -1.18545900 -3.90057100 H -0.81502400 0.06820900 -2.71212600 H -0.64676400 -3.57589300 -0.43363200 H 0.28745300 -2.06803400 -0.72206700 H 0.02421100 -3.22902600 -2.03652900 H -3.62177300 -1.86125200 2.70520000 365 H -4.82849100 -0.58715800 2.93741400 H -3.12606200 -0.14200900 2.72689600 H -5.16491100 0.90923000 -1.01316100 H -4.16169100 1.71546200 0.20771700 H -5.78752100 1.13549600 0.64043600 H -5.72938300 -2.07830300 -0.96513200 H -6.38604400 -1.87146400 0.67608000 H -5.12805700 -3.09350700 0.36382400 C -3.23765200 -3.11878000 -2.35917300 H -3.56449100 -3.85333200 -1.60755800 H -2.74599200 -3.66416500 -3.18008100 H -4.13799400 -2.63593200 -2.76937900 N 2.59858300 -0.40004800 0.47095800 Si 3.40431500 -1.18367800 -0.89648900 C 5.20844000 -0.65864400 -1.03707900 C 2.52149300 -0.76269500 -2.50696800 C 3.33214100 -3.06027300 -0.69530100 Si 2.75733000 -0.95771000 2.13818500 C 2.44134400 0.45465900 3.33635300 C 4.54258200 -1.50842600 2.41511600 C 1.61394000 -2.42260600 2.54946500 H 2.75373300 0.25120000 -2.86402700 H 1.42831200 -0.84558700 -2.40620900 H 2.84426800 -1.47723200 -3.28057900 H 3.73765900 -3.41163600 0.26434800 H 3.90993700 -3.54408000 -1.49839600 H 2.29141700 -3.40958900 -0.77252600 H 5.29031100 0.42266900 -1.22376400 H 5.69012100 -1.18153600 -1.87798400 H 5.77417300 -0.89313600 -0.12406700 H 3.06725600 1.32147200 3.07267800 H 2.69901500 0.15090800 4.36288200 H 1.38959900 0.76865400 3.30821100 H 0.74726700 -2.07494500 3.13528300 H 2.12342900 -3.18946700 3.15242200 H 1.26747100 -2.90870600 1.62294400 H 5.22794100 -0.65892300 2.27244700 H 4.87232700 -2.32441600 1.75661600 H 4.65385100 -1.85571900 3.45431400 N -1.68430600 3.18367200 0.95854500 C -2.12512900 2.59449100 2.21477200 H -3.14775100 2.20205400 2.11450600 H -1.44854200 1.76782700 2.48006400 H -2.11802800 3.33547500 3.04139600 C -2.57517600 4.25325500 0.54159800 H -2.24384500 4.66034800 -0.42454600 366 H -3.60012800 3.87315800 0.42533500 H -2.59599500 5.08378100 1.27779400 C -0.31961200 3.67487700 1.10226900 H 0.33775700 2.83918100 1.38095200 H 0.03507200 4.09735200 0.15106800 H -0.25709900 4.46365600 1.88091300 367 Table A.1.82. Atomic coordinates and single point energies for TS-9. G = –2873.868031 GSP = –2875.95519 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.33270948 C 1.17607780 0.00000000 -0.64131980 C 1.16348927 0.04308608 2.09976913 C 2.39450394 0.07116460 0.04472064 C 2.38657421 0.09952456 1.43522180 H -0.97925972 -0.03296322 1.82046401 H 1.10315555 0.04376465 3.18789608 H 3.32214614 0.15846778 1.99389113 H 3.32075743 0.10360442 -0.52945824 C 1.16321816 0.01240707 -2.14870233 N 0.25124365 0.62945662 -2.82728482 Na -1.69023709 0.96525526 -1.50333295 Na -1.31283724 -0.80565741 -3.84281815 N 2.20500127 -0.46335236 -2.88335628 N -3.18685888 -0.50620963 -2.55815980 Si 1.40053158 0.60249244 -4.40531150 Si 2.98551507 -2.02792790 -2.76937501 C 2.17442305 2.31777193 -4.19402725 C -0.11509483 0.82435566 -5.62410514 C 2.50370899 -0.26799849 -5.72766033 C 4.84304474 -1.86094461 -3.01196856 C 2.27409912 -3.20640292 -4.06653502 C 2.67127845 -2.87723212 -1.10826576 Si -4.34702682 0.47545247 -3.32705557 368 Si -3.31725424 -1.88178632 -1.56159254 C -4.61270074 -0.02099306 -5.14439023 C -3.70447549 2.26713445 -3.35590313 C -6.05567180 0.51170406 -2.51249213 C -4.73744771 -3.07173642 -1.96687602 C -3.52396405 -1.42383765 0.27042723 C -1.68568997 -2.85692469 -1.68675328 H 1.41041944 3.07850986 -3.97682962 H 2.70898005 2.61762303 -5.10755526 H 2.89986139 2.30654805 -3.36666291 H -0.93466056 1.41566619 -5.18064413 H -0.53555415 -0.12781584 -6.00056406 H 0.22884885 1.35560947 -6.52534894 H 3.52193448 -0.47112918 -5.36061616 H 2.58324265 0.39452543 -6.60511012 H 2.08133706 -1.21891064 -6.08733186 H 5.08303818 -1.39211139 -3.97698266 H 5.33020262 -2.84765968 -2.98226755 H 5.28370598 -1.23892456 -2.21791898 H 2.66365352 -3.00319298 -5.07317961 H 1.17406825 -3.12415222 -4.09732389 H 2.52502035 -4.24709670 -3.80898806 H 3.23049621 -2.43313778 -0.27345933 H 2.98843814 -3.92809006 -1.20015026 H 1.60221693 -2.87668037 -0.84169943 H -3.65039192 -0.07936073 -5.68418695 H -5.25128585 0.69696660 -5.68225715 H -5.09604024 -1.01023089 -5.20425284 H -2.70455646 2.31850176 -3.82118700 H -3.62615926 2.68816738 -2.33875354 H -4.36437320 2.93339562 -3.93241531 H -6.53513795 -0.47847087 -2.55084159 H -6.72442881 1.22814297 -3.01470995 H -5.97565227 0.80629667 -1.45426290 H -4.45812178 -0.85973832 0.42057870 H -2.68630258 -0.78614158 0.59764256 H -3.54752032 -2.30725351 0.92736949 H -5.71069781 -2.58909493 -1.78835027 H -4.68984514 -3.97070058 -1.33221577 H -4.71538564 -3.40017181 -3.01739900 H -1.51681597 -3.25947222 -2.70012734 H -1.65393076 -3.70727440 -0.98825919 H -0.83939496 -2.19374818 -1.43192064 O -1.35737182 -2.55390027 -5.23047935 C -2.66424014 -3.12113628 -5.30772826 C -0.68516610 -2.89576163 -6.43290545 369 C -3.04876722 -3.09161137 -6.80108795 C -1.74218851 -2.68010332 -7.51187979 H -1.77024517 -1.61624395 -7.78780184 H -1.54285267 -3.26192949 -8.42049386 H 0.20175696 -2.25540118 -6.52456047 H -0.35851587 -3.95036577 -6.38631457 H -3.39728242 -4.07883985 -7.13107497 H -3.85379241 -2.37125193 -6.99343670 H -2.63363954 -4.15296096 -4.91819592 H -3.32383292 -2.52150821 -4.66371316 O -1.29322127 3.03951713 -0.72183350 C -0.85172649 3.41068488 0.57206265 H -1.21269091 2.65956326 1.28762999 H -1.29030436 4.38837783 0.83958528 C 0.67982685 3.49833795 0.47245122 H 1.14968346 2.58062888 0.85116190 H 1.06886581 4.33950509 1.06090484 C 0.93685670 3.65891838 -1.04350143 H 1.44235561 2.77277984 -1.44920652 H 1.54452352 4.53963031 -1.28792851 C -0.46956321 3.74834253 -1.64060161 H -0.55547260 3.26443403 -2.62278824 H -0.82153081 4.79307392 -1.71107752 370 Table A.1.83. Atomic coordinates and single point energies for 71. G = –2873.907517 GSP = –2875.996392 N 3.86905100 -0.72617900 -0.31701500 C 5.05788400 -1.30841300 -0.17258800 C 2.82400300 -1.27161800 0.30425800 C 5.26571100 -2.45620200 0.59104600 C 2.92471600 -2.42316000 1.09530600 C 4.16980600 -3.02483400 1.23925800 H 5.89640500 -0.83667000 -0.69416000 H 6.26229700 -2.88973300 0.67317000 H 4.28696700 -3.92314500 1.84789400 H 2.03543700 -2.82623600 1.58402500 C 1.48477100 -0.58892700 0.12973600 N 0.69340200 -0.96348600 -0.86439600 Na -0.11847200 1.37378400 -0.88927300 Na -1.11754200 -0.64578500 0.77683500 N 1.13623100 0.35915900 0.98374300 N -2.36556900 1.04333700 -0.19463300 Si 0.89260600 -2.24721300 -2.03027700 Si 1.94442500 0.94164900 2.41850700 C 0.04617300 -3.80205400 -1.36210400 C 2.66753900 -2.71378200 -2.48477800 C 0.05349600 -1.72412400 -3.62962900 C 1.26358600 0.02104600 3.92125900 C 1.55924700 2.78019100 2.55068800 C 3.82654600 0.75996100 2.50470400 Si -3.11474200 0.61341100 -1.65872000 Si -2.67074100 2.26640700 0.94507000 371 C -3.22033900 -1.28118400 -1.79680100 C -2.10614800 1.23507100 -3.15199600 C -4.87504400 1.25971300 -1.92832200 C -4.46352500 2.85575300 1.10017200 C -1.60580700 3.80824100 0.59482900 C -2.15495200 1.64915800 2.66750500 H 0.54428300 -4.14435400 -0.44066800 H 0.08541400 -4.62562000 -2.09159200 H -1.01347800 -3.60750900 -1.13230700 H 3.21482900 -3.19244900 -1.65870700 H 3.24216700 -1.83033100 -2.80147300 H 2.63793200 -3.42266400 -3.32761100 H -1.00817000 -1.48343500 -3.47929000 H 0.12090200 -2.52885400 -4.37799600 H 0.54704400 -0.83304300 -4.04904600 H 0.16773300 0.08762500 3.98882500 H 1.68475700 0.42457400 4.85507000 H 1.53874300 -1.04432700 3.86384800 H 0.48022200 2.96390200 2.65554800 H 1.90376400 3.30285200 1.64297900 H 2.06926600 3.23177400 3.41520300 H 4.14557200 -0.29224900 2.55611900 H 4.17272200 1.26067400 3.42329100 H 4.33972200 1.22461500 1.65071000 H -2.25351100 -1.74428300 -1.53791800 H -3.49475700 -1.62069100 -2.80814700 H -3.97980300 -1.66564300 -1.09723700 H -1.07792400 0.83690400 -3.16943700 H -2.04318700 2.33610100 -3.12558100 H -2.56633700 0.95009100 -4.11125000 H -5.53549200 0.98801300 -1.09014000 H -5.30323600 0.83754800 -2.85131500 H -4.88929100 2.35653100 -2.02269500 H -1.81982500 4.19752700 -0.41456800 H -0.53232300 3.55514000 0.64361700 H -1.77380400 4.62263600 1.31696900 H -4.82083900 3.33355300 0.17607100 H -4.55859100 3.58608400 1.91924800 H -5.13556800 2.01119300 1.32077200 H -2.78626500 0.80455400 2.98979800 H -2.22520900 2.43194000 3.43895400 H -1.10853100 1.30446400 2.64534800 O -2.49745900 -2.16016600 1.67838700 C -3.85796300 -1.72367600 1.76289300 C -2.47927000 -3.57891600 1.68514100 C -4.72090700 -2.90579400 1.27271700 372 C -3.68926800 -3.96119800 0.84428300 H -3.44188100 -3.85095800 -0.22170500 H -4.02586500 -4.99096400 1.01927200 H -1.51837600 -3.91286600 1.27137200 H -2.57325700 -3.95392600 2.72078600 H -5.34931200 -3.28636000 2.08951600 H -5.38724400 -2.61846600 0.44908400 H -4.09070800 -1.46181100 2.80765800 H -3.94612200 -0.81741800 1.14416400 O 1.44147300 2.62273800 -1.89004400 C 1.77613900 3.98427700 -1.63014000 H 1.06085200 4.37026100 -0.89044500 H 1.66397300 4.57182300 -2.55555800 C 3.23828000 3.98454500 -1.13138900 H 3.34263900 4.46854400 -0.15163000 H 3.88321100 4.52555100 -1.83764500 C 3.60352600 2.49340900 -1.09053800 H 3.36720300 2.04746200 -0.11440000 H 4.65899000 2.28985800 -1.31110700 C 2.65118900 1.90446400 -2.11700100 H 2.45983500 0.83264100 -1.97335700 H 3.00026700 2.07994000 -3.15129400 373 Table A.1.84. Atomic coordinates and single point energies for TS-14. G = –1839.020386 GSP = –1840.520422 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32786671 C 1.16813262 0.00000000 -0.62796067 C 1.16440283 0.01415115 2.09735708 C 2.39738095 -0.02421222 0.04558909 C 2.38943296 -0.00331646 1.43590960 H -0.98217867 -0.00472658 1.81126803 H 1.10499114 0.03386068 3.18559598 H 3.32680805 -0.00150373 1.99433630 H 3.32321280 -0.04765980 -0.52865114 C 1.24340925 -0.01373381 -2.10259237 N 1.88369306 -0.36235611 -3.02558634 Na 0.56871181 0.69361745 -4.63886364 N -0.46092245 1.24228831 -2.63457359 Si -1.97961507 0.45721444 -2.47898422 Si -0.06057424 2.87698646 -2.34598686 C -3.03239858 0.91184800 -0.97172723 C -1.73662913 -1.41928664 -2.52565210 C -3.09629399 0.84300293 -3.98004317 C 0.59539314 3.23923861 -0.60392743 C -1.47444042 4.11989537 -2.59934062 C 1.33756228 3.34958974 -3.55877988 H -3.36867867 1.91114734 -4.00856241 H -4.03141909 0.26127961 -3.94444444 H -2.57921070 0.59643644 -4.92324504 H -2.49981637 0.68105018 -0.03968010 H -3.98259282 0.35448893 -0.98002675 H -3.27757723 1.98548687 -0.97216790 H -1.14723751 -1.75758118 -1.66103671 H -1.19937461 -1.72412583 -3.43945268 374 H -2.70303234 -1.94699899 -2.51505205 H 2.16936474 2.62969891 -3.46145760 H 1.74424889 4.35484121 -3.36927719 H 0.98427856 3.33297724 -4.60572924 H -2.27712240 3.94464634 -1.86630160 H -1.92404862 4.06350274 -3.60159926 H -1.11009539 5.14927715 -2.45290727 H -0.13984729 2.91233281 0.14852477 H 0.76870250 4.31847946 -0.46792322 H 1.54152224 2.71647418 -0.39535424 O -0.53989396 1.55212593 -6.39873612 C -1.32397156 2.74322492 -6.32569951 C -0.79838748 0.84433428 -7.61217622 C -2.41577756 2.56108292 -7.37069320 C -1.66753782 1.77781852 -8.45139436 H -1.03762059 2.45733048 -9.04539743 H -2.32719063 1.23336752 -9.13880550 H 0.16237318 0.58444345 -8.07977182 H -1.33214992 -0.09036814 -7.37119156 H -0.68631301 3.61516460 -6.55874942 H -1.69765992 2.84071106 -5.29801648 H -3.23458381 1.95649700 -6.95186730 H -2.83050062 3.51366103 -7.72369441 H 1.76670382 2.39849972 -6.82984042 C 2.61527500 1.70177609 -6.85843312 O 2.21203577 0.50087503 -6.21813998 H 3.62451684 3.02531809 -5.43285637 C 3.86482847 2.18302937 -6.09423840 H 2.85920075 1.48533224 -7.91436311 H 3.16149460 -0.95213424 -5.13107408 C 3.41202149 -0.17098397 -5.85681884 H 4.04996721 1.06244152 -4.21827289 C 4.29194272 0.93838475 -5.28353050 H 4.64673067 2.51499184 -6.78987882 H 3.86309036 -0.62130665 -6.76033385 H 5.36280980 0.71415631 -5.36938536 375 Table A.1.85. Atomic coordinates and single point energies for TS-13. G = –2071.092467 GSP = –2072.855558 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32633265 C 1.17179927 0.00000000 -0.62971121 C 1.16498182 0.01862830 2.09774975 C 2.39839984 -0.01906159 0.04523597 C 2.38920855 0.00512069 1.43734134 H -0.98173617 -0.00450907 1.81023503 H 1.10454164 0.04163776 3.18583341 H 3.32647906 0.01222012 1.99604565 H 3.32658307 -0.04467444 -0.52568591 C 1.21826663 -0.00913768 -2.10407935 N 1.70544977 -0.46671297 -3.07157991 Na 0.71844224 1.11815914 -4.58222298 N -0.06294518 1.67918300 -2.44929343 Si -1.73427264 1.28784758 -2.45071918 Si 0.66420125 3.10786895 -1.86079516 C -2.72725033 1.89485905 -0.95550608 C -1.98379575 -0.58006432 -2.61920958 C -2.57948507 2.07179634 -3.97283003 C 2.53167203 3.02489829 -2.21460950 C 0.50166069 3.40632710 0.00599324 C 0.00034913 4.66438894 -2.72620049 H -2.55549018 3.17142303 -3.89783218 H -3.63146142 1.76019542 -4.07715846 H -2.04573899 1.78825036 -4.89535601 H -2.30282067 1.49019965 -0.02510349 H -3.77921079 1.57567713 -1.02645356 H -2.71414751 2.99493854 -0.89116248 376 H -1.67463364 -1.08437744 -1.69273736 H -1.35803216 -0.96582404 -3.43871241 H -3.03632195 -0.83145303 -2.82695583 H 0.08949477 4.56463771 -3.82070755 H 0.54001955 5.57375151 -2.41755563 H -1.06698006 4.81136328 -2.49491869 H 1.02340462 2.62256840 0.57890415 H -0.55285597 3.40574607 0.32115384 H 0.94245076 4.37638204 0.28684141 H 3.02512947 2.31109959 -1.53562411 H 3.02225855 4.00354657 -2.09252523 H 2.70403050 2.66869080 -3.24153048 O 0.03801073 2.22913314 -6.50397197 C -0.53463402 3.51247113 -6.74022585 C 0.48384073 1.64123750 -7.72679730 C -0.88019460 3.51958729 -8.22342398 C 0.28486548 2.71287045 -8.79900335 H 1.17832408 3.35108340 -8.88260726 H 0.08139466 2.28464379 -9.78882055 H 1.52842026 1.31883213 -7.60204877 H -0.12479146 0.74578116 -7.93369598 H 0.20594512 4.29805819 -6.50421349 H -1.39782894 3.63483404 -6.07282201 H -1.83254432 2.99384645 -8.39243659 H -0.96566349 4.53175889 -8.63880592 H 2.62193608 3.74212405 -5.19281721 C 3.03302312 3.02878274 -5.92834414 O 2.76576838 1.70054008 -5.48584978 H 4.91372795 4.16036844 -5.86198275 C 4.55419497 3.13663793 -6.02647180 H 2.52513178 3.19731258 -6.89014412 H 3.77346820 0.47622805 -4.17797870 C 3.97348787 1.03736098 -5.10069780 H 4.93481677 2.60274659 -3.95576933 C 5.00944268 2.14595890 -4.95357898 H 4.89721718 2.80724847 -7.01908430 H 4.25988994 0.32448215 -5.89351997 H 6.03671411 1.78707290 -5.09720505 C 0.15802759 -1.90430976 -5.63448053 O -0.33691636 -0.57534915 -5.66698289 C -1.62848217 -0.62891047 -6.24952727 C -1.57581848 -1.77225530 -7.28774193 C -0.22500192 -2.46236966 -7.00347642 H 1.23344353 -1.86395003 -5.42533718 H -0.33401291 -2.46438958 -4.81802558 H -2.37548570 -0.83211786 -5.46320624 377 H -1.84113834 0.36061940 -6.67746340 H -2.42053481 -2.45974251 -7.14984775 H -1.62687973 -1.39400143 -8.31752720 H -0.29081229 -3.55771128 -7.01033968 H 0.52697260 -2.16279540 -7.74743009 378 Table A.1.86. Atomic coordinates and single point energies for 72. G = –2873.868207 GSP = –2875.965991 N -5.96667100 -0.87692000 -0.43066700 C -6.84524100 -1.14062100 -1.39016800 C -4.72317500 -0.58297000 -0.80616700 C -6.52548700 -1.11897100 -2.75117400 C -4.28812000 -0.52809000 -2.13448100 C -5.22329700 -0.80518800 -3.12789400 H -7.86037200 -1.38306100 -1.06433600 H -7.28935400 -1.34571000 -3.49510800 H -4.93476900 -0.77844700 -4.17926200 H -3.24996100 -0.27999300 -2.36176000 C -3.76652500 -0.29894400 0.24869500 N -2.96814000 -0.05934100 1.04561700 Na -0.56575500 0.53905700 0.82846400 Na 2.04511100 -0.92675500 0.19731800 N 0.11072600 -1.71555500 1.22087300 N 1.49110500 1.36957200 -0.06986300 Si -0.29364400 -3.06392600 0.25974100 Si -0.08561600 -1.65616100 2.91997500 C 0.83526400 -3.09815400 -1.27994500 C -2.07179600 -3.07463000 -0.40389900 C -0.00638600 -4.75532300 1.07394200 C 1.33596400 -2.48301300 3.86435200 C -1.70260500 -2.40428100 3.56702000 C -0.12205300 0.16915300 3.48812600 Si 2.73624700 2.09545400 0.84034700 379 Si 0.95978700 1.63963400 -1.66248400 C 3.66278400 0.74080100 1.82245800 C 2.22821100 3.32355200 2.19881900 C 4.00977400 3.09030700 -0.16671500 C 2.16641700 1.00599000 -2.99070900 C 0.53667000 3.43115300 -2.12017600 C -0.66311200 0.66757900 -1.96878500 H 0.85862500 -2.14377300 -1.83546600 H 0.51917500 -3.87748500 -1.99061000 H 1.86448300 -3.34488500 -0.97313200 H -2.23811000 -2.20685400 -1.06233900 H -2.79934200 -3.02132900 0.42124800 H -2.27600700 -3.98537100 -0.98869500 H 1.04567200 -4.85623000 1.38476500 H -0.23438100 -5.57653400 0.37599300 H -0.63145100 -4.89468600 1.96906500 H 1.37356000 -3.55725300 3.62462600 H 1.22206500 -2.38266000 4.95512700 H 2.30697400 -2.04523800 3.58155700 H -1.77299800 -3.48175700 3.35313600 H -2.56091200 -1.90708700 3.08906600 H -1.79389300 -2.27374200 4.65702900 H 0.70803800 0.75400500 3.05546600 H -0.02682700 0.23564600 4.58238500 H -1.07766700 0.65730100 3.22602300 H 2.96340700 0.22441500 2.50336300 H 4.45110200 1.17971400 2.45280300 H 4.15137400 -0.02210100 1.19465100 H 1.50389200 2.89730500 2.90933200 H 1.80122200 4.24849400 1.78255200 H 3.12583800 3.60565200 2.77240900 H 4.44568700 2.54398600 -1.01581600 H 4.83749900 3.42572800 0.47824600 H 3.52796800 3.99336600 -0.57510300 H 1.36612600 4.11747500 -1.88940400 H -0.34639900 3.75830600 -1.54928900 H 0.30370100 3.52932300 -3.19217200 H 3.09971800 1.59255500 -2.98729700 H 1.73187900 1.07377200 -4.00051200 H 2.42779700 -0.04925100 -2.80000700 H -0.60100900 -0.38156700 -1.63045200 H -0.91067300 0.65723800 -3.04198300 H -1.49667000 1.15733100 -1.43858100 O 3.89968900 -1.50366300 -1.07009600 C 4.20219300 -2.61756000 -1.91833600 C 4.82361800 -0.43727100 -1.30817400 380 C 5.52433800 -2.27493800 -2.59926000 C 5.45572400 -0.74909400 -2.65572000 H 4.79018700 -0.42076200 -3.46843400 H 6.43262500 -0.26664000 -2.78628000 H 4.26505700 0.50701100 -1.28162700 H 5.58431900 -0.42278800 -0.50837800 H 6.37332800 -2.59380100 -1.97633300 H 5.62232200 -2.75080700 -3.58318200 H 4.25024700 -3.53105100 -1.30852100 H 3.38914900 -2.73296700 -2.65285500 O -1.66327900 2.57188600 0.60768200 C -2.94654400 2.98574400 0.15692200 C -0.97882500 3.65372000 1.24482300 C -2.87446600 4.50647000 0.09384300 C -1.97810100 4.80893400 1.29548000 H -3.71885400 2.65025300 0.87054000 H -3.14684200 2.51356400 -0.81763600 H -3.86253600 4.98098400 0.15083300 H -2.38811600 4.82670100 -0.83997700 H -2.56675300 4.76857900 2.22400100 H -1.48754700 5.78911100 1.24359900 H -0.64385100 3.32954200 2.24059100 H -0.08723800 3.89492800 0.64676800 381 Table A.1.87. Atomic coordinates and single point energies for 73. G = –1839.029923 GSP = –1840.535752 N -4.80660200 -1.12204500 -2.01585400 C -6.09664800 -0.99246700 -1.73425600 C -3.93742300 -0.67792200 -1.10814200 C -6.56928800 -0.42129200 -0.54791900 C -4.28965000 -0.09496500 0.11230700 C -5.64853300 0.03397100 0.38990100 H -6.79728700 -1.35952600 -2.48910400 H -7.64200300 -0.33812200 -0.37231400 H -5.97686400 0.48785400 1.32556400 H -3.51751300 0.24960700 0.80017000 C -2.52852400 -0.82440600 -1.43295100 N -1.40173300 -0.92970000 -1.65296900 Na 0.83389900 -0.37584900 -0.87848800 N 0.69793600 1.54072600 0.26838200 Si 1.61043300 2.74863000 -0.49463100 Si -0.55572100 1.75094300 1.37852300 C 0.70014700 4.38931400 -0.80668200 C 2.13362400 2.15836900 -2.23493200 C 3.18050200 3.24082800 0.46110200 C -1.14004200 0.05656000 2.04193100 C -2.10456500 2.59605200 0.64936200 C -0.11079100 2.76334200 2.92333900 H 2.88683300 3.75569300 1.39013100 H 3.82584500 3.92444200 -0.11351600 H 3.77630900 2.36432400 0.75728400 H -0.20162600 4.22809200 -1.41813000 H 1.34550800 5.11074200 -1.33313300 H 0.38412600 4.85495500 0.14111800 382 H 1.23377000 2.07832300 -2.86833200 H 2.63064200 1.17408200 -2.23872100 H 2.81501200 2.87246000 -2.72379700 H 0.75456700 2.31714700 3.43834000 H -0.94530600 2.82472000 3.64025700 H 0.16742500 3.79221200 2.64308200 H -2.40367800 2.12419900 -0.30137700 H -1.87949800 3.65000600 0.42360800 H -2.96632100 2.58315300 1.33834400 H -1.33656100 -0.65176600 1.21883400 H -2.04824000 0.13811300 2.66258300 H -0.35394200 -0.38647800 2.67511600 O 3.01602100 -1.03870000 -1.05164500 C 4.09153800 -0.34894000 -0.41279100 C 3.41892300 -2.34495500 -1.45832500 C 5.34348600 -1.12719600 -0.79813800 C 4.80628800 -2.55756900 -0.85471100 H 4.72573000 -2.97155600 0.16221900 H 5.42519800 -3.23995500 -1.45121600 H 2.66764600 -3.06769600 -1.10525400 H 3.45219300 -2.38240400 -2.55983300 H 3.92971200 -0.35254800 0.67941100 H 4.09122800 0.69449000 -0.75317500 H 5.69567200 -0.81139500 -1.79158700 H 6.16396700 -0.99216800 -0.08217700 H 1.64182300 -1.04551700 1.67398600 C 1.59343100 -2.12602100 1.46411800 O 0.74069700 -2.30305300 0.33500300 H 0.84634800 -2.35975800 3.52371000 C 0.98061900 -2.95478900 2.61118400 H 2.61021300 -2.47522500 1.21365700 H -0.98174000 -3.31485600 -0.08515900 C -0.08547900 -3.43518200 0.53788500 H -1.16035000 -2.73830900 2.27520200 C -0.35631000 -3.44754600 2.03752400 H 1.63223100 -3.80380700 2.86076200 H 0.44470400 -4.35347600 0.22059900 H -0.64341800 -4.43969600 2.40912100 383 Table A.1.88. Atomic coordinates and single point energies for 74. G = –2071.105061 GSP = –2072.873364 N -3.39606000 -2.88597100 0.67304800 C -4.66907800 -2.91531100 0.29593700 C -2.92279000 -1.72590000 1.12730900 C -5.51453500 -1.80419500 0.36479600 C -3.66783700 -0.54927500 1.23082200 C -5.00293000 -0.60160500 0.84156200 H -5.04124000 -3.87139800 -0.08187000 H -6.55187600 -1.88714800 0.04025100 H -5.62818500 0.29051900 0.89865600 H -3.19842100 0.36370000 1.59406900 C -1.53289500 -1.72105900 1.54890400 N -0.43737500 -1.71748600 1.91307100 Na 0.70801200 -0.36865100 0.12052600 N -1.08518400 0.90508000 -0.55404300 Si -1.51197600 0.33651900 -2.09395300 Si -1.58854400 2.35768100 0.14830900 C -3.28322200 -0.34037600 -2.25508300 C -0.39380300 -1.14241300 -2.53400500 C -1.36847300 1.61733600 -3.49811700 C -1.43376100 2.25674000 2.05952400 C -3.39728700 2.84465600 -0.21087300 C -0.59736500 3.89711600 -0.38491200 H -2.11816800 2.41294100 -3.35435000 H -1.55195200 1.16511000 -4.48591900 H -0.38188100 2.10499800 -3.52057900 H -3.41967300 -1.24126900 -1.63549000 H -3.50822700 -0.61418400 -3.29865500 H -4.02491900 0.40824900 -1.93307000 H -0.54883900 -1.95031700 -1.79658000 384 H 0.67588200 -0.87458300 -2.51921600 H -0.62647700 -1.55611900 -3.52750100 H 0.46458400 3.83501800 -0.09676200 H -1.00959100 4.81525500 0.06445100 H -0.63666900 4.00858200 -1.48043600 H -4.10148800 2.05551800 0.09687500 H -3.54743700 3.00930600 -1.29029900 H -3.67625700 3.77363400 0.31187700 H -2.40595700 2.37985800 2.56479300 H -0.76665400 3.03413800 2.46747800 H -1.02588800 1.27224100 2.34476100 O 2.42147800 0.45221600 -1.14155200 C 2.24594200 1.55114300 -2.03589900 C 3.79338500 0.25727000 -0.82792800 C 3.64636300 1.88112800 -2.54503700 C 4.51158100 1.50423100 -1.34106000 H 4.48219400 2.30606100 -0.58736500 H 5.56270000 1.31403400 -1.59383400 H 3.88207300 0.09868300 0.25808800 H 4.16438500 -0.64717000 -1.34332500 H 1.79011500 2.39359900 -1.48854400 H 1.54701400 1.24958800 -2.82788600 H 3.89921800 1.24492600 -3.40676600 H 3.74986200 2.92978100 -2.85111300 H 1.16202800 2.16196700 1.17049500 C 2.07818000 1.83097800 1.68423500 O 2.00128800 0.41500300 1.86610700 H 1.68553700 3.39803900 3.17083200 C 2.21121600 2.43807000 3.08420500 H 2.93646600 2.06909000 1.03690000 H 1.41854600 -0.78400500 3.42030800 C 2.06912000 0.08345200 3.24926300 H 0.53091200 1.40574900 3.99605300 C 1.62788800 1.34392100 3.98117000 H 3.27018100 2.60671200 3.33092600 H 3.10849700 -0.18506800 3.51521900 H 1.99547100 1.38611500 5.01458600 C 2.53322800 -2.85290200 0.95423900 O 1.86514100 -2.31263700 -0.17808600 C 2.31260600 -2.93757800 -1.37793300 C 3.35064000 -3.97980000 -0.94909500 C 3.82699600 -3.43371500 0.39831000 H 2.68027400 -2.04214500 1.68068300 H 1.90872400 -3.63312000 1.42316900 H 1.45487200 -3.37954200 -1.90462100 H 2.74275200 -2.15953400 -2.03035100 385 H 2.87177300 -4.95982400 -0.80721100 H 4.15584800 -4.10027500 -1.68527800 H 4.26943900 -4.19810700 1.05007100 H 4.56766200 -2.63273300 0.25141700 386 Table A.1.89. Atomic coordinates and single point energies for 76. G = –1839.033016 GSP = –1840.537153 N 3.66560700 -0.27306400 -0.16799200 C 4.99551100 -0.19349300 -0.21879600 C 2.94633200 0.82720000 -0.39763300 C 5.68341700 0.98479000 -0.49194900 C 3.54971400 2.05948700 -0.69522700 C 4.93362800 2.13812100 -0.73643600 H 5.54519000 -1.12216000 -0.03112200 H 6.77339200 0.99561500 -0.51545500 H 5.42987900 3.08494500 -0.95899100 H 2.88994600 2.90588600 -0.88444300 C 1.42991400 0.77534000 -0.36310100 N 0.68824800 1.72075900 -0.66741200 Na -1.21461800 0.49401400 -0.47996000 N 0.91317800 -0.58093800 0.14025300 Si 1.15538600 -1.99229800 -0.88257900 Si 0.72182800 -0.57186100 1.88298300 C 2.30519800 -3.31835100 -0.19849200 C 1.72077300 -1.41766400 -2.58198200 C -0.52652300 -2.84411800 -1.14943400 C 2.21783000 0.14931600 2.76129800 C 0.40435900 -2.30521800 2.55781900 C -0.76037400 0.53399100 2.31788700 H -0.92358600 -3.26196300 -0.21092900 H -0.41804600 -3.67955800 -1.85946900 H -1.28180100 -2.15394000 -1.56162000 H 3.19231100 -2.84485000 0.24349700 H 2.63318500 -3.98185100 -1.01419800 387 H 1.80942600 -3.94244800 0.55918800 H 2.76088200 -1.06498700 -2.56190700 H 1.09191800 -0.59116100 -2.94724700 H 1.64896000 -2.24989700 -3.29915600 H -0.60801700 1.52752200 1.86397400 H -0.83962600 0.67043400 3.40725600 H -1.72593500 0.12654500 1.97189300 H 1.33558200 -2.88965300 2.57753900 H -0.33621900 -2.87167500 1.97336800 H 0.03287600 -2.23136700 3.59183800 H 3.11394400 -0.44962300 2.54379100 H 2.05626400 0.16846900 3.85032200 H 2.41202900 1.17839000 2.42239000 O -3.09245000 -0.71369200 -0.16935700 C -3.34813500 -1.76857200 0.75734700 C -4.01314600 -0.76629200 -1.26409100 C -4.19969200 -2.76966500 -0.01049100 C -5.03523800 -1.83564700 -0.88748000 H -5.85405300 -1.39400900 -0.29984000 H -5.47087400 -2.32803200 -1.76588300 H -4.44092000 0.23490900 -1.41327400 H -3.46135800 -1.04518200 -2.17814800 H -3.89077200 -1.36455800 1.63007700 H -2.38472600 -2.17011600 1.10187700 H -3.55404600 -3.40674000 -0.63411900 H -4.79848300 -3.41303400 0.64638100 H -3.80625700 1.58923500 0.72952500 C -3.55662700 2.51845300 0.19731700 O -2.67994700 2.18297200 -0.86563400 H -2.42114600 3.10600500 1.97768700 C -2.80378200 3.55677000 1.05261000 H -4.48607400 2.94915500 -0.21738400 H -1.09210400 3.10551600 -1.78072400 C -1.98879500 3.38133400 -1.21325400 H -0.68368100 3.60663900 0.46114800 C -1.64964200 4.01699400 0.13310300 H -3.46747100 4.38396300 1.33725400 H -2.65679200 4.02025300 -1.81953600 H -1.56238700 5.10919200 0.07022200 388 Table A.1.90. Atomic coordinates and single point energies for 75. G = –2071.103551 GSP = –2072.859828 N -4.00330800 0.29811400 -0.04183200 C -5.30352100 0.43494500 -0.30242700 C -3.17592600 -0.02294400 -1.03956100 C -5.85598000 0.25345600 -1.56657600 C -3.63946200 -0.21630500 -2.35153700 C -4.99400400 -0.08085800 -2.61464900 H -5.94302500 0.70347100 0.54559500 H -6.92838100 0.37229600 -1.72363400 H -5.38197000 -0.23186000 -3.62421600 H -2.89787700 -0.46524300 -3.11029000 C -1.68737100 -0.17414100 -0.78189500 N -0.83581400 -0.34705100 -1.66571100 Na 0.92919700 -0.09289800 -0.19467600 N -1.35979100 -0.13959900 0.71380700 Si -1.53740600 1.38426600 1.57906200 Si -1.52697200 -1.69539800 1.50765600 C -2.84802200 1.36341200 2.93400200 C -1.86755200 2.77785500 0.36184700 C 0.11105400 1.77661700 2.44070400 C -0.85800800 -3.02095500 0.34680800 C -3.29225800 -2.15494400 1.97413200 C -0.46362800 -1.70660700 3.07318800 H 0.31981000 1.05360800 3.24432100 H 0.08356800 2.78095500 2.89326300 H 0.95170100 1.74974200 1.72875200 H -3.82730200 1.13812900 2.49001000 H -2.89581400 2.34452900 3.43203100 H -2.63116600 0.60847100 3.70568500 H -2.88439100 2.72284000 -0.04964000 389 H -1.15029900 2.71015200 -0.46907400 H -1.74142300 3.75187400 0.86028700 H 0.58677400 -1.46925600 2.83679000 H -0.48909700 -2.70495700 3.53706700 H -0.81321600 -0.98241800 3.82454300 H -3.91185600 -2.25769200 1.07143400 H -3.75171600 -1.37942200 2.60352500 H -3.30994400 -3.11070100 2.52157200 H -1.47535100 -3.08692300 -0.56167600 H -0.84258600 -4.00522400 0.84036500 H 0.16292400 -2.76680500 0.02379400 O 2.94366800 0.30035300 0.85980600 C 3.46273600 0.17783200 2.18118000 C 3.99263600 0.55397800 -0.07686500 C 4.86203900 0.77752200 2.11602900 C 5.29202200 0.37407900 0.70507800 H 5.60757300 -0.68067500 0.69413800 H 6.11414500 0.97934000 0.30242600 H 3.87707900 -0.13655400 -0.92441100 H 3.89212800 1.58481900 -0.45582500 H 3.50174000 -0.88926200 2.46362800 H 2.78521800 0.69781700 2.87226300 H 4.80952600 1.87380400 2.20096600 H 5.52483300 0.40198800 2.90594200 H 2.40306000 -3.04815000 0.57901000 C 2.94135700 -2.76516600 -0.34311000 O 2.15863500 -1.82631500 -1.06943200 H 3.24389000 -4.90790400 -0.72386700 C 3.12256500 -3.96516400 -1.27272500 H 3.89399100 -2.29465900 -0.05038600 H 0.63156100 -2.05721200 -2.42232700 C 1.66839900 -2.39815000 -2.29102900 H 0.99692200 -4.32179500 -1.56087200 C 1.84778700 -3.90119900 -2.11707900 H 4.00817800 -3.82304300 -1.91061200 H 2.28030000 -2.02082300 -3.12946000 H 1.93192100 -4.43108900 -3.07457600 C 0.88349200 2.26964500 -2.28193300 O 1.21802100 2.03705100 -0.91929600 C 1.79594100 3.23169400 -0.43036800 C 2.55748400 3.85329200 -1.62472700 C 2.11664700 2.98719100 -2.82398700 H 0.62939500 1.30479100 -2.73770500 H -0.00917500 2.92084800 -2.33562500 H 0.99660000 3.90441600 -0.07167100 H 2.43520000 2.97111900 0.42547200 390 H 2.27429700 4.90561100 -1.75904900 H 3.64603200 3.82480000 -1.47969400 H 1.90441700 3.57642600 -3.72504800 H 2.89115600 2.24807200 -3.07534400 391 Table A.1.91. Atomic coordinates and single point energies for TS-16. G = –1839.002191 GSP = –1840.497489 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.33230061 C 1.17018497 0.00000000 -0.63747287 C 1.16458616 -0.00235375 2.09739953 C 2.39697762 -0.03601633 0.04243296 C 2.39138022 -0.02844869 1.43056176 H -0.98094980 0.00105146 1.81840842 H 1.10807077 -0.00031666 3.18615026 H 3.32764078 -0.05167937 1.99131775 H 3.31072897 -0.08277370 -0.55053826 C 1.17395355 -0.01166309 -2.13747225 N 2.22194303 -0.17059729 -2.84803661 N -0.00913873 0.09882767 -2.88345722 Si 0.91779578 -0.65706347 -4.38167874 C 2.07867864 -2.14847344 -4.68277909 C 1.30128353 0.71596851 -5.67157994 C -0.65078099 -1.51032608 -5.13379661 Si -1.63512804 0.69295379 -2.59895921 C -1.77993685 2.11784775 -1.35838587 C -2.83871372 -0.67323863 -2.14385725 C -2.16718401 1.57153700 -4.19774273 H 2.29878711 1.17197618 -5.56285025 H 0.53170890 1.50890502 -5.69600581 H 1.27921111 0.25311925 -6.66918645 H -0.83787033 -2.43402089 -4.55844667 H -0.45780184 -1.82228164 -6.17368060 392 H -1.58584420 -0.93422037 -5.12230745 H 3.13243274 -1.83564893 -4.70451352 H 1.82667280 -2.68624251 -5.61000151 H 1.97725009 -2.85821231 -3.84542781 H -1.71438707 1.79211339 -0.31331034 H -2.75671247 2.60367346 -1.51578975 H -1.00341441 2.87754693 -1.54659110 H -2.51863629 -1.12675527 -1.19440082 H -2.84461441 -1.45729777 -2.91486780 H -3.86374552 -0.29047309 -2.02519975 H -1.59293143 2.50969742 -4.29869725 H -3.22921196 1.85692603 -4.13099824 H -2.02851560 0.99454814 -5.12006567 Na 1.53189272 2.07821903 -3.45248430 O 3.68003922 2.76116278 -3.67561865 C 4.54485317 2.47086238 -4.76615643 C 5.04128575 1.06085098 -4.47241835 C 5.17770408 1.06352032 -2.93846449 C 4.33223001 2.27406022 -2.49956571 H 5.37655692 3.19936926 -4.78158132 H 3.97216003 2.57400714 -5.69745629 H 5.97682302 0.82269703 -4.99438817 H 4.27247782 0.33146591 -4.76623361 H 6.22259229 1.17796569 -2.61945634 H 4.75833386 0.13821611 -2.52637991 H 4.95633673 3.08259143 -2.07924756 H 3.55442199 2.00521403 -1.77188043 O 1.44603418 3.53162596 -1.73512622 C 1.42878610 3.34419199 -0.31578642 C 1.77163158 4.88944972 -2.05896800 C 1.26441206 4.74452840 0.25458907 C 2.09932739 5.56515247 -0.72902924 H 0.20691255 5.04689613 0.21140467 H 1.60633111 4.82144207 1.29435926 H 0.61217827 2.65408162 -0.06555463 H 2.38277008 2.89030300 0.00530702 H 0.89404608 5.35296787 -2.53909270 H 2.61120424 4.88756904 -2.76945018 H 3.16963890 5.45605177 -0.49823166 H 1.85694296 6.63528980 -0.73191035 393 Table A.1.92. Atomic coordinates and single point energies for 77. G = –1839.051189 GSP = –1840.546333 N -2.63553000 -0.00230700 1.26897000 C -3.43237500 0.46297100 2.22648300 C -1.39994500 -0.39053100 1.58522500 C -3.03693100 0.57908400 3.55864100 C -0.91483300 -0.32325700 2.89808800 C -1.74601800 0.17448500 3.89590000 H -4.44010400 0.76270800 1.91957800 H -3.72635300 0.97188800 4.30643500 H -1.39539200 0.24176700 4.92757000 H 0.10082600 -0.66909500 3.08396700 C -0.50422700 -0.91100200 0.46152300 N 0.74034500 -1.19893800 0.83364700 N -0.95662400 -0.97906400 -0.77294500 Si 1.60932200 -2.49668500 0.08766600 C 2.99288500 -3.03295300 1.25278400 C 2.43121300 -2.06580200 -1.58677600 C 0.49958300 -3.98556200 -0.22987000 Si -2.49898300 -1.07353700 -1.55467100 C -3.37010600 0.57807300 -1.87893200 C -3.69384500 -2.30330600 -0.76783100 C -2.08515500 -1.74451800 -3.27788500 H 3.06297000 -1.16300300 -1.53509300 H 1.67501700 -1.94170200 -2.38149800 H 3.08549700 -2.89195000 -1.90491600 H 0.03566800 -4.32000800 0.71056100 H 1.06474600 -4.82923000 -0.65471100 H -0.30426500 -3.71014700 -0.92789300 H 3.70832000 -2.22523300 1.46617600 394 H 3.55434900 -3.88342700 0.83627100 H 2.55753800 -3.34886700 2.21297100 H -3.78835300 1.00721000 -0.95787300 H -4.18948900 0.42815900 -2.59961200 H -2.66860600 1.30462000 -2.32139000 H -4.08140200 -1.93643200 0.19176200 H -3.18172400 -3.26157200 -0.58913300 H -4.54394600 -2.49586000 -1.44103100 H -1.40197700 -1.05679300 -3.80341400 H -2.98151600 -1.87153800 -3.90469900 H -1.57906700 -2.71947300 -3.20072600 Na 0.94004600 0.21584400 -1.31643500 O 2.79369200 1.31727300 -0.60289800 C 4.20251100 1.19745400 -0.70436400 C 4.62839000 0.44184800 0.55933300 C 3.49976400 0.76242000 1.56669700 C 2.52428100 1.62839100 0.76215300 H 4.65159700 2.20680100 -0.73653200 H 4.43953000 0.68029700 -1.64357400 H 5.61967300 0.76005900 0.90661000 H 4.67499500 -0.63733500 0.35824500 H 3.86476100 1.28479800 2.46018000 H 2.97664000 -0.15110500 1.88135500 H 2.69575200 2.70908000 0.92393100 H 1.47561000 1.38330100 0.97424800 O 0.05517900 2.27110600 -1.07716100 C -0.97199800 2.49841200 -0.10741000 C 0.59298100 3.50891100 -1.54272400 C -1.41454200 3.93330900 -0.34718200 C -0.08393700 4.59618600 -0.70809100 H -2.11266000 3.97441600 -1.19741100 H -1.90568600 4.37832700 0.52736300 H -1.75293800 1.74225500 -0.24658900 H -0.55359300 2.37785300 0.91009800 H 0.35165000 3.61710400 -2.61298300 H 1.68718100 3.48309000 -1.43084700 H 0.49650900 4.79438900 0.20579700 H -0.19148100 5.54092900 -1.25614800 395 Table A.1.93. Atomic coordinates and single point energies for 78. G = –1839.066163 GSP = –1840.561724 N 2.77804700 -0.48782900 1.02826000 C 4.05073100 -0.52070200 1.41947700 C 2.49399400 0.06194000 -0.15371600 C 5.10489600 -0.03271300 0.64851200 C 3.48072500 0.57911000 -1.00258700 C 4.80846800 0.52179900 -0.59643900 H 4.24627800 -0.96683600 2.39954800 H 6.12971500 -0.09448200 1.01490700 H 5.60398500 0.90218500 -1.23988600 H 3.19137000 1.00407400 -1.96450500 C 1.03459700 0.10047000 -0.56072200 N 0.44856400 1.28530500 -0.65540300 N 0.41122500 -1.03827900 -0.79282800 Si 1.00723600 2.86652600 -0.23040200 C 2.00465500 2.91332400 1.37808300 C -0.54333700 3.92523900 -0.00187900 C 2.02121700 3.71084700 -1.58650600 Si 1.05125400 -2.64851300 -0.85640100 C 1.05822100 -3.51247500 0.82679000 C 2.79730700 -2.78147100 -1.57477000 C -0.10742000 -3.61971900 -1.98728800 H -1.18141000 3.55252400 0.81433700 H -1.14125900 3.91977700 -0.92730700 H -0.28581600 4.97072300 0.22696800 H 3.05340900 3.33380700 -1.62601400 H 2.06965400 4.79615300 -1.40585600 H 1.55793400 3.55053100 -2.57211400 H 1.50100100 2.33125000 2.16614100 H 2.12443000 3.94763600 1.73674200 H 3.00932700 2.48300100 1.24231100 396 H 1.55725000 -2.87585100 1.57289300 H 1.60143300 -4.46861000 0.76352600 H 0.03846800 -3.73594600 1.17615400 H 3.56631800 -2.42279900 -0.87346800 H 2.88692300 -2.19793900 -2.50416600 H 3.02097200 -3.83385300 -1.81151500 H -1.14150100 -3.57846900 -1.60888400 H 0.18351400 -4.67900600 -2.05868800 H -0.10547700 -3.19313700 -3.00202200 Na -1.53684900 0.19565800 -0.99663700 O -3.74365600 0.26875400 -1.45831400 C -4.43320200 -0.90597600 -1.02676700 C -5.31198800 -0.45909700 0.13535000 C -5.65144000 0.97376000 -0.27652700 C -4.32579900 1.43536900 -0.87087000 H -3.69292700 -1.67045300 -0.74353400 H -5.03275400 -1.29846400 -1.86477600 H -4.71873500 -0.44829000 1.06122600 H -6.19175500 -1.10006600 0.27431500 H -5.98118000 1.60465400 0.55843500 H -6.43821200 0.97824200 -1.04584700 H -3.65427300 1.81768900 -0.08146400 H -4.43329600 2.20450200 -1.64785500 O -2.21248200 -0.21306900 1.17699600 C -1.47783800 0.62348700 2.07839700 C -2.07096500 -1.58704200 1.55644900 C -0.46994200 -0.30012300 2.74500000 C -1.28726700 -1.58656100 2.86804000 H 0.40208700 -0.45284200 2.08874300 H -0.11771800 0.08627100 3.71053700 H -1.00664100 1.42518500 1.49476400 H -2.17516400 1.06411900 2.81339200 H -1.51331900 -2.10858200 0.76138800 H -3.07222700 -2.03679400 1.65385800 H -1.97428600 -1.52541000 3.72607400 H -0.66906300 -2.48556800 2.98207900 397 Table A.1.94. Atomic coordinates and single point energies for 79. G = –2873.865458 GSP = –2875.963605 N -4.37658900 0.39783700 1.65313700 C -5.40401200 -0.39166600 1.94242600 C -3.15545600 -0.09606600 1.84585600 C -5.25575600 -1.68558000 2.45095600 C -2.88451400 -1.37247200 2.34131800 C -3.97210500 -2.18228300 2.65443500 H -6.39955100 0.02391500 1.76581300 H -6.13601700 -2.28895100 2.67278000 H -3.81517400 -3.19117300 3.03832900 H -1.85509000 -1.71030400 2.45894600 C -2.04764500 0.79966600 1.56339200 N -1.16195700 1.52384900 1.41704200 Na 0.84588100 2.41666600 0.50462100 Na 0.70282800 -0.99170400 -0.09483500 N -1.39705700 -1.07700300 -0.94911500 N 2.27755800 0.60317200 0.61785800 Si -1.99088900 -2.66781500 -1.05280200 Si -1.85904000 0.17417500 -2.00151400 C -3.88941300 -2.78596000 -0.99179300 C -1.33010300 -3.75579200 0.37579600 C -1.50225200 -3.59346000 -2.64686900 C -3.56431400 0.94676600 -1.67030500 C -1.89039200 -0.30428300 -3.84218600 C -0.65679800 1.66652400 -1.89314000 Si 2.43282400 0.36013500 2.29585000 Si 3.38115800 0.88741700 -0.64668500 C 1.21074600 -0.98896300 2.85424100 398 C 1.94376400 1.92656100 3.26767400 C 4.14607900 -0.12177600 2.94590800 C 3.20341100 2.67399400 -1.29672900 C 3.02691300 -0.25110000 -2.12595000 C 5.21602400 0.67483600 -0.22537900 H -4.30003400 -2.15288000 -0.18946000 H -4.24139200 -3.81858000 -0.83542300 H -4.31772900 -2.42831800 -1.94257200 H -1.94384000 -3.65720800 1.28327900 H -0.28848900 -3.51284400 0.64659200 H -1.35818700 -4.81984900 0.08942300 H -2.05053500 -3.19423800 -3.51329400 H -1.72787800 -4.67016700 -2.57599200 H -0.42937100 -3.47923600 -2.86560100 H -4.35715400 0.18341600 -1.72146500 H -3.79278900 1.71828900 -2.42453600 H -3.63014100 1.41458800 -0.67523800 H -2.70377900 -1.01950200 -4.04423300 H -0.94602300 -0.78172800 -4.14835000 H -2.05755000 0.57610900 -4.48319900 H -0.96606900 2.33553400 -1.07394600 H -0.68505400 2.25228800 -2.82602000 H 0.38761000 1.34442900 -1.74093100 H 0.18403900 -0.66766200 2.61109100 H 1.25083600 -1.16332100 3.94030800 H 1.40017100 -1.95356900 2.35380200 H 0.87730400 2.17867100 3.13960400 H 2.54921300 2.78841100 2.93824400 H 2.11089400 1.80462100 4.34906900 H 4.52785400 -1.04590700 2.48662000 H 4.09841800 -0.28385900 4.03442200 H 4.88255700 0.67350300 2.75663300 H 3.67536200 -0.01730100 -2.98444000 H 1.98238000 -0.17141000 -2.47323700 H 3.20095700 -1.30239000 -1.84722500 H 2.21287900 2.84896700 -1.75072900 H 3.94884300 2.90112900 -2.07456300 H 3.34925200 3.40353300 -0.48077500 H 5.53735400 1.40609900 0.53215800 H 5.83368200 0.82758400 -1.12445900 H 5.43768300 -0.32918200 0.16894900 O 2.00512200 -2.86883400 -0.17860400 C 3.29337400 -2.90211700 0.43736100 C 1.90533800 -3.86479500 -1.19977100 C 4.14958100 -3.79222600 -0.45702400 C 3.10953200 -4.77690200 -0.99278100 399 H 2.88271800 -5.54187400 -0.23502500 H 3.41636600 -5.28530300 -1.91553200 H 0.93699000 -4.37448300 -1.10173400 H 1.94058600 -3.37088600 -2.18644500 H 4.57905300 -3.20324800 -1.28214500 H 4.97300000 -4.27051400 0.08848000 H 3.66264300 -1.87002000 0.52450200 H 3.19953600 -3.32619300 1.45216800 O 0.08178500 4.47267900 0.01981400 C -1.22582100 4.85418600 0.46437300 H -1.12749400 5.56603000 1.30091300 H -1.75042300 3.95773400 0.82278000 C -1.88083800 5.50508200 -0.74598400 H -2.68647500 6.19691200 -0.46988200 H -2.29740300 4.73288800 -1.41069500 C -0.68186400 6.18641100 -1.40551600 H -0.43020100 7.11576300 -0.87281200 H -0.83902300 6.42787900 -2.46423400 C 0.41073500 5.14155400 -1.20373400 H 1.42031500 5.56631600 -1.11640900 H 0.40761100 4.40155400 -2.02138600 400 Table A.1.95. Atomic coordinates and single point energies for 80. G = –3105.936285 GSP = –3108.296925 N -1.22528100 4.08789100 -0.99027200 C -1.01253300 5.39899600 -0.97115200 C -0.22127800 3.31125700 -1.40104000 C 0.19369400 5.98076400 -1.37125800 C 1.02629500 3.77710300 -1.81479200 C 1.22678700 5.15463800 -1.80331000 H -1.84012300 6.02085600 -0.61928600 H 0.31500000 7.06343000 -1.33447800 H 2.18552500 5.57268100 -2.11286700 H 1.80023000 3.06956000 -2.10409800 C -0.51626000 1.89025900 -1.39091900 N -0.85795500 0.78809700 -1.37576900 Na -2.06390800 -0.56491200 0.27068700 Na 1.23367100 -0.66633800 -0.34507100 N 2.16070800 1.39771900 0.08633400 N -0.35984900 -2.21479000 0.43020700 Si 3.69659800 1.47031700 -0.62704500 Si 1.65210600 2.05353700 1.56282400 C 4.47199400 3.20975400 -0.71173200 C 3.58949200 0.83261100 -2.42153200 C 5.02514100 0.40898500 0.22283800 C 1.52820200 3.95455500 1.63520000 C 2.74887200 1.58533300 3.04398500 C -0.12295600 1.45370200 1.95797200 Si -0.50240100 -3.25162400 -0.92248600 Si -0.55007200 -2.66391900 2.06872300 C 0.06799300 -2.35506700 -2.50380200 401 C -2.29866600 -3.81801500 -1.21444700 C 0.54277000 -4.83447000 -0.90506100 C -0.69319300 -4.52422800 2.41335800 C -2.14739200 -1.87382200 2.76689100 C 0.81914600 -2.03884500 3.22443600 H 3.80729200 3.95119400 -1.18173200 H 5.41906600 3.19760300 -1.27453000 H 4.69437600 3.57111200 0.30563000 H 2.98957700 1.49253600 -3.06963700 H 3.11319500 -0.16219800 -2.44917900 H 4.58467900 0.73675000 -2.88423300 H 5.19084300 0.74953900 1.25687500 H 5.98961000 0.44678000 -0.30914300 H 4.69424500 -0.63872400 0.26639100 H 2.45690300 4.42664700 1.27639600 H 1.35548200 4.29302200 2.66974800 H 0.69813600 4.33663600 1.01945000 H 3.72351200 2.09369400 2.95728200 H 2.94633400 0.50220200 3.07399400 H 2.30323900 1.88135400 4.00707500 H -0.86329400 1.97092700 1.32373500 H -0.38962600 1.64243700 3.01071300 H -0.21426100 0.36754400 1.78741400 H -0.36300500 -1.34892000 -2.61558800 H -0.19543900 -2.93882100 -3.39984800 H 1.16618800 -2.25409500 -2.49799700 H -2.98540900 -2.95684600 -1.23539400 H -2.62495300 -4.47600900 -0.39264600 H -2.41394900 -4.37647600 -2.15761600 H 1.61055800 -4.57165400 -0.85118800 H 0.38250800 -5.40213800 -1.83582500 H 0.30318200 -5.49601500 -0.06033800 H -3.03670400 -2.13121300 2.16362600 H -2.04614800 -0.77543500 2.80047600 H -2.34424400 -2.20574100 3.79796200 H -1.47292000 -5.00402500 1.80125400 H -0.94021200 -4.69567800 3.47296900 H 0.25900400 -5.03745900 2.20733800 H 1.71803500 -2.67057900 3.16590300 H 0.47220800 -2.06125200 4.26996200 H 1.11696600 -1.00335100 2.99644800 O 2.91320700 -2.22365500 -0.60610000 C 3.15120100 -2.74998000 0.70297500 C 3.88308800 -2.70685100 -1.53100200 C 4.49360700 -3.47372800 0.62108900 C 4.53238000 -3.90493300 -0.84641200 402 H 3.92454300 -4.80946900 -0.99853500 H 5.54600100 -4.10309600 -1.21785500 H 3.37364900 -2.96065000 -2.47260700 H 4.62168600 -1.91178500 -1.73311600 H 5.31796800 -2.77669000 0.83344700 H 4.55939300 -4.31153500 1.32678000 H 3.14996400 -1.91680400 1.42362000 H 2.32376300 -3.43247700 0.95928500 O -3.54493000 0.91200900 1.23396400 C -4.13655400 1.14992200 2.50054800 H -3.81835800 0.35817900 3.18891500 H -5.23782700 1.11148700 2.39883800 C -3.67028700 2.55589000 2.88356300 H -2.70847900 2.49876200 3.40954100 H -4.38865500 3.06332700 3.54003500 C -3.49685500 3.25311800 1.51565700 H -2.49203500 3.68131600 1.40675200 H -4.22228800 4.06272600 1.36127400 C -3.71306800 2.11920600 0.49935100 H -2.99962800 2.13388700 -0.33356200 H -4.73821700 2.14693200 0.08721400 C -3.51808800 -0.76823900 -2.68604700 O -3.71188500 -0.56177400 -1.29241900 C -5.10683600 -0.60920600 -1.05460400 C -5.58959400 -1.77710800 -1.91137000 C -4.65785700 -1.70603400 -3.13925800 H -3.56478300 0.20437800 -3.20512400 H -2.51463300 -1.19025300 -2.82567800 H -5.26573400 -0.72549500 0.02514600 H -5.57311800 0.33975900 -1.38133900 H -5.44004400 -2.72077300 -1.36860300 H -6.65280800 -1.69717900 -2.17137500 H -4.27754200 -2.69953100 -3.40803500 H -5.17300500 -1.29595400 -4.01784400 403 Table A.1.96. Atomic coordinates and single point energies for TS-10. G = –2873.855561 GSP = –2875.950672 N -4.10645700 0.07440600 -0.44870300 C -5.35075700 0.42113600 -0.75493400 C -3.16205400 0.29395100 -1.35860700 C -5.71254400 0.98916900 -1.97959300 C -3.41056200 0.83631500 -2.62344600 C -4.72016800 1.19344200 -2.93319900 H -6.10728200 0.23912700 0.01426900 H -6.75029200 1.26020600 -2.17331700 H -4.95885800 1.62687100 -3.90546900 H -2.59365500 0.96382800 -3.33391900 C -1.80385300 -0.16469500 -1.05185100 N -0.91838300 -0.90041900 -1.25966000 Na 0.59914000 -2.49383000 -0.52711700 Na 0.81140100 0.78187500 -0.21403400 N -1.34703600 1.32494100 0.58172500 N 2.34966200 -0.98567200 -0.53748100 Si -1.70967100 2.96819800 0.24439400 Si -1.55629100 0.58420600 2.11602700 C -3.54763700 3.36051000 -0.03011400 C -0.79618200 3.46702100 -1.34475900 C -1.22160400 4.16822500 1.63718500 C -3.31148600 0.62147200 2.82301600 C -0.45294500 1.34675200 3.46548500 C -1.04065900 -1.24896200 2.00893600 Si 2.66592100 -0.90800000 -2.20746700 Si 3.26391100 -1.39700400 0.83395300 C 1.78281300 0.58559000 -2.98924200 C 1.94534400 -2.42956900 -3.11250500 404 C 4.48722800 -0.81217000 -2.72103300 C 2.73990500 -3.11592800 1.48755100 C 2.92124500 -0.18900400 2.25532600 C 5.14367100 -1.47544800 0.60447900 H -3.94192500 2.95714200 -0.97358200 H -3.69927600 4.45186700 -0.04581800 H -4.15138400 2.94720200 0.79349800 H -1.11645000 2.82296500 -2.18095900 H 0.29682600 3.35613900 -1.24558200 H -1.00542800 4.50935600 -1.63173100 H -1.95494400 4.09820600 2.45727800 H -1.23182400 5.20938200 1.27540000 H -0.23198700 3.95591200 2.06411400 H -3.63717600 1.66243100 2.98151300 H -3.35902400 0.10557100 3.79523000 H -4.01544000 0.14429500 2.12669500 H -0.86408600 2.30786400 3.80912700 H 0.56962100 1.53341900 3.10116700 H -0.38210000 0.68105600 4.34101300 H -1.67921000 -1.79863800 1.30070400 H -1.11416800 -1.72835000 2.99818400 H 0.00972400 -1.33839500 1.67748400 H 0.68942000 0.47928300 -2.89140900 H 2.00587300 0.66229900 -4.06467500 H 2.07999600 1.53892600 -2.52238400 H 0.84179400 -2.44027000 -3.07479200 H 2.32510500 -3.36805300 -2.67254400 H 2.21950200 -2.43723600 -4.17872700 H 4.99853600 0.05064400 -2.26708000 H 4.56775100 -0.71313600 -3.81506800 H 5.03582500 -1.71822100 -2.42299300 H 3.54859100 -0.38947000 3.13765300 H 1.86947600 -0.25536300 2.57770600 H 3.10078500 0.84993700 1.93383000 H 1.68820500 -3.11411700 1.82578200 H 3.34337000 -3.43288700 2.35229500 H 2.85506800 -3.88710700 0.70588500 H 5.42848000 -2.25937000 -0.11369200 H 5.63671100 -1.70054000 1.56331600 H 5.55163200 -0.52222800 0.23272700 O 2.38218400 2.45826300 -0.01614700 C 3.73610400 2.26500200 -0.43129200 C 2.28211500 3.57525600 0.87011900 C 4.57566800 3.06921900 0.55279800 C 3.65039800 4.25190700 0.84037900 H 3.69885500 4.97997000 0.01684300 405 H 3.87950800 4.77628600 1.77664800 H 1.46341200 4.22683300 0.53326100 H 2.03684100 3.20515700 1.88059700 H 4.75095100 2.48527600 1.46938000 H 5.54899500 3.36076900 0.13789400 H 3.94329700 1.18598900 -0.42750100 H 3.86033700 2.64339900 -1.46123100 O -0.82202000 -4.10220900 0.09938800 C -2.18180900 -4.05055200 -0.35292100 H -2.28564200 -4.70264600 -1.23570900 H -2.41907600 -3.01777500 -0.64650300 C -3.01567600 -4.55725900 0.81807400 H -3.96600200 -5.00119000 0.49593900 H -3.23582000 -3.73194400 1.51178000 C -2.05882000 -5.55585000 1.46942600 H -2.04331800 -6.49894500 0.90259800 H -2.30446600 -5.78405700 2.51420500 C -0.72724400 -4.82874600 1.32878700 H 0.14254500 -5.49794600 1.27584600 H -0.57709700 -4.11373600 2.15531300 406 Table A.1.97. Atomic coordinates and single point energies for TS-15. G = –3105.933339 GSP = –3108.290578 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.32668799 C 1.17697033 0.00000000 -0.62081698 C 1.16700878 0.00774975 2.09690498 C 2.40507833 0.04283798 0.04631647 C 2.39180445 0.03947226 1.43908394 H -0.98121961 -0.00795681 1.81051384 H 1.10631594 -0.00555955 3.18496248 H 3.32774108 0.05821978 1.99918757 H 3.33547966 0.07553323 -0.52004191 C 1.17470741 0.05276249 -2.08459687 N 1.37745062 0.56959155 -3.11176075 Na 0.62748597 1.44828543 -5.16614521 Na 1.17177418 -1.62574922 -4.46796167 N 0.35094672 -2.09347218 -2.33649248 N 0.93310317 -0.46782004 -6.48702633 Si 1.33431926 -3.31616022 -1.66135600 Si -1.36045285 -2.08031262 -2.38492585 C 1.21555649 -3.47395119 0.22704374 C 3.15506106 -2.94264620 -2.06581678 C 0.95565754 -5.04809487 -2.34578047 C -2.24307386 -2.48084037 -0.75542632 C -2.06532369 -3.33239104 -3.63141134 C -1.94554821 -0.37095804 -2.97644389 Si 2.55397392 -0.41901434 -7.03199858 Si -0.44162042 -0.34576828 -7.49270583 C 3.72324957 -0.52057610 -5.53166779 407 C 2.99946769 1.19173635 -7.94366330 C 3.08798134 -1.84072633 -8.16753822 C -0.16061764 -0.77037778 -9.32012174 C -1.11636222 1.44685798 -7.45920981 C -1.88554718 -1.42396160 -6.91821004 H 1.47969704 -2.53460670 0.73657212 H 1.88747745 -4.26215904 0.60305700 H 0.18817927 -3.73502067 0.52474486 H 3.47795184 -1.99569659 -1.60573035 H 3.31700807 -2.85142969 -3.15195169 H 3.82390336 -3.73599016 -1.69630741 H -0.02030341 -5.40621002 -1.98090104 H 1.71716430 -5.78554138 -2.04424715 H 0.91299569 -5.01569624 -3.44585028 H -2.07800974 -3.53546138 -0.48134179 H -3.33010156 -2.33024260 -0.85226675 H -1.87496230 -1.84995848 0.06547518 H -1.71553067 -4.35163855 -3.40407998 H -1.75958577 -3.08889152 -4.65999992 H -3.16722799 -3.33884011 -3.61206122 H -1.70191963 0.38941039 -2.21835319 H -3.03093377 -0.35196885 -3.16557764 H -1.43054088 -0.09578521 -3.91457430 H 3.45426877 0.20245617 -4.74452817 H 4.76569022 -0.32683349 -5.82946277 H 3.70242543 -1.52887185 -5.08370444 H 2.81386887 2.06114344 -7.29264149 H 2.38588120 1.31398234 -8.85069428 H 4.05766049 1.20817563 -8.24996948 H 2.94795861 -2.79840352 -7.64378432 H 4.15324512 -1.74904420 -8.43352187 H 2.50611659 -1.86898915 -9.10056835 H -0.32547290 2.16984372 -7.72450677 H -1.51518112 1.72168312 -6.46595260 H -1.94365638 1.58622100 -8.17215602 H 0.65019708 -0.17312121 -9.76568233 H -1.07527699 -0.59032784 -9.90643981 H 0.10597919 -1.83307679 -9.43404577 H -1.62590756 -2.49333728 -6.96339198 H -2.77022737 -1.26816203 -7.55579573 H -2.17515092 -1.19302301 -5.88119740 O 1.95717254 -3.58016874 -5.35999690 C 0.89693501 -4.11691181 -6.15667075 C 3.07780694 -4.46117183 -5.34312710 C 1.28749091 -5.56635251 -6.42928404 C 2.81436903 -5.47849380 -6.44969261 408 H 3.16213589 -5.09004994 -7.41863392 H 3.31183671 -6.43899012 -6.26372020 H 3.99272333 -3.87002582 -5.50127922 H 3.13818363 -4.94743723 -4.35434862 H 0.95411525 -6.21210098 -5.60285787 H 0.85630687 -5.94893927 -7.36301796 H -0.04499234 -4.02194278 -5.59557946 H 0.81754627 -3.52326269 -7.08383338 O -0.66364076 2.94898626 -4.05668096 C -2.07755139 3.01956686 -3.87429459 H -2.50802666 2.07221364 -4.22625466 H -2.48478253 3.84018974 -4.48691327 C -2.31592647 3.25594085 -2.36909181 H -2.99833678 2.51016185 -1.94193233 H -2.75392768 4.24956199 -2.20026803 C -0.90898020 3.17067963 -1.75902313 H -0.68138364 2.14190840 -1.44353725 H -0.77463324 3.83369078 -0.89444218 C -0.02669384 3.55043742 -2.93902267 H 0.99669547 3.15666808 -2.88136352 H 0.01198745 4.64928303 -3.07270858 C 3.37597407 3.14272293 -4.56933148 O 2.11558712 3.12445457 -5.23456241 C 1.83393378 4.38909500 -5.83453825 C 3.09109105 5.23258777 -5.62402532 C 3.67398577 4.62023841 -4.34907388 H 3.28255276 2.55300549 -3.64570864 H 4.13736950 2.66847866 -5.21340331 H 1.59054554 4.23674441 -6.89662226 H 0.95161388 4.82099506 -5.33394788 H 3.78905303 5.08941214 -6.46222124 H 2.87104582 6.30427553 -5.53975009 H 4.74331991 4.82456783 -4.21165458 H 3.13242561 4.98838342 -3.46389177 409 Table A.1.98. Atomic coordinates and single point energies for 82. G = –2873.877325 GSP = –2875.96409 N -3.90440300 -0.85232700 -0.29209600 C -5.23056800 -0.73044000 -0.23271500 C -3.17459800 -0.44175600 0.74646900 C -5.90450700 -0.21757100 0.87256800 C -3.76217400 0.09770900 1.90171100 C -5.14489400 0.19915300 1.96834900 H -5.78927600 -1.06647600 -1.11264800 H -6.99281000 -0.15464500 0.87567700 H -5.63129400 0.59645900 2.86151200 H -3.10775900 0.41600300 2.71383100 C -1.66256800 -0.49681700 0.64622200 N -0.92106400 0.36220100 1.15435600 Na 0.05807200 2.27984700 0.50501800 Na 1.12072800 -0.61134900 0.43712000 N -1.17075700 -1.67380300 -0.14287800 N 2.24254800 1.45924200 0.22467500 Si -1.18226200 -3.18185100 0.76743000 Si -1.18752200 -1.52855300 -1.90201500 C -2.90360600 -3.60320300 1.40324600 C -0.01796800 -2.97760000 2.23687100 C -0.58612000 -4.61490700 -0.30059300 C -2.56225600 -2.44628600 -2.80154900 C 0.44282000 -2.19530500 -2.59768100 C -1.28062100 0.31626400 -2.27913000 Si 2.80925800 1.69178200 1.81374500 Si 2.73975100 2.10775700 -1.26666500 C 2.31956900 0.20602400 2.89692600 410 C 1.96761100 3.18970200 2.65061000 C 4.67489000 1.95211400 2.02317900 C 1.52167300 3.45452900 -1.85981500 C 2.73078900 0.79155900 -2.63416200 C 4.45492300 2.91460000 -1.28727500 H -3.26322600 -2.86117100 2.13155600 H -2.90167200 -4.58945600 1.89287900 H -3.62058000 -3.62622600 0.56845400 H -0.30647400 -2.09394400 2.82749000 H 1.02858500 -2.84178500 1.91590000 H -0.05078000 -3.85590500 2.89950800 H -1.21673400 -4.76583600 -1.18911600 H -0.62903600 -5.53841800 0.29783700 H 0.45113400 -4.47878000 -0.63461300 H -2.61722500 -3.49927000 -2.48630800 H -2.37697200 -2.43175400 -3.88709000 H -3.53133100 -1.97781400 -2.59037300 H 0.45718800 -3.29567000 -2.59365800 H 1.32407000 -1.83525400 -2.04220800 H 0.56028700 -1.86866200 -3.64337100 H -2.20368100 0.73909200 -1.85420900 H -1.27183300 0.49715800 -3.36493400 H -0.42054800 0.84747500 -1.83887500 H 1.22094200 0.10504100 2.92121800 H 2.66022200 0.34317900 3.93470700 H 2.74820400 -0.74411100 2.53573200 H 0.89358400 3.00832900 2.83580100 H 2.06390300 4.09378900 2.02630800 H 2.41357700 3.41489100 3.63186600 H 5.25234200 1.14348000 1.54868900 H 4.93833000 1.97315100 3.09248400 H 5.00372300 2.90135100 1.57518500 H 3.08213700 1.19987500 -3.59471300 H 1.71377100 0.39893100 -2.79240000 H 3.37745400 -0.06257900 -2.37386400 H 0.51642300 3.03753700 -2.04461600 H 1.84921900 3.91644700 -2.80431800 H 1.42626300 4.26188100 -1.11324800 H 4.48867700 3.79187800 -0.62207900 H 4.71417100 3.25214800 -2.30309000 H 5.23521700 2.21347600 -0.95231000 O 2.89291000 -2.04691100 0.17051900 C 4.18319900 -1.42525400 0.19811700 C 3.01712900 -3.42536400 -0.18870500 C 5.05209600 -2.30599500 -0.68504300 C 4.51630300 -3.69327600 -0.33020100 411 H 4.94038900 -4.02628600 0.62862000 H 4.73365100 -4.45954600 -1.08496800 H 2.53879600 -4.04803200 0.58245500 H 2.48855700 -3.58418000 -1.14231400 H 4.86631500 -2.07871100 -1.74607100 H 6.12403800 -2.18333900 -0.48499500 H 4.06450900 -0.38848700 -0.14310300 H 4.56176100 -1.41042500 1.23582700 O -1.71389600 3.50034800 -0.13718100 C -2.81943500 3.24214800 0.73439600 H -3.02236200 4.13948600 1.34537100 H -2.54248400 2.40052900 1.38520700 C -3.97938000 2.93704400 -0.19943300 H -4.95921400 3.07541300 0.27587400 H -3.91197700 1.89458900 -0.54975500 C -3.70570500 3.91804400 -1.34151600 H -4.05962300 4.92340700 -1.06853400 H -4.18284300 3.63437800 -2.28825700 C -2.17776100 3.89353200 -1.43211000 H -1.74252700 4.86926100 -1.69262300 H -1.83056500 3.15019000 -2.16730300 412 Table A.1.99. Atomic coordinates and single point energies for 81. G = –3105.95436 GSP = –3108.304119 N 3.79088400 -1.97902200 0.35196900 C 5.12152600 -2.01549200 0.30745500 C 3.14885600 -1.03693400 -0.34288800 C 5.88868200 -1.13023400 -0.44621700 C 3.83662300 -0.08882900 -1.11599300 C 5.22249800 -0.14410200 -1.17626900 H 5.60643000 -2.79755700 0.90116900 H 6.97559300 -1.21370100 -0.45868300 H 5.78291900 0.57002700 -1.78316600 H 3.24716800 0.66566700 -1.63796400 C 1.63290800 -0.95295000 -0.26387200 N 0.99874900 0.08886100 -0.51086700 Na -0.05903800 2.03711700 -0.04267900 Na -1.12931600 -0.84822600 -0.08086100 N 0.99577900 -2.23707900 0.14889500 N -2.27151800 1.16136300 0.38491200 Si 0.90354700 -3.45395600 -1.12128400 Si 1.01186200 -2.62081800 1.87335300 C 2.55252900 -4.28380400 -1.49546100 C 0.32087300 -2.58519700 -2.69016000 C -0.33465500 -4.78000200 -0.61467500 C 2.07493200 -4.10979800 2.31257900 C -0.75590100 -2.99047500 2.43656100 C 1.59174800 -1.08337400 2.79295600 Si -3.08858800 1.52661300 -1.06659300 Si -2.65184300 1.70364400 1.95526300 413 C -2.37020900 0.43207400 -2.45062700 C -2.86119600 3.32340100 -1.64384200 C -4.96626300 1.22722000 -1.06675900 C -4.42236300 2.34468300 2.18676900 C -1.49778000 3.12749800 2.48467000 C -2.39041600 0.35721100 3.26596600 H 3.27472200 -3.56755600 -1.91479100 H 2.41371500 -5.10005300 -2.22193700 H 2.99240100 -4.70071900 -0.57731000 H 1.07726500 -1.85619800 -3.02009900 H -0.61785700 -2.02838800 -2.54177700 H 0.16419600 -3.30950700 -3.50445000 H 0.02810000 -5.37870600 0.23451500 H -0.50823000 -5.46857000 -1.45636200 H -1.29206300 -4.32166200 -0.32928800 H 1.72102200 -5.02451200 1.81289800 H 2.05096000 -4.29277100 3.39801300 H 3.11096300 -3.92102500 2.00064100 H -1.17992000 -3.85686900 1.90832700 H -1.42436100 -2.13065900 2.27113900 H -0.77411200 -3.20568400 3.51678200 H 2.64479000 -0.86466300 2.56082300 H 1.49162800 -1.22238900 3.88031700 H 0.98628800 -0.21096200 2.49765800 H -1.26846000 0.48888200 -2.46919900 H -2.73924000 0.72810900 -3.44487500 H -2.64808200 -0.62400700 -2.29848200 H -1.79903200 3.55296700 -1.83060400 H -3.23017800 4.02132400 -0.87425200 H -3.41896700 3.52421900 -2.57263600 H -5.22548400 0.26185400 -0.60483700 H -5.36070100 1.23026000 -2.09600600 H -5.49305600 2.01262700 -0.50445800 H -1.54038700 3.95105500 1.75091700 H -0.45365600 2.77621500 2.54934300 H -1.76935100 3.53910000 3.46948600 H -4.62850200 3.20002200 1.52336100 H -4.58736200 2.67565800 3.22419100 H -5.16195500 1.56091300 1.95919700 H -3.05524700 -0.50593100 3.10247400 H -2.59177200 0.74552000 4.27692000 H -1.35159800 -0.01076700 3.25405100 O -2.83063700 -2.38073600 -0.36465400 C -3.88302400 -2.09363500 0.57033400 C -3.36420800 -3.06659600 -1.49168500 C -5.19227800 -2.50537100 -0.11728800 414 C -4.79618400 -2.56563100 -1.59463000 H -4.80754000 -1.55880300 -2.03960600 H -5.43961000 -3.22271500 -2.19360500 H -2.73697600 -2.83835800 -2.36485900 H -3.33531100 -4.15794000 -1.31963800 H -5.51404400 -3.49874200 0.22766300 H -6.00747600 -1.79805100 0.08367600 H -3.70287200 -2.65425100 1.50055900 H -3.83892500 -1.01469100 0.79016400 O 1.62839000 3.10588300 1.08540800 C 1.77372100 4.30221800 1.82809400 H 0.79102500 4.78426700 1.90438700 H 2.46566400 4.97986100 1.29358100 C 2.36371300 3.86740600 3.17889000 H 1.56752900 3.75486500 3.92646400 H 3.07901200 4.60693200 3.56130400 C 3.02150400 2.50301500 2.86249700 H 2.52516700 1.69324800 3.41347400 H 4.08893200 2.47401400 3.11575000 C 2.79050300 2.33289100 1.35658600 H 2.59716000 1.30516200 1.02448700 H 3.63954700 2.73954900 0.77456500 C 0.85311100 2.31963900 -3.05727800 O 0.63497400 3.14321900 -1.90720800 C 1.53903700 4.24016000 -1.89157000 C 2.02627300 4.36906300 -3.32908000 C 2.08720600 2.89953600 -3.74836400 H 0.98696900 1.28091400 -2.71725800 H -0.03948800 2.38005300 -3.70217800 H 1.00629300 5.12734300 -1.51983300 H 2.37305900 4.01908900 -1.20228400 H 1.28391800 4.91022300 -3.93492200 H 2.98811600 4.89187900 -3.40924400 H 2.07104700 2.74875200 -4.83521200 H 3.00274900 2.43393300 -3.35280200 415 Table A.1.100. Atomic coordinates and single point energies for 83. G = –2873.886683 GSP = –2875.973666 N -2.06076800 -2.00567000 0.85804300 C -2.78056800 -3.02676100 1.32178700 C -2.68727100 -0.99865900 0.23221900 C -4.15949400 -3.13587100 1.15213800 C -4.07078300 -1.03429700 0.00056000 C -4.81167200 -2.12042200 0.45352300 H -2.23009500 -3.80522400 1.86052600 H -4.69798900 -3.99528200 1.55092200 H -5.88741400 -2.17127100 0.27466800 H -4.53430100 -0.19951200 -0.52534600 C -1.83128100 0.16524800 -0.26038600 N -0.68255500 0.00486100 -0.72434900 Na 0.29267100 -1.85917600 0.26985900 Na 1.38340500 0.88545700 -0.62037800 N -2.54871900 1.43037000 -0.21358300 N 2.26090100 -0.66392700 0.87853000 Si -2.13819900 2.47563000 -1.57611400 Si -3.19268200 2.04744700 1.31337300 C -2.16754000 1.49074700 -3.17838200 C -0.46746900 3.35361400 -1.38522500 C -3.48844800 3.78935900 -1.72918000 C -5.04857500 2.36236100 1.21436100 C -2.32770900 3.66110600 1.77624100 C -2.85869900 0.82230900 2.70571300 Si 3.56907200 -1.59604100 0.32643000 Si 1.84549100 -0.06384300 2.41550000 416 C 5.29361000 -1.00440900 0.86159200 C 3.54001800 -1.60358000 -1.57549400 C 3.46239700 -3.41804000 0.85917500 C 3.30118100 0.27250600 3.58196600 C 0.66708700 -1.22802300 3.35139600 C 0.89699900 1.57671000 2.20111200 H -1.32359400 0.78941600 -3.22392600 H -2.11697700 2.16896200 -4.04445800 H -3.10173900 0.91225200 -3.25468000 H 0.30402200 2.86236100 -1.99823200 H -0.14224800 3.33819900 -0.33300000 H -0.51743100 4.40620100 -1.70374200 H -4.46351600 3.31489200 -1.91891400 H -3.26143300 4.44269200 -2.58626200 H -3.59098800 4.43184600 -0.84284600 H -5.29939000 3.07242100 0.41331400 H -5.41286300 2.78114900 2.16543600 H -5.59720800 1.42680900 1.02828600 H -2.37564400 4.42340400 0.98528200 H -1.26693200 3.46813100 1.99721800 H -2.78982800 4.08735200 2.68046600 H -3.53325200 -0.04599200 2.67918700 H -3.00475000 1.33574800 3.66914300 H -1.82257900 0.45109700 2.67541800 H 5.46667500 0.05158700 0.60191600 H 6.08042000 -1.60433800 0.37683700 H 5.42104200 -1.09993900 1.95070200 H 3.53217200 -0.57267700 -1.96799200 H 2.63088300 -2.11070300 -1.93958200 H 4.40681500 -2.12330600 -2.01262800 H 3.47589200 -3.49917000 1.95813700 H 4.29733100 -4.01873900 0.46528400 H 2.52671800 -3.87939800 0.49995800 H 1.14714300 -2.20936000 3.50184800 H -0.27537900 -1.39112900 2.80041900 H 0.39630700 -0.83093200 4.34251800 H 3.81412600 -0.66687300 3.84328300 H 2.96089800 0.74146600 4.51852800 H 4.04547100 0.93915400 3.11814400 H 1.54211800 2.36752600 1.77918500 H 0.50544300 1.95529000 3.15855200 H 0.03467700 1.43379100 1.52475400 O 3.18159000 2.11841600 -1.21418700 C 3.95865200 2.45826900 -0.05611200 C 3.99983300 2.14796600 -2.37717700 C 5.40513900 2.60790900 -0.54307200 417 C 5.39659300 1.83376300 -1.86317900 H 5.48865700 0.75239800 -1.67741400 H 6.19001800 2.14140600 -2.55618400 H 3.60965400 1.41215300 -3.09443800 H 3.95900200 3.14880600 -2.84257200 H 5.64361100 3.66566300 -0.72666000 H 6.13016400 2.21845000 0.18339400 H 3.56531200 3.38714200 0.38422800 H 3.84105700 1.63895300 0.67132000 O -0.06069600 -3.25994300 -1.49490300 C -1.01345400 -4.30773700 -1.51571900 H -1.17369000 -4.64765700 -0.48345200 H -0.61421300 -5.15327100 -2.10418700 C -2.26785600 -3.71555800 -2.17951700 H -3.00652900 -3.41272500 -1.42526900 H -2.74758300 -4.44806400 -2.84196100 C -1.72858400 -2.48448100 -2.94269800 H -2.11189000 -1.55560900 -2.50028300 H -1.98679900 -2.49432400 -4.00960400 C -0.21608400 -2.55565100 -2.71983300 H 0.24517200 -1.56682000 -2.60439700 H 0.29178100 -3.11566600 -3.52639000 418 Table A.1.101. Atomic coordinates and single point energies for 84. G = –2873.903188 GSP = –2875.990727 N -0.92460300 -1.57129400 1.25050400 C -0.91006000 -2.60896200 2.09093900 C -1.92120400 -0.67974700 1.33167900 C -1.87918500 -2.81429500 3.06855100 C -2.93292800 -0.80586700 2.29315900 C -2.90975900 -1.88121600 3.17280500 H -0.07233500 -3.30571900 1.98914700 H -1.81640500 -3.67614200 3.73243100 H -3.68350600 -1.98865600 3.93499700 H -3.71233400 -0.04829600 2.34724500 C -1.93582200 0.50509900 0.35920900 N -0.72922400 0.88743700 -0.09176100 Na 0.22382500 -1.18371300 -0.84474000 Na 1.42911100 0.78026000 0.83402500 N -3.06631100 1.04265600 0.04255700 N 2.50763300 -0.93640300 -0.32987600 Si -0.74694800 2.34218700 -1.07714200 Si -4.69434400 1.48934700 0.21309600 C -1.50203300 2.09169000 -2.78620100 C 1.08515400 2.80946000 -1.27262200 C -1.55051600 3.83434900 -0.24393300 C -5.25828800 2.36450100 -1.35900300 C -4.85578000 2.68072600 1.67191800 C -5.95622500 0.09300700 0.48103400 Si 3.17383900 -0.79581500 -1.89622000 Si 3.04965800 -1.95458700 0.92669100 C 4.41058000 0.63727500 -2.05358100 C 1.77105400 -0.49858300 -3.15579200 419 C 4.06539900 -2.34085900 -2.54176400 C 4.93092300 -2.09618500 1.13921700 C 2.41930300 -3.73969100 0.73911600 C 2.41680500 -1.28440300 2.59732000 H -1.02532500 1.26372300 -3.33324300 H -1.39834500 3.00261900 -3.39605400 H -2.57365200 1.87010000 -2.67695900 H 1.71437600 1.97033300 -1.60813900 H 1.49035100 3.17695200 -0.31513400 H 1.20719300 3.62439700 -2.00265400 H -2.63866900 3.83850800 -0.38993700 H -1.13855900 4.77208700 -0.64887800 H -1.35711600 3.81547800 0.84060300 H -4.64166200 3.25163300 -1.56753600 H -6.30968700 2.68344100 -1.28721200 H -5.17000500 1.68619000 -2.22268400 H -4.15735500 3.52304900 1.55985300 H -4.63027900 2.18729700 2.63019900 H -5.87771100 3.08560400 1.73527900 H -6.10532300 -0.49044400 -0.43981700 H -6.92832800 0.53807300 0.74780600 H -5.67912300 -0.61020000 1.28085600 H 3.97478300 1.59001400 -1.71029300 H 4.75296900 0.77398600 -3.09111900 H 5.29781300 0.42855100 -1.43254500 H 1.09722400 0.32495800 -2.86766000 H 1.16176300 -1.41063600 -3.28527900 H 2.17407300 -0.24867700 -4.14917000 H 4.95540400 -2.58631800 -1.94304400 H 4.39441300 -2.19638300 -3.58304600 H 3.39309800 -3.21324400 -2.51969700 H 2.97786800 -4.24381100 -0.06548800 H 1.35559500 -3.75735700 0.44939700 H 2.53792500 -4.33797000 1.65649600 H 5.40480800 -2.54993900 0.25593700 H 5.17658100 -2.72693600 2.00845000 H 5.39578800 -1.11099200 1.29919600 H 2.88018100 -0.31141800 2.83525600 H 2.67629300 -1.96845400 3.42010100 H 1.32166500 -1.15961200 2.61703100 O 2.98317700 2.17559800 1.68608600 C 4.31064100 1.69642900 1.44234500 C 3.04660200 3.57966600 1.88103000 C 5.12427200 2.90632300 0.94042100 C 4.08829300 4.03909100 0.86937800 H 3.63051100 4.08404400 -0.12980500 420 H 4.50833600 5.02560800 1.10304000 H 2.04194500 3.99581700 1.72309900 H 3.36322600 3.80364200 2.91602900 H 5.92437500 3.15424900 1.65109200 H 5.58973200 2.70859700 -0.03347200 H 4.72690300 1.28763300 2.37803600 H 4.23170000 0.88289500 0.70671000 O -1.46506300 -2.30679300 -1.78091500 C -1.84203900 -3.59924000 -1.33889300 H -1.05450200 -3.97716200 -0.67154100 H -1.92168100 -4.27622600 -2.20835200 C -3.20001500 -3.41032000 -0.65491400 H -3.06883000 -3.25295200 0.42493800 H -3.84499000 -4.28799000 -0.79005700 C -3.76616900 -2.13645000 -1.32115200 H -3.96886000 -1.36470900 -0.56985100 H -4.69637800 -2.32562000 -1.87308000 C -2.64380800 -1.66906100 -2.25914700 H -2.48110100 -0.58245400 -2.22977900 H -2.82655800 -1.98266200 -3.30185600 421 Table A.1.102. Atomic coordinates and single point energies for 85. G = –2873.909439 GSP = –2875.996627 N 2.33887300 0.10715100 -1.18564500 C 3.35629400 -0.04284100 -2.03668500 C 2.27124700 1.23105200 -0.46304300 C 4.38171500 0.88851400 -2.17567500 C 3.25542900 2.22459300 -0.53471800 C 4.33406000 2.04118500 -1.39096400 H 3.35579700 -0.95612800 -2.64076400 H 5.19462900 0.71009200 -2.87938800 H 5.12387900 2.79154100 -1.45699000 H 3.15962200 3.11870600 0.08286000 C 1.08238600 1.38225400 0.46795700 N 1.04902400 0.47495400 1.43913200 Na 1.06885000 -1.53103100 0.18823800 Na -1.37061100 0.48372300 0.11293600 N 0.18217200 2.30522000 0.22814900 N -1.14990100 -1.75410100 -0.56358100 Si 0.23614900 0.81412900 2.94615600 Si 0.04481000 3.66656700 -0.84028000 C 0.57591900 2.57203500 3.52991100 C 0.93076000 -0.37218800 4.23587000 C -1.65489500 0.60174500 2.87663000 C 0.75726500 5.20197600 -0.00261500 C -1.80215700 3.94694100 -1.08465400 C 0.83398200 3.51002000 -2.55316900 Si -1.76367500 -3.00369100 0.42387600 Si -1.11622000 -1.67122800 -2.26915000 C -3.54392400 -2.69045400 1.01381800 C -0.68596100 -3.15104500 1.98541900 422 C -1.77035900 -4.73331700 -0.35496200 C -2.57916800 -2.46163700 -3.18445200 C 0.44491300 -2.47698000 -2.99765700 C -1.05148400 0.16085400 -2.77125900 H 1.66029400 2.74360400 3.61165300 H 0.12627700 2.75668700 4.51765800 H 0.16701400 3.29532500 2.81057300 H 1.98896000 -0.13061700 4.42211300 H 0.87682900 -1.42390300 3.91842100 H 0.39323300 -0.27706600 5.19184200 H -2.10868500 1.42240700 2.29716900 H -2.07640400 0.65383100 3.89234800 H -1.97243000 -0.36319000 2.44737600 H 0.29592400 5.34975200 0.98533400 H 0.56443200 6.10116500 -0.60818600 H 1.84542100 5.12536300 0.14360700 H -2.27766200 4.15757600 -0.11416400 H -2.28613000 3.05376800 -1.51050100 H -1.99586700 4.79862900 -1.75429300 H 1.93230600 3.48928000 -2.51960200 H 0.53293500 4.37887500 -3.16039900 H 0.49029500 2.60430800 -3.07447500 H -3.66355300 -1.67122800 1.41879600 H -3.84745500 -3.40547300 1.79431700 H -4.24407800 -2.80105300 0.16929700 H -0.58444800 -2.17778100 2.49058000 H 0.32864100 -3.51846400 1.75006200 H -1.11774800 -3.85546300 2.71289300 H -2.47748900 -4.80032400 -1.19533800 H -2.06081200 -5.49407300 0.38690100 H -0.76980200 -4.99694700 -0.73325300 H 0.48226900 -3.54732400 -2.73847100 H 1.34477500 -1.99017900 -2.58684600 H 0.48984700 -2.39059000 -4.09461500 H -2.55309700 -3.55838800 -3.09881800 H -2.54060500 -2.21214000 -4.25672900 H -3.54982900 -2.11798100 -2.79495700 H -1.96065400 0.70772800 -2.46600000 H -0.94027800 0.29369800 -3.85849100 H -0.18056800 0.64039400 -2.29254000 O -3.49934500 1.09597000 -0.21800300 C -4.34023300 0.16120900 -0.89306100 C -4.33535300 2.00476600 0.47724000 C -5.64995300 0.09592000 -0.07836500 C -5.42460500 1.11118600 1.05639200 H -5.03785100 0.60893300 1.95562900 423 H -6.33287800 1.66215600 1.33172700 H -3.72819200 2.53172100 1.22502600 H -4.74943900 2.74958900 -0.22739800 H -6.50697100 0.38498200 -0.70142700 H -5.84011100 -0.91344000 0.30762600 H -4.52183700 0.51267000 -1.92293700 H -3.79435700 -0.79125900 -0.93513500 O 3.03116700 -2.46800800 0.77056700 C 3.99288700 -2.96618800 -0.15148400 H 3.56692300 -2.87325600 -1.16182400 H 4.17532300 -4.03535100 0.04318200 C 5.27194300 -2.12594900 0.04897200 H 5.62612800 -1.67890300 -0.88937500 H 6.08205100 -2.75309000 0.44639600 C 4.85180400 -1.06321900 1.07544700 H 4.47726600 -0.15848600 0.57410400 H 5.66779700 -0.77062300 1.74864500 C 3.70239400 -1.74923000 1.80087600 H 2.98040000 -1.05062900 2.24402900 H 4.06923900 -2.45335800 2.56990200 424 Table A.1.103. Atomic coordinates and single point energies for TS-18. G = –2873.900477 GSP = –2875.989278 N 0.00000000 0.00000000 0.00000000 C 0.00000000 0.00000000 1.33280190 C 1.17540561 0.00000000 -0.64157754 C 1.16445323 0.05234105 2.09635419 C 2.39811543 0.06232459 0.03731608 C 2.38780291 0.10453053 1.42737442 H -0.98166565 -0.03318043 1.81769750 H 1.10954953 0.05771914 3.18495564 H 3.32346731 0.16254931 1.98638893 H 3.32985407 0.07068343 -0.53010132 C 1.08627382 -0.06977498 -2.15546693 N 0.54865269 1.00995502 -2.74005111 Na -1.51812992 1.15065923 -1.62490025 Na -0.60249600 -0.71745937 -4.01016442 N 1.38773308 -1.17703939 -2.76122167 N -2.72694161 -0.19119376 -3.13121609 Si 1.32976934 2.40643241 -3.35846826 Si 2.04107825 -2.70826662 -2.23612766 C 3.19705257 2.12715614 -3.40102616 C 0.97910419 3.92853642 -2.28822367 C 0.73177237 2.80885147 -5.10292180 C 3.92421501 -2.62010973 -2.30077114 C 1.45706590 -3.96829104 -3.50623045 C 1.52610282 -3.29895255 -0.51580746 Si -3.40035751 0.91809078 -4.22401340 Si -3.34767755 -1.38318214 -2.09288160 C -2.52337590 0.82125100 -5.91267179 C -3.14353379 2.70568355 -3.61217643 425 C -5.25258546 0.72051941 -4.56805663 C -4.95308879 -2.23668015 -2.63342412 C -3.71232414 -0.68386438 -0.35219949 C -2.01934953 -2.71319039 -1.85533519 H 3.59510901 2.02817964 -2.37849511 H 3.72798346 2.95808066 -3.88972912 H 3.42898509 1.19787611 -3.94407425 H 1.43678173 3.80667394 -1.29362897 H -0.10562133 4.06777086 -2.14611579 H 1.38272985 4.84921940 -2.73771379 H 0.94770541 1.97483668 -5.78947158 H 1.23101589 3.70899908 -5.49426996 H -0.35367670 2.99259966 -5.12321558 H 4.25479977 -2.22112029 -3.27134488 H 4.36857021 -3.61881698 -2.16942601 H 4.32712562 -1.96807811 -1.51112519 H 1.87181164 -3.71712196 -4.49473184 H 0.35903355 -3.95359550 -3.58756831 H 1.77525900 -4.98937377 -3.24716109 H 1.89836121 -2.64435749 0.28590481 H 1.94023233 -4.30593932 -0.34659959 H 0.43237131 -3.36707931 -0.42473297 H -1.44197941 1.02089981 -5.82404930 H -2.92399850 1.56144944 -6.62294974 H -2.64737906 -0.17753913 -6.36157656 H -2.07248210 2.93249444 -3.46681561 H -3.65739339 2.86544159 -2.64883923 H -3.53416785 3.45128875 -4.32207889 H -5.47584712 -0.28062493 -4.96943725 H -5.60426308 1.46662417 -5.29777201 H -5.83996858 0.84624851 -3.64457861 H -4.47660286 0.10879435 -0.41645949 H -2.80243422 -0.25778384 0.10695942 H -4.08846109 -1.45782882 0.33523637 H -5.78859396 -1.52204541 -2.68227065 H -5.22573387 -3.02700079 -1.91608250 H -4.85671869 -2.70480087 -3.62537496 H -1.78296058 -3.20770201 -2.81220682 H -2.29845603 -3.49156431 -1.12825536 H -1.09956219 -2.22364261 -1.49363464 O -1.07750665 -2.38602808 -5.44069153 C -2.41320960 -2.85603337 -5.58303601 C -0.34263916 -2.87637126 -6.54743490 C -2.67372288 -2.93972371 -7.10268334 C -1.28869280 -2.67767708 -7.72932638 H -1.21675072 -1.64067058 -8.08629779 426 H -1.06176328 -3.34538424 -8.57012053 H 0.59785542 -2.31365941 -6.61472044 H -0.10498687 -3.94524616 -6.39421195 H -3.06059934 -3.93024748 -7.37562878 H -3.41163326 -2.19613017 -7.43074185 H -2.50065946 -3.84923193 -5.10897199 H -3.06428894 -2.15197848 -5.04711399 O -1.82030539 2.76455419 -0.09080032 C -3.04517755 3.05709630 0.55890769 H -3.83311527 2.44376201 0.10257299 H -3.29703239 4.12469130 0.42249422 C -2.76431019 2.73137672 2.02223514 H -2.87804876 1.64866898 2.17771091 H -3.44432630 3.24712122 2.71184833 C -1.29245173 3.16100560 2.18510002 H -0.71654766 2.43163402 2.76930936 H -1.21146574 4.12983336 2.69550433 C -0.77547173 3.26722902 0.73345779 H 0.12552563 2.67007218 0.53471019 H -0.56644878 4.31387211 0.45681170 427 Table A.1.104. Atomic coordinates and single point energies for 86. G = –2873.90509 GSP = –2875.993758 N 2.76671400 0.75636200 -0.46449200 C 3.99558100 0.78748800 -0.98049700 C 2.27959100 1.86937200 0.10254700 C 4.81960300 1.90891000 -0.92128900 C 3.03388200 3.04158700 0.21304800 C 4.32810900 3.05453300 -0.29676300 H 4.34344300 -0.12977200 -1.46573600 H 5.82040200 1.87917600 -1.35121100 H 4.94545400 3.95106000 -0.21664000 H 2.59648800 3.91890500 0.69051800 C 0.84097700 1.76023900 0.57842900 N 0.58888800 0.96227900 1.61558000 Na 1.05975900 -0.95675100 0.13628700 Na -1.57693300 0.68914800 0.59401100 N -0.09230400 2.32789700 -0.13897800 N -1.18046800 -1.48581400 -0.30227300 Si 1.58071900 0.62631900 2.99727000 Si -0.11930500 3.34890200 -1.54212700 C 2.20261700 2.21852700 3.79881000 C 3.09863800 -0.45401500 2.62797500 C 0.52557500 -0.31540100 4.23680100 C 0.74034900 5.01595000 -1.28298300 C -1.93654400 3.72279700 -1.86580400 C 0.64286300 2.53247800 -3.06421900 Si -1.89219000 -2.41364800 0.93246400 Si -1.13721900 -1.59260000 -1.99923800 C -2.63265300 -1.26889300 2.27060300 C -0.65533600 -3.52104500 1.86478600 C -3.30043000 -3.56664500 0.39453700 428 C -1.60814500 -3.27806100 -2.73626500 C 0.63143300 -1.21820900 -2.61767000 C -2.23824100 -0.31618900 -2.87184700 H 2.90402000 2.74852500 3.13625100 H 2.72606900 2.00851400 4.74432100 H 1.36072400 2.89363000 4.01428600 H 3.81162900 0.05543400 1.96077500 H 2.81691400 -1.41509700 2.16540600 H 3.62346500 -0.68911500 3.56750000 H -0.35750700 0.27604100 4.52235700 H 1.09672300 -0.54310100 5.14986200 H 0.17110200 -1.26743100 3.81206700 H 0.50958000 5.42795900 -0.28829800 H 0.38126500 5.73481100 -2.03632800 H 1.83269900 4.94438200 -1.38625000 H -2.33647000 4.33625800 -1.04285300 H -2.53103200 2.79743400 -1.90851500 H -2.07963900 4.27613600 -2.80644800 H 1.68599000 2.23147900 -2.87372800 H 0.64086000 3.22956100 -3.91688600 H 0.07734700 1.63524400 -3.35718200 H -1.86146800 -0.61749000 2.71623100 H -3.06440000 -1.85931500 3.09338700 H -3.43762400 -0.63057700 1.86915700 H 0.31114200 -3.01624100 2.03443300 H -0.45065100 -4.44156900 1.29613400 H -1.05245100 -3.82242500 2.84716900 H -4.09948700 -3.02149200 -0.13351900 H -3.75178600 -4.06377400 1.26788700 H -2.92968400 -4.35009400 -0.28414400 H 1.36628600 -1.95034400 -2.24273700 H 0.96648200 -0.21482700 -2.30454000 H 0.67804500 -1.24281700 -3.71768500 H -1.00918900 -4.10006200 -2.31179500 H -1.45911500 -3.28045400 -3.82782700 H -2.66728700 -3.50748700 -2.54246900 H -3.29598300 -0.61966000 -2.84466300 H -1.95524200 -0.19374000 -3.92952000 H -2.15709800 0.66826400 -2.38163400 O -3.69853200 1.24615100 0.05861000 C -4.60654000 0.28068800 -0.45018300 C -4.48644300 2.29622600 0.58855200 C -5.78911100 0.26690600 0.53726400 C -5.61307900 1.57854500 1.33749100 H -5.29855300 1.36268500 2.36777100 H -6.52950600 2.18034500 1.38398700 429 H -3.84549200 2.92476300 1.22036600 H -4.88144300 2.91420700 -0.23819200 H -6.74706500 0.23098100 0.00286400 H -5.74539100 -0.60949200 1.19735900 H -4.93200400 0.58927900 -1.45878500 H -4.06591500 -0.67246100 -0.53349800 O 2.31849500 -2.83084000 0.08434100 C 1.76830800 -4.00482500 -0.50262800 H 0.71634600 -3.79249400 -0.73976000 H 1.80261700 -4.82581600 0.23299600 C 2.64802800 -4.31350100 -1.73284800 H 2.10672100 -4.13425200 -2.67102800 H 2.96593100 -5.36413900 -1.72935700 C 3.84742100 -3.35321300 -1.58002400 H 3.74268600 -2.49755600 -2.26323000 H 4.81320900 -3.83398600 -1.78092900 C 3.71713400 -2.87596900 -0.13480500 H 4.12545000 -1.87589600 0.06314300 H 4.18217500 -3.59134200 0.56815500 430 CHAPTER 1 REFERENCES AND FOOTNOTES 431 Chapter 1 References and Footnotes 1. (a) Mulvey, R. E.; Robertson, S. D. Synthetically Important Alkali-Metal Utility Amides: Lithium, Sodium, and Potassium Hexamethyldisilazides, Diisopropylamides, and Tetramethylpiperidides. Angew. Chem., Int. Ed. 2013, 52, 11470. (b) Robertson, S. D.; Uzelac, M.; Mulvey, R. E. Alkali-Metal- Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry. Chem. Rev. 2019, 119, 8332. (c) McLellan, R.; Uzelac, M.; Bole, L. J.; Gil- Negrete, J. M.; Armstrong, D. R.; Kennedy, A. R.; Mulvey, R. E.; Hevia, E. Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH2SiMe3)3 Metalation Reactions Synthesis 2019, 51, 1207. (d) Garden, J. A.; Armstrong, D. R.; Clegg, W.; Garcia-Alvarez, J.; Hevia, E.; Kennedy, A. R.; Mulvey, R. E.; Robertson, S. D.; Russo, L. Donor-Activated Lithiation and Sodiation of Trifluoromethylbenzene: Structural, Spectroscopic, and Theoretical Insights. Organometallics 2013, 32, 5481. (e) Wong, H. C. Is Sodium Finally Coming of Age? Nat. Catal. 2019 2, 282. (f) Lochmann, L.; Janata, M. 50 Years of Superbases Made from Organolithium Compounds and Heavier Alkali Metal Alkoxides. Eur. J. Chem. 2014, 12, 537. (g) Seyferth, D. Alkyl and Aryl Derivatives of the Alkali Metals: Strong Bases and Reactive Nucleophiles. 2. Wilhelm Schlenk’s Organoalkali-Metal Chemistry. The Metal Displacement and the Transmetalation Reactions. Metalation of Weakly Acidic Hydrocarbons. Superbases. Organometallics 2009, 28, 2. (h) The quest for Organo-Alkali Metal Monomers: Unscrambling the Structure–Reactivity Relationship. Davison, N; Lu, E. Dalton Trans. 2023, 52, 8172. 432 2. Structure, Reactivity, and Synthetic Applications of Sodium Diisopropylamide. Woltornist, R. A.; Ma, Y. Algera, R. F.; Zhou, Y.; Zhang, Z.; Collum, D. B. Synthesis 2020, 52, 1478. 3. For a recent studies of illustrating the synthetic potential of organosodium chemistry, see: (a) Gentner, T. X.; Mulvey, R. E. Alkali-Metal Mediation: Diversity of Applications in Main-Group Organometallic Chemistry. Angew. Chem. Int. Ed. 2021, 60, 9247. (b) Anderson, D. E.; Tortajada, A.; Hevia, E. Highly Reactive Hydrocarbon Soluble Alkylsodium Reagents for Benzylic Aroylation of Toluenes Using Weinreb Amides. Angew. Chem. Int. Ed. 2023, 62, e202218498. (c) Harenberg, J. H.; Reddy, R.; Reddy, A.; Karaghiosoff, K.; Knochel, P. Continuous Flow Preparation of Benzylic Sodium Organometallics. Angew. Chem. Int. Ed. 2022, 61, e202203807. (d) Davison, N.; McMullin, C. L.; Zhang, L.; Hu, S.-X.; Waddell, P. G.; Wills, C.; Dixon, C.; Lu, E. Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation. J. Am. Chem. Soc. 2023, 145, 6562. (e) De, P. B.; Asako, S.; Ilies, L. Recent Advances in the Use of Sodium Dispersion for Organic Synthesis. Synthesis 2021, 53, 3180. 4. Ma, Y.; Lui, N. M.; Keresztes, I.; Woltornist, R. A.; Collum, D. B. Sodium Isopropyl(trimethylsilyl)amide (NaPTA): A Stable and Highly Soluble Lithium Diisopropylamide Mimic. J. Org. Chem. 2022, 87, 14223. 5. "Sodium hexamethyldisilazide." Watson, B. T.; Lebel, H. In e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, New York; 2005, p 1–10. 433 6. (a) Driess, M.; Pritzkow, H.; Skipinski, M.; Winkler, U. Synthesis and Solid State Structures of Sterically Congested Sodium and Cesium Silyl(fluorosilyl)phosphanide Aggregates and Structural Characterization of the Trimeric Sodium Bis(trimethylsilyl)amide. Organometallics 1997, 16, 5108. (b) Kennedy, A. R.; Mulvey, R. E.; O’Hara, C. T.; Robertson, S. D.; Robertson, G. M. Catena-Poly[Sodium-µ2-(N,N,N′,N′- Tetramethylethane-1,2-Diamine)-k2-N,N′- Sodium- Bis[µ2-Bis(Trimethylsilyl)Azanido-k2 N:N]]. Acta Crystallogr. Sect. E Struct. Rep. Online 2012, 68, m1468. (c) Schüler, P.; Görls, H.; Westerhausen, M.; Kriec, S. Bis(trimethylsilyl)amide Complexes of s-Block Metals with Bidentate Ether and Amine Ligands. Dalton Trans. 2019, 48, 8966. (d) Ojeda-Amador, A. I.; Martínez-Martínez, A. J.; Kennedy, A. R.; Armstrong, D. R.; O’Hara, C. T. Monodentate Coordination of the Normally Chelating Chiral Diamine (R,R)- TMCDA. Chem. Commun. 2017, 53, 324. (e) Sarazin, Y.; Coles, S. J.; Hughes, D. L.; Hursthouse, M. B.; Bochmann, M. Cationic Brønsted Acids for the Preparation of Sn(IV) Salts: Synthesis and Characterisation of [Ph3Sn(OEt2)][H2N{B(C6F5)3}2],[Sn(NMe2)3(HNMe2)2][B(C6F5)4] and [Me3Sn(HNMe2)2][B(C6F5)4]. Eur. J. Inorg. Chem. 2006, 2006, 3211. (f) Karl, M.; Seybert, G.; Massa, W.; Harms, K.; Agarwal, S.; Maleika, R.; Stelter, W.; Greiner, A.; Neumüller, W. H.; Dehnicke, K. Amidometallate von Seltenerdelementen. Synthese Und Kristallstrukturen von [Na(12-Krone-4)2][M{N(SiMe3)2}3(OSiMe3)] (M = Sm, Yb), [Na(THF)3Sm{N(SiMe3)2}3(C≡C-Ph)], [Na(THF)6][Lu2(μ-NH2)(μ- NSiMe3){N(SiMe3)2}4] Sowie von [NaN(SiMe3)2(THF)]2. Z. Anorg. Allg. Chem. 1999, 625, 1301. (g) Neufeld, R.; Michel, R.; Herbst-Irmer, R.; Schöne, R.; Stalke, D. Introducing a Hydrogen-Bond Donor into a Weakly Nucleophilic Brønsted Base: Alkali Metal Hexamethyldisilazides (MHMDS, M=Li, Na, K, Rb, and Cs) with Ammonia. Chem. - Eur. J. 2016, 22, 12340. (h) Edelmann, F. T.; Pauer, F.; Wedler, M.; Stalke, D. Preparation and Structural Characterization of Dioxane 434 Coordinated Alkali Metal Bis(Trimethylsilyl)Amides. Inorg. Chem. 1992, 31, 4143. (i) Also, see reference 10a. 7. (a) Sodium Hexamethyldisilazide: Using 15N–29Si Scalar Coupling to Determine Aggregation and Solvation States. Woltornist, R. A.; Collum, D. B. J. Am. Chem. Soc. 2020, 142, 6852. (b) Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum. Woltornist, R. A.; Collum, D. B. J. Org. Chem. 2021, 86, 2406. (c) Ketone Enolization with Sodium Hexamethyldisilazide: Solvent- and Substrate-Dependent E–Z Selectivity and Affiliated Mechanisms. Woltornist, R. A. and Collum, D. B. J. Am. Chem. Soc. 2021, 143, 17452. 8. (a) Brown, D. G. Boström, J. Analysis of Past and Present Synthetic Methodologies on Medicinal Chemistry: Where Have All the New Reactions Gone? J. Med. Chem. 2016, 59, 4443. (b) Guan, Y.; Lee, T.; Wang, K.; McWilliams, C. J. SNAr Regioselectivity Predictions: Machine Learning Triggering DFT Reaction Modeling through Statistical Threshold. J. Chem. Inf. Model. 2023, 63, ASAP. 9. (a) Harrington, A.; Tal-Gan, Y. The Importance of Amide Protons in Peptide Drug Development. Future Med. Chem. 2019, 11, 2759. (c) Kumari, S.; Carmona, A. V.; Tiwari, A. K.; Trippier, P. C. Amide Bond Bioisosteres: Strategies, Synthesis, and Successes. J. Med. Chem. 2020, 63, 12290. 10. For a NaHMDS-sodium enolate mixed aggregates, see: (a) Williard, P. G.; Hintze, M. J. Mixed Aggregates: Crystal Structures of a Lithium Ketone Enolate/Lithium Amide and of a Sodium Ester Enolate/Sodium Amide. J. Am. 435 Chem. Soc. 1990, 112, 8602. (b) Zhang, Z.; Collum, D. B. Structures and Reactivities of Sodiated Evans Enolates: Role of Solvation and Mixed Aggregation on the Stereochemistry and Mechanism of Alkylations. J. Am. Chem. Soc. 2019, 141, 388. (c) Ojeda-Amador, A. I.; Martinez-Martinez, A. J.; Kennedy, A. R.; O'Hara, C. T. Synthetic and Structural Studies of Mixed Sodium bis(Trimethylsilyl) Amide/Sodium Halide Aggregates in the Presence of η2-N,N-, η3-N,N,N/N,O,N-, and η4-N,N,N,N-Donor Ligands. Inorg. Chem. 2015, 54, 9833. (d) Knapp, C.; Lork, E.; Borrmann, T.; Stohrer, W.-D.; Mews, R. Versuche Zur Darstellung Vont-BuCN5S3 Und Die Unerwartete Isolierung Einer Kovalenten Modifikation von Tetraschwefelpentastickstoff-Chlorid S4N5Cl. Z. Anorg. Allg. Chem. 2005, 631, 1885. (e) Clark, N. M.; García-Álvarez, P.; Kennedy, A. R.; O’Hara, C. T.; Robertson, G. M. Reactions of (–)-Sparteine with Alkali Metal HMDS Complexes: Conventional Meets the Unconventional. Chem. Commun. 2009, 39, 5835. (f) Williard, P. G.; Nichols, M. A. Structural Characterization of Mixed Alkali Metal Bis(trimethylsilyl) Amide Bases. J. Am. Chem. Soc. 1991, 113, 9671. 11. We suspect that our failures and other failures to undergo 1,4-addition derives from a thermodynamic problem in which the reaction is endothermic. Products of cinnamate self-condensation of the tert-butylcinnamate dominated reaction contents. Ongoing studies of enolization with NaHMDS/THF-based enolizations suggest a delicately balanced equilibrium for some substrates (unpublished). 1,4- Addition to the malonate analog [PhCH=C(CO2Me)2, by contrast, are successful (unpublished). A 1,4-addition of LiHMDS to an unsaturated ester has been reported.12 436 12. Rico, J. G. Synthesis of Novel β-Amino Acid Precursors: β-Amino- Hydrocoumarins as Unusual Aspartic Acid Mimetics Used in Fibrinogen Receptor Antagonists. Tetrahedron Lett. 1994, 35, 6599. 13. (a) Krüger, C.; Rochow, E. G.; Wannagat, U. Uber die Reaktion von Natrium- bis-trimethylsilyl-amid mit Derivaten der Benzoesaure. Chem. Ber. 1963, 96, 2138. (b) Afifi, M. S.; El-Sayed, B. A. Spectroscopic Investigation of the Reaction Products Between the Sodium Salt of Hexamethyldisilazane and Ethyl Aalicylate. Mass Spectra, Proton Magnetic Resonance and Infrared Analysis Egypt. J. Chem. 1983, 26, 551. 14. Hwu, J. R.; Hsu, C. H.; Wong, F. F.; Chung, C.-S.; Hakimelahi, G. H. Sodium Bis(trimethylsilyl)amide in the “One-Flask” Transformation of Aromatic Esters to Nitriles. Synthesis, 1998, 329 15. (a) Abou-Elkhair, R. A. I.; Hassan, A. E. A.; Boykin, D. W.; Wilson, W. D. Lithium Hexamethyldisilazane Transformation of Transiently Protected 4- Aza/benzimidazole Nitriles to Amidines and Their Dimethyl Sulfoxide-Mediated Imidazole Ring Formation. Org. Lett. 2016, 18, 4714. (b) Alharbi, N.; Díaz- Moscoso, A.; Tizzard, G. J.; Coles, S. J.; Cook, M. J.; Cammidge, A. N. Improved Syntheses of meso-Aryl Tetrabenzotriazaporphyrins (TBTAPs). Tetrahedron, 2014, 70, 7370. 16. (a) Baumann, M.; Baxendale, I. R. Bioorg. Med. Chem. 2017, 25, 6218. (b) Dorsey, B. D.; Dugan, B. J.; Fowler, K. M.; Hudkins, R. L.; Mesaros, E. F.; Monck, N. J; Morris, E. L.; Olowoye, I.; Ott, G. R.; Pave, G. A.; Roffey, J. R. A.; 437 Soudy, C. N.; Zificsak, C. A.; Zulli, A. L. Preparation of Azaquinazoline Inhibitors of Atypical Protein Kinase C. WO2015148597 October 1, 2015. 17. Chen, J.; Xu, Z.; Wang, T.; Lyssikatos, J. P.; Ndubaku, C. O. A Versatile Annulation Route to Primary-Amino-Substituted Naphthyridine Esters. SynLett 2014, 25, 89. 18. Guedira, N. E.; Beugelmans, R. Ambident Behavior of Ketone Enolate Anions in SNAr Substitutions on Fluorobenzonitrile Substrates. J. Org. Chem. 1992, 57, 5577. 19. Sun, K.; Sagisaka, K.; Peng, L.; Watanabe, H,; Xu, F.; Pawlak, R.; Meyer, E.; Okuda, Y.; Orita, A.; Kawai, S. Head-to-Tail Oligomerization by Silylene-Tethered Sonogashira Coupling on Ag(111). Angew. Chem. Int. Ed. 2021, 60, 19598. 20. Li, G.; Ji, C.; Hong, X.; Szostak, M. Highly Chemoselective, Transition-Metal- Free Transamidation of Unactivated Amides and Direct Amidation of Alkyl Esters by N–C/O–C Cleavage J. Am. Chem. Soc. 2019, 141, 11161 and references cited therein. 21. Hwu, J. R.; Chuang, K.-S.; Chuang, S. H.; Tsay, S.-C. 1,2-Eliminations in a Novel Reductive Coupling of Nitroarenes to Give Azoxy Arenes by Sodium Bis(trimethylsilyl)amide. Org. Lett. 2005, 7, 3211. 22. For a discussion and leading references to the challenges of metalating nitroarenes, see: Nagaki, A.; Kim, H.; Yoshida, J.-i. Nitro-Substituted Aryl Lithium 438 Compounds in Microreactor Synthesis: Switch Between Kinetic and Thermodynamic Control. Angew. Chem. Int. Ed. 2009, 48, 8063. 23. For a similar trimethylsilyl transfer that occurs when benzyne is trapped by metal silazides, see: Ikawa, T.; Masuda, S.; Akai, S. One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols. Chem. Eur. J. 2020, 26, 4320. 24. Schnürch, M.; Spina, M.; Khan, A. F.; Mihovilovic, M. D.; Stanetty, P. Halogen Dance Reactions—A Review. Chem. Soc. Rev. 2007, 36, 1046. 25. Estel, L. Marsais, F.; Queguiner, G. Metalation/SRN1 Coupling in Heterocyclic Synthesis. A Convenient Methodology for Ring Functionalization. J. Org. Chem. 1988, 53, 2740. 26. Kadambar, V. K.; Bachu, S.; Reddy, M. R.; Torlikonda, V.; Manjunatha, S. G.; Ramasubramanian, S.; Nambiar, S.; Howell, G. B. Withnall, J.; Murugan, A. Regioselective Synthesis of 1,2-Aminoalcohols from Epoxides and Chlorohydrins. Tetrahedron Lett. 2012, 53, 5739. 27. (a) Wang, J.; Rosingana, M.; Discordia, R. P.; Soundararajan, N.; Polniaszek, R. Aminolysis of Esters or Lactones Promoted by NaHMDS - A General and Efficient Method for the Preparation of N-Aryl Amides. Synlett 2001, 12, 1485. (b) Jones, C. D.; Bunyard, P.; Pitt, G.; Byrne, L.; Pesnot, T.; Guisot, N. Heterocyclylamino-substituted Triazoles as Modulators of rho-Associated Protein Kinase. WO2019145729, August 1, 2019. 439 28. Several general-purpose reviews on determining reaction mechanism: (a) Meek, S. J.; Pitman, C. L.; Miller, A. J. M. Deducing Reaction Mechanism: A Guide for Students, Researchers, and Instructors. J. Chem. Educ. 2016, 93, 275. (b) Simmons, E. M.; Hartwig, J. F. On the Interpretation of Deuterium Kinetic Isotope Effects in C–H Bond Functionalizations by Transition Metal Complexes. Angew. Chem., Int. Ed. 2012, 51, 3066. (c) Collum, D. B.; McNeil, A. J.; Ramírez, A. Lithium Diisopropylamide: Solution Kinetics and Implications for Organic Synthesis. Angew. Chem., Int. Ed. 2007, 46, 3002. (d) Algera, R. F.; Gupta, L.; Hoepker, A. C.; Liang, J.; Ma, Y.; Singh, K. J.; Collum, D. B. Lithium Diisopropylamide: Non-Equilibrium Kinetics and Lessons Learned about Rate Limitation. J. Org. Chem. 2017, 82, 4513. 29. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams- Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision C.01; Gaussian, Inc., Wallingford CT, 2016. 440 30. (a) Mardirossian, N.; Head-Gordon, M. Thirty Years of Density Functional Theory in Computational Chemistry: An Overview and Extensive Assessment of 200 Density Functionals. Mol. Phys. 2017, 115, 2315. (b) Wang, Y.; Verma, P.; Jin, X.; Truhlar, D. G.; He, X. Revised M06 Density Functional for Main-Group and Transition-Metal Chemistry. Proc. Nat. Acad. Sci. 2018 115, 10257. (c) Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Function. Theor. Chem. Acc. 2008, 120, 215. (d) Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297. (e) CYLview, 1.0b; C. Y. Legault, Université de Sherbrooke 2009 (http://www.cylview.org; accessed 2023- 7-6). 31. Chen, J.; Xia, Y.; Lee, S. Transamidation for the Synthesis of Primary Amides at Room Temperature. Org. Lett. 2020, 22, 3504. 32. Jones, A. C.; Williams, M. T. J.; Morrill, L. C.; Browne, D. L. Mechanical Activation of Zero-Valent Metal Reductants for Nickel-Catalyzed Cross- Electrophile Coupling. ACS Catal. 2022, 12, 13681. 33. Amidine 31 (Scheme 1.5) can be isolated after a month at 25 °C. 34. The computations use the Gaussian standard state of 1.0 atm. If the THF concentration is corrected to neat THF (approximately 13 M), each solvation step benefits from approximately 2.0 kcal/mol of additional stabilization at –78 °C (195 http://www.cylview.org/ 441 K). Pratt, L. M.; Merry, S.; Nguyen, S. C.; Quan, P.; Thanh, B. T. A Computational Study of Halomethyllithium Carbenoid Mixed Aggregates with Lithium Halides and Lithium Methoxide. Tetrahedron 2006, 62, 10821. 35. Rein, A. J.; Donahue, S. M.; Pavlosky, M. A. In Situ FTIR Reaction Analysis of Pharmaceutical-Related Chemistry and Processes. Curr. Opin. Drug Discov. Dev. 2000, 3, 734. 36. For leading references to open-dimer-based mechanisms, mechanisms that appear to involve monomer-to-dimer pre-aggregation, triple ion-based mechanisms, and solvation of sodium cation, see 7c and references cited therein. 37. Intrinsic reaction coordinate (IRC) calculations are defined as “the minimum energy reaction pathway (MERP) in mass-weighted cartesian coordinates between the transition state of a reaction and its reactants and products.” They show the minima preceding and following transition state. 38. For crystal structure of a lithium amidinates akin to 30 characterized crystallographically and excellent references to the applications of such amidinates, see: N,N′-Bis-Silylated Lithium Aryl Amidinates: Synthesis, Characterization, and the Gradual Transition of Coordination Mode from σ Toward π Originated by Crystal Packing Interactions. Aharonovich, S.; Kapon, M.; Botoshanski, M.; Eisen, M. S. Organometallics 2008, 27, 1869 39. Verstuyft, A. W.; Nelson, J. H.; Cary, L. W. Utility of Virtual Coupling in the Carbon-13 {proton} Nuclear Magnetic Resonance Spectra of Bis-phosphite 442 Complexes of Palladium and Platinum. Algebraic Cancellation of Spin-Spin Coupling Inorg.Chem. 1976, 15, 732. 40. Reich, H. J.; Dykstra, R. R. Solution Structure of Lithium Benzeneselenolate and Lithium Diphenylphosphide: NMR Identification of Cyclic Dimers and Mixed Dimers. Organometallics 1994, 13, 4578. 41. Perrin, C. L.; Shrinidhi, A.; Burke, K. D. Isotopic-Perturbation NMR Study of Hydrogen-Bond Symmetry in Solution: Temperature Dependence and Comparison of OHO and ODO Hydrogen Bonds. J. Am. Chem. Soc. 2019, 141, 17278. 42. Edwards, J. O.; Greene, E. F.; Ross, J. From Stoichiometry and Rate Law to Mechanism. J. Chem. Educ. 1968, 45, 381. 43. Ashby, E. C.; Dobbs, F. R.; Hopkins, H. P., Jr. Composition of Complex Aluminum Hydrides and Borohydrides, as Inferred from Conductance, Molecular Association, and Spectroscopic Studies. J. Am. Chem. Soc. 1973, 95, 2823. 44. Me4THF binds to NaHMDS, CsHMDS, and RbHMDS at least reluctantly as evidenced by x-ray crystal structures of the disolvated dimers showing significant distortions when compared with the THF solvates. LiHMDS crystallizes from Me4THF as a solvent-free tetramer, although there is evidence it binds weakly in solution.45 Krieck, S.; Schüler, P.; Görls, H.; Westerhausen, M. Straightforward Synthesis of Rubidium Bis(trimethylsilyl)amide and Complexes of the Alkali Metal Bis(trimethylsilyl)amides with Weakly Coordinating 2,2,5,5- Tetramethyltetrahydrofuran. Dalton Trans. 2018, 47, 12562. https://pubs.rsc.org/en/results?searchtext=Author%3APhilipp%20Sch%C3%BCler https://pubs.rsc.org/en/results?searchtext=Author%3AHelmar%20G%C3%B6rls 443 45. Lucht, B. L.; Collum, D. B. Ethereal Solvation of Lithium Hexamethyldisilazide (LiHMDS): Unexpected Relationships of Solvation Number, Solvation Energy, and Aggregation State. J. Am. Chem. Soc. 1995, 117, 9863. 46. (a) Bates, R. B.; Kroposki, L. M.; Potter, D. E. Cycloreversions of Anions from Tetrahydrofurans. A Convenient Synthesis of Lithium Enolates of Aldehydes. J. Org. Chem. 1972, 37, 560. (b) Byrne, F.; Forier, B.; Bossaert, G.; Hoebers, C.; Farmer, T. J.; Clark, J. H.; Hunt, A. J. 2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): a Non-polar, Non-peroxide Forming Ether Replacement for Hazardous Hydrocarbon Solvents. Green Chem. 2017, 19, 3671. 47. The dielectric constants of substituted tetrahydrofurans are slightly lower than THF. (a) Harada, Y.; Salomon, M.; Petrucci, S. Molecular Dynamics and Ionic Associations of Lithium Hexafluoroarsenate (LiAsF6) in 4-Butyrolactone Mixtures with 2-Methyltetrahydrofuran. J. Phys. Chem. 1985, 89, 2006. (b) Carvajal, C.; Tolle, K. J.; Smid, J.; Szwarc, M. Studies of Solvation Phenomena of Ions and Ion Pairs in Dimethoxyethane and Tetrahydrofuran. J. Am. Chem. Soc. 1965, 87, 5548. 48. The Principle of Detailed Balance asserts that individual equilibria within an ensemble of equilibria are maintained. It is particularly useful in understanding the complex equilibria observed in organolithium chemistry. Alberty, R. A. Principle of Detailed Balance in Kinetics. J. Chem. Educ. 2004, 81, 1206. 49. Linder, T.; Sutherland, T. C.; Baumgartner, T.; Extended 2,5-Diazaphosphole Oxides: Promising Electron-Acceptor Building Blocks for π-Conjugated Organic Materials. Chem.–Eur. J. 2010, 16, 7101. 444 50. Substitution of the p-bound substrate in 43 with benzene is endothermic by 6.1 kcal/mol. 51. The mathematics is in the Supporting Information of 7b. 52. The order in THF cannot be determined from a fit with values of –4 through –6 all providing adequate fits to the data. The presumed value of –6 comes from the assigned solvation states of NaHMDS monomer as tetrasolvated,7b and transition structure 50 as a disolvate. 53. A monomer-based N-to-N’ silicon transfer analogous to that depicted in Figure 1.18 is substantially less favorable. 54. (a) Zhao, P.; Collum, D. B. Ketone Enolization by Lithium Hexamethyldisilazide: Structural and Rate Studies of the Accelerating Effects of Trialkylamines. J. Am. Chem. Soc. 2003, 125, 14411. (b) Mack, K. A.; McClory, A.; Zhang, H.; Gosselin, F.; Collum, D. B. Lithium Hexamethyldisilazide- Mediated Enolization of Highly Substituted Aryl Ketones: Structural and Mechanistic Basis of the E/Z Selectivities. J. Am. Chem. Soc. 2017, 139, 12182. 55. Structures of Lithium N‑Monosubstituted Anilides: Trisolvated Monomer to Tetrasolvated Dimer. Su, C.; Guang, J.; Williard* P. G. J. Org. Chem. 2014, 79, 1032. 445 CHAPTER 2 SODIUM ALKYL(TRIMETHYLSILYL)AMIDES: SUBSTITTUENT- AND SOLVENT-DEPENDENT SOLUTION STRUCTURES AND REACTIVITIES 446 Sodium Alkyl(trimethylsilyl)amides: Substitutent- and Solvent-Dependent Solution Structures and Reactivities Abstract The preparation of sodium isopropyl(trimethylsilyl)amide (NaPTA), sodium (2- phenylethyl)amide (NaPETA), sodium tert-butyl(trimethylsilyl)amide (NaBTA), and isotopomers [15N]NaBTA and [15N]NaBTA are described. Solution structural studies using a combination of 29Si NMR spectroscopy, the Method of Continuous Variations (MCV), and density functional theory (DFT) computations provided insights into aggregation and solvation in a range of solvents including toluene, N,N-dimethylethylamine, triethylamine, MTBE, THF, dimethoxyethane (DME), diglyme, N,N,N’,N’-tetramethylethylenediamine (TMEDA), N,N,N’,N’- tetramethylcyclohexanediamine (TMCDA), N,N,N’,N’’,N’’- pentamethyldiethylenetriamine (PMDTA), 12-crown-4, 15-crown-5, and 18- crown-6 revealed solvent- and substituent-dependent dimer-monomer mixtures with affiliated solvation numbers. Complexation of the three crown ethers documented both crown and substituent dependencies. Qualitative studies of reactivity showed a variety of reactions of NaPETA. Aminolysis of methyl benzoate with dialkylamines mediated by NaPTA afforded high yields of benzamides. Quantitative rate studies of aminolysis of methyl benzoate by NaPTA revealed a 47,000-old range of rates. Detailed rate studies in toluene and THF showed dimer-based mechanisms. The role of primary- and secondary-shell solvation by THF is discussed, including nuances of methods used to separate the two contributions. PMDTA-solvated NaPTA monomer reacts as a monomer whereas bis-diglyme solvated monomer reacts as a dimer. Rate studies exploring the structure-reactivity correlations of the three crown ethers show mono- and bis- 447 crown-based pathways in which 15-crown-5—the crown ether often said to be of choice for sodium—was decidedly inferior as an accelerant. Introduction Sodium comprises 2.6% of the Earth’s crust, and sodium chloride is dug from the Earth >95% pure with bulldozers. In the vernacular, sodium is dirt cheap. It stands to reason, therefore, that the potential importance of organosodium chemistry is almost limitless provided that the legendarily high reactivities can be harnessed. Nonetheless, the field has remained largely dormant for more than a century, only occasionally interrupted by brief bursts of activity.1,2,3 Imagine, for example, how many times per day lithium diisopropylamide (LDA) is used across the globe juxtaposed on the several dozen literature reports of sodium diisopropylamide (NaDA) during its first half-century of existence.4,5,6 After 30 years of scrutinizing structural and mechanistic organolithium chemistry, we diverted our attention to sodium. The reason for the delay of such a seemingly obvious move was simple: we had no clue how to determine solution structures in the absence of viable Na–X scalar coupling, rendering detailed mechanistic studies impossible. After finally arriving at workable solutions to that problem,7 we formulated a two-pronged approach to join a small cadre of chemists3 trying to nudge organosodium chemistry forward: (1) examine the fundamental relationships between structure, reactivity, and selectivity of known reagents, and (2) develop and refine Bronsted base-solvent combinations for generating potentially important organosodium intermediates. An initial focus on the structure and reactivity of NaDA in a range of solvents revealed no fundamental limitations that we could discern and that NaDA is not merely a more reactive variant of LDA.4 Followup investigations of the less reactive but widely used sodium hexamethyldisilazide (NaHMDS) in >30 solvents 448 established how solvation influences, aggregation, reactivity, and selectivity.8 Most recently, we examined sodium isopropyl(trimethylsilyl)amide (NaPTA)9 manifesting a pKb intermediate to that of NaDA and NaHMDS while manifesting exceptional solubilities in hydrocarbons and stability in ethereal ligands. A survey of several dozen transformations revealed that NaPTA–THF is more reactive than LDA in every case. Despite a focus on NaPTA’s Bronsted basicity, several reactions underscored an untapped potential of sodium alkyl(trimethylsilyl)amides for C–N bond formation. We describe herein several functionally simple sodium alkyl(trimethylsilyl)amides (Chart 2.1). Sodium alkylsilazides have been characterized crystallographically10,11 and used for specialized applications,12 but the underlying basic principles and more generalized applications by the synthetic organic community remain unexplored.13 Solution structural studies in this paper include NaPTA (1) solvated by monodentate ligands (donor solvents) as well as the chelating polyfunctional ligands shown in Chart 2.2. Analogous studies of sodium tert-butyl(trimethylsilyl)amide (NaBTA, 2)11a and a less ambitious examination of sodium (2-phenylethyl)amide (NaPETA, 3) reveal the influence of steric effects on aggregation.14 A few reactions of NaPETA are described that reveal no surprises but might pique the interest of synthetic chemists. We close the circle with mechanistic and rate studies to ascertain foundational structure-reactivity principles by focusing on NaPTA-mediated ester aminolysis in a half-dozen solvents. Chart 2.1. Sodium alkyl(trimethylsilyl)amides. 449 Chart 2.2. Polydentate ligands. Results and Discussion Preparation of sodium alkyl(trimethylsilyl)amides. Alkyl(trimethylsilyl)amine are routinely prepared by mixing Me3SiCl/Et3N and an alkylamine. Unhindered n-alkylamines that appear to be prone to disilylation15 as well as more precious 15N-labelled amines stored as ammonium salts were silylated as their lithium alkylamides (RNHLi).16 The sodium silazides were generated from the silylamines as shown in eq 1. We use dimethylethylamine (DMEA) largely for historical reasons emanating from studies of NaDA4 but have no doubt that many solvents would suffice for generating concentrated stock solutions adequate for N Me3Si i-Pr 1 (NaPTA) Na N Me3Si tert-Bu Na 2 (NaBTA) N Me3Si Ph(Me)CH Na 3 (NaPETA) O O O O O O O O O O O O OO O 12-crown-4 15-crown-5 18-crown-6 Me2N NMe2 N Me2N NMe2 Me TMEDA PMDTA MeO OMe DME O MeO OMe diglyme Me2N NMe2 (R,R)-TMCDA 450 most applications. Our emphasis on structure and mechanism, however, prompted us to isolate and purify the sodium amides as white solids. Solution Structure: General Methods. The results from spectroscopic and computational studies for NaPTA, NaBTA, and NaPETA are summarized in Tables 2.1–2.3 Partial results for NaPTA in THF (Table 2.1, entry 4) were archived in a Supporting Information in 2022.9 ‘AmSn’ is a shorthand in which ‘m’ is the number of silazide subunits and ‘n’ is the number of ligands irrespective of their hapticities. Chart 2.3. Structural forms of NaPTA described in Table 2.1. Table 2.1. Spectroscopic and computational data for NaPTA dimers and monomers (Chart 2.3) in different solvents.a Entry Solvent Structure 29Si shift [ppm (1JN-Si)] 15N shifts (ppm) Solvation energy per S–Na (kcal/mol) 1 toluene A2S2 –13.47 (6.3) –13.30 (5.7) 68.4 –3.9 2 Et3N A2S2 –12.99 (6.4) –12.97 (6.3) 68.0 67.5 –4.2 N Me3Si R H Na(0) / isoprene solvent N Me3Si R Na (1) N Na N Na SiMe3Me3Si RR S S cis-4 (A2S2) N Me3Si R 5 (ASn) NaSnN Na N Na RMe3Si SiMe3R S S trans-4 (A2S2) 451 3 MTBE A2S2 –13.43 (6.7) –13.39 (6.5) 67.6 67.2 –4.9 4 1.8 M THF 12.3 M THF A2S2/4 –15.56 (6.7) –16.79 (6.7) 66.4 67.1 –5.7 (S2) –2.9 (S4) 5 HMPAb (2.0 equiv) A2S2 –14.98 (7.3) 66.4 –10.8 6 HMPAb (4.0 equiv) A2S2 AS3 –16.80 (--)e 67.7 –12.7 –8.3 7 TMEDAb (12.0 equiv) A2S2 –16.01 (6.7) –16.49 (6.9) 66.4 66.3 –8.8 8 TMCDAb (4.0 equiv) A2S2 –15.39 (6.3) –16.49 (6.6) 65.2 64.7 –5.2 9 PMDTAb (1.0 equiv) AS1 –22.78 (9.2) 71.7 –21.4 10 DME c (6.5 M) A2S2 –15.12 (6.6) 69.3 –6.3 11 diglymeb (2.0 equiv) A2S2 –14.97 (6.3) 77.8 –10.5 12 diglymeb (35.0 equiv) AS2 –22.78 (9.2) 72.4 –12.9 13 12-crown-4d (1.0 equiv) AS1 –22.26 (9.2) 71.7 –22.3 14 15-crown-5d (1.0 equiv) AS1 –23.84 (8.7) 72.3 –28.2 15 18-crown-6d (1.0 equiv) AS1 –23.85 (--)e 72.1 –19.9 aAdditional details of the cosolvent and temperatures are found in the Supporting Information. bIn pentane. cIn hexane. dIn THF. eBroad mound. Table 2.2. Spectroscopic data for NaBTA dimers and monomers in different solvents.a Entry Solvent Structure 29Si shift [ppm(1JN–Si)] 15N shifts (ppm) Solvation energy per S–Na (kcal/mol) 452 1 toluene A2S2 –17.65 (6.5) –18.69 (7.3) 75.6 –2.3 2 DMEA A2S2 –19.33 (7.4) –19.43 (7.3) 75.3 –4.9 3 Et3N A2S2 –19.05 (7.5) –19.10 (7.2) 76.4 –3.5 4 MTBE A2S2 –19.66 (7.7) –19.75 (7.7) 77.0 –5.2 5 1.2 M THFb A2S2 –19.89 (7.0) 77.2 –5.7 6 6.0 M THF AS4 –29.69 (11.4) 80.0 –4.3 7 HMPAb (1.0 equiv) A2S2 –20.59 78.4 –11.2 8 HMPAc (3.0 equiv) AS3 –29.72 (11.2) –30.18 (11.3) 79.6 –8.3 9 TMEDAc (1.0 equiv) AS1 –28.89 (11.6) 74.5 –17.4 10 TMCDAc (1.0 equiv) AS1 –27.98 (11.3) 78.5 –26.5 11 PMDTAc (1.0 equiv) AS1 –29.44 (11.3) 80.0 –29.7 12 DME c (1.0 equiv) A2S2 –20.07 (6.8) 78.1 –7.5 13 DMEc (2.0 equiv) AS2 –30.06 (11.9) 73.6 –10.5 14 diglymec (1.0 equiv) AS1 –29.52 (11.4) 77.8 –16.8 15 12-crown-4d (2.0 equiv) AS1 –29.64 (11.5) 77.5 –24.2 16 15-crown-5d (2.0 equiv) AS1 –29.67 (11.2) 80.0 –25.7 17 18-crown-6d (2.0 equiv) AS1 –30.26 (11.9) 76.5 –22.6 a0.15 M NaBTA. Additional details of the cosolvent and temperatures are found in the Supporting Information. bIn toluene. cIn MTBE. dIn THF. 453 Table 2.3. Spectroscopic and computational data for NaPETA dimers and monomers (Chart 2.3) in different solvents.a Entry Solvent Structure 29Si shift Solvation energy per S–Na (kcal/mol) 1 toluene A2S2 –12.05 –13.20 –1.5 2 DMEA A2S2 –12.65 –14.41 –4.6 3 Et3N A2S2 –13.19 –13.43 –1.2 4 MTBE A2S2 –13.60 –7.7 5 1.8 M THFb A2S2 –13.88 –14.47 –5.0 6 12.3 M THFc A2S2 AS4 –14.01 –21.00 –5.0 –4.1 7 TMEDAd (1.0 equiv) AS1 –20.10 –17.1 8 PMDTAd (1.0 equiv) AS1 –20.88 –28.0 9 HMPAd (1.0 equiv) AS1 –20.70 –17.8 10 DMEd (0.50 equiv) A2S2 AS2 –14.34 –21.30 –7.1 –11.0 11 DMEd (4.0 equiv) AS2 –21.30 –11.0 12 diglymed (2.0 equiv) AS2 –19.72 –12.9 13 12-crown-4e (1.0 equiv) AS1 –21.31 –25.2 14 15-crown-5e (1.0 equiv) AS1 –20.26 –27.7 15 18-crown-6e (1.0 equiv) AS1 –21.34 –22.0 454 a0.10 M NaPETA. bPentane cosolvent. cDimer-monomer = 1:5. dIn MTBE. eIn THF. Solvent-concentration-dependent aggregation states are conveniently monitored using serial titrations of a single NMR spectroscopic sample using protocols that have their roots in the 1960s alkali metal literature.17 Aside from the influence of solvent structure and concentration on aggregation, increasing steric demands of the sodium alkyl(trimethylsilyl)amide subunit promotes deaggregation as often seen in lithium amides.18 Sodium amide dimers are detected and confirmed using a combination of techniques. The inequivalent substituents on nitrogen cause a doubling of the dimer resonances (see Figure 2.1) owing to cis-4 and trans-4 isomers. Our first experience with such peak doublings as diagnostic of dimerization occurred during studies of lithiated imines in 1986 and unsymmetric lithium dialkylamides in 1988.19 The stereoisomer resolution by 29Si NMR spectroscopy is temperature and cosolvent-dependent (Supporting Information). As noted in other studies of alkali metal silazides, occasionally the 29Si resonances disappear owing to coalescence or precipitation of the sodium amide.8,20 There are instances, however, that we cannot confidently explain the disappearance but suspect from previous studies it may correlate with ion pair formation. Resolutions of stereoisomeric dimers and monomers by 1H and 15N NMR spectroscopies are included in Supporting Information, but these two spectroscopies played marginal roles in this study. A more formal approach to characterize the sodium amide dimers is to use the Method of Continuous Variations (MCV)7 in which homo- and heterodimers (eq 2) are monitored by 29Si NMR spectroscopy as a function of measured mole fraction21 (X) to provide a Job plot.22 This is illustrated using a NaPTA-NaBTA pairing in Figure 2.1 and 2. Figure 2.1 also underscores the markedly different 29Si 455 chemical shifts observed for dimeric NaPTA (13–16 ppm) and NaBTA (19–20 ppm). The monomers appear 5–10 ppm upfield of their respective dimers as noted in previous metal silazide studies.8,20 Although we completed only a few Job plots (Supporting Information), they serve a critical role of confirming the ranges for the dimer and monomer 29Si chemical shifts and 15N–29Si coupling constants (see below).23 Figure 2.1. 29Si NMR spectra (99.36 MHz) of NaPTA and NaBTA homodimers A2 and B2, respectively, and the NaPTA-NaBTA heterodimer (AB) at 0.15 M total AB + B2A2 (2)N Na N Na SiMe3Me3Si t-But-Bu S S N Na N Na i-PrMe3Si SiMe3i-Pr S S N Na N Na SiMe3Me3Si t-Bui-Pr S S -22-20-18-16-14-12 29Si (ppm) A2 AB ABB2 1 : 1 * A2 B2 only A2 only B2 * * 456 base concentration in neat DMEA at –50 °C. The asterisk (*) corresponds to an unknown impurity that appeared uniquely to this experiment. Figure 2.2. Job plot showing the relative integration of NaPTA-derived homodimer (A2, red), NaBTA-derived homodimer (B2, blue), and the NaPTA– NaBTA heterodimer (AB, green) versus the measured mole fraction21 of NaPTA (XA) at 0.15 total base molarity in neat DMEA at –50 °C. The curves result from a parametric fit to a dimer model.7 Studies of [15N]NaHMDS,8a,b [15N]LiHMDS,8a and [15N]KHMDS20 revealed that the magnitude of 15N–29Si splittings (Figure 2.3) are diagnostic of dimers, monomers, and ion pairs, allowing considerable shortcuts when surveying solvents and solvent concentrations. The 15N–29Si coupling has the desirable feature that it can be monitored at any temperature even in the limit of rapid exchange provided the resonances are not coalescing to the baseline.8,20 1.0 0.8 0.6 0.4 0.2 0.0 R el at iv e In te gr at io n 1.00.80.60.40.20.0 χB 457 Figure 2.3. 29Si NMR spectrum (99.36 MHz) of [15N]NaPTA in THF at –80 oC displaying a dimer: d –16.79 (d, JN–Si = 6.7 Hz). Solvation numbers can be measured directly under conditions of slow solvent exchange,18 but that was possible only in a few cases. The assigned solvation numbers and hapticities in the current study rely heavily on density functional theory (DFT) computations24,25 using explicit solvation models albeit with serious concerns delineated below.26 Although the computed cis–trans ratios are solvent-dependent, a modest preference for the trans over the cis isomer (Figure 2.4) is the norm. The highly symmetric tert-butyl moiety renders computations of NaBTA relatively simple. The solvation energies in Table 2.2 correspond to the most computationally stable trans form and correspond to the average per-solvent energy irrespective of hapticities and correlated solvation effects.27 -17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 A (d) -15.28 J(6.04) B (d) -15.65 J(6.68) 458 Figure 2.4. Ball-and-stick structures showing cis and trans isomers of NaPTA dimer solvated by MTBE. NaPTA presented challenges owing to inequivalent rotamers for the two isopropyls in both the cis and trans isomers but especially so in the cis isomer wherein the two isopropyls are proximate. Using the CREST subroutine in Gaussian to find the lowest energy conformers was not very effective in our hands. Nevertheless, the rotameric distributions typically reside in a narrow energetic range (0.0-2.2 kcal/mol). Given the cis and trans isomers are experimentally almost thermoneutral, we focused on the trans isomer to complete the solvation numbers and energies in Table 2.1. The lack of symmetry in the phenethyl group of NaPETA exacerbates the rotamer problem, again causing us to focus the discussions below on the trans isomers. A phenomenon that we underestimated at the outset is a computational penchant for the aromatic ring to coordinate to sodium even with donor solvents present. The most favorable unsolvated dimers 6 and 7 manifest h6,h6 π cis trans 459 complexation. Various π-complexed solvated dimers and monomers (8–10), while not the most stable forms and certainly not making the study any easier, captivated our attention and may explain some anomalous observations described below. If p complexation is involved, analogous complexes are likely important in controlling reactivity and selectivity more than many suspect.28 We feel compelled to offer some general reservations about the computational results. Of course, non-isodesmic29 comparisons of dimers and monomers always require special caution. While comparing relative stabilities of solvated cations are interesting, computed stabilities of ion pairs relative to their neutral counterparts afford ridiculous energies that are of no value whatsoever owing to correlation effects.30 Our limited experience with detailed theory- N Me3Si Me H Na Na N SiMe3 Me H 6 N Me3Si Me H Na Na N SiMe3 Me H 7 N Me3Si Me H Na Na N SiMe3 Me H 8 9 Sn N Me3Si Me H Na Na N SiMe3 Me H Sn Sn N Me3Si Me H NaSn 10 460 experiment comparisons in the heavier alkali metals4,8,20 are not as compelling as those for lithium salts. The number of undeniably failed correlations is disquieting. Thus, despite the specific energies listed in Tables 2.1–2.3, we resist the urge to interpret the numbers too literally and urge the reader to do the same. Qualitative statements about relative stabilities and allusions to “computationally viable” species being “credible” in lieu of citing explicit energies are not an oversight. The explicit energies are archived in Supporting Information. Toluene. Resonance doubling, chemical shifts, and couplings observed by 29Si NMR spectroscopy for NaPTA are fully consistent with stereoisomeric dimers. The ball-and-stick depiction of the toluene-solvated trans isomer (11) is shown in Figure 2.5. Many h6 toluene-sodium complexes31 and other alkali metal-arene π complexes have been characterized crystallographically.28 Facile substitutions by weakly coordinating ethereal and trialkylamine ligands (below) suggest relatively weak arene coordination. Toluene-solvated NaBTA and NaPETA form analogous h6,h6-disolvated stereoisomeric dimers (Supporting information). A 1:1 mixture of (R)- and (S)-NaPETA in toluene also shows the two homochiral cis and trans isomeric dimers along with a single resonance for an (R)–(S) heterodimer.32 Figure 2.5. DFT-computed h6,h6-toluene-complexed trans dimer 11. 11 N Na N Na SiMe3i-Pr i-PrMe3Si Me Me 461 Monofunctional Solvents. Weak donor solvents such as MTBE and trialkylamines (Et3N and DMEA) afford disolvated NaPTA stereoisomeric dimers (12) to the exclusion of monomers for all three sodium amides. One should be careful not to overestimate the importance of solvent–silazide van der Waals interactions and underestimate the importance of solvent–solvent interactions in the monomers to explain failed deaggregations.18 A standard Job plot from NaPTA- KBTA pairings in DMEA is shown in Figure 2.2. Mixtures of (R)- and (S)-NaPETA include the homochiral stereoisomeric dimers and heterochiral dimers, all observable by 1H and 29Si NMR spectroscopies. The Job plot for such scalemic NaPETA mixtures in MTBE is shown in Figure 2.6. An analogous Job plot using scalemic NaPETA in DMEA is in Supporting Information. We hasten to add that alkali metal amides solvated by weakly coordinating trialkylamines can manifest high reactivities and selectivities, rendering them more than just scientific curiousities.33,34 N Na N Na SiMe3R RMe3Si S S R = i-Pr-, t-Bu-, or Ph(CH3)CH- S = MTBE, DMEA, Et3N, HMPA 12 462 Figure 2.6. Job plot showing relative integrations of NaPETA-derived enantiomeric homodimers (red) and R–S heterodimers (green) versus the measured mole fraction21 of (R)-NaPETA (X(R)-NaPETA) at 0.30 total base molarity in MTBE at –100 °C observed by 29Si NMR spectroscopy. The curves result from a parametric fit to a dimer model.7 NaPTA solvated by 2.0 equiv of the strongly coordinating hexamethylphosphoramide (HMPA) affords only dimers. Several studies have noted that HMPA’s reputation for deaggregating lithium aggregates may be overstated.35 At 4.0 equiv a mound with the chemical shift of a dimer is observed. At 10 equiv the 29Si resonance disappears, suggesting an ionization.8b This result is qualitatively similar to the more facile sequential deaggregation and subsequent ionization of NaHMDS by HMPA8b while contrasting with the destruction of HMPA by the more basic NaDA.4 Although NaBTA follows NaPTA quite closely, NaPETA diverges markedly. At 1.0 equiv of HMPA a 29Si chemical shift of –20.7 ppm clearly implicates monomer, which is initially counterintuitive at such a low coordination number. Is the arene functioning as more than merely a large substituent? The mono- and di- 463 HMPA-solvated arene-complexed monomers corresponding to 13 and 14 are computationally viable. We deferred the discussion of THF because of the added complexity of the protocols. Neat THF displays no penchant to deaggregate NaPTA, which parallels NaDA in THF4 yet contrasts with the facile deaggregation of NaHMDS in THF.8b Given that computations supported bis-THF-solvated dimers of NaHMDS8a,b and NaDA,4 dimer 15 would be logical, especially at low THF concentrations. However, di- and tetrasolvated NaPTA dimers 15 and 16 are computed to be equally stable.36 THF-concentration-dependent chemical shifts of the cis and trans dimers lend tacit support to the notion of a shifting solvation number. There was a flurry of revisionist thinking when rate data surfaced that appeared to show saturation kinetics consistent with a shift from di- to tetrasolvate (vide infra). NaPETA with a sterically demanding phenethyl group manifests a THF- concentration-dependent deaggregation, affording 80% monomer in neat THF at – 110 °C. Monomer 10 (Sn = (THF)3) manifesting a p complex is not necessary to explain the partial deaggregation but can’t be excluded either. N Me3Si Me H Na(HMPA)1 13 N Me3Si Me H Na(HMPA)2 14 15 16 N N SiMe3Me3Si i-Pri-PrN Na N Na i-PrMe3Si SiMe3i-Pr THF THF Na THF THF Na THF THF 464 The most hindered of the three amides, NaBTA, is dimeric at low THF concentrations (17) and >95% monomer 18 in 6.0 M THF/toluene (Figure 2.7). Plotting the NaBTA dimer-monomer ratio versus THF concentration (Figure 2.8), and fitting it to a model based on eq 3 (Supporting Information) implicates a pentasolvated hexacoordinate monomer 18 (n = 3.9). We hasten to add that a fit to a tetrasolvated monomer by forcing n = 3.0 also looks quite reasonable. DFT shows exothermic serial solvation of the monomer to a trisolvate and a thermoneutral addition of a fourth THF,36 but a minimum corresponding to a pentasolvate 18 (n = 4) could not be found. The apparent disagreement between theory and experiment is minor; the case for either tetra- or pentasolvated monomers can be made. Experimental and computational data from NaHMDS supports a tetra-THF-solvated monomer by analogy.8b 17 Na N Na N t-Bu Me3Si t-Bu SiMe3 THF THF nTHF (3) 18 N Me3Si t-Bu Na(THF)n+11/2 465 Figure 2.7. 29Si NMR spectra (99.36 MHz) of 0.15 M NaBTA at varying THF concentrations in toluene at –110 °C. Figure 2.8. Parametric fit of the dimer of NaBTA (0.15 M) as a function of THF concentration in toluene cosolvent at –110 ºC based on the model in eq 3 implicating a hexacoordinate, pentasolvated monomer. The curve depicts an unweighted least-squares fit (Supporting Information) to y = (0.25axn – 0.25(16b + a2 x2n)1/2)2: a = (1.7 ± 0.1) × 10−3; b = (1.4 ± 0.1) × 10−1; n = 3.9 ± 0.6. Polyamines. N,N,N’,N’-tetramethylethylenediamine (TMEDA) is a bifunctional ligand that has profoundly shaped the thinking of researchers about structure-reactivity relationships in alkali metal chemistry.37 N,N,N’,N’- Tetramethylcyclohexanediamine (TMCDA) is a strongly coordinating TMEDA surrogate in organolithium chemistry8b,18 with the added appeal of chirality.38 NaPTA solvated by TMEDA and TMCDA exists as dimers 19 and 20 to the 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 [A 2T H F 2 ] ( M ) 86420 [THF] (M) 466 exclusion of monomers 21a or 23a, consistent with results for NaDA and NaHMDS.4,8b Both NaBTA and NaPETA with > 1.0 equiv of TMEDA show monomers that we assign as 21b and 21c. There are other possibilities, however. The computationally viable bis-chelated monomers of type 22 are possible at elevated TMEDA concentrations. TMEDA-solvated monomers in MTBE cosolvent could also form computationally viable mixed solvate 24. We should also not overlook a possible role of arene-chelated monomer 25. TMCDA affords analogous NaBTA monomers 23b and 23c. N N i-PrMe3Si SiMe3i-Pr 20 NMe2 Na Me2N Me2N Na NMe2 N N i-PrMe3Si SiMe3i-Pr 19 NMe2 Na Me2N Me2N Na NMe2 Me2 N N Me2 N R Me3Si Na 23a; R = i-Pr 23b; R = t-Bu 23c; R = CH(Me)Ph R Me3Si N Na N Me Me MeMe N 21a; R = i-Pr 21b; R = t-Bu 21c; R = CH(Me)Ph N R Me3Si Na L L L L 22; L = NMe2 N Me3Si Me H 25; L = NMe2 N R Me3Si Na L L 24; L = NMe2 S Na L L 467 One equiv of trifunctional ligand, N,N,N’,N’’,N’’- pentamethyldiethylenetriamine (PMDTA) in pentane affords exclusively NaPTA, NaPETA, and NaBTA monomers 26a–c to the exclusion of solvated dimers. DFT computations support the penchant for k3 monomers stemming from only k2,k2 dimers 27a-c being computationally viable. Binary (1:1) mixtures of the NaPETA– PMDTA and NaBTA–PMDTA show no evidence of heteroaggregation, consistent with the assignments.32 Polyethers. One of the advantages offered by sodium alkyl(trimethylsilyl)amides is that they are more basic than NaHMDS8b but less destructive than NaDA to ether and polyethers.4 Incremental additions of DME to NaPTA in neat MTBE cause small but measurable 29Si upfield chemical shifts indicating that the dimer saturates with 1.0 equiv of DME (28a). Excess (50 equiv) of DME elicited only a slight upfield shift of the 29Si resonance, leaving it well within the range of NaPTA dimers. Titration of NaPETA with 0.0–2.0 equiv of DME in MTBE cosolvent affords a dimer-monomer mixture in which the 29Si chemical shifts suggest lurking complexity stemming from either mixed DME- MTBE mixed-solvated dimers or arene p interactions. Exclusive monomer formation at 4.0 equiv of DME consistent with bis-chelate 29b is supported by DFT computations. NaBTA was largely but not exclusively dimer 28c with 1.0 equiv of DME and exclusively monomer 29c with 2.0 equiv. N N SiMe3 Me3Si Na R Me2N N NMe2 R Na N NMe2Me2N 27a-c not observed Me Me N Na R Me3Si Me2N N Me2N 26a; R = i-Pr 26b; R = t-Bu 26c; R = CH(Me)Ph Me 468 NaPTA shows dimers persist up to 4.0 equiv of diglyme, a coalescence (loss of resonance) at 8–15 equiv, and the emergence of monomer at >20 equiv. DFT computations support the dimer-monomer equilibrium shown in Scheme 2.1. The k2,k2 dimer, 30a, is the computationally preferred dimer. The diglyme concentration dependence implicates two diglymes on monomer 31a. A single k3- coordinated diglyme (32a) offers inadequate stabilization of the monomer to promote observable deaggregation. DFT computations support k3,k3 7-coordinate monomer 31a as a viable minimum, admittedly to our surprise. Figure 2.9 depicts ball-and-stick renditions of 30a and 31a. Scheme 2.1. NaPTA solvated by diglyme. N R Me3Si Na O O O O Me Me Me Me N N SiMe3 Me3Si Na R MeO OMe R Na MeO OMe 28a; R = i-Pr 28b; R = CH(Me)Ph 28c; R = t-Bu 29a; R = i-Pr 29b; R = CH(Me)Ph 29c; R = t-Bu 469 Figure 2.9. Ball-and-stick structures showing bis-diglyme-solvated NaPTA dimer 30a and monomer 31a. Whereas mono-diglyme-complexed monomer 32a appears to be insufficiently stabilized relative to the dimer to promote deaggregation, both NaPETA and NaBTA afford monomers (32b and 32c, respectively) with 1.0 equiv N N SiMe3 Me3Si Na i-Pr MeO O OMe i-Pr Na O OMeMeO 1/2 Na MeO O OMe OMe OMeO N Me3Si i-Pr 31a 30a diglyme N Na i-Pr Me3Si MeO O MeO 32a not observed 30a 31a 470 of diglyme. To repeat, the steric demands of the hindered dimers are driving deaggregation. Whether NaBTA and NaPETA can coordinate a second diglyme ligand at higher concentrations is not known but is supported as possible by DFT. Our interest in crown ether complexes was piqued years ago when the three most central crown ethers—12-crown-4, 15-crown-5, and 18-crown-6—failed to bind LiHMDS monomer in THF and bound identically relative to each other in toluene.18 We were unprepared for these results. More recent studies of NaHMDS showed the three crowns were superior to THF for binding the monomer but, again, showed identical binding constants for the three crowns.8b Titrations of NaPTA, NaBTA, and NaPETA with the three crowns showed quantitative binding in THF with the anticipated 1:1 stoichiometry for all nine base-crown combinations. Competition studies illustrated emblematically in Figure 2.10 and summarized in Scheme 2.2 and Table 2.4 revealed a substituent dependence. Because the competitions employed 1.0 equiv of each of two crowns, the values of Keq in Table 2.4 are mathematically the square of the ratios measured spectroscopically. Moreover, 33a/35a and 34a/35a pairings resolve by 29Si NMR spectroscopy, providing direct measures of Keq(15C5/12C4) and Keq(15C5/18C6). By contrast, the 33a/34a pair does not resolve; Keq(12C4/18C6) is calculated from the other two. The ‘>’ sign results from an inability to detect any 18-crown-6 complex 33a in the 33a/35a mixture (<5%). Caveat: whereas the comparisons across the rows N Na R Me3Si MeO O MeO 32a; R = i-Pr 32b; R = CH(Me)Ph 32c; R = t-Bu 471 are valid relative binding estimates for each crown to a given amide, there is no meaning to the numbers within a given column.39 Figure 2.10. 29Si NMR spectrum of [14N]NaPTA in neat THF at –110 °C with 1.0 equiv 12-crown-4 and 1.0 equiv 15-crown-5: d –22.11 and –23.85. The three crowns bind to the most hindered amide, NaBTA, with nearly equal affinity akin to what was observed for NaHMDS.8b (The values in Table 2.1 for NaBTA are measured values rounded to the nearest integer, which happen to be 1.0 for all three.) The least hindered NaPTA displayed a >400-fold range of affinities with 18-crown-6 the weakest and 15-crown-5 the strongest. NaPETA shows a similar trend spanning a more limited 50-fold range of binding. Overall, increasing the steric bias appears to override the oft-cited cation-crown preferences.40 We hasten to add that the DFT computations in Tables 2.1–2.3 got the trends right, but the magnitudes are wildly exaggerated, which underscores our -26.0-24.5-23.0-21.5-20.0 ppm NaPTA-15-C-5 –22.11 ppm NaPTA-18-C-6 –23.85 ppm 472 concerns about DFT computations in organosodium chemistry. Comparing the computed structures with crystal structures failed to reveal distortions in the computed structures. 473 Scheme 2.2. Competing 12-crown-4, 15-crown-5, and 18-crown-6 for NaPTA, NaPETA, and NaBTA. Table 2.4. Relative binding affinity (Keq, Scheme 2.2) of crown ethers for NaPTA, NaPETA, and NaBTA. Keq(15C5)/(18C6) Keq(15C5)/(12C4) Keq(12C4)/(18C6) NaPTA >400 9 >45 NaPETA 140 3 50 NaBTA 1 1 1 Reactivities. In a previous communication we described the reactivity of several dozen substrates with NaPTA/THF.9 We have now examined a limited series of reactions with NaPETA (Table 2.5) merely to underscore potential applications of sodium alkylsilazides in synthesis. An aqueous acid workup is R(Me3Si)NNa(18-C-6) 33a; R = i-Pr 33b; R = CH(Me)Ph 33c; R = t-Bu R(Me3Si)NNa(15-C-5) 34a; R = i-Pr 34b; R = CH(Me)Ph 34c; R = t-Bu 35a; R = i-Pr 35b; R = CH(Me)Ph 35c; R = t-Bu R(Me3Si)NNa(12-C-4) +15-C-5 –12-C-4 +15-C-5 –18-C-6 +12-C-4 –18-C-6 Keq(15/12) Keq(12/18) Keq(15/18) crown amide 474 necessary to desilylate several of the partially or wholly N- and O-silylated products. The results do not constitute a systematic survey of temperature or solvent to optimize the outcome. Table 2.5. Reactions of electrophiles with 0.12 M (1.2 equiv) NaPETA. Entry substrate solvent temp, time product (yield) 1 THF –80 °C, 2 h (93%) 2 THF –80 °C, 0.25 h (96%) 3 THF –80 °C, 2 h (76 %) 4 toluene or THF 25 °C, 1 h THF: 82%; 8:1 toluene: 84%; 1:13 5 THF 25 °C, 1 h <5% yield (26% conversion) 6 THF 25 °C, 0.5 h (78%) 7 (X = Cl) THF 25 °C, 1 h Ph OMe O N H O PhPh Me N OMe O N N H O Ph Me Ph O-t-Bu O Ph O-t-Bu O Ph O O-t-Bu Ph OMe O Ph N H O Me Ph Ph OMe ONHPh Me + NO2 F N F N H N Me Ph N X N H N Me Ph SiMe3 475 (X= Br) (X = Cl; 62%) (X = Br; 67%) 8 THF 25 °C, 24 h (85%) 9 THF 25 °C, 24 h (85%) 10 THF 25 °C, 24 h (96%, 5:1) The divergent reactivity of NaPETA with cinnamates in entries 3 and 4 is somewhat baffling. The solvent-dependent chemoselectivity in entry 4 is notable synthetically and suggestive of fundamental solvent-dependent mechanistic changes. Alas, the 1,4-adduct showed no evidence of stereocontrol, which contrasts with isostructural lithium phenethylamide derivatives.41,42 The dependence of the SNAr substitutions on the halide in entries 6 and 7 suggests a fluoride-dependent desilylation in entry 6 may be important in preventing the silyl-Fries rearrangement observed for 2-bromo- and 2-chloropyridine in entry 7.43,44 The N-alkylation in entry 8 is potentially useful and contrasts with the almost exclusive elimination by NaDA4 and mixed alkylation and elimination by LDA.4 The epoxide openings in entries 9 and 10 are clean and high yielding, yet optically pure styrene epoxide (entry 10) partially epimerizes. Casual attempts to exploit this for a dynamic kinetic resolution of the racemate offered no evidence of stereoselectivity. Despite previous studies of reactions of NaPTA,9 we were drawn back to examine several NaPTA-mediated aminolyses by mono- and dialkylamines (Scheme 2.3). By way of explanation and on a humorous note, the reaction was n-C6H13 Br n-C6H13 N H Ph Me n-C6H13 O n-C6H13 N H Ph Me HO Ph O Ph N H Ph Me OH Ph N H Ph Me + OH 476 discovered when traces of Me2NH contaminant in TMEDA afforded N,N- dimethylbenzamide as a byproduct. Although such aminolyses cannot compete with the convenience and economy of simply heating the ester with the amine, cases in which simple thermal aminolyses fail owing to lack of regio- or chemoselectivity might benefit from aggregation and solvation of alkali metal salts as potential control elements.45 We refer to the solvent-dependent reversal in chemoselectivity in entry 4 as cases in point. By contrast, aminolyses with LiHMDS/R2NH mixtures fail to react at ambient temperature,46 NaHMDS/R2NH reacts slowly at ambient temperature to give aminolysis by the NaHMDS/R2NH,47 and LDA/R2NH48 mixtures provide products from aminolysis by both the LDA and the amine. Spectroscopic studies (Supporting Information) show no detectable R2NNa intermediates in NaPTA/R2NH mixtures. Several attempts to aminolyze aliphatic methyl esters with alpha protons formed enolates as shown by IR spectroscopy.46c Scheme 2.3. NaPTA-mediated aminolyses of methyl benzoate. HN H2N Me Me Me OMe O R2NH NaPTA/toluene –80 °C NR2 O Me2NH (99%) Et2NH (91%) i-Pr2NH (<5%) HN (95%) (92%) (87%) 477 Kinetics: Aminolysis of methyl benzoate.49 Guided by recent rate studies of NaHMDS-based aminolyses,8d we settled on the NaPTA-mediated aminolysis of methyl benzoate to provide N-isopropylbenzamide (36) after workup to explore basic structure-reactivity principles (eq 4). The reader should bear in mind that mechanisms often change with seemingly minor changes in the substrate, so this is merely a slice of mechanism that should not lead to sweeping generalizations. We begin with a survey of solvent-dependent relative rates (Table 2.6) spanning a 47,000-fold range at –78 °C. Table 2.6. Solvent-dependent rates of aminolysis of methyl benzoate with NaPTA (eq 4).a solvent krel (–80 °C) toluene 1 MTBE 20 DMEA 50 Et3N 80 THF 680 DMEb (2.0 equiv) 120 diglymeb (2.0 equiv) 240 HMPAb (2.0 equiv) 900 PMDTAb (2.0 equiv) 10,300 Ph OMe O NaPTA solvent N H O i-Pr Ph (4) 36 (90–100%) 478 12-crown-4c (1.0 equiv) 47,000 15-crown-5c (1.0 equiv) 790 18-crown-6c (1.0 equiv) 30,000 aNaPTA (0.06 M), PhCO2Me (0.005 M). bEquiv of ligand relative to NaPTA in toluene cosolvent. cEquiv of ligand relative to NaPTA in THF cosolvent. Any mechanistic study must necessarily be founded on sound structural assignments of the reactants as found in Table 2.1.50 If the well-characterized reactants vary with initial conditions, the rate study becomes somewhat more challenging but often still manageable. However, additional complexity arises from solvent structure- and solvent-concentration-dependent complexation of methyl benzoate to NaPTA (Scheme 2.4). When mixtures are observed, the complexed form 37 is favored at high NaPTA and low solvent concentration as to be expected. Although the mixtures offer insights into relative solvation energies that can be experimentally elusive using other methods, they were assiduously avoided for detailed rate studies. The quantitative complexation in all toluene/hexane proportions and the absence of complexation in all THF/hexane proportions represent ideal opportunities. Methyl benzoate also shows no evidence of complexation to NaPTA at any concentration of the polyamines and polyethers in Chart 2.1. We focused the mechanistic studies on toluene, THF, diglyme, PMDTA, and three crown ethers. Scheme 2.4. Complexation of methyl benzoate to NaPTA dimer. 479 Kinetics: general protocols. The mechanistic studies were prefaced by 29Si and 1H NMR spectroscopic studies under near stoichiometric conditions (typically 0.10 M methyl benzoate and 0.12 M NaPTA) to monitor potentially consequential intermediates. The reactions requiring near-ambient temperatures were regularly interrupted by thermal quenching to –80 °C to record the spectra. [15N]NaPTA distinguished O–Si versus N–Si-containing species. Analogous reactions monitored by IR spectroscopy provided support. Rate studies were carried out under pseudo-first-order conditions in which the methyl benzoate is the limiting reagent (0.005 M) with the base and solvent (ligand) maintained at high, yet adjustable, concentrations using inert cosolvents. The loss of benzoate IR absorbances followed clean first-order decays; Figure 2.11 is emblematic. The supportive computational studies offer transition structures that fill in structural details that are not available from experiment and provided to provoke ideas about what might be happening. All are characterized by a single negative frequency. Intrinsic reac+on coordinate (IRC) calculations51 provide the minima excess NaPTA Ph OMe –20 °C 20% toluene* 1:>20 toluene 1:>20 20% Et3N* 1:10 Et3N 1:2 20% MTBE* 4:3 MTBE >20:1 20% THF* >20:1 THF >20:1 1724–1734 cm–1 1711–1712 cm–1 *pentane cosolvent N N SiMe3 Me3Si Na i-Pr i-Pr Na 37 solvent O Ph OMe O 480 immediately preceding and following the transition structures offering an enlightening peek at structural events proximate to the transition structures. Aminolysis Mechanism: NaPTA-toluene. Qualitative evaluation of the reaction coordinate by reacting excess (3.0 equiv) methyl benzoate with 1.0 equiv [15N]NaPTA in neat toluene at –80 °C—conditions affording the bis-benzoate- solvated NaPTA dimer—for 80 min converts methyl benzoate to imino ether 38 (d 18.51 ppm) and TMSOMe (δ 18.29 ppm) in a 10:1 ratio by integration. Aging at 23 °C results in the conversion of imino ether 38 to a 1:4 mixture of 38 and 39 (δ 18.56 ppm) with eventual conversion of both imino ethers to Me3SiOMe over 3.5 hr. An imino ether absorbance at 1661 cm–1 corresponding to 38 aged to give a mixture of 1661 cm–1 and 1650 cm–1 corresponding to 39 consistent with reported related structures.52 DFT computations support the stereochemistries of 38 and 39 as drawn based on the equilibrium population. An authentic sample was prepared from benzamide 36 using NaPTA in Et3N at –80 °C followed by TMSCl/Et3N at 23 °C, affording the absorbance at 1650 cm–1 (39). A slight change in the aminolysis by reacting 1.0 equiv of methyl benzoate with excess [15N]NaPTA (3.0 equiv) at 23 °C afforded almost exclusively a previously unseen downfield Si singlet at δ 23.42—an Si–O-bonded species—with no imino ether IR absorbance. It was shown to be a NaPTA/TMSOMe complex by preparing an authentic NaPTA/TMSOMe mixture. Quenching with CH₃OD or D₂O at –80 °C and warming to RT causes this 29Si resonance to be replaced with that of free Me3SiOMe. OSiMe3 N i-Pr OSiMe3 N i-Pr 38 39 481 Detailed rate studies under pseudo-first-order conditions described above revealed a first-order decay of complexed dimer 37 (S = toluene; 1711–1713 cm–1) shown in Figure 2.11. Zeroth-order dependencies on NaPTA (Figure 2.12) and toluene (Figure 2.13) provide the idealized rate law in eq 553 and the generic mechanism in eq 6. Figure 2.11. Plot of the concentration of methyl benzoate-NaPTA complex 37 (1712 cm–1) formed from methyl benzoate (0.005 M) and 0.12 M NaPTA in 5.6 M toluene/hexane at –20 °C. The curve depicts an unweighted least-squares fit to y = ae−bx: a = (8.1 ± 0.1) × 10−3; b = (1.5 ± 0.1) × 10−3). 5 4 3 2 1 0 [e st er ] x 1 03 (M ) 2000150010005000 time (s) 482 Figure 2.12. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) by NaPTA in neat toluene at –20 °C measured by monitoring the loss of 37 (1711–1713 cm–1) by IR spectroscopy. The curve depicts an unweighted least- squares fit to y = ax + b: a = (1.0 ± 0.1) x 10–3; b = (1.5 ± 0.1) x 10–3). Figure 2.13. Plot of kobsd vs [toluene] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.10 M) at –20 °C measured by IR 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 0.40.30.20.10.0 [NaPTA] (M) 2.5 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 1086420 [toluene] (M) 483 spectroscopy (1711–1713 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b: a = (1.4 ± 0.1) x 10–3; b = (–3.9 ± 0.1) x 10–5. –d[37]/dt = k’[37]1[NaPTA]0[toluene]0 (5) A2(toluene)(ester) [A2(toluene)(ester)]‡ (6) 37 (T1 or T2) DFT computations offered viable transition structures T1 and T2 in Figure 2.14 with a 2.2 kcal/mol preference for T1 (DG‡ = 32.2 kcal/mol at –80 °C). In related aminolyses of methyl-2-picolinate with NaHMDS we computationally examined the reaction coordinate including intimate details of the underlying organosilicon chemistry. We did not repeat such adventures in this study. N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na T1 N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na T2 484 Figure 2.14. Ball-and-stick and ChemDraw renditions of DFT-computed transition structures T1 and T2. Aminolysis Mechanism: NaPTA-THF. Monitoring a nearly stoichiometric reaction of methyl benzoate with 1.2 equiv of NaPTA in neat THF by 1H and 29Si NMR spectroscopies at –80 °C reveals formation of Me3SiOMe that correlates temporally with the loss of methyl benzoate. The absence of imino ether absorbance at 1661 cm–1 suggests a facile disilylation by the resulting NaOMe. The 1H NMR spectra are complex. The 29Si NMR spectra at early conversion display two doublets with equal integrations at –16.05 ppm (1JN-Si = 8.8) and –17.13 ppm (1JN-Si = 6.9 Hz) in the region expected for aggregated NaPTA subunits. By analogy with NaHMDS-amidinate mixed aggregates,8d computationally viable stereoisomeric mixed dimers 40 with a k2,k2-bound imidate would be logical.54 Prolonged aging at ambient temperature converts the putative mixed aggregates to complex spectra notably lacking resonances displaying 15N–29Si splitting; aggregates of imidate 41 are the likely culprits. Attempts to confirm the assignment by regenerating 40 from PhC(=O)NHi-Pr (36) and [15N]NaPTA affords a new species. This doesn’t refute the assignment, however, given the evidence of aging effects in kinetically formed aggregates.55 Failure to rigorously assign the mixture of salts resulting from post-rate- limiting steps does not impair detailed rate studies. An apparent obsession over the N Na N Na i-Pr SiMe3i-Pr O THF THF Ph O N i-Pr Na n 40 41 485 details of the solvation by THF is based on the dearth of such data in organosodium chemistry and the central importance of THF. First-order decays of the uncomplexed methyl benzoate, a zeroth-order dependence on free THF concentration (Figure 2.15, Curve A), and a first-order dependence on the observable NaPTA dimer (Figure 2.16) appeared to implicate an [A2S2(ester)]‡ transition structure. Figure 2.15. Plot of kobsd vs [THF] (M) in pentane (Curve A, red), MTBE (Curve B, blue), and Me4THF (Curve C, green) for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.12 M) at –78 °C measured by IR spectroscopy (1727 cm– 1). All fits were to y = ax/1+bx. Curve A: a = (6.3 ± 0.1) × 10–3; b = 91.6 ± 1.0); Curve B: a = (2.6 ± 0.1) × 10–4; b = 0.3 ± 0.1; Curve C: a = (4.8 ± 0.1) × 10–5; b = 0). 0.6 0.4 0.2 0.0 k o bs d x 10 3 / se c–1 121086420 [THF] (M) A: hexane B: MTBE C: Me4THF 486 Figure 2.16. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) in neat THF at –78 °C measured by IR spectroscopy (1727 cm–1). The curve is a least-squares fit to y = axb: a = (6.6 ± 0.1) x 10–2; b = 1.1 ± 0.1. We suspected that Curve A in Figure 2.15 might be the result of saturation kinetics involving an A2S2-to-A2S4 conversion that would elude spectroscopic detection; however, solubility precluded probing the rates at low THF concentrations. Attempting to rectify the solubility problem at the low THF concentrations using MTBE as a cosolvent afforded Curve B in Figure 2.15, which was not expected. Either MTBE was competing with THF for coordination to sodium—intuition suggested not but the solvation energies in Table 2.1 left the issue open—or the polarity of the medium is important in determining the curve shapes. 29Si NMR spectroscopy showed that 10 equiv of THF (1.0 M) to NaPTA in neat MTBE were required to convert the MTBE-solvated NaPTA dimer (–13.41 ppm) to the THF-solvated NaPTA dimer (–16.79 ppm). Although this surprised us, 30 20 10 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaPTA] (M) 487 it is compatible with the computed relative solvation energies in Table 2.1. More to the point, however, the observable THF-MTBE mixed solvates only influenced the lowest three points of Curve B; they cannot be the origin of the entirety of Curve B. Following the polarity thesis, we turned to a standard control experiment used repeatedly throughout our studies of lithium amides by using the hindered 2,2,5,5-tetramethyltetrahydrofuran (Me4THF) as a non-coordinating surrogate of THF with a comparable dielectric constant to hold the medium polarity constant.56 Crystallographic studies of higher alkali metal disilazides solvated Me4THF displayed structural distortions leading Kriek et al. to conclude Me4THF was a poor ligand. It was a decidedly weak ligand for NaHMDS.57 DFT computations on Me4THF-solvated NaPTA dimer show a –4.4 kcal/mol/solvent, which is a considerable 1.4 kcal/mol/ligand than with THF. Nonetheless, 29Si NMR spectroscopy showed that approximately 10 equiv of THF are required to fully convert the Me4THF-solvated NaPTA dimer (–13.78 ppm) to the THF-solvated dimer (–16.70 ppm). As coordinating ligands, MTBE and Me4THF are surprisingly similar. (Attempts to use 2,5-dimethyltetrahydrofuran, Me2THF, as a non- coordinating polar medium led to complexity beyond the scope of this manuscript owing to mixed solvation up to equal volumes of THF and Me2THF. Me2THF is far from non-coordinating.) Using Me4THF as the cosolvent (Curve C, Figure 2.15) shows an approximate first-order dependence on THF. The apparent zeroth-order dependence on THF using hexane as the cosolvent and first-order dependence on THF using Me4THF as the cosolvent are striking, especially in light of our experiences with lithium amide chemistry. With that said, similarly large medium effects were noted in NaHMDS-THF-mediated aminolyses8d and alkylations of sodium enolates.58 488 We describe these primary- and secondary-shell solvent effects in Figure 2.15 according to eq 7, such that P is a general term for medium polarity—a fudge factor in the vernacular. We do not profess to fully understand the basis of P, but one could imagine relating it to changing dielectric constant. If there is no change in polarity with changing THF concentration as one would expect using Me4THF as the cosolvent, P » 0, and the THF dependence reduces to a first order as observed in Curve C. With hexane as the cosolvent, the aminolysis is inhibited by the polar medium as the influence of P becomes significant. Eq 7 reduces to a zeroth-order THF dependence as observed in Curve A. An intermediate change in polarity using MTBE as the cosolvent produces an apparent fractional-order curvature (Curve B). That polarity inhibits the reaction is indisputable: at low THF concentration the reaction is markedly faster in hexane than in Me4THF. This seems likely to be a net stabilization of the ground state rather than a destabilization of the transition state. We surmise that Lewis basicity of THF is attenuated in polar media. Such inhibition has been noted in several studies and attributed to groundstate stabilization.8d,58 rate µ [THF]1/(1 + P[THF]) (7) The complete rate law including the polarity correction in eq 8 is consistent with the generic mechanisms in eq 9 and 10. DFT computations exploring the [A2S3(ester)]‡ transition structure probing various placements of bound THF and ester provided transition structures T3-T5 with T5 preferred by approximately 2.0 kcal/mol over T3 and T4 (Figure 2.16). –d[PhCO2Me]/dt = k’[PhCO2Me][NaPTA]1[THF]1/(1 + P[THF]) (8) 489 A2S2 + S A2S3 (9) (10) (11) A2S3 + PhCO2Me [A2S3(ester)]‡ (10) (11) (T3–T5) N i-Pr SiMe3 OMeO Na Ni-Pr Me3Si Na THF THF T3 THF N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THF T4 N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THF T5 490 Figure 2.16. Ball-and-stick and ChemDraw renditions of DFT-computed transition structures T3–T5. We are obligated to consider contributions from an alternative, computationally viable transition structure T6 based on triple ions (Figure 2.17). At first blush, T6 seems unlikely in the face of considerable evidence that large sodium gegenion prefers at least six coordinated THF ligands.8b,59 (Even the smaller +Li(THF)6 is documented.60) Even if NaPTA is an A2S4 tetrasolvated dimer rather than the disolvate as noted in the structural studies, the implicit +Na(THF)5 cation is still undersolvated. However, if one squints at Curve C in Figure 2.15, it curves upward and displays a 1.2 order if allowed to be an adjustable parameter. Could that be the triple ion? We are well within the experimental error of both experimental and computational data: it is largely speculation. Figure 2.17. Ball-and-stick and ChemDraw renditions of DFT-computed triple ion based transition structures T6 with the sodium cation not shown. Aminolysis Mechanism: NaPTA-PMDTA. Reaction of 0.060 M PMDTA- solvated NaPTA monomer 26a with 0.0050 M uncomplexed methyl benzoate (1724 cm–1) affords imino ether 38 (d 18.51 ppm, 1661 cm–1) and Me3SiOMe (1:5). N i-Pr Me3Si MeO O Na N SiMe3 i-Pr T6 +Na(THF)6 491 Over time, 38 disappears (accompanied by the loss of the 1661 cm–1 absorbance in the IR spectra) with a proportionate increase in Me3SiOMe. Rate studies reveal a first order in methyl benzoate, first order in PMDTA- solvated NaPTA, and zeroth order in PMDTA, consistent with the rate law in eq 11 and generic mechanism in eq 12. Transition structure T7 is quite reasonable (Figure 2.18, DG‡ = 8.2 kcal/mol) except for the k2-PMDTA ligand. The large sodium ion could, in theory, leave room for coordination of the substrate, base, and trifunctional ligand, but all efforts to locate a transition structure bearing a k3- PMDTA ligand irresistibly pulls open to the k2 form shown in T7 with, at best, a weakly interacting 3.6 Å N–Na contact. –d[ester]/dt = k’[ester][NaPTA]0[PMDTA]0 (11) AS + ester [AS(ester)]‡ (12) (26a) (T7) Figure 2.18. Ball-and-stick and ChemDraw renditions of DFT-computed transition structures T7. IRC calculations are particularly informative in this case. The minimum preceding T7 shows considerable lengthening of the elongated N–Na contact. The N i-Pr Me3Si MeO O Na N N N Me Me Me Me Me T7 492 minimum following T7 has a full k3-PMDTA as well as a fully fractured silazide N-–Na contact. Suspecting that we might be witnessing an unexpected preference for a larger bite angle in T7, we examined isostructural transition structures with either TMEDA and TMPDA (N,N,N’,N’-tetramethylpropanediamine) only to find that T7 is the most stable of the three and the TMPDA chelate the least stable, arguing against that thesis. Aminolysis Mechanism: NaPTA-Diglyme. Reaction of methyl benzoate with 3.0 equiv of NaPTA and 10 equiv of diglyme in toluene gave results akin to those observed in THF in which the loss of NaPTA correlated with the formation of TMSOMe as the only observable silicon-containing product. We ignored one of our guidelines again by examining the mechanism of NaPTA solvated by diglyme: the reactant shifts from dimer to monomer over the full range of diglyme concentrations. A plot of kobsd versus diglyme concentration (Figure 2.19) reveals that driving the disolvated NaPTA dimer 30a to disolvated monomer 31a (Scheme 2.1) inhibits the reaction. The curvature approaching the left-hand y-intercept shows a rate flattening in the limit of the A2S2 dimer. The sharpness of the sigmoid qualitatively implicates a high-order inhibition. Most importantly, monomer 31a is oversolvated. From experience with NaHMDS, we were not surprised to find that NaPTA in neat diglyme displays a second-order dependence (Figure 2.20): the observable monomer associates to a dimer before reacting with methyl benzoate. With this knowledge, the parametric fit of the solvent dependence in Figure 2.19 to the model in eq 13 and 14 (Supporting Information) affords rate µ [diglyme]–3.2. It is not a great fit but adequate. 493 Figure 2.19. Plot of kobsd vs [diglyme] in hexane for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.12 M) at –50 °C measured by IR spectroscopy (1728–1730 cm–1). The fit to the model in eq 13 and 14 affords a solvation order, n, of –3.2. The curve depicts an unweighted least-squares fit to y = (0.25axn – 0.25(16b + a2x2n)1/2)2: a = (6.9 ± 0.1) × 10−2; b = (2.3 ± 0.1) × 10−1; n = 3.2 ± 0.6). Details are in Supporting Information. 60 50 40 30 20 10 0 k o bs d x 10 3 / se c–1 6543210 [diglyme] (M) 50 40 30 20 10 0 k o bs d x 10 3 / se c–1 0.200.150.100.050.00 [NaPTA] (M) 494 Figure 2.20. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) in 6.3 M diglyme/hexane at –78 °C measured by IR spectroscopy (1730 cm–1). The curve is a least-squares fit to y = axn: a = 2.0 ± 0.1 ; n = 2.2 ± 0.2. 2AS2 A2S + 3S (13) (31a) A2S + PhCO2Me [A2S(ester)]‡ (14) (T8) To complete the NaPTA-diglyme story, DFT computations of the monosolvated-open-dimer-based transition structure offered T8 (Figure 2.21). Diglyme retains k3 coordination. Figure 2.21. Ball-and-stick and ChemDraw renditions of DFT-computed mono- diglyme-solvated dimer-based transition structure T8. Motivated by the divergent mechanisms for two seemingly isostructural trifunctional ligands, diglyme and PMDTA, in a more creative moment we monitored the aminolysis rates vs diglyme mole fraction, Xdiglyme, in diglyme- PMDTA mixtures in hexane at a fixed 2.0 M ligand concentration (Figure 2.22). The left-hand y-axis corresponds to the rate in 2.0 M PMDTA via a monomer- N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na T8 O O O Me Me 495 based addition. The right-hand y-axis corresponds to the rate in 2.0 M diglyme via a disolvated dimer. The notable spike in rates at 19:1 PMDTA:diglyme flags a cooperatively-solvated [An(PMDTA)(diglyme)(ester)]‡ transition structure. Ascertaining the aggregation number, n, is well beyond the resolution of the data. However, the potential prevalence and importance of cooperative solvation surfaces again in the context of crown-ether-mediated aminolyses. Figure 2.22. Plot of kobsd vs mole fraction of diglyme, Xdiglyme, for the aminolysis of methyl benzoate (0.0050 M) by NaPTA (0.060 M) in fixed 2.0 M diglyme-PMDTA mixtures in hexane at –78 °C as measured by IR spectroscopy (1729 cm–1). Aminolysis Mechanism: NaPTA-crown ethers. The binding constants for the three primary crown ethers (Table 2.4) establish a foundation for the study of their influence on NaPTA-mediated aminolysis of methyl benzoate. The results diverged substantially from what we expected, although we have come to expect such divergences. The relative binding constants in Table 2.4 showing 15-crown-5 > 12- crown-4 > 18-crown-6 contrast with the relative rates of NaPTA-mediated 120 100 80 60 40 20 0 k o bs d x 10 3 / se c-1 1.00.80.60.40.20.0 χdiglyme 496 aminolysis of methyl benzoate in Table 2.5 showing 12-crown-4 > 18-crown-6 >> 15-crown-5. Figure 2.23 shows a plot of kobsd versus free (uncoordinated) crown concentrations: the points listed as zero concentration of free crown have an equivalent of crown complexed to the NaPTA monomer and correspond to the values of krel reported in Table 2.5. The non-zero intercepts and significant first- order dependencies for both 12-crown-4 and 18-crown-6 reveal crown- concentration-independent and crown-concentration-dependent pathways (eq 15). The dominant zeroth-order dependence on 15-crown-5 (see insert) reflects a dominant crown-concentration-independent pathway with only a minor acceleration from the added crown. A zeroth-order dependence on THF concentrations using pentane cosolvent for all three crowns shows either no role of THF or an offsetting influence on the ground and transition states. Figure 2.23. Plot of kobsd vs free (uncomplexed) crown ether (M) for 12-crown-4 (red), 15-crown-5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.0050 M) by 0.060 M NaPTA in neat THF at –78 °C measured by IR spectroscopy 300 250 200 150 100 50 0 k o bs d x 10 3 / se c–1 0.120.100.080.060.040.020.00 [free crown] (M) 3.0 2.0 1.0 0.0k o bs d x 1 03 / se c–1 0.100.00 [free 15-crown-5] (M) 12-C-4 18-C-6 15-C-5 497 (1733 cm–1). All curves were to fit to y = ax + b. 12-C-4: a = 1.0 ± 0.1; b =(6.0 ± 0.1) x 10–2; 15-C-5: a = (4.3 ± 0.1) x 10–3; b = (1.2 ± 0.1) x 10–3; 18-C-6: a = 0.7 ± 0.1; b = (3.1 ± 0.1) x 10–2. rate µ a[crown]0 + b[crown]1 (15) Technical problems precluded obtaining orders in NaPTA for the crown- dependent pathway. The reaction orders in NaPTA of the crown-independent pathway was determined by varying the concentration of NaPTA solvated by 1.0 equiv of 12-crown-4 (Figure 2.24) and 15-crown-5 (Figure 2.25.) Distinct upward curvatures arising from net orders of 1.31 and 1.22, respectively, demand several comments: (1) these are challenging experiments, which should elicit caution in over-interpreting subtle rate effects; (2) it is undeniable a fractional order arising from a free-ion-based pathway is absent;61 and (3) these curvatures are considerably outside the the norm for first-order dependencies, are self-consistent, and reflect the possibleintervention of a second-order dependence affiliated with a dimer-based pathway akin to the results in diglyme. 160 140 120 100 80 60 40 20 0 k o bs d x 10 3 / se c-1 0.150.100.050.00 [NaPTA•12-crown-4] (M) 498 Figure 2.24. Plot of kobsd versus the concentration of NaPTA–12-crown-4 complex 34a (M) for the aminolysis of methyl benzoate (0.005 M) in neat THF at –78 °C measured by IR spectroscopy (1731 cm–1). The curve is a least-squares fit to y = axb: a = 1.7 ± 0.4; b = 1.3 ± 0.1. Figure 2.25. Plot of kobsd versus the concentration of NaPTA–15-crown-5 complex 35a (M) (complexed) for the aminolysis of methyl benzoate (0.0050 M) in neat THF at –78 °C measured by IR spectroscopy (1730 cm–1). The curve is a least- squares fit to y = axb: a = (4.2 ± 0.1) x 10–2; b = 1.2 ± 0.1. The crown-mediated aminolyses are described by the idealized rate law in eq 15 and the generic mechanisms in eqs 16–18 corresponding to aminolyses by NaPTA-crown monomer (eq 16), NaPTA-bis-crown complexed monomer (eq 17), and NaPTA-bis-crown complexed dimer (eq 18). –d[ester]/dt = k’[ester][A(crown)]>1 + k’[ester][A(crown)]n[crown]1) (15) 8 6 4 2 0 k o bs d x 10 3 / se c-1 0.300.250.200.150.100.050.00 [NaPTA•15-crown-5] (M) 499 A(crown) + ester [A(crown)(ester)]‡ (16) (33a–35a) (T9–T11) A(crown) + crown + ester [A(crown)2(ester)]‡ (17) (33a–35a) (T9) 2 A(crown) + ester [A2(crown)2(ester)]‡ (18) (33a–35a) (T13) Transition structures containing a mono-complexed crown are illustrated in Figure 2.26. The oxygens rendered in red are those that show a distinct Na–O contact. The calculated activation energies of T9–T11 are DG‡12C4 = 11.2 kcal/mol, DG‡15C5 = 6.9 kcal/mol, and DG‡18C6 = 15.1 kcal/mol, which don’t even predict the order of reactivity correctly because of large errors in the computed NaPTA-crown binding . The [A(crown)2(ester)]‡ transition structures labelled T12 differ only in the coordination sphere of the sandwiched counterion, +Na(crown)2. Previous calculations of such sandwiched sodium cations spanned 15 kcal/mol range,8b which have little relationship to either our measured binding constants or rate data. T13 is isostructural to triple ion T6 but with the well-documented +Na(crown)2 counterion.8c,11a,62,63,64 N i-Pr Me3Si MeO O Na O O O O T9 500 T10 N i-Pr Me3Si MeO O Na O O O OO T11 N i-Pr Me3Si MeO O Na O O O O O O T12 MeO N i-Pr Me3Si O +Na(crown)2 N i-Pr Me3Si MeO O Na N SiMe3 i-Pr T13 +Na(crown)2 501 Figure 2.26. Ball-and-stick and ChemDraw renditions of DFT-computed transition structures T9–T13. Red in the ChemDraw structures designates the oxygens within bonding distance to sodium. An unorthodox experiment examined the crown-concentration-dependent pathway by exploiting the structurally dominant NaPTA–15-crown-5 monomer reactant, 35a, to probe the influence of adding 12-crown-4 or 18-crown-6 (Figure 2.27). The y-intercept corresponds to the rate for NaPTA–15-crown-5 complex 45a. The subsequent points correspond to the rates for 45a with additional 12- crown-4 (red), 15-crown-5 (green), and 18-crown-6 (blue). The slopes reflect the acceleration by additional equivalents of crowns. (The data for adding 15-crown-5 repeated from Figure 2.23.) The data for 18-crown-6 in Figure 2.27 is most instructive because 18-crown-6 does not compete with 15-crown-5 for binding to NaPTA. The mechanistic scenario is illustrated in Scheme 2.5. Figure 2.27. Plot of kobsd vs free (uncomplexed) crown ether for 12-crown-4 (red), 15-crown-5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.005 M) by 0.060 M NaPTA/15-crown-5 complex in neat THF at –78 °C 80 60 40 20 0 k o bs d x 10 3 / se c–1 0.120.100.080.060.040.020.00 [free crown] (M) 12-C-4 18-C-6 15-C-5 NaPTA-15-C-5 502 measured by IR spectroscopy (1733 cm–1). All curves were to fit to y = ax + b. 12- C-4 : a = 0.7 ± 0.1; b = (4.5 ± 1.0) x 10–3; 15-C-5 : a = (1.2 ± 0.1) x 10–3; b = (4.3 ± 0.1) x 10–3; 18-C-6: a = (2.8 ± 0.1) x 10–1; b = (2.4 ± 0.1) x 10–1. Scheme 2.5. Mechanism of methyl benzoate aminolysis by NaPTA(15-crown-5) (35a) with added 18-crown-6. Scheme 2.5 illustrates two pathways: (1) a substitution to produce a fleeting but potentially more reactive NaPTA–18-crown-6 complex 33a with addition via T11, and (2) an aminolysis proceeding via T13 with a mixed-crown counterion.63 Both pathways would manifest a first-order dependence on 18-crown-6 as observed in Figure 2.27. However, the substitution pathway via T11 would manifest an inverse-first-order dependence on 15-crown-5 whereas the bis-crown- based pathway via T13 would be unaffected by added 15-crown-5. The dependence on 15-crown-5 illustrated in Figure 2.28 clearly shows the inverse order expected for the T11 pathway. However, the saturation of the rate at the highest 18-crown-6 concentration is at a tenfold higher rate than with the mono-crown pathway (included in Figure 2.28 for comparison). The significant acceleration by having both crowns present at the saturation implicates the aminolysis via T13. Thus, both pathways in Scheme 2.5 are operative. NaPTA(18-C-6) 18-C-6 NaPTA(15-C-5) +18-C-6 –15-C-5 [NaPTA(18-C-6)(ester)][NaPTA(15-C-5)(18-C-6)(ester)] ester ester T13 T11 35a 33a 503 Figure 2.28. Plot of kobsd vs free (uncomplexed) crown (M) for the aminolysis of PhCO2Me (0.005 M) by NaPTA–18-crown-6 complex 33a in neat THF at –78 °C with varying concentrations of added free 15-crown-5 measured by IR spectroscopy (1730 cm–1). The curve corresponds to a least-squares fit to y = (axn/(1+bxn)) + c: a = (1.0 ± 0.1) × 10–3; b = (1.5 ± 0.1) × 10–2; c = (8.0 ± 0.1) × 10–3; n = –1.1 ± 0.1. We surmise—it is only a guess—that most organic chemists looking to accelerate the reaction of a sodium salt instinctively would reach for 15-crown-5 because of the putative optimal cation-crown pairings, which by this one case study would be decidedly incorrect. Scheme 2.6 is a free energy diagram that accounts for the reactivities of the mono-crown-complexed NaPTA dissected into ground state and transition state stabilization. At the risk of stating the obvious, the free crowns must be included to balance the equations for obtaining valid energies. The relative binding constants in Table 2.4 afford DG°1 and DG°2, and the activation energies in Table 2.6 allow us to calculate the relative energies of the transition states DG°3 and DG°4. The lower limit of the value of DG°1 merely puts a 60 50 40 30 20 10 0 k o bs d x 10 3 / se c-1 0.250.200.150.100.050.00 [free 15-crown-5] (M) NaPTA-15-C-5 + 15-C-5 NaPTA-15-C-5 + 18-C-6 + 15-C-5 NaPTA-15-C-5 + 18-C-6 504 lower limit of the same magnitude on DG°3 without altering the relative energetic ordering. The strong binding of the reactant with 15-crown-5 is necessarily deleterious to the rate: stabilizing the reactants necessarily raises the barrier. The problem is that offsetting stabilization of the transition state is meager. The highest stabilization of the transition state by complexed 12-crown-4 offset by a meager offsetting stabilization of the ground state produces optimal rates. Scheme 2.6. Relative free energies of the mono-complexed crown ground states and transition states determined from measured binding constants (Table 2.4) and relative rate constants (Table 2.6). Conclusion Sodium alkylsilazides are close to optimizing reactivity and basicity relative to NaHMDS without sacrificing ethereal solvent lability observed for NaDA. We invested considerable effort to develop the chemistry of NaDA bases. However, unless practitioners require a half-dozen more pKb units of basicity, sodium alkylsilazides like NaPTA and NaBTA should cannibalize many of the applications NaPTA(15-C-5) 12-C-4 + 18-C-6 ester [NaPTA(15-C-5)(ester)] 12-C-4 + 18-C-6 NaPTA(12-C-4) 15-C-5 + 18-C-6 ester NaPTA(18-C-6) 12-C-4 + 15-C-5 ester [NaPTA(18-C-6)(ester)] 12-C-4 + 15-C-5 [NaPTA(12-C-4)(ester)] 15-C-5 + 18-C-6 ΔG2= 0.8 kcal/mol ° ΔG1> 1.5 kcal/mol ° ΔG4= 0.7 kcal/mol ΔG3 > 1.0 kcal/mol ° ° 505 of NaDA. The structural and mechanistic studies described herein were largely intended to examine and ultimately push this narrative while simultaneously examining how solvation influences aggregation and reactivity—developing the basic coordination chemistry of sodium. What have we learned? Peering at organosodium chemistry through a wide- angle lens, sodium and lithium are often treated minimally as gegenions simply to maintain charge balance. To state the obvious, sodium is not just a larger variant of lithium: they are different metals. From the perspective of physical organic studies, the solution structural and mechanistic organosodium chemistry is more challenging than organolithium chemistry. Higher ligand and subunit exchange rates, the absence of scalar coupling, and the expanded coordination sphere for the large sodium ion have demanded less direct methods to probe solution structures. It was not obvious at the outset that the coordination chemistry of sodium would be tractable. The unexpected central role of 29Si NMR spectroscopy during studies of alkali metal silazides—the correlation of 29Si chemical shift and 15N–29Si coupling with aggregation state—cannot be overstated.65 Our sense is that other organometallic chemists generating metal silazides would benefit from exploring such correlations. As noted previously,8b 29Si NMR spectroscopy appears to be overlooked by all but organosilicon and mechanistic chemists. With the explosion in silicon-based protecting groups because of the invention of trialkylsilyl triflates, 29Si NMR spectroscopy should be used routinely to monitor reactions, probe for biproducts, and measure selectivities. 29Si is on par with 19F or 31P. A requisite reliance on less direct methods to study solution structures of sodium salts forced a disproportionate reliance on DFT computations. The resulting theory-experiment correlations emerging from these studies have, somewhat ironically, undermined our confidence in using computations too 506 quantitatively. There may a basis set or protocol in the community to resolve these issues, but our failure to find it was not from lack of trying. Beginning with a 1992 review37b in which we threw down a few gauntlets about solvation, aggregation, and reactivity, we remind the reader that solvents are ligands, putative strong ligands do not always promote deaggregation, and lower aggregates are not necessarily more reactive. Organosodium chemistry has reinforced our conviction that dogmatic ideas from the past and sweeping generalizations can be quite misleading. The aminolysis of methyl benzoate by NaPTA in diglyme, for example, shows that driving the NaPTA dimer to monomer at high diglyme concentration retards the rates because the monomers must reassociate to form lesser-solvated dimers to react. This is an excellent example of a requisite aggregation step preceding the rate-limiting step, but it is not the first.8c,d The crown ethers offer additional evidence that our expectations are often wrong. As transient visitors to the field of crown ethers, we are at risk of failing to understand context in the enormous literature. (A recent Google Scholar search affords over 200,000 hits.) With that caveat, the repeated failure of the crown ethers to match our expectations continued with the study of NaPTA. The oft-cited correlation of crown and metal ion size with binding constant and reactivity has not held up to scrutiny. Admittedly, 15-crown-5 shows the greatest penchant for binding sodium, but only for two of the three sodium silazides studied. Crown- cation selectivity is eroded with increasing bulk of the sodium amide; however, much of the crown literature scrutinizing the principles of binding focuses on sterically undemanding inorganic salts. Moreover, the relative binding constants did not correlate with relative NaPTA reactivities. Any urge to presume that a given crown-metal ion combination—15-crown-5 for binding sodium, for example—is 507 the best choice to accelerate a reaction should be resisted: 15-crown-5 was decidedly the worst for a NaPTA-mediated aminolysis. Aminolyses in THF revealed what has become a recurring theme: secondary-shell (medium) effects are much more pronounced in organosodium chemistry than in organolithium chemistry. Those interested in unraveling the role of solvation must pay attention to this detail. Even when merely optimizing yields or selectivities, the influence of cosolvent can be pronounced. Using a standard control from organolithium chemistry in which 2,2,5,5-Me4THF is used as a polar, non-coordinating cosolvent showed polarity matters and inadvertently revealed a remarkable capacity of hindered ligands to coordinate to the much larger sodium ion. The underlying mechanistic complexity of alkali metal chemistry virtually guaranteed that sweeping generalizations about the role of solvation and aggregation would often fail. For example, any suggestion that an additive known to strongly bind the metal will necessarily increase the reaction rate is bordering on nonsensical. We offer two obvious truisms: (1) rates are a function of the stabilities of the ground states and transition states, and (2) reaction rates depend on mechanism. The highest reactivities are not necessarily elicited by strong ligands that stabilize lower aggregates. Any reaction parameter that stabilizes the reactants will necessarily retard reactivity. This includes strongly coordinating solvents even if they are only intended to dissolve the reagents. Forcing deaggregation by stabilizing monomers is counterproductive. By contrast, forcing deaggregation by destabilizing aggregates will often lead to high reactivities. The highest reactivities will be attained by minimally stabilizing the reactant and maximally stabilizing the transition structures through a combination of controlling the steric demands of the alkali metal salts and achieving transition-state-selective solvation. 508 We salted some potential ideas throughout this paper for the more synthetically inclined, but synthetic methods are more effectively driven by the practical needs of consumers than the imaginations of the mechanistically inclined. We do offer, however, one last idea with synthetic chemists as the target. An obvious Holy Grail of organoalkali metal chemistry—ligand-based catalysis of stoichiometric reactions—may be more achievable with sodium than lithium because of the ease of attaining ligand exchange and turnover.66,67,68,69 We examined PMDTA-catalyzed reactions of NaDA in both solution phase and by solid-liquid phase transfer.66 We achieved both high accelerations and turnovers. However, NaDA is in a narrow niche of Bronsted bases and is too destructive to use ethereal ligands as catalysts. We surmised that sodium alkylsilazides may be compatible with more ligands and far more versatile reagents. To this end, we have taken the liberty of burying a few results in the Supporting Information. Ligand-catalyzed reactions of NaBTA were not examined, and NaPETA was disappointing (possibly owing to its steric demands), but NaPTA was promising (Scheme 2.7). The reaction of focus herein—the aminolysis of methyl benzoate—showed a 25-fold acceleration with 10 mol percent PMDTA, corresponding to a kcat = 250. Moreover, all of the ligands in Chart 2.1 catalyzed the 1,4-addition to methyl cinnamate, some by as much as >300-fold acceleration (kcat of >3,000). Scheme 2.7. Ligand-catalyzed NaPTA-mediated C–N bond formation. 509 Why finish with this teaser? To reiterate, need is the Mother of Invention and should drive the applications; we lack both the skills and temperament to pursue this challenge to practical ends. The accelerations also display odd curvatures suggesting a mechanistic complexity—possibly autocatalysis and autoinhibition— beyond the scope of this study. The most definitive answer is far less abstract: this is our last contribution to organosodium chemistry. Although a review article is written and will be submitted at some point, the experiments are done. Hopefully, the ongoing progress in the field is durable rather than another “brief burst of activity” only to go “dormant” yet again. Organosodium chemistry is currently looking healthy and is in capable hands.3 Experimental Reagents and solvents. Hydrocarbons, monofunctional trialkylamines, mono-functional ethers, HMPA, TMEDA, (R,R)-TMCDA, (S,S)-TMCDA, PMDTA, diglyme, and triglyme were distilled from blue or purple solutions containing sodium benzophenone ketyl. 12-crown-4, 15-crown-5, and 18-crown-6 were dried over 4 Å mol sieves before use. NaPTA and [15N]NaPTA were prepared as described previously.9 tert-Butyl(trimethylsilyl)amine and (R)-(1- phenyl)ethyl(trimethylsilyl)amine are commercially available. NaPETA, NaBTA, and [15N]NaBTA were prepared as described below. NaPTA/toluene Ph OMe O Ph OMe O Ph OMe Oi-PrNH Ph NH-i-Pr O 10% catalyst 510 (R)-Sodium (1-phenyl)ethyl(trimethylsilyl)amide. Method A. Sodium slices (6.0 g) cut from sodium cubes were placed in a 250 mL pear-shaped flask. Dry DMEA (100 mL) and (R)-(1-phenyl)ethyl(trimethylsilyl)amine (24.4 mL, 112.5 mmol) were added to the flask under positive argon pressure, and to the mixture at –0 °C was added isoprene (8.0 mL, 11.2 mmol) all at once. Stirring for 120 min yielded a clear red solution, which can be transferred by cannula and used as is. To isolate purified NaPTA, the mixture was filtered through a fine frit and evaporated to dryness to give a yellowish solid. Washing with hexane and drying in vacuo gave NaPETA as a pale white solid (15.4 g, 61% yield). The spent sodium is quenched by adding hexane followed by isopropanol. 1H NMR (500 MHz, [d8]THF) δ 7.78 (d, J = 7.5 Hz, 2H), 7.53 (t, J = 7.5 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 4.75 (d, J = 6.9 Hz, 1H), 3.98 (s, 1H), 1.60 (d, J = 6.5 Hz, 3H), 0.24 (s, 9H). 13C{1H} NMR (126 MHz, [d8]THF) δ 158.3, 128.6, 127.1, 125.1, 57.8, 31.5, 4.2. 29Si NMR (toluene, 99.36 MHz, –80 oC) d –12.05. [15N]Pivalamide. The stepwise preparation of [15N]NaBTA begins with the synthesis of the labeled amine. Thus, pivaloyl chloride (12.0 mL, 100.0 mmol) in the Et2O (50 mL) was layered onto a solution of [15N]NH4Cl (5.0 g, 91.5 mmol) in H2O (20.0 mL) in 250.0 mL flask. The flask was cooled to 0 °C, and NaOH (20.0 g, 500 mmol) in H2O (30 mL) was slowly added by pipette to the aqueous layer with slow stirring to avoid mixing of layers. A white precipitate formed during the addition. The flask was warmed to room temperature with stirring for 15 mins followed by vigorous stirring for an additional 10 min. The white solid was collected by filtration and washed with Et2O. After drying under vacuum, the resulting white solid was washed with aqueous acetone extraction (50 mL x 3), and dried in vacuo to give [15N]pivalamide (8.5 g, 83% yield). 1H NMR (500 MHz, D2O): d 1.17 (s, 9H). 13C{1H} NMR (CDCl3, 125.8 MHz): d 186.04 (1JC–N = 15.3 511 Hz), 38.2 (1JC–N = 5.8 Hz), 26.6. HRMS (DART-Orbitrap) m/z[M+H]+ calcd for C5H12NO 103.0884, found 103.0890. [15N]tert-Butyl ammonium tosylate. To a 250 mL flask containing [15N]pivalamide (8.24 g, 8.0 mmol) in CH3CN (150 mL) was added [hydroxy(tosyloxy)]iodobenzene (HTIB) at room temperature. The solution was refluxed for 3.0 hr and then cooled to –20 °C overnight. The resulting white solid was collected by filtration and washed with cold acetonitrile to give [15N]tert-butyl ammonium tosylate (17.5 g, 82% yield.) 1H NMR (500 MHz, D2O): d 7.66 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H), 1.33 (s, 9H). 13C{1H} NMR (D2O, 125.8 MHz): d 142.5, 139.4, 129.5, 125.37, 51.9 (d, 1JC–N = 3.8 Hz), 26.6, 20.5. HRMS (DART-Orbitrap) m/z[M+H]+calcd for C4H1215NH2 75.0935, found 75.0942. [15N]tert-Butylamine. [15N]tert-Butylammonium tosylate (17.1 g, 0.080 mol) with granular NaOH (12.0 g, 0.30 mol) was added to a 50 mL one-neck round-bottom flask equipped with an NaOH-filled drying tube used to transfer the amine gas to a 15 mL pear flask cooled to –78 °C. The mixture was heated with a heat gun for approximately 30 min. After the transfer of the amine was complete, it was distilled at atmospheric pressure (BP = 45 °C) to afford [15N]tert-butylamine (3.0 g, 50% yield). 1H NMR (500 MHz, CDCl3): d 1.95 (s, 2H), 1.10 (s, 9H). 13C{1H} NMR (CDCl3, 125.8 MHz): d 47.4 (d, JC–N = 3.5 Hz), 32.6 (d, JC–N = 2.3 Hz). 15N{1H} NMR (CDCl3, 50.66 MHz): d 60.14. HRMS (DART-Orbitrap) m/z[M+H]+calcd for C4H1215NH2 75.0935, found 75.0942. [15N]tert-Butyl(trimethylsilyl)amine. n-BuLi (2.50 M, 40.0 mmol) was added dropwise at RT to a stirred solution of [15N]tert-butylamine (3.0 g, 40.0 mmol) in THF (30 mL) and stirred for 6.0 hr. To the resulting solution Me3SiCl (4.8 g, 44.00 mmol) in THF (40.0 mL) was added dropwise at 0 °C. The colorless 512 suspension was warmed to ambient temperature and stirred for 1.0 hr. The solvent was removed in vacuo, and the colorless residue was extracted with hexane (30 mL) and filtered. Removal of solvent in vacuo afforded [15N]tert- butyl(trimethylsilyl)amine as a colorless liquid (4.4 g, 75% yield). 1H NMR (CDCl3, 500 MHz): d 3.15 (s, 9H), 0.53 (d, JN–H = 6.3, JH–N = 71.7 Hz, 1H), 0.06 (s, 9H). 13C{1H} NMR (CDCl3, 125.8 MHz): d 49.6 (d, JC–N = 7.4 Hz), 33.90 (d, JC–N = 1.2 Hz), 2.7 (d, JC–N = 2.6 Hz). 29Si NMR (CDCl3, 99.36 MHz): d –1.84 (d, JN–Si = 6.5 Hz). 15N{1H} NMR (CDCl3, 50.66 MHz): d 58.5. HRMS (DART- Orbitrap) m/z[M+H]+ calcd for C6H1815NSi 147.1330, found 147.1333. [15N]Sodium tert-butyl(trimethylsilyl)amide. The prep of NaBTA is illustrated here for the labeled isotopomer, [15N]NaBTA. Sodium dispersion in toluene (2.3 mL, 18 mmol) was added to a 50 mL Schlenk flask. The toluene was removed in vacuo and N,N-dimethylethylamine (20.0 mL) and [15N]tert- butyl(trimethylsilyl)amine (2.2 g, 15 mmol) were added to the flask. While stirring, isoprene (750 μL, 7.5 mmol) was added over 10 min at 0 °C. After 30 min of stirring, the mixture was filtered through a fine frit and evaporated to dryness to give a yellowish solid. Recrystallization from hexane gave [15N]NaBTA as a white solid (2.0 g, 80% yield.) 1H NMR (500 MHz, 6.0 M THF/toluene-d8, –100 °C): d 1.2 (s, 9H), 0.21 (s, 9H). 13C{1H} NMR (6.0 M THF/toluene-d8, 125.8 MHz, –100 °C): d 52.9 (d, JC–N = 2.9 Hz), 38.9 (d, JC–N = 2.2 Hz), 6.8 (d, JC–N = 3.6 Hz). 29Si NMR (6.0 M THF/toluene-d8, 125.8 MHz, –100 °C): d –29.92 (d, JN–Si = 11.3 Hz). 15N{1H} NMR (6.0 M THF/toluene-d8, 125.8 MHz, –100 °C): d 76.2. NMR spectroscopic analysis. Standard 1H, 13C, 15N, and 31Si direct detection spectra were recorded on an 11.8 T spectrometer at 500.1, 125.8, 50.7, and 99.3 MHz, respectively. 1H, 13C, and 29Si resonances are referenced to Me4Si at 0.0 ppm. 15N resonances are referenced to neat Me2NEt at 25.7 ppm. Samples for 513 recording spectra at low temperature were prepared as follows. An NMR tube fitted with a double-septum under vacuum was flame-dried on a Schlenk line and allowed to passively cool to room temperature, backfilled with argon, placed in a dry ice/acetone cooling bath, and charged with NaPTA, solvents of choice, and substrate using stock solutions. The sample was mixed with a vortex mixer maintaining the sample at –78 °C and promptly placed in the NMR spectrometer at the pre-set temperature. Samples requiring warming to room temperature were removed from the spectrometer and placed in an acetone bath at 25 °C. IR Rate Studies. IR spectra were recorded with an in situ IR spectrometer fitted with a 30-bounce, silicon-tipped probe. The spectra were acquired at a gain of 1 and a resolution of 4 cm−1. A representative reaction was carried out as follows: The IR probe was inserted through a Teflon adapter and O-ring seal into an oven-dried, cylindrical flask fitted with a magnetic stir bar and a T-joint. The T- joint was capped with a septum for injections and an argon line. After evacuation under full vacuum, heating, and flushing with argon, the flask was charged with the desired coordinating solvent (ligand) in a cosolvent (hexane or MTBE) and cooled to −78 °C in a dry ice−acetone bath. A 0.60 M stock solution of NaPTA was injected through the septum, a quantity sufficient to afford a final 0.060 M final solution. The spectrometer was configured to collect spectra every 5 seconds from 16 scans. A set of 256 baseline scans was collected to zero the baseline. The reaction vessel was then charged with neat methyl benzoate (1710–1733 cm–1). Aminolysis was monitored to >5 half-lives (typically 10–60 min total reaction time.) Density functional theory (DFT) computations. All DFT calculations were carried out using Gaussian 16.24 Prompted by a recent benchmarking of modern density functionals, all calculations were conducted at the M06-2X level of theory.25a-c A pruned (99, 590) integration grid (equivalent to Gaussian’s 514 “UltraFine” option) was used for all calculations. The Ahlrichs basis set def2-svp was used for geometry optimizations and the expanded def2-tsvp basis set for single-point energy calculations.25d Ball-and-stick models were rendered using CYLview 1.0b.25e A large number of DFT-computed energies and Cartesian coordinates are archived in the Supporting Information. 515 CHAPTER 2 APPENDIX 516 Chapter 2 Appendix Table of Content Contents Compound number in SI Synthesis General procedure A S-18 General procedure B S-18 Synthesis of [15N]NaBTA [15N]Pivalamide S-19 Figure A.2.1. 1H NMR spectrum of [15N]pivalamide. S-20 Figure A.2.2. 13C NMR spectrum of [15N]pivalamide. S-21 [15N]tert-Butyl ammonium tosylate. S-22 Figure A.2.3. 1H NMR spectrum of [15N]tert-butylammonium tosylate. S-23 Figure A.2.4. 13C NMR spectrum of [15N]tert-butyl ammonium tosylate. S-24 [15N]tert-Butylamine. S-25 Figure A.2.5. 1H NMR spectra of [15N]tert-butylamine. S-26 Figure A.2.6. 13C NMR spectrum of [15N]tert-butylamine. S-27 Figure A.2.7. 15N NMR spectrum of [15N]tert-butylamine. S-28 [15N]tert-Butyl(trimethylsilyl)amine. S-29 Figure A.2.8. 1H NMR spectrum of [15N]tert-butyl(trimethylsilyl)amine. S-30 Figure A.2.9. 13C NMR spectrum [15N]tert-butyl(trimethylsilyl)amine. S-31 Figure A.2.10. 29Si NMR spectrum of [15N]tert-butyl(trimethylsilyl)amine. S-32 Figure A.2.11. 15N NMR spectrum of [15N]tert-butyl(trimethylsilyl)amine. S-33 [15N]Sodium tert-butyl(trimethylsilyl)amide. S-34 Figure A.2.12. 1H NMR spectrum of [15N]NaBTA. S-35 Figure A.2.13. 13C NMR spectrum of [15N]NaBTA. S-36 Synthesis of NaPETA 1,1,1-trimethyl-N-(1-phenylethyl)silanamine. S-37 517 Figure A.2.14. 1H NMR spectrum of HPETA. S-38 Figure A.2.15. 13C NMR spectrum of HPETA S-39 Sodium (1-phenylethyl)(trimethylsilyl)amide. S-40 Figure A.2.16. 1H NMR spectrum of NaPETA. S-41 Figure A.2.17. 13C NMR spectrum of NaPETA. S-42 Part A: NaPTA Structure Table A.2.1. Structure optimization of trans disolvated NaPTA dimer utilizing CREST process. S-43 Table A.2.2. Structure optimization of cis disolvated NaPTA dimer utilizing CREST process. S-44 Table A.2.3. Energy comparison between cis and trans isomers for the dimer disolvated NaPTA, utilizing CREST optimized structures for each. S-45 Figure A.2.18. NMR spectra of 0.10 M [15N]NaPTA in toluene at –80 °C. S-46 Figure A.2.19. 29Si NMR spectra of NaPTA at varying triethylamine concentrations in pentane at –80 oC. S-47 Figure A.2.20. 15N NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv triethylamine in pentane at –80 oC. S-48 Figure A.2.21. 29Si NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv triethylamine in pentane at –80 oC. S-48 Figure A.2.22. 29Si NMR spectra of NaPTA in 1.68 M MTBE/pentane varying temperature. S-49 Figure A.2.23. 29Si NMR spectra of NaPTA in 4.0 equiv MTBE/pentane varying temperature. S-50 Figure A.2.24. 29Si NMR spectra of NaPTA at varying MTBE concentrations in pentane at –80 oC. S-51 Figure A.2.25. 29Si NMR spectrum of [15N]NaPTA with 2.0 equiv MTBE in pentane at –80 oC. S-52 Figure A.2.26. 15N NMR spectrum of [15N]NaPTA with 2.0 equiv MTBE in pentane at –80 oC. S-53 Figure A.2.27. 29Si NMR spectra of NaPTA at varying THF concentrations in toluene at –110 oC. S-54 Figure A.2.28. 29Si NMR spectrum of [15N]NaPTA in 10% THF/toluene at – 110 oC. S-55 Figure A.2.29. 29Si NMR spectrum of [15N]NaPTA in 50% THF/toluene-d8 at –110 oC. S-56 Figure A.2.30. 15N NMR spectra of [15N]NaPTA at varying THF concentrations in toluene-d8 at –110 °C. S-57 Figure A.2.31. 29Si NMR spectrum of [15N]NaPTA in THF at –80 oC. S-58 518 Figure A.2.32. 29Si NMR spectra of 0.10 M NaPTA at varying THF concentrations in MTBE at –80 oC. S-59 Figure A.2.33. 29Si NMR spectra of 0.10 M NaPTA at varying THF concentrations in 2,5- Me2THF at –80 oC. S-60 Figure A.2.34. 29Si NMR spectra (99.36 MHz) of 0.10 M NaPTA at varying THF concentrations in 2,2,5,5-Me4THF at –80 oC. S-61 Figure A.2.35. 29Si NMR spectrum of 0.10 M [15N]NaPTA with 2.0 equiv HMPA in pentane at –80 oC. S-62 Figure A.2.36. 15N NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv HMPA in pentane at –80 oC. S-63 Figure A.2.37. NMR spectra of 0.10 M [15N]NaPTA in toluene with 4.0 equiv HMPA at –80 °C. S-64 Figure A.2.38. 29Si NMR spectra of 0.15 M NaPTA at varying TMEDA concentrations in pentane at –60 oC. S-66 Figure A.2.39. 29Si NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv TMEDA in pentane at –60 oC. S-67 Figure A.2.40. 15N NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv TMEDA in pentane at –60 oC. S-68 Figure A.2.41. 29Si NMR spectra of 0.10 M NaPTA at varying TMCDA concentrations in pentane at –80 oC. S-70 Figure A.2.42. 29Si NMR spectrum of 0.10 M [15N]NaPTA with 2.0 equiv TMCDA in pentane at –80 oC. S-71 Figure A.2.43. 15N NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv TMCDA in pentane at –60 oC. S-72 Figure A.2.44. 29Si NMR spectra of 0.10 M NaPTA at varying PMDTA concentrations in pentane at –80 oC. S-73 Figure A.2.45. 29Si NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv PMDTA in pentane at –80 oC. S-74 Figure A.2.46. 15N NMR spectrum of 0.15 M [15N]NaPTA with 2.0 equiv PMDTA in pentane at –80 oC. S-74 Figure A.2.47. 29Si NMR spectra of 0.10 M NaPTA at varying DME concentrations in pentane at –60 oC. S-75 Figure A.2.48. 29Si NMR spectrum of 0.10 M [15N]NaPTA with 2.0 equiv DME in pentane at –60 oC. S-76 Figure A.2.49. 29Si NMR spectra of 0.10 M NaPTA at varying concentrations in pentane at –80 oC. S-78 Figure A.2.50. 29Si NMR spectra of 0.10 M [15N]NaPTA with 31.0 equiv diglyme in pentane at –80 oC. S-79 Figure A.2.51. 15N NMR spectrum of 0.10 M [15N]NaPTA with 31.0 equiv diglyme in pentane at –80 oC. S-79 Figure A.2.52. NMR spectra of 0.10 M [15N]NaPTA in toluene with 2.0 equiv diglyme at –80 °C. S-80 Figure A.2.53. NMR spectra of 0.10 M [15N]NaPTA in hexane with various PMDTA and diglyme concentrations at –110 °C. S-81 Figure A.2.54. 29Si NMR spectra of 0.10 M NaPTA at varying S-82 519 12-crown-4 concentrations in THF at –120 oC. Figure A.2.55. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 12-crown-4 at –80 °C. S-83 Figure A.2.56. 29Si NMR spectra of 0.10 M NaPTA at varying 15-crown-5 concentrations in THF at –120 oC. S-84 Figure A.2.57. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 15-crown-5 at –80 °C. S-85 Figure A.2.58. 29Si NMR spectra of 0.10 M NaPTA at varying 18-crown-6 concentrations in THF at –120 oC. S-86 Figure A.2.59. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 18-crown-6 at –110 °C. S-87 Figure A.2.60. 29Si NMR spectra of 0.10 M NaPTA at varying 12-crown-4 and 15-crown-5 concentrations in THF at –120 oC. S-88 Figure A.2.61. 29Si NMR spectra of 0.10 M NaPTA at varying 15-crown-5 and 18-crown-6 concentrations in THF at –120 oC. S-89 Figure A.2.62. 29Si NMR spectra of 0.10 M NaPTA at varying 12-crown-4 and 18-crown-6 concentrations in THF at –120 oC. S-90 Part B: NaBTA Structure Table A.2.4. Energy comparison between cis and trans isomers for the dimer disolvated NaBTA. S-91 Figure A.2.63. NMR spectra of 0.10 M [15N]NaBTA in toluene at –80 °C. S-92 Figure A.2.64. NMR spectra of 0.10 M [15N]NaBTA in DMEA at –80 °C. S-93 Figure A.2.65. NaPTA and NaBTA job plot NMR spectra. S-95 Figure A.2.66. NaPTA and NaBTA job plot. S-96 Figure A.2.67. NMR spectra of 0.10 M [15N]NaBTA in Et3N at –80 °C. S-97 Figure A.2.68. NMR spectra of 0.10 M [15N]NaBTA in MTBE at –80 °C. S-98 Figure A.2.69. 29Si NMR spectra of [15N]NaTBA in toluene-d8 at varying THF concentrations at –110 °C. S-100 Figure A.2.70. 15N NMR spectrum of [15N]NaBTA in 6.0 M THF/toluene-d8 at –100 °C. S-101 Figure A.2.71. 15N NMR spectrum of [15N]NaBTA in 1.2 M THF/MTBE at – 80 °C. S-101 Figure A.2.72. 29Si NMR spectra of NaBTA at varying THF concentrations in toluene at –110 °C. S-102 Figure A.2.73. Percentage of dimer vs. THF concentration, 0.15 M NaBTA in toluene cosolvent, at –110 ºC. S-103 520 Figure A.2.74. Parametric fit of the dimer of NaBTA (0.15 M) as a function of THF concentration in toluene cosolvent at –110 ºC with derivation. S-104 Figure A.2.75. NMR spectra of 0.10 M [15N]NaBTA in MTBE with 3.0 equiv HMPA at –100 °C. S-106 Figure A.2.76. NMR spectra of 0.10 M [15N]NaBTA in toluene with 1.0 equiv HMPA at –100 °C. S-107 Figure A.2.77. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv TMEDA/MTBE at –100 °C. S-108 Figure A.2.78. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv TMEDA/MTBE at –100 °C. S-109 Figure A.2.79. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv. TMCDA/MTBE at –100 °C. S-111 Figure A.2.80. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv. TMCDA/MTBE at –80 °C. S-111 Figure A.2.81. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv PMDTA/MTBE at –100 °C. S-113 Figure A.2.82. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv PMDTA/MTBE at –100 °C. S-113 Figure A.2.83. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv DME/MTBE at –100 °C. S-115 Figure A.2.84. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv DME/MTBE at –100 °C. S-115 Figure A.2.85. NMR spectra of 0.10 M [15N]NaBTA in MTBE with at 1.0 equiv DME at –90 °C. S-116 Figure A.2.86. 29Si NMR spectra of NaBTA at varying diglyme concentrations in MTBE at –100 °C. S-118 Figure A.2.87. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv diglyme/MTBE at –100 °C. S-119 Figure A.2.88. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv diglyme/MTBE at –100 °C. S-119 Figure A.2.89. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 12-crown- 4/THF at –100 °C. S-120 Figure A.2.90. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv 12-crown- 4/THF at –100 °C. S-120 Figure A.2.91. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 15-crown- 5/THF at –100 °C. S-121 521 Figure A.2.92. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv 15-crown- 5/THF at –100 °C. S-122 Figure A.2.93. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 18-crown- 6/THF at –100 °C. S-123 Figure A.2.94. 15N NMR spectrum of [15N]NaBTA in 2.0 equiv 18-crown- 6/THF at –100 °C. S-124 Figure A.2.95. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 15-crown-5 and 2.0 equiv 12-crown-4/THF at –100 °C. S-125 Figure A.2.96. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 18-crown-6 and 2.0 equiv 12-crown-4/THF at –100 °C. S-126 Figure A.2.97. 29Si NMR spectra of [15N]NaBTA in 2.0 equiv 18-crown-6 and 2.0 equiv 15-crown-5/THF at –100 °C. S-127 Part C: NaPETA Structure Intramolecular benzene ring complexation for NaPETA dimer S-128 Figure A.2.98. NMR spectra of 0.10 M (R)-NaPETA in toluene at –80 °C. S-129 Figure A.2.99. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)- NaPETA mixed with 0.060 M (S)-NaPETA in toluene at –80 °C. S-130 Figure A.2.100. NMR spectra of 0.30 M (R)-NaPETA in DMEA at –80 °C. S-131 Figure A.2.101. Job plot of NaPETA-derived enantiomeric homodimers (blue) and R–S heterodimers in DMEA. S-132 Figure A.2.102. NMR spectra of 0.30 M (R)-NaPETA in Et3N at various temperature. 29Si spectrum at –100 °C. S-133 Figure A.2.103. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)- NaPETA mixed with 0.060 M (S)-NaPETA in Et3N at –100 °C. S-134 Figure A.2.104. NMR spectra of 0.30 M (R)-NaPETA in MTBE at various temperature. 29Si spectrum at –100 °C. S-135 Figure A.2.105. Job plot of NaPETA-derived enantiomeric homodimers (blue) and R–S heterodimers in DMEA. S-136 Figure A.2.106. NMR spectra of 0.10 M (R)-NaPETA in 1.8 M THF pentane cosolvant at various temperature. S-138 Figure A.2.107. NMR spectra of 0.10 M (R)-NaPETA in 3.6 M THF pentane cosolvant at various temperature. S-139 Figure A.2.108. 29Si NMR spectra of 0.15 M (R)-NaPETA at varying THF concentrations in pentane at –110 °C. S-140 Figure A.2.109. 29Si NMR spectra of 0.15 M (R)-NaPETA at varying THF concentrations in pentane at –10 °C. S-141 Figure A.2.110. 29Si NMR spectra of 0.15 M (R)-NaPETA at varying TMEDA concentrations in MTBE at –100 °C. S-143 Figure A.2.111. NMR spectra of 0.15 M (R)-NaPETA in MTBE with various concentrations of PMDTA at –100 °C. S-145 522 Figure A.2.112. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)- NaPETA mixed with 0.060 M (S)-NaPETA in MTBE with 2.0 equiv PMDTA at –100 °C. S-146 Figure A.2.113. NMR spectrum of 0.15 M (R)-NaPETA with 1.0 equiv HMPA in MTBE at –100 °C. S-148 Figure A.2.114. NMR spectra of 0.10 M (R)-NaPETA in MTBE with various concentrations of DME at –100 °C. S-150 Figure A.2.115. NMR spectra of 0.15 M (R)-NaPETA in MTBE with 2.0 equiv diglyme at –80 °C. S-152 Figure A.2.116. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 12-crown-4 at –110 °C. S-153 Figure A.2.117. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 15-crown-5 at –110 °C. S-154 Figure A.2.118. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 18-crown-6 at –110 °C. S-155 Figure A.2.119. 29Si NMR spectra of 0.10 M (R)-NaPETA at varying 12-crown-4 and 15-crown-5 concentrations in THF at –120 oC. S-156 Figure A.2.120. 29Si NMR spectra of 0.10 M (R)-NaPETA at varying 15-crown-5 and 18-crown-6 concentrations in THF at –120 oC. S-157 Figure A.2.121. 29Si NMR of 0.10 M (R)-NaPETA at varying 12-crown-4 and 18-crown-6 concentrations in THF at –120 oC. S-158 Part D: Synthetic Methods Synthesis of N,N-dimethylbenzamide D2 S-159 Figure A.2.122. 1H NMR spectrum of N,N-dimethylbenzamide D2. S-160 Figure A.2.123. 13C NMR spectrum of N,N-dimethylbenzamide D2. S-161 Synthesis of N,N-diethylbenzamide D3 S-162 Figure A.2.124. 1H NMR spectrum of N,N-diethylbenzamide D3. S-163 Figure A.2.125. 13C NMR spectrum of N,N-diethylbenzamide D3. S-164 Synthesis of phenyl(piperidin-1-yl)methanone D4. S-165 Figure A.2.126. 1H NMR spectrum of phenyl(piperidin-1-yl)methanone D4. S-166 Figure A.2.127. 13C NMR spectrum of phenyl(piperidin-1-yl)methanone D4. S-167 Synthesis of phenyl(pyrrolidin-1-yl)methanone D5 S-168 Figure A.2.128. 1H NMR spectrum of phenyl(pyrrolidin-1-yl)methanone D5. S-169 Figure A.2.129. 13C NMR spectrum of phenyl(pyrrolidin-1-yl)methanone D5. S-170 Synthesis of N-(tert-butyl)benzamide D6. S-171 Figure A.2.130. 1H NMR spectrum of N-(tert-butyl)benzamide D6. S-172 523 Figure A.2.131. 13C NMR spectrum of N-(tert-butyl)benzamide D6. S-173 Synthesis of N-isopropylbenzamide 36. S-174 Figure A.2.132. 1H NMR spectrum of N-isopropylbenzamide 36. S-175 Figure A.2.133. 13C NMR spectrum of N-isopropylbenzamide 36. S-176 Synthesis of (R)-N-(1-phenylethyl)benzamide D7. S-177 Figure A.2.134. 1H NMR spectrum of (R)-N-(1-phenylethyl)benzamide D7. S-178 Figure A.2.135. 13C NMR spectrum of (R)-N-(1-phenylethyl)benzamide D7. S-179 Synthesis of (R)-N-(1-phenylethyl)benzamide D8. S-180 Figure A.2.136. 1H NMR spectrum of di-tert-butyl (E)-2-benzylidene-3- phenylpentanedioate D8. S-181 Figure A.2.137. 13C NMR spectrum of di-tert-butyl (E)-2-benzylidene-3- phenylpentanedioate D8. S-182 Synthesis of (R)-N-(1-phenylethyl)cinnamamide D9 S-183 Figure A.2.138. 1H NMR spectrum of (R)-N-(1-phenylethyl)cinnamamide D9. S-184 Figure A.2.139. 13C NMR spectrum of (R)-N-(1-phenylethyl)cinnamamide D9. S-185 Synthesis of methyl 3-phenyl-3-(((R)-1-phenylethyl)amino)propanoate D10. S-186 Figure A.2.140. 1H NMR spectrum of methyl 3-phenyl-3-(((R)-1- phenylethyl)amino)propanoate D10. S-187 Figure A.2.141. 13C NMR spectrum of methyl 3-phenyl-3-(((R)-1- phenylethyl)amino)propanoate D10. S-188 Synthesis of (R)-N-(1-phenylethyl)pyridin-2-amine D11. S-189 Figure A.2.142. 1H NMR spectrum of (R)-N-(1-phenylethyl)pyridin-2-amine D11. S-190 Figure A.2.143. 13C NMR spectrum of (R)-N-(1-phenylethyl)pyridin-2-amine D11. S-191 Synthesis of (R)-N-(1-phenylethyl)-3-(trimethylsilyl)pyridin-2-amine D12. S-192 Figure A.2.144. 1H NMR spectrum of (R)-N-(1-phenylethyl)-3- (trimethylsilyl)pyridin-2-amine D12. S-193 Figure A.2.145. 13C NMR spectrum of (R)-N-(1-phenylethyl)-3- (trimethylsilyl)pyridin-2-amine D12. S-194 Synthesis of (R)-N-(1-phenylethyl)octan-1-amine D13. S-195 524 Figure A.2.146. 1H NMR spectrum of (R)-N-(1-phenylethyl)octan-1-amine D13. S-196 Figure A.2.147. 13C NMR spectrum of (R)-N-(1-phenylethyl)octan-1-amine D13. S-197 Synthesis of 1-(((R)-1-phenylethyl)amino)octan-2-ol D14 Figure A.2.148. 1H NMR spectrum of 1-(((R)-1-phenylethyl)amino)octan-2- ol D14. S-198 Figure A.2.149. 13C NMR spectrum of 1-(((R)-1-phenylethyl)amino)octan-2- ol D14. S-200 Synthesis of 1-phenyl-2-(((R)-1-phenylethyl)amino)ethan-1-ol D15. S-201 Figure A.2.150. 1H NMR spectrum of 1-phenyl-2-(((R)-1- phenylethyl)amino)ethan-1-ol D15. S-202 Figure A.2.151. 13C NMR spectrum of 1-phenyl-2-(((R)-1- phenylethyl)amino)ethan-1-ol D15. S-203 NMR spectra of NaPTA and methyl benzoate reactions Figure A.2.152. 29Si NMR spectra of 0.10 M NaPTA in toluene at –80 °C with incremental additions of methyl benzoate in toluene:pentane = 1:2 at – 80 °C. S-204 Figure A.2.153. 29Si NMR spectra of a reaction mixture containing 0.18 M methyl benzoate and 0.060 M [15N]NaPTA in toluene reacting at –80 ºC and 23 ºC, recorded at –80 ºC. S-205 Figure A.2.154. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.13 M [15N]NaPTA in toluene reacting at 25 ºC, recorded at –80 ºC. S-206 Figure A.2.155. 29Si NMR spectra of TMSOMe at different condition recorded at –80 ºC. S-207 Figure A.2.156. 1H NMR spectra of 0.10 M NaPTA in THF at –80 °C with the addition of methyl benzoate in THF at –80 °C. S-208 Figure A.2.157. 1H NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC, recorded at –80 ºC. S-209 Figure A.2.158. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC, recorded at –80 ºC. S-210 Figure A.2.159. 1H NMR spectra of attempts to replicate in situ reaction solutions. All spectra were recorded at –80 ºC. S-211 Figure A.2.160. 29Si NMR spectra of attempts to replicate in situ reaction solutions. All spectra were recorded at –80 ºC. S-212 525 Figure A.2.161. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate, 0.15 M NaPTA, 0.60 M diglyme in toluene reacting at –80 ºC, recorded at –80 ºC. S-213 Figure A.2.162. 29Si NMR spectra of a reaction mixture containing 0.010 M methyl benzoate, 0.10 M NaPTA, 0.20 M PMDTA in toluene reacting at –80 ºC, recorded at –80 ºC. S-214 Figure A.2.163. 29Si NMR spectra of a reaction mixtures of methyl benzoate, piperidine and NaPTA in toluene recorded at –80 ºC. S-215 Figure A.2.164. 29Si NMR spectra of a reaction mixture containing 0.10 M methyl benzoate, 0.30 M (R)-NaPETA in MTBE reacting at –23 ºC, recorded at –80 ºC. S-216 Figure A.2.165. 29Si NMR spectra of a reaction mixture containing 0.10 M methyl benzoate, 0.30 M (R)-NaPETA and 0.60 M PMDTA in MTBE reacting at –23 ºC, recorded at –80 ºC. S-217 IR spectroscopy and Solution Kinetics Figure A.2.166. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in toluene/pentane cosolvent. S-219 Figure A.2.167. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in Et3N/pentane cosolvent. S-220 Figure A.2.168. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in MTBE/pentane cosolvent. S-221 Figure A.2.169. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –45 °C in THF/pentane cosolvent. S-222 Figure A.2.170. Imino-ether reappearance experiments. S-223 Figure A.2.171. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene with 0.12 M PMDTA at –20 °C. S-224 Figure A.2.172. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene or toluene with 2.0 equiv PMDTA at –20 °C. S-224 Figure A.2.173. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene with 10 mol% PMDTA added during reaction at –78 °C. S-225 Figure A.2.174. Plot of the concentration of methylbenzoate-NaPTA complex 37 (1712 cm–1) formed from methyl benzoate (0.005 M) and 0.12 M NaPTA in 5.6 M toluene/hexane at –20 °C. S-226 Figure A.2.175. Plot of kobsd vs [toluene] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.10 M) at –20 °C. S-227 Table A.2.5. Average pseudo-first-order rate constants (kobsd) at various toluene (pentane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.10 M) to at –20 °C. S-227 Figure A.2.176. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methylbenzoate (0.005 M) by NaPTA in neat toluene at –20 °C. S-228 Table A.2.6. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.10 M) at –20 °C in neat toluene. S-228 Figure A.2.177. Plot of kobsd vs [THF] (M) with different cosolvent for the addition of methyl benzoate (0.0050 M) to 0.10 M NaPTA at –78 °C. S-229 526 Table A.2.7. Pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. S-230 Table A.2.8. Pseudo-first-order rate constants (kobsd) at various THF (MTBE cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. S-231 Table A.2.9. Pseudo-first-order rate constants (kobsd) at various THF (tetramethylTHF cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. S-232 Figure A.2.178. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methylbenzoate (0.005 M) in neat THF at –78 °C. S-233 Table A.2.10. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA at –78 °C in THF. S-233 Figure A.2.179. Plot of kobsd vs [PMDTA] (M) in toluene cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) at –78 °C. S-234 Table A.2.11. Average pseudo-first-order rate constants (kobsd) at various PMDTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C in toluene. S-234 Figure A.2.180. Plot of kobsd vs [NaPTA] (M) in toluene with 2.0 M PMDTA for the aminolysis of methyl benzoate (0.005 M) by NaPTA at –78 °C. S-235 Table A.2.12. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA at –78 °C in toluene with 2.0 M PMDTA. S-235 Figure A.2.181. Plot of kobsd vs [diglyme] (M) in hexane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) at –50 °C. S-236 Table A.2.13. Pseudo-first-order rate constants (kobsd) at various diglyme (hexane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. S-236 Figure A.2.182. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) in 6.3 M diglyme/hexane at –78 °C. S-237 Table A.2.14. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –50 °C in 6.3 M diglyme. S-237 Figure A.2.183. Plot of kobsd vs Xdiglyme for the aminolysis of methyl benzoate (0.0050 M) by NaPTA (0.060 M) in a fixed 2.0 M diglyme-PMDTA mixtures in hexane at –78 °C. S-238 Table A.2.15. Average pseudo-first-order rate constants (kobsd) for the aminolysis of methyl benzoate (0.0050 M) by NaPTA (0.060 M) in a fixed 2.0 M diglyme-PMDTA mixtures in hexane at –78 °C. S-238 Figure A.2.184. Plot of kobsd vs free (uncomplexed) crown ether (M) for 12- crown-4 (red), 15-crown-5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.0050 M) by 0.060 M NaPTA in neat THF at –78 °C. S-239 Table A.2.16. Pseudo-first-order rate constants (kobsd) at various free 15- crown-5 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in THF at –78 °C. S-240 527 Table A.2.17. Pseudo-first-order rate constants (kobsd) at various free 12- crown-4 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in THF at –78 °C. S-240 Table A.2.18. Pseudo-first-order rate constants (kobsd) at various free 18- crown-6 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in THF at –78 °C. S-241 Figure A.2.185. Plot of kobsd vs [NaPTA-12-crown-4] (M) (complexed) for the aminolysis of methyl benzoate (0.0050 M) by NaPTA-12-crown-4 in neat THF at –78 °C. S-242 Table A.2.19. Pseudo-first-order rate constants (kobsd) at various NaPTA-12- crown-4 concentrations for the addition of methyl benzoate to NaPTA-12- crown-4 in THF at –78 °C. S-242 Figure A.2.186. Plot of kobsd vs [NaPTA-15-crown-5] (M) (complexed) for the aminolysis of methyl benzoate (0.0050 M) by NaPTA-15-crown-5 in neat THF at –78 °C. S-243 Table A.2.20. Pseudo-first-order rate constants (kobsd) at various NaPTA-15- crown-5 concentrations for the addition of methyl benzoate to NaPTA-15- crown-5 in THF at –78 °C. S-243 Figure A.2.187. Plot of kobsd vs free (uncomplexed) crown ether for 12- crown-4 (red), 15-crown-5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.005 M) by 0.060 M NaPTA/15-crown-5 complex in neat THF at –78 °C. S-244 Table A.2.21. Pseudo-first-order rate constants (kobsd) at various free 12- crown-4 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) in THF at –78 °C. S-245 Table A.2.22. Pseudo-first-order rate constants (kobsd) at various free 18- crown-6 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) in THF at –78 °C. S-245 Figure A.2.188. Plot of kobsd vs free (uncomplexed) crown (M) for the aminolysis of PhCO2Me (0.005 M) by NaPTA containing 1.0 equiv of 18- crown-6 complex in neat THF at –78 °C. S-246 Table A.2.23. Pseudo-first-order rate constants (kobsd) at various free 15- crown-5 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) containing 1.0 equiv of 18-crown-6 in THF at –78 °C. S-246 Figure A.2.189. Plot of kobsd vs [THF] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) with 1.0 equiv 12-crown-4 at –78 °C. S-247 Table A.2.24. Pseudo-first-order rate constants (kobsd) at various THF concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/12- crown-4 complex (0.060 M) at –78 °C. S-247 Figure A.2.190. Plot of kobsd vs [THF] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) with 1.0 equiv 15-crown-5 at –78 °C. S-248 528 Table A.2.25. Pseudo-first-order rate constants (kobsd) at various THF concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15- crown-5 complex (0.060 M) at –78 °C. S-248 Figure A.2.191. Plot of kobsd vs [THF] (M) in Me2THF cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.12 M) at –78 °C. S-249 Table A.2.26. Reactions of tert-butyl cinnamate with NaPTA in different catalytic solvent. S-251 Figure A.2.192. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% THF and 160% THF at –78 °C. S-252 Figure A.2.193. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% PMDTA at –78 °C. S-253 Figure A.2.194. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% diglyme at –78 °C. S-254 Figure A.2.195. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% triglyme at –78 °C. S-255 Figure A.2.196. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% TMEDA at –78 °C. S-256 Figure A.2.197. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy at 1691 cm–1 for the addition of 0.10 M tert- butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% TMCDA at –78 °C. S-257 Figure A.2.198. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% DME at –78 °C. S-258 Figure A.2.199. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 12-crown-4 at –78 °C. S-259 Figure A.2.200. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 15-crown-5 at –78 °C. S-260 Figure A.2.201. Plot of tert-butyl cinnamate concentration versus time for the addition of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 18-crown-6 at –78 °C. S-261 Part E: DFT Calculated Reaction Pathways Scheme A.2.1. DFT-computed energy profile of aminolysis of methyl benzoate by NaPTA via an anion pathway. S-263 Scheme A.2.2. DFT-computed energy profile of aminolysis of methyl benzoate by NaPTA via a triple ion pathway. S-263 Scheme A.2.3. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono benzene solvated dimer pathway. S-265 529 Scheme A.2.4. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a triTHF solvated dimer pathway. S-266 Scheme A.2.5. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono PMDTA solvated monomer pathway. S-267 Scheme A.2.6. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono diglyme solvated dimer pathway. S-268 Scheme A.2.7. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 12-crown-4 solvated monomer pathway. S-269 Scheme A.2.8. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 15-crown-5 solvated monomer pathway. S-270 Scheme A.2.9. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 18-crown-6 solvated monomer pathway. S-271 Scheme A.2.10. DFT-computed energy comparison of the different crown transition structures of aminolysis of methyl benzoate by NaPTA. S-272 530 Compound number in SI N Me3Si i-Pr 1 (NaPTA) Na N Me3Si tert-Bu Na 2 (NaBTA) N Me3Si Ph(Me)CH Na 3 (NaPETA) N Na N Na SiMe3Me3Si RR S S cis-4 (A2S2) N Me3Si R 5 (ASn) NaSnN Na N Na RMe3Si SiMe3R S S trans-4 (A2S2) N Me3Si Me H Na Na N SiMe3 Me H 6 N Me3Si Me H Na Na N SiMe3 Me H 7 N Me3Si Me H Na Na N SiMe3 Me H 8 9 Sn N Me3Si Me H Na Na N SiMe3 Me H Sn Sn N Me3Si Me H NaSn 10 11 N Na N Na SiMe3i-Pr i-PrMe3Si Me Me N Na N Na SiMe3R RMe3Si S S R = i-Pr-, t-Bu-, or Ph(CH3)CH- S = MTBE, DMEA, Et3N, HMPA 12 N Me3Si Me H Na(HMPA)1 13 N Me3Si Me H Na(HMPA)2 14 15 16 N N SiMe3Me3Si i-Pri-PrN Na N Na i-PrMe3Si SiMe3i-Pr THF THF Na THF THF Na THF THF 17 Na N Na N t-Bu Me3Si t-Bu SiMe3 THF THF 18 N Me3Si t-Bu Na(THF)n+1 N N i-PrMe3Si SiMe3i-Pr 20 NMe2 Na Me2N Me2N Na NMe2 N N i-PrMe3Si SiMe3i-Pr 19 NMe2 Na Me2N Me2N Na NMe2 Me2 N N Me2 N R Me3Si Na 23a; R = i-Pr 23b; R = t-Bu 23c; R = CH(Me)Ph R Me3Si N Na N Me Me MeMe N 21a; R = i-Pr 21b; R = t-Bu 21c; R = CH(Me)Ph N R Me3Si Na L L L L 22; L = NMe2 N Me3Si Me H 25; L = NMe2 N R Me3Si Na L L 24; L = NMe2 S Na L L N N SiMe3 Me3Si Na R Me2N N NMe2 R Na N NMe2Me2N 27a-c not observed Me Me N Na R Me3Si Me2N N Me2N 26a; R = i-Pr 26b; R = t-Bu 26c; R = CH(Me)Ph Me N R Me3Si Na O O O O Me Me Me Me N N SiMe3 Me3Si Na R MeO OMe R Na MeO OMe 28a; R = i-Pr 28b; R = CH(Me)Ph 28c; R = t-Bu 29a; R = i-Pr 29b; R = CH(Me)Ph 29c; R = t-Bu N N SiMe3 Me3Si Na i-Pr MeO O OMe i-Pr Na O OMeMeO Na MeO O OMe OMe OMeO N Me3Si i-Pr 31a30a N Na i-Pr Me3Si MeO O MeO 32a not observed N Na R Me3Si MeO O MeO 32a; R = i-Pr 32b; R = CH(Me)Ph 32c; R = t-Bu N H O i-Pr Ph 36 Ph OMe N N SiMe3 Me3Si Na i-Pr i-Pr Na 37 solvent O OSiMe3 N i-Pr OSiMe3 N i-Pr 38 39 N Na N Na i-Pr SiMe3i-Pr O THF THF Ph O N i-Pr Na n 40 41 B9 C12A16 C3 C4 A2 A4, A34, A3, A10 B5, B3, B4, B14 C8, C6, C7, C31 C32 C34 A5, A5-2 A8, A8-2 B7, B7-2 B10–B13 A14, A14-2 A18, A18-2 A15, B18, C23 A17, B19, C25 A19, B21 C23 A15, B18, C28 A20, B23, C27 A22, B25, C37 A23, B27, C41 A26 A24 A25 A25, B30, C44 36 37 38 39 E12 41 paper SI paper SI paper SI paper SI paper SI paper SI paper SI 531 General Experimental Procedure Reagents and solvents. NaPTA, [15N]NaPTA, NaBTA, [15N]NaBTA and NaPETA were prepared as white crystalline solids. All solvents were distilled from blue or purple solutions containing sodium benzophenone ketyl. Substrates are all commercially available, and all products are either commercially available or available by literature procedures. General procedure A: Synthesis of N-isopropylbenzamide: N-isopropylbenzamide. Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138 mg, 0.90 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaPTA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Methyl benzoate (5.0 μL of 0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.10 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded N-isopropylbenzamide as a white solid. General procedure B: Synthesis of phenyl(pyrrolidin-1-yl)methanone: phenyl(pyrrolidin-1-yl)methanone. Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. 1.0 mL of the NaPTA (0.60 mmol) solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Add 35.0 μL pyrrolidine (0.50 mmol) to the solution. Cool the solution to –78 °C using a dry ice-acetone bath. Then, add 35.0 μL of methyl benzoate (0.30 mmol) to the reaction solution. Stir the reaction at – 78 °C for 0.1 hr. Add 100.0 μL of MeOD to the solution and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded phenyl(pyrrolidin-1-yl)methanone as a white solid. 532 Synthesis of [15N]NaBTA [15N]Pivalamide. Pivaloyl chloride (12.0 mL, 100.0 mmol) in the Et2O (50.0 mL) was layered onto a solution of [15N]NH4Cl (5.0 g, 91.5 mmol) in H2O (20.0 mL) in 250.0 mL flask. The flask was cooled 0 °C, and NaOH (20.0 g, 500.0 mmol) in H2O (30.0 mL) was slowly added by pipette to the aqueous layer with slow stirring to avoid mixing of layers. A white precipitate formed during the addition. The flask was warmed to room temperature with stirring for 15 mins followed by vigorous stirring for an additional 10 min. The white solid was collected by filtration and washed with Et2O. After drying under vacuum, the resulting white solid was purified by acetone extraction (50 mL x 3), then removed solvent to give [15N]pivalamide (8.5 g, 83% yield). 1H NMR (500 MHz, CDCl3) d 1.17 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) d 186.04 (JC–N = 15.3 Hz), 38.2 (JC–N = 5.8 Hz), 26.6. HRMS (DART-Orbitrap) m/z[M+H]+ calcd for C5H12NO 103.0884, found 103.0890. t-Bu O NaOH-H2O/Et2O 0 oC - 10 oC + 15NH4Cl t-Bu 15NH2 O Cl 533 Figure A.2.1. 1H NMR (500 MHz, D2O) of [15N]pivalamide at room temperature: d 1.17 (s, 9H). 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 A (s) 1.17 534 Figure A.2.2. 13C{1H} NMR (125.8 MHz, CDCl3) of [15N]pivalamide at room temperature. d 186.04 (JC–N = 15.3 Hz), 38.2 (JC–N = 5.8 Hz), 26.6. 0102030405060708090100110120130140150160170180190200 A (d) 186.04 J(15.3) B (d) 38.22 J(5.8) C (s) 26.58 535 [15N]tert-Butyl ammonium tosylate. To a 250 mL flask containing [15N]pivalamide (8.3 g, 8.0 mmol) in CH3CN (150.0 mL) was added [hydroxy(tosyloxy)]iodobenzene (HTIB) at room temperature. The solution was refluxed for 3.0 hrs and then cooled to –20 °C overnight. The resulting white solid was collected by filtration and washed with cold acetonitrile to give [15N]tert-butyl ammonium tosylate (17.5 g, 82% yield.) 1H NMR (500 MHz, CDCl3) d 7.66 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H), 1.33 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) d 142.5, 139.4, 129.5, 125.37, 51.9 (d, JC–N = 3.8 Hz), 26.6, 20.5. HRMS (DART-Orbitrap) m/z[M+H]+calcd for C4H1215NH2 75.0935, found 75.0942. t-Bu 15NH2 O + HTIB CH3CN reflux t-Bu15NH3OTs 536 Figure A.2.3. 1H NMR (500 MHz, D2O) of [15N]tert-butylammonium tosylate at room temperature: d 7.66 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H), 1.33 (s, 9H). 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 8 .6 4 2 .9 3 2 .0 6 2 .0 0 A (d) 7.66 J(8.0) B (d) 7.34 J(8.0) C (s) 2.36 D (s) 1.33 537 Figure A.2.4. 13C{1H} NMR (125.8 MHz, CDCl3) of [15N]tert-butyl ammonium tosylate at room temperature: d 142.5, 139.4, 129.5, 125.37, 51.9 (d, JC–N = 3.8 Hz), 26.6, 20.5. 0102030405060708090100110120130140150160170180 A (s) 142.50 B (s) 139.41 C (s) 129.47 D (s) 125.37 E (d) 51.94 J(3.8) F (s) 26.62 G (s) 20.51 538 [15N]tert-Butylamine. [15N]tert-Butylammonium tosylate (17.1 g, 0.080 mol) with granular NaOH (12.0 g, 0.30 mol) were added to a 50 mL one-neck round-bottom flask equipped with an NaOH-filled drying tube used to transfer the amine gas to an empty 15 mL pear flask cooled to – 78 °C. The mixture was heated with a heat gun for approximately 30 min. After the transfer of the amine was complete, it was distilled at atmospheric pressure (BP = 45 °C) to afford [15N]tert- butylamine (3.0 g, 50% yield). 1H NMR (500 MHz, CDCl3) d 1.95 (s, 2H), 1.10 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) d 47.4 (d, JC–N = 3.5 Hz), 32.6 (d, JC–N = 2.3 Hz). 15N{1H} NMR (50.66 MHz, CDCl3) d 60.14. HRMS (DART-Orbitrap) m/z[M+H]+calcd for C4H1215NH2 75.0935, found 75.0942. t-Bu15NH3OTs + NaOH (s) heat t-Bu15NH2 539 Figure A.2.5. 1H NMR (500 MHz, CDCl3) of [15N]tert-butylamine at room temperature: d 1.95 (s, 2H), 1.10 (s, 9H). 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 9 .0 0 1 .9 5 A (s) 1.19 B (s) 1.10 540 Figure A.2.6. 13C{1H} NMR (125.8 MHz, CDCl3) of [15N]tert-butylamine at room temperature. d 47.4 (d, JC–N = 3.5 Hz), 32.6 (d, JC–N = 2.3 Hz). 5101520253035404550556065707580859095100105110 A (d) 47.43 J(3.5) B (d) 32.59 J(2.1) 541 Figure A.2.7. 15N{1H} NMR (50.66 MHz, CDCl3) of [15N]tert-butylamine at room temperature: d 60.14. -100-50050100150200250300350 A (s) 60.15 542 [15N]tert-Butyl(trimethylsilyl)amine. To a stirred solution of [15N]tert-butylamine (3.0 g, 40.0 mmol) in THF (30.0 mL), n-BuLi (2.5 M, 40.0 mmol) was added dropwise at rt and stirred for 6.0 hrs. To the resulting solution Me3SiCl (4.8 g, 44.0 mmol) in THF (40.0 mL) was added dropwise at 0 °C. The colorless suspension was warmed to ambient temperature and stirred for 1.0 hr. The solvent was removed in vacuo, and the colorless residue was extracted with hexane (30.0 mL) and filtered. Removal of solvent in vacuo afforded [15N]tert- butyl(trimethylsilyl)amine as a colorless liquid (4.4 g, 75% yield). 1H NMR (500 MHz, CDCl3) d 3.15 (s, 9H), 0.53 (d, JH–N = 71.7 Hz, 1H), 0.060 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) d 49.6 (d, JC-N = 7.4 Hz), 33.9 (d, JC-N = 1.2 Hz), 2.7 (d, JC-N = 2.6 Hz). 29Si{1H} NMR (99.36 MHz, CDCl3) d –1.84 (d, JSi–N = 6.5 Hz). 15N{1H} NMR (50.66 MHz, CDCl3) d 58.5. HRMS (DART-Orbitrap) m/z[M+H]+ calcd for C6H1815NSi 147.1330, found 147.1333. t-Bu15NH2 n-BuLi/hexane 0 oC to rt. t-Bu15NHLi Me3SiCl/Et2O t-Bu15NHSiMe3 543 Figure A.2.8. 1H NMR (500 MHz, CDCl3) of [15N]tert-butyl(trimethylsilyl)amine at room temperature: d 3.15 (s, 9H), 0.53 (d, JH–N = 71.7 Hz, 1H), 0.060 (s, 9H). -1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 8 .9 0 0 .8 0 9 .0 0 A (s) 1.15 B (s) 0.06 C (d) 0.53 J(71.7) 544 Figure A.2.9. 13C{1H} NMR (125.8 MHz, CDCl3) of [15N]tert-butyl(trimethylsilyl)amine in CDCl3 at room temperature: d 49.6 (d, JC-N = 7.4 Hz), 33.90 (d, JC-N = 1.2 Hz), 2.7 (d, JC-N = 2.6 Hz). 05101520253035404550556065707580859095100105110115120125130 A (d) 49.56 J(7.4) B (d) 33.90 J(1.2) C (d) 2.67 J(2.6) 545 Figure A.2.10. 29Si{1H} NMR (99.36 MHz, CDCl3) of [15N]tert-butyl(trimethylsilyl)amine at room temperature: d –1.84 (d, JSi–N = 6.5 Hz). -9-8-7-6-5-4-3-2-10123456 A (d) -1.84 J(16.5) 546 Figure A.2.11. 15N{1H} NMR (50.66 MHz, CDCl3) of [15N]tert-butyl(trimethylsilyl)amine at room temperature: d 58.5. 05101520253035404550556065707580859095100 A (s) 58.45 547 [15N]Sodium tert-butyl(trimethylsilyl)amide: Purified [15N]NaBTA can be prepared as a white powder as illustrated for [15N]NaBTA. Sodium dispersion in toluene (2.3 mL, 18.0 mmol) was added to a 50 mL Schlenk flask. The toluene was removed in vacuo and N,N-dimethylethylamine (20.0 mL) and [15N]tert-butyl trimethylsilyl)amine (2.2 g, 15.0 mmol) were added to the flask. While stirring, isoprene (750.0 μL, 7.5 mmol) was added over the course of 10 min at 0 °C. Stirring was halted after 30 min, and the mixture was filtered through a fine frit and evaporated to dryness to give a yellowish solid. Recrystallization from hexane gave [15N]NaBTA as a white solid (2.0 g, 80% yield.) 1H NMR (500 MHz) d 1.29 (s, 9H), 0.21 (s, 9H). 13C{1H} NMR (125.8 MHz) d 52.9 (d, JC–N = 2.9 Hz), 38.9 (d, JC–N =2.2 Hz), 6.8 (d, JC–N = 3.6 Hz). t-Bu15NHSiMe3 25 oC t-Bu15NNaSiMe3 Isoprene/DMEA Na 548 Figure A.2.12. 1H NMR (500 MHz) of [15N]NaBTA in 6.0 M THF/toluene-d8 at –100 °C: d 1.29 (s, 9H), 0.21 (s, 9H). -1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 A (s) 1.29 B (s) 0.21 THFTHF TMS 549 Figure A.2.13. 13C{1H} NMR (125.8 MHz) of [15N]NaBTA in 6.0 M THF/toluene-d8 at –100 °C: d 52.9 (d, JC–N = 2.9 Hz), 38.9 (d, JC–N =2.2 Hz), 6.8 (d, JC–N = 3.6 Hz). 05101520253035404550556065707580859095100 A (d) 52.89 J(2.9) B (d) 38.94 J(2.2) C (d) 6.88 J(3.6) THF THF THS Tolune-d8 550 Synthesis of HPETA 1,1,1-trimethyl-N-(1-phenylethyl)silanamine. To a stirred solution of 1-phenylethan-1-amine (7.7 g, 40.0 mmol) in THF (30.0 mL), n-BuLi (2.5 M, 40.0 mmol) was added dropwise at rt and stirred for 6.0 hrs. To the resulting solution Me3SiCl (4.8 g, 44.0 mmol) in THF (40.0 mL) was added dropwise at 0 °C. The colorless suspension was warmed to ambient temperature and stirred for 1.0 hr. The solvent was removed in vacuo, and the colorless residue was extracted with hexane (30.0 mL) and filtered. Removal of solvent in vacuo afforded 1,1,1-trimethyl-N-(1- phenylethyl)silanamine as a colorless liquid (5.87 g, 76% yield). 1H NMR (500 MHz, [d8]THF) δ 7.34 (dd, J = 19.3, 7.6 Hz, 2H), 7.24 (t, J = 7.5 Hz, 2H), 7.13 (q, J = 8.3 Hz, 1H), 4.05 (dt, J = 13.6, 6.7 Hz, 1H), 3.60 (s, 1H), 1.35 (d, J = 6.7 Hz, 3H), -0.02 (s, 9H). 13C{1H} NMR (126 MHz, [d8]THF) δ 150.7, 128.9, 126.9, 126.8, 52.6, 28.7, 0.7. n-BuLi/hexane 0 oC to rt. NHLi Me3SiCl/Et2O Ph Me NH2Ph Me NHSiMe3Ph Me 551 Figure A.2.14. 1H NMR (500 MHz, [d8]THF) of (R)-1,1,1-trimethyl-N-(1- phenylethyl)silanamine at 25 °C. 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm A (dd) 7.34 B (t) 7.24 C (q) 7.13 D (dt) 4.05 E (s) 3.60 H (d) 1.35 F (s) -0.02 6 .5 3 2 .1 1 1 .8 8 0 .9 9 1 .0 0 1 .9 2 2 .0 4 552 Figure A.2.15. 13C{1H} NMR (125.8 MHz, [d8]THF) of (R)-1,1,1-trimethyl-N-(1- phenylethyl)silanamine at 25 °C. 0102030405060708090100110120130140150160170 ppm 0 .7 4 2 8 .6 9 5 2 .6 1 6 7 .5 7 T H F -d 8 1 2 6 .8 1 1 2 6 .9 3 1 2 8 .9 0 1 5 0 .7 0 553 Synthesis of NaPETA Sodium (1-phenylethyl)(trimethylsilyl)amide: Sodium dispersion in toluene (2.3 mL, 18.0 mmol) was added to a 50 mL Schlenk flask. The toluene was removed in vacuo and N,N- dimethylethylamine (20.0 mL) and 1,1,1-trimethyl-N-(1-phenylethyl)silanamine (2.9 g, 15.0 mmol) were added to the flask. While stirring, isoprene (750.0 μL, 7.5 mmol) was added over the course of 10 min at 0 °C. Stirring was halted after 2.0 hrs, and the mixture was filtered through a fine frit and evaporated to dryness to give a yellowish solid, which was washed by hexane to give NaPETA as a pale white solid (2.6 g, 80% yield). 1H NMR (500 MHz, [d8]THF) δ 7.78 (d, J = 7.5 Hz, 2H), 7.53 (t, J = 7.5 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 4.75 (d, J = 6.9 Hz, 1H), 3.98 (s, 1H), 1.60 (d, J = 6.5 Hz, 3H), 0.24 (s, 9H). 13C{1H} NMR (126 MHz, [d8]THF) δ 158.3, 128.6, 127.1, 125.1, 57.8, 31.5, 4.2. Isoprene/DMEA Na NHSiMe3Ph Me NNaSiMe3Ph Me 0 oC to rt. 554 Figure A.2.16. 1H NMR (500 MHz, [d8]THF) of sodium (R)-(1- phenylethyl)(trimethylsilyl)amide at 25 °C. 0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm A (t) 7.37 B (t) 7.53 C (d) 7.78 D (d) 4.75 E (s) 3.98 F (d) 1.60 G (s) 0.24 5 .5 3 2 .0 6 0 .8 4 0 .9 8 1 .0 0 1 .8 7 1 .9 1 0 .2 4 1 .5 9 1 .6 0 3 .9 8 4 .7 4 4 .7 5 4 .7 6 7 .3 6 7 .3 7 7 .3 8 7 .4 1 7 .5 2 7 .5 3 7 .5 5 7 .7 7 7 .7 9 555 Figure A.2.17. 13C{1H} NMR (125.8 MHz, [d8]THF) of sodium (R)-(1- phenylethyl)(trimethylsilyl)amide at 25 °C. 020406080100120140160180 ppm 4 .2 1 3 1 .5 3 5 7 .7 9 6 7 .5 7 T H F -d 8 1 2 5 .1 0 1 2 7 .1 3 1 2 8 .5 5 1 5 8 .2 6 556 NaPTA trans disolvated dimer CREST optimization solvent CREST optimization energy (kcal/mol) benzene –1.1 toluene 0.0 Et3N solvent extruded from Na DMEA solvent extruded from Na MTBE –1.8 THF –1.1 TMEDA solvent extruded from Na TMCDA 0.0 PMDTA (k2,k2) –0.8 DME 0.0 diglyme (k2,k2) 0.8 HMPA 0.5 Table A.2.1. Structure optimization of trans disolvated NaPTA dimer utilizing CREST process. Na N Na N i-Pr Me3Si SiMe3 i-Pr S S trans 557 NaPTA cis disolvated dimer CREST optimization solvent CREST optimization energy (kcal/mol) benzene –3.5 toluene –1.1 Et3N solvent excluded from Na DMEA solvent excluded from Na MTBE –2.0 THF –3.0 TMEDA –1.3 TMCDA 0.0 PMDTA (k2,k2) –3.2 DME –4.2 diglyme (k2,k2) –1.5 HMPA –2.5 Table A.2.2. Structural optimization of cis disolvated NaPTA dimer utilizing the CREST process. Na N Na N i-Pr Me3Si i-Pr SiMe3 S S cis 558 NaPTA disolvated dimer cis-trans energy difference solvent cis trans cis to trans energy (kcal/mol) benzene –1.8 toluene –2.4 Et3N 1.8 DMEA –0.7 MTBE –2.5 THF –1.1 TMEDA –5.1 TMCDA 3.4 PMDTA (k2, k2) –7.9 DME –0.2 diglyme (k2, k2) –1.7 HMPA –4.0 Table A.2.3. Energy comparison between cis and trans isomers for the dimer disolvated NaPTA, utilizing CREST optimized structures for each. Green represents the energy-preferred isomer. Toluene Na N Na N i-Pr Me3Si SiMe3 i-Pr S S trans Na N Na N i-Pr Me3Si i-Pr SiMe3 S S cis 559 Figure A.2.18. NMR spectra of 0.10 M [15N]NaPTA in toluene at –80 °C. 29Si{1H} NMR (99.36 MHz): d –13.30 (d, 1JSi–N = 5.7 Hz) and d –13.47 (d, 1JSi–N = 6.3 Hz). 15N{1H} NMR (50.66 MHz): d 68.43. N Na N Na SiMe3i-Pr i-PrMe3Si N Na N Na SiMe3i-Pr i-PrMe3Si Me Me ∆G° = –7.8 kcal/mol + 2 toluene A1 A2 -14.4-14.0-13.6-13.2-12.8-12.4 ppm 68.1068.2568.4068.5568.70 ppm 68.4 ppm 15N{1H} spectrum 29Si{1H} spectrum –13.30 ppm 1J N-Si = 5.7 Hz –13.47 ppm 1J N-Si = 6.3 Hz 560 Et3N Figure A.2.19. 29Si{1H} NMR (99.36 MHz) of NaPTA at varying triethylamine concentrations in pentane at –80 oC. N Na N Na SiMe3I-Pr i-PrMe3Si N Na N Na SiMe3i-Pr i-PrMe3Si Et3N Et3N ∆G° = –8.4 kcal/mol + 2 Et3N A1 A3 0.0 equiv. Et3N 0.3 equiv. Et3N 0.6 equiv. Et3N 0.9 equiv. Et3N 1.0 equiv. Et3N 1.5 equiv. Et3N 1.7 equiv. Et3N 2.0 equiv. Et3N 7.2 equiv. Et3N -16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 561 Figure A.2.20. 29Si{1H} NMR (99.36 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv triethylamine in pentane at –80 oC: d –12.97 (d, JSi–N = 6.3 Hz), –12.99 (d, JSi–N = 6.4 Hz). Figure A.2.21. 15N{1H} NMR (50.66 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv triethylamine in pentane at –80 oC: d 68.16, 67.45. -15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 C (d) -12.99 J(6.39) B (d) -12.97 J(6.28) 505560657075808590 A (s) 68.16 B (s) 67.45 562 MTBE Figure A.2.22. 29Si{1H} NMR (99.36 MHz) of NaPTA in 1.68 M MTBE/pentane varying temperature: (A) –20 oC, (B) –50 oC, (C) –80 oC, (D) –90 oC, (E) –100 oC, (G) –110 oC. N Na N Na SiMe3i-Pr i-PrMe3Si N Na N Na SiMe3i-Pr i-PrMe3Si MTBE MTBE ∆G° = –9.8 kcal/mol + 2 MTBE A1 A4 -19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 A B C D E F G 563 Figure A.2.23. 29Si{1H} NMR (99.36 MHz) of NaPTA in 4.0 equiv MTBE/pentane varying temperature: (A) –20 oC, (B) –50 oC, (C) –80 oC, (D) –90 oC, (E) –110 oC. -20.0-19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 A B C D E 564 Figure A.2.24. 29Si{1H} NMR (99.36 MHz) of NaPTA at varying MTBE concentrations in pentane at –80 oC. -18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 2% MTBE 4% MTBE 8% MTBE 12% MTBE 14% MTBE 20% MTBE 50% MTBE 565 Figure A.2.25. 29Si{1H} NMR (99.36 MHz) of [15N]NaPTA with 2.0 equiv MTBE in pentane at –80 oC: d –13.43 (d, JSi–N = 6.6 Hz), –13.39 (d, JSi–N = 6.5 Hz). -18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 C (d) -13.43 J(6.60) B (d) -13.39 J(6.52) 566 Figure A.2.26. 15N{1H} NMR (50.66 MHz) of [15N]NaPTA with 2.0 equiv MTBE in pentane at –80 oC: d 67.63, 67.22. 505152535455565758596061626364656667686970717273747576777879 A (s) 67.63 B (s) 67.22 567 THF Figure A.2.27. 29Si{1H} NMR (99.36 MHz) of NaPTA at varying THF concentrations in toluene at –110 oC. N Na N Na SiMe3i-Pr i-PrMe3Si N Na N Na SiMe3i-Pr i-PrMe3Si THF THF ∆G° = –14.7 kcal/mol + 2 THF N Na N Na SiMe3i-Pr i-PrMe3Si THF THF ∆G° = 0.8 kcal/mol + THF ∆G° = –1.8 kcal/mol + THF THF N Na N Na SiMe3i-Pr i-PrMe3Si THF THF THF THF A1 A5 A6 A7 0% THF 1% THF 2% THF 4% THF 6% THF 10% THF 60% THF -17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 568 Figure A.2.28. 29Si{1H} NMR (99.36 MHz) of [15N]NaPTA in 10% THF/toluene at –110 oC displaying two stereoisomeric dimers: d –15.28 (d, JSi–N = 6.0 Hz), –15.65 (d, JSi–N = 6.7 Hz). -17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 A (d) -15.28 J(6.04) B (d) -15.65 J(6.68) 569 Figure A.2.29. 29Si{1H} NMR (99.36 MHz) of [15N]NaPTA in 50% THF/toluene-d8 at –110 oC displaying two stereoisomeric dimers. d –14.9 (d, JSi–N = 6.5 Hz), –15.3 (d, JSi–N = 6.5 Hz). -29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10-9-8-7-6-5 570 Figure A.2.30. 15N{1H} NMR (50.66 MHz) of [15N]NaPTA at varying THF concentrations in toluene-d8 at –110 °C: (A) no THF: d 65.82, 65.04; (B) 10% THF: d 66.14, 66.09; (C) neat THF: d 67.80. 50515253545556575859606162636465666768697071727374757677787980 A B C 571 Figure A.2.31. 29Si{1H} NMR (99.36 MHz) of [15N]NaPTA in THF at –80 oC displaying a dimer: d –16.79 (d, JSi–N = 6.7 Hz). -17.4-17.2-17.0-16.8-16.6-16.4-16.2 29Si (ppm) 572 Titration of THF to NaPTA in MTBE Figure A.2.32. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying THF concentrations in MTBE at –80 oC. Na N Na N i-Pr Me3Si SiMe3 i-Pr MTBE MTBE THF ? THF Na N Na N i-Pr Me3Si SiMe3 i-Pr THF THF -18.0-17.0-16.0-15.0-14.0 ppm 29Si{1H} spectra 0.0 equiv 2.0 equiv 10.0 equiv 4.0 equiv 6.0 equiv neat 573 Titration of THF to NaPTA in 2,5-Me2THF Figure A.2.33. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying THF concentrations in 2,5-Me2THF at –80 oC. Na N Na N i-Pr Me3Si SiMe3 i-Pr Me2THF Me2THF THF THF Na N Na N i-Pr Me3Si SiMe3 i-Pr THF THF ? A8 -18.5-17.5-16.5-15.5-14.5-13.5 ppm 29Si{1H} spectra 0.0 equiv 10.0 equiv 30.0 equiv 20.0 equiv neat 574 Titration of THF to NaPTA in Me4THF Figure A.2.34. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying THF concentrations in Me4THF at –80 oC. Na N Na N i-Pr Me3Si SiMe3 i-Pr Me4THF Me4THF THF THF Na N Na N i-Pr Me3Si SiMe3 i-Pr THF THF ? A9 -18.5-17.5-16.5-15.5-14.5-13.5 ppm A (s) -16.70 1 .0 0 29Si{1H} spectrum 0.0 equiv 5.0 equiv 14.0 equiv neat 575 HMPA Figure A.2.35. 29Si{1H} NMR (99.36 MHz) of 0.10 M [15N]NaPTA with 2.0 equiv HMPA in pentane at –80 oC. d –14.97 (d, JSi–N = 7.3 Hz). N Na N Na SiMe3i-Pr i-PrMe3Si N Na N Na SiMe3i-Pr i-PrMe3Si HMPA HMPA ∆G° = –21.6 kcal/mol + 2 HMPA N Na N Na SiMe3i-Pr i-PrMe3Si HMPA HMPA ∆G° = 13.6 kcal/mol + HMPA ∆G° = –7.1 kcal/mol + HMPA 1/2 N Me3Si i-Pr Na(HMPA)1 N Me3Si i-Pr Na(HMPA)2 ∆G° = –2.3 kcal/mol + HMPA N Me3Si i-Pr Na(HMPA)2 N Me3Si i-Pr Na(HMPA)3 A1 A10 A10 A11 A12 A12 A13 -24-23-22-21-20-19-18-17-16-15-14-13-12-11 A (d) -14.97 J(7.3) 576 Figure A.2.36. 15N{1H} NMR (50.66 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv HMPA in pentane at –80 oC: d 66.42. 50515253545556575859606162636465666768697071727374757677787980 A (s) 66.42 577 Figure A.2.37. NMR spectra of 0.10 M [15N]NaPTA in toluene with 4.0 equiv HMPA at –80 °C. 29Si{1H} NMR (99.36 MHz): d –16.80; 15N{1H} NMR: d 67.74. -19.0-18.0-17.0-16.0-15.0-14.0 ppm 29Si{1H} spectrum –16.80 ppm 67.5567.6567.7567.8567.95 ppm 67.7 ppm 15N{1H} spectrum 578 TMEDA N N SiMe3 Me3Si Na i-Pr Me2N NMe2 i-Pr Na Me2N NMe2 N Na N Na SiMe3i-Pr i-PrMe3Si ∆G° = –17.6 kcal/mol + 2 TMEDA N N SiMe3 Me3Si Na i-Pr Me2N NMe2 I-Pr Na Me2N NMe2 i-Pr Me3Si N Na N Me Me MeMe N∆G° = 9.8 kcal/mol1/2 i-Pr Me3Si N Na N Me Me MeMe N ∆G° = –16.8 kcal/mol + TMEDA N i-Pr Me3Si Na Me2N NMe2 Me2N NMe2 ∆G° = –7.4 kcal/mol + TMEDA N Me3Si i-Pr Na A1 A14 A14 A15 A16 A15 A17 579 Figure A.2.38. 29Si{1H} NMR (99.36 MHz) of 0.15 M NaPTA at varying TMEDA concentrations in pentane at –60 oC. -20.0-19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 0.25 equiv 0.0 equiv 0.5 equiv 1.0 equiv 2.0 equiv 4.0 equiv 12.0 equiv 580 Figure A.2.39. 29Si{1H} NMR (99.36 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv TMEDA in pentane at –60 oC: d –16.01 (d, JSi–N = 6.68 Hz), d –16.49 (d, JSi–N = 6.87 Hz). -20.0-19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0 A (d) -16.01 J(6.68) B (d) -16.49 J(6.87) 581 Figure A.2.40. 15N{1H} NMR (50.66 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv TMEDA in pentane at –60 oC: d 66.39, 66.25. 5556575859606162636465666768697071727374 A (s) 66.39 B (s) 66.25 582 TMCDA N N SiMe3 Me3Si Na i-Pr Me2N NMe2 i-Pr Na Me2N NMe2 N Na N Na SiMe3i-Pr i-PrMe3Si ∆G° = –10.4 kcal/mol + 2 TMCDA i-Pr Me3Si N Na N Me Me MeMe N∆G° = 9.1 kcal/molN N SiMe3 Me3Si Na i-Pr Me2N NMe2 i-Pr Na Me2N NMe2 1/2 A1 A18 A18 A19 583 Figure A.2.41. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying TMCDA concentrations in pentane at –80 oC. -20.0-19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 0.0 equiv. TMCDA 0.5 equiv. TMCDA 1.0 equiv. TMCDA 2.0 equiv. TMCDA 2.5 equiv. TMCDA 4.0 equiv. TMCDA 584 Figure A.2.42. 29Si{1H} NMR (99.36 MHz) of 0.10 M [15N]NaPTA with 2.0 equiv TMCDA in pentane at –80 oC: d –15.39 (d, JSi–N = 6.4 Hz), –15.90 (d, JSi–N = 6.6 Hz). -19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5-10.0 A (d) -15.39 J(6.37) B (d) -15.90 J(6.59) 585 Figure A.2.43. 15N{1H} NMR (50.66 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv TMCDA in pentane at –60 oC: d 65.23, 64.66. 505560657075808590 A (s) 65.23 B (s) 64.66 586 PMDTA Figure A.2.44. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying PMDTA concentrations in pentane at –80 oC. N N SiMe3 Me3Si Na i-Pr Me2N N NMe2 i-Pr Na N NMe2Me2N Me Me ∆G° = 5.5 kcal/mol N Na i-Pr Me3Si Me2N N Me2N Me 1/2 ∆G° = –25.0 kcal/mol + PMDTA N Na i-Pr Me3Si Me2N N Me2N Me N Me3Si i-Pr Na A20 A21 A16 A21 -30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10-9-8-7-6-5 0.0 equiv. 0.5 equiv. 1.0 equiv. 2.0 equiv. 3.7 equiv. 587 Figure A.2.45. 29Si{1H} NMR (99.36 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv PMDTA in pentane at –80 oC: d –22.87 (d, JSi–N = 9.8 Hz). Figure A.2.46. 15N{1H} NMR (50.66 MHz) of 0.15 M [15N]NaPTA with 2.0 equiv PMDTA in pentane at –80 oC: d 71.72. -29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10 A (d) -21.87 J(9.75) 505254565860626466687072747678808284868890 588 DME Figure A.2.47. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying DME concentrations in pentane at –60 oC. N N SiMe3 Me3Si Na i-Pr MeO OMe i-Pr Na MeO OMe N Na N Na SiMe3i-Pr i-PrMe3Si ∆G° = –15.6 kcal/mol + 2 DME N N SiMe3 Me3Si Na i-Pr MeO OMe i-Pr Na MeO OMe 1/2 N i-Pr Me3Si Na MeO OMe MeO OMe ∆G° = 3.2 kcal/mol + DME A1 A22 A22 A23 -20.0-19.5-19.0-18.5-18.0-17.5-17.0-16.5-16.0-15.5-15.0-14.5-14.0-13.5-13.0-12.5-12.0-11.5-11.0-10.5 0.0 equiv. DME 0.5 equiv. DME 1.0 equiv. DME 2.0 equiv. DME 4.0 equiv. DME 50.0 equiv. DME 589 Figure A.2.48. 29Si{1H} NMR (99.36 MHz) of 0.10 M [15N]NaPTA with 2.0 equiv DME in pentane at –60 oC: d –15.12 (d, JSi–N = 6.6 Hz). -19-18-17-16-15-14-13-12-11-10 A (d) -15.12 J(6.56) 590 Diglyme N N SiMe3 Me3Si Na i-Pr MeO O OMe i-Pr Na O OMeMeO N Na N Na SiMe3i-Pr i-PrMe3Si ∆G° = –21.0 kcal/mol + 2 diglyme N N SiMe3 Me3Si Na i-Pr MeO O OMe i-Pr Na O OMeMeO ∆G° = 0.8 kcal/mol + diglyme Na MeO O OMe OMe OMeO N i-Pr Me3Si 1/2 ∆G° = –19.6 kcal/mol + diglyme N Na i-Pr Me3Si MeO O MeO ∆G° = –6.2 kcal/mol + diglyme Na MeO O OMe OMe OMeO N i-Pr Me3Si N Me3Si i-Pr Na A1 A24 A24 A25 A16 A26 A25 591 Figure A.2.49. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying concentrations in pentane at –80 oC. Resonance-free spectra at 8.0–15.0 equiv are common, representing a solvent- concentration-dependent coalescence. -30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10-9 0.0 equiv. 8.0 equiv. 1.0 equiv. 2.0 equiv. 4.0 equiv. 0.5 equiv. 12.0 equiv. 15.0 equiv. 20.0 equiv. 23.0 equiv. 31.0 equiv. 35.0 equiv. 592 Figure A.2.50. 29Si{1H} NMR (99.36 MHz) of 0.10 M [15N]NaPTA with 31.0 equiv diglyme in pentane at –80 oC: d –22.78 (d, JSi–N = 9.2 Hz). Figure A.2.51. 15N{1H} NMR (50.66 MHz) of 0.10 M [15N]NaPTA with 31.0 equiv diglyme in pentane at –80 oC: d 70.32. -30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10 A (d) -22.78 J(9.18) 505560657075808590 A (s) 70.32 593 Figure A.2.52. NMR spectra of 0.10 M [15N]NaPTA in toluene with 2.0 equiv diglyme at – 80 °C. 29Si{1H} NMR (99.36 MHz): d –14.97 (d, JSi–N = 6.3 Hz). 15N{1H} NMR (50.66 MHz): d 67.72. -15.5-15.2-14.9-14.6-14.3-14.0 ppm 77.6077.7577.9078.05 ppm 29Si{1H} spectrum 67.7 ppm 15N{1H} spectrum –14.97 ppm 1J N-Si = 6.3 Hz 594 Figure A.2.53. 29Si{1H} NMR (99.36 MHz) of 0.10 M [15N]NaPTA in hexane with various PMDTA and diglyme concentrations at –110 °C. -24.6-24.0-23.4-22.8-22.2 ppm 29Si{1H} spectrum [PMDTA] [diglyme] 2.0 M 0.0 M 1.9 M 0.1 M 1.5 M 1.5 M 595 12-crown-4 Figure A.2.54. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 12-crown-4 concentrations in THF at –120 oC. ∆G° = –25.5 kcal/mol + 12-crown-4 O O OO Na O O O O Na THF ∆G° = –1.2 kcal/mol + THFN Me3Si i-Pr Na N Me3Si i-Pr N Me3Si i-Pr A16 A27 A28 -26.5-25.5-24.5-23.5-22.5-21.5-20.5-19.5-18.5-17.5-16.5-15.5-14.5 29Si (ppm) 1.0 equiv 0.5 equiv 2.0 equiv 0.0 equiv 596 Figure A.2.55. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 12-crown-4 at –80 °C. 29Si{1H} NMR (99.36 MHz): d –22.26 (d, JSi–N = 9.2 Hz). 15N{1H} NMR (50.66 MHz): d 71.72. -22.7-22.5-22.3-22.1-21.9 ppm 71.5071.6071.7071.8071.90 ppm 29Si{1H} spectrum 71.7 ppm 15N{1H} spectrum –22.26 ppm 1J N-Si = 9.2 Hz 597 15-crown-5 Figure A.2.56. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 15-crown-5 concentrations in THF at –120 oC. ∆G° = –28.2 kcal/mol + 15-crown-5 Na O O O O O Na O O O O O THF Na O OO O O THF + THF + THF ∆G° = –0.3 kcal/mol ∆G° = 5.0 kcal/mol N Me3Si i-Pr Na N Me3Si i-Pr N Me3Si i-Pr N Me3Si i-Pr A16 A29 A30 A31 -23.5-22.5-21.5-20.5-19.5-18.5-17.5-16.5-15.5 ppm 1.0 equiv 0.5 equiv 2.0 equiv 0.0 equiv 598 Figure A.2.57. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 15-crown-5 at –80 °C. 29Si{1H} NMR (99.36 MHz): d –23.84 (d, JSi–N = 8.7 Hz). 15N{1H} NMR (50.66 MHz): d 72.31. -24.7-24.4-24.1-23.8-23.5-23.2 ppm -12.6-12.3-12.0-11.7-11.4 ppm 29Si{1H} spectrum 72.3 ppm 15N{1H} spectrum –23.84 ppm 1J N-Si = 8.7 Hz 599 18-crown-6 Figure A.2.58. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 18-crown-6 concentrations in THF at –120 oC. ∆G° = –19.9 kcal/mol + 18-crown-6 Na O O O O O O N Me3Si i-Pr Na N Me3Si i-Pr A16 A32 -25.0-24.0-23.0-22.0-21.0-20.0-19.0-18.0-17.0-16.0-15.0 29Si (ppm) 1.0 equiv 0.7 equiv 2.0 equiv 0.0 equiv 600 Figure A.2.59. NMR spectra of 0.10 M [15N]NaPTA in THF with 2.0 equiv 18-crown-6 at –110 °C. 29Si{1H} NMR (99.36 MHz): d –23.85. 15N{1H} NMR (50.66 MHz): d 72.13. -25.0-24.4-23.8-23.2-22.6 ppm 71.771.972.172.372.5 ppm 29Si{1H} spectrum 72.1 ppm 15N{1H} spectrum –23.85 ppm 601 12-crown-4, 15-crown-5 mix Figure A.2.60. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 12-crown-4 and 15- crown-5 concentrations in THF at –120 oC. NaN i-Pr Me3Si O O OO O O O O O NaN i-Pr Me3Si + -24.8-24.4-24.0-23.6-23.2-22.8-22.4-22.0-21.6-21.2-20.8 ppm 1.0 equiv 12-C-4 1.0 equiv 15-C-5 1.0 equiv 15-C-5 2.0 equiv 12-C-4 2.0 equiv 12-C-4 2.0 equiv 15-C-5 1.0 equiv 15-C-5 1.0 equiv 12-C-4 602 15-crown-5, 18-crown-6 mix Figure A.2.61. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 15-crown-5 and 18- crown-6 concentrations in THF at –120 oC. O O O O O NaN i-Pr Me3Si O O O O O O NaN i-Pr Me3Si + -25.0-24.5-24.0-23.5-23.0-22.5-22.0-21.5-21.0 ppm 1.0 equiv 15-C-5 1.0 equiv 18-C-6 1.0 equiv 15-C-5 2.0 equiv 18-C-6 2.0 equiv 15-C-5 2.0 equiv 18-C-6 1.0 equiv 15-C-5 1.0 equiv 18-C-6 603 12-crown-4, 18-crown-6 mix Figure A.2.62. 29Si{1H} NMR (99.36 MHz) of 0.10 M NaPTA at varying 12-crown-4 and 18- crown-6 concentrations in THF at –120 oC. NaN i-Pr Me3Si O O OO O O O O O O NaN i-Pr Me3Si + -24.7-24.5-24.3-24.1-23.9-23.7-23.5-23.3-23.1-22.9 ppm 1.0 equiv 12-C-4 1.0 equiv 18-C-6 1.0 equiv 12-C-4 1.0 equiv 18-C-6 604 solvent cis trans cis to trans energy (kcal/mol) benzene 0.3 toluene 1.1 Et3N 0.8 DMEA 0.1 MTBE –1.5 THF –0.2 TMEDA –3.9 TMCDA 0.1 PMDTA (k2, k2) –2.2 DME 0.4 diglyme (k2, k2) 0.8 HMPA 1.2 Table A.2.4. Energy comparison between cis and trans isomers for the dimer disolvated NaBTA. Green represents the energy-preferred isomer. Na N Na N t-Bu Me3Si t-Bu SiMe3 S S Na N Na N t-Bu Me3Si SiMe3 t-Bu S S cis trans 605 Toluene Figure A.2.63. NMR spectra of 0.10 M [15N]NaBTA in toluene at –80 °C. 29Si{1H} NMR (99.36 MHz): d –17.65 (d, 1JSi–N = 6.5 Hz) and d –18.96 (d, 1JSi–N = 7.3 Hz). 15N{1H} NMR (50.66 MHz): d –75.62. B1 N Na N Na SiMe3t-Bu t-BuMe3Si B2 N Na N Na SiMe3t-Bu t-BuMe3Si Me Me ∆G° = –4.6 kcal/mol + 2 toluene -21.0-20.0-19.0-18.0-17.0-16.0 ppm 75.075.275.475.675.876.0 ppm –17.65 ppm 1J N-Si = 6.5 Hz –18.96 ppm 1J N-Si = 7.3 Hz 75.6 ppm 15N{1H} spectrum 29Si{1H} spectrum 606 DMEA Figure A.2.64. NMR spectra of 0.10 M [15N]NaBTA in DMEA at –80 °C. 29Si{1H} NMR (99.36 MHz): d –19.33 (d, 1JSi–N = 7.4 Hz) and d –19.43 (d, 1JSi–N = 7.3 Hz). 15N{1H} NMR (50.66 MHz): d 75.34. B1 N Na N Na SiMe3t-Bu t-BuMe3Si B3 N Na N Na SiMe3t-Bu t-BuMe3Si DMEA DMEA ∆G° = –9.8 kcal/mol + 2 DMEA 7374757677 ppm 75.3 ppm -20.1-19.8-19.5-19.2-18.9 ppm 29Si{1H} spectrum 15N{1H} spectrum –19.33 ppm 1J N-Si = 7.4 Hz –19.43 ppm 1J N-Si = 7.3 Hz 607 AB + B2A2 (2)N Na N Na SiMe3Me3Si t-But-Bu S S N Na N Na i-PrMe3Si SiMe3i-Pr S S N Na N Na SiMe3Me3Si t-Bui-Pr S S -22-20-18-16-14-12 29Si (ppm) A2 AB ABB2 1 : 1 * A2 B2 only A2 only B2 * * 608 Figure A.2.65. 29Si{1H} NMR (99.36 MHz) of NaPTA and NaBTA homodimers A2 and B2, respectively, and the NaPTA-NaBTA heterodimer (AB) at 0.15 M total base concentration in neat DMEA at –50 °C. -21.0-20.7-20.4-20.1-19.8-19.5-19.2-14.2-13.8-13.4-13.0-12.6 ppm 609 Figure A.2.66. Job plot showing the relative integration of NaPTA-derived homodimer (A2, red), NaBTA-derived homodimer (B2, blue), and the NaPTA– NaBTA heterodimer (AB, green) versus the measured mole fractionref 21 of NaPTA (XA) at 0.15 total base molarity in neat DMEA at –50 °C. The curves result from a parametric fit to a dimer model. 610 Et3N Figure A.2.67. NMR spectra of 0.10 M [15N]NaBTA in Et3N at –80 °C. 29Si{1H} NMR (99.36 MHz): d –19.05 (d, 1JSi–N = 7.5 Hz) and d –19.10 (d, 1JSi–N = 7.2 Hz). 15N{1H} NMR (50.66 MHz): d 76.33. B1 N Na N Na SiMe3t-Bu t-BuMe3Si B4 N Na N Na SiMe3t-Bu t-BuMe3Si Et3N Et3N ∆G° = –7.0 kcal/mol + 2 Et3N -19.7-19.4-19.1-18.8-18.5 ppm 76.076.276.476.6 ppm 29Si{1H} spectrum 15N{1H} spectrum 76.3 ppm –19.05 ppm 1J N-Si = 7.5 Hz –19.10 ppm 1J N-Si = 7.2 Hz 611 MTBE Figure A.2.68. NMR spectra of 0.10 M [15N]NaBTA in MTBE at –80 °C. (TMS chemical shift = 0.0 ppm for each). Standard 15N and 29Si spectra were recorded on a 500 MHz spectrometer at 50.66, and 99.36 MHz, respectively. 29Si{1H} NMR (99.36 MHz): d –18.89 (d, 1JSi–N = 7.5 Hz). B1 N Na N Na SiMe3t-Bu t-BuMe3Si B5 N Na N Na SiMe3t-Bu t-BuMe3Si MTBE MTBE ∆G° = –10.4 kcal/mol + 2 MTBE -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13 A (s) -19.85 B (s) -19.92 612 THF B1 N Na N Na SiMe3t-Bu t-BuMe3Si B6 N Na N Na SiMe3t-Bu t-BuMe3Si THF THF ∆G° = –11.4 kcal/mol + 2 THF B1 N Na N Na SiMe3t-Bu t-BuMe3Si B6 N Na N Na SiMe3t-Bu t-BuMe3Si THF THF ∆G° = –11.4 kcal/mol + 2 THF B7 N Na N Na SiMe3t-Bu t-BuMe3Si THF THF ∆G° = 1.4 kcal/mol + THF B8 THF N Na N Na SiMe3t-Bu t-BuMe3Si THF THF THF THF B10 N t-Bu Me3Si B9 ∆G° = –8.7 kcal/mol + THF B11 ∆G° = –4.1 kcal/mol + THF B12B13 ∆G° = –0.6 kcal/mol + THF Na N t-Bu Me3Si Na(THF)1 N t-Bu Me3Si Na(THF)2 N t-Bu Me3Si Na(THF)3N t-Bu Me3Si Na(THF)4 ∆G° = –2.0 kcal/mol + THF ∆G° = –4.5 kcal/mol + THF 613 29Si{1H} spectra Figure A.2.69. 29Si{1H} NMR (99.36 MHz) of [15N]NaTBA in toluene-d8 at varying THF concentrations at –110 °C: (A) 1.80 M THF: d –19.89 (d, JSi–N = 7.0 Hz); (B) 3.60 M THF: d – 20.33 (d, JSi–N = 8.1 Hz), –28.80 (d, JSi–N = 9.4 Hz); (C) 7.2 M THF: d –29.69 (d, JSi–N = 11.3 Hz). -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18 A (d) -29.67 J(11.33) A (d) -20.33 J(8.08) B (d) -28.80 J(9.36) A (d) -19.89 J(7.02) A B C 614 15N{1H} spectrum Figure A.2.70. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 6.0 M THF/toluene-d8 at –100 °C. d 76.2. 15N{1H} spectrum Figure A.2.71. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 1.2 M THF/MTBE at –80 °C. d 77.2. 72.573.073.574.074.575.075.576.076.577.077.5 A (s) 76.42 76.476.676.877.077.277.477.677.8 ppm 77.2 ppm 615 Figure A.2.72. 29Si{1H} NMR (99.36 MHz) of NaTBA at varying THF concentrations in toluene at –110 °C: (A) 0.25 equiv, d –16.77, –22.24; (B) 0.50 equiv, d –16.77, –22.24; (C) 1.0 equiv, d – 22.24; (C) 2.0 equiv, d –22.24. Na N Na N t-Bu Me3Si t-Bu SiMe3 THF THF NaN t-Bu Me3Si nTHF (THF)n 60% 50% 40% 30% 20% 10% THF -34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0-23.5-23.0-22.5-22.0-21.5-21.0-20.5 616 Figure A.2.73. Percentage of dimer vs. THF concentration, 0.15 M NaBTA in toluene cosolvent, at –110 ºC. 40 30 20 10 0 D im er /d im er +m on or m er (% ) 806040200 [THF] (%) 617 Figure A.2.74. Parametric fit of the dimer of NaBTA (0.15 M) as a function of THF concentration in toluene cosolvent at –110 ºC based on the model in eq 3 implicating a hexacoordinate, pentasolvated monomer. The curve depicts an unweighted least-squares fit to y = (0.25axn – 0.25(16b + a2 x2n)1/2)2: a = (1.7 ± 0.1) × 10−3; b = (1.4 ± 0.1) × 10−1; n = 3.9 ± 0.6. 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 [A 2T H F 2 ] ( M ) 86420 [THF] (M) 618 Derivation: 𝐾 = [𝐴!𝑆"#!] '[𝐴$𝑆$] ⋅ 𝑆" [𝐴$𝑆$]% = [𝐴$𝑆$] + [𝐴$𝑆"#!] 2 [𝐴$𝑆"#!] = 2 ⋅ ([𝐴$𝑆$]% − [𝐴$𝑆$]) 𝐾 = 2 ⋅ ([𝐴$𝑆$]% − [𝐴$𝑆$]) '[𝐴$𝑆$] ⋅ 𝑆" [𝐴$𝑆$] = ( 𝐾 ⋅ 𝑆" 4 − '16 ⋅ [𝐴$𝑆$]% + 𝐾$ ⋅ 𝑆$⋅" 4 )$ 1/2 [A2S2] + Sn K [A1S(n+1)] 619 HMPA Figure A.2.75. NMR spectra of 0.10 M [15N]NaBTA in MTBE with 3.0 equiv HMPA at –100 °C. 29Si{1H} NMR (99.36 MHz): d –29.74 (d, 1JSi–N = 11.2 Hz) and d –30.25 (d, 1JSi–N = 11.3 Hz). 15N{1H} NMR (50.66 MHz): d 79.64. B1 N Na N Na SiMe3t-Bu t-BuMe3Si B14 N Na N Na SiMe3t-Bu t-BuMe3Si HMPA HMPA ∆G° = –22.4 kcal/mol + 2 HMPA B14 N Na N Na SiMe3t-Bu t-BuMe3Si HMPA HMPA B15 ∆G° = 2.5 kcal/mol + HMPA B16 ∆G° = –4.3 kcal/mol + HMPAN t-Bu Me3Si Na(HMPA)2 N t-Bu Me3Si Na(HMPA)3 -31.0-30.6-30.2-29.8-29.4-29.0 ppm –29.74 ppm 1J N-Si = 11.2 Hz –30.25 ppm 1J N-Si = 11.3 Hz 79.279.479.679.880.0 ppm 79.6 ppm 29Si{1H} spectrum 15N{1H} spectrum 620 Figure A.2.76. NMR spectra of 0.10 M [15N]NaBTA in toluene with 1.0 equiv HMPA at – 100 °C. 29Si{1H} NMR (99.36 MHz): d –20.54. -24.5-23.5-22.5-21.5-20.5-19.5-18.5 ppm –20.54 ppm 29Si{1H} spectrum 621 TMEDA 29Si{1H} spectrum Figure A.2.77. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv TMEDA/MTBE at –100 °C: d –28.89 (d, JSi–N = 11.6 Hz). N N SiMe3 Me3Si Na t-Bu Me2N NMe2 t-Bu Na Me2N NMe2 B17 N Na N Na SiMe3t-Bu t-BuMe3Si ∆G° = –12.8 kcal/mol + 2 TMEDA B1 t-Bu Me3Si N Na N Me Me MeMe N ∆G° = –17.4 kcal/mol + TMEDA B18 N t-Bu Me3Si Na Me2N NMe2 Me2N NMe2 B19 ∆G° = –3.9 kcal/mol + TMEDA N t-Bu Me3Si B9 Na N N SiMe3 Me3Si Na t-Bu Me2N NMe2 t-Bu Na Me2N NMe2 B17 t-Bu Me3Si N Na N Me Me MeMe N∆G° = 5.6 kcal/mol B18 1/2 -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16 A (d) -28.89 J(11.6) 622 15N{1H} spectrum Figure A.2.78. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv TMEDA/MTBE at –100 °C: d 79.50. 75767778798081828384858687888990919293949596979899100 A (s) 79.56 623 TMCDA N N SiMe3 Me3Si Na t-Bu Me2N NMe2 t-Bu Na Me2N NMe2 B20 B1 N Na N Na SiMe3t-Bu t-BuMe3Si ∆G° = –17.3 kcal/mol + 2 TMCDA t-Bu Me3Si N Na N Me Me MeMe N∆G° = –1.2 kcal/mol B21 N N SiMe3 Me3Si Na t-Bu Me2N NMe2 t-Bu Na Me2N NMe2 B20 1/2 ∆G° = –26.5 kcal/mol + TMCDA t-Bu Me3Si N Na N Me Me MeMe N B21 N t-Bu Me3Si Na Me2N NMe2 Me2N NMe2 ∆G° = –2.7 kcal/mol + TMCDA B22 N t-Bu Me3Si B9 Na 624 29Si{1H} spectrum Figure A.2.79. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv. TMCDA/MTBE at –100 °C: d –27.98 (d, JSi–N = 11.3Hz). 15N{1H} spectrum Figure A.2.80. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv. TMCDA/MTBE at –80 °C: d: 78.55. -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16 A (d) -27.98 J(11.3) 6065707580859095100105110115 A (s) 78.55 625 PMDTA N N SiMe3 Me3Si Na t-Bu Me2N N NMe2 t-Bu Na N NMe2Me2N B23 Me MeB1 N Na N Na SiMe3t-Bu t-BuMe3Si ∆G° = –19.8 kcal/mol + 2 PMDTA N N SiMe3 Me3Si Na t-Bu Me2N N NMe2 t-Bu Na N NMe2Me2N B23 Me Me ∆G° = –3.2 kcal/mol N Na t-Bu Me3Si Me2N N Me2N B24 Me 1/2 ∆G° = –29.7 kcal/mol + PMDTA N Na t-Bu Me3Si Me2N N Me2N B24 Me N t-Bu Me3Si B9 Na 626 29Si{1H} spectrum Figure A.2.81. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv PMDTA/MTBE at –100 °C: d –29.44 (d, JSi–N = 11.3 Hz). 15N{1H} spectrum Figure A.2.82. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv PMDTA/MTBE at –100 °C: d 80.03. -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15 A (d) -29.44 J(11.4) 65707580859095100105110115120 A (s) 80.03 627 DME N N SiMe3 Me3Si Na t-Bu MeO OMe t-Bu Na MeO OMe B25 N Na N Na SiMe3t-Bu t-BuMe3Si ∆G° = –15.0 kcal/mol + 2 DME B1 t-Bu Me3Si O Na O Me N ∆G° = –15.1 kcal/mol + DME B26 N t-Bu Me3Si Na MeO OMe MeO OMe B27 ∆G° = –6.9 kcal/mol + DME Me N t-Bu Me3Si B9 Na N N SiMe3 Me3Si Na t-Bu MeO OMe t-Bu Na MeO OMe B25 ∆G° = 5.6 kcal/mol t-Bu Me3Si O Na O Me N B26 Me 1/2 628 29Si{1H} spectrum Figure A.2.83. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv DME/MTBE at –100 °C: d –30.06 (d, JSi–N = 11.9Hz). 15N{1H} spectrum Figure A.2.84. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv DME/MTBE at –100 °C: d: 74.50. -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16 A (d) -30.06 J(11.9) 6065707580859095100105110115120 A (s) 73.60 629 Figure A.2.85. NMR spectra of 0.10 M [15N]NaBTA in MTBE with at 1.0 equiv DME at –90 °C. 29Si{1H} NMR: d –20.07 (d, 1JSi–N = 6.8 Hz). 15N{1H} NMR (50.66 MHz): d 78.12. 77.477.677.878.078.278.478.678.8 ppm 78.1 ppm 15N{1H} spectrum -21.0-20.6-20.2-19.8-19.4-19.0 ppm 29Si{1H} spectrum –20.07 ppm 1J N-Si = 6.8 Hz 630 Diglyme N N SiMe3 Me3Si Na t-Bu MeO O OMe t-Bu Na O OMeMeO B28B1 N Na N Na SiMe3t-Bu t-BuMe3Si ∆G° = –14.9 kcal/mol + 2 diglyme ∆G° = 0.8 kcal/molN N SiMe3 Me3Si Na t-Bu MeO O OMe t-Bu Na O OMeMeO B28 ∆G° = –16.8 kcal/mol + diglyme N Na t-Bu Me3Si MeO O MeO B29 ∆G° = –6.4 kcal/mol + diglyme Na MeO O OMe OMe OMeO N t-Bu Me3Si B30 N t-Bu Me3Si B9 Na Na MeO O OMe OMe OMeO N t-Bu Me3Si B30 631 Figure A.2.86. 29Si{1H} NMR (99.36 MHz) of NaBTA at varying diglyme concentrations in MTBE at –100 °C: (A) 0.0 equiv, d –19.92, 19.98; (B) 0.50 equiv, d –29.26; (C) 1.0 equiv, d – 29.30; (D) 2.0 equiv, d –29.52; (E) 4.0 equiv, d –29.59. -32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15-14-13-12-11-10 A B C D E 632 29Si{1H} spectrum Figure A.2.87. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv diglyme/MTBE at –100 °C: d –29.52 (d, JSi–N = 11.4 Hz). 15N{1H} spectrum Figure A.2.88. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv diglyme/MTBE at –100 °C: d 77.79. -35-34-33-32-31-30-29-28-27-26-25-24-23-22-21-20-19-18-17-16-15 A (d) -29.52 J(11.4) 6065707580859095100105110115120 A (s) 77.79 633 12-crown-4 Figure A.2.89. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 12-crown-4/THF at – 100 °C: d –29.64 (d, JSi–N = 11.5 Hz). Figure A.2.90. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv 12-crown-4/THF at – 100 °C: d 77.63. ∆G° = –24.2 kcal/mol + 12-crown-4 N t-Bu Me3Si B9 Na O O OO N t-Bu Me3Si B31 Na -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0 A (d) -29.64 J(11.46) 6065707580859095100105110115120 A (s) 77.62 634 15-crown-5 Figure A.2.91. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 15-crown-5/THF at –100 °C: d –29.67 (d, JSi–N = 11.2 Hz). ∆G° = –25.7 kcal/mol + 15-crown-5 N t-Bu Me3Si B9 Na O O O O O N t-Bu Me3Si B32 Na -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0 F (d) -29.67 J(11.16) 635 Figure A.2.92. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv 15-crown-5/THF at –100 °C: d 80.03. 6065707580859095100105110115120 A (s) 77.57 636 18-crown-6 Figure A.2.93. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 18-crown-6/THF at –100 °C: d –30.26 (d, JSi–N = 11.9 Hz). ∆G° = –25.7 kcal/mol + 15-crown-5 N t-Bu Me3Si B9 Na O O O O O N t-Bu Me3Si B33 Na -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5 E (d) -30.20 J(11.85) 637 Figure A.2.94. 15N{1H} NMR (50.66 MHz) of [15N]NaBTA in 2.0 equiv 18-crown-6/THF at –100 °C: d 78.83. 6163656769717375777981838587899193959799 A (s) 78.53 638 12-crown-4 and 15-crown-5 mix Figure A.2.95. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 15-crown-5 and 2.0 equiv 12-crown-4/THF at –100 °C: d –29.63 (d, JSi–N = 11.1 Hz). Peaks superimposed. NaN t-Bu Me3Si O O OO O O O O O NaN t-Bu Me3Si + -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0 E (d) -29.63 J(11.06) 639 12-crown-4 and 18-crown-6 mix Figure A.2.96. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 18-crown-6 and 2.0 equiv 12-crown-4/THF at –100 °C: d –29.70 (d, JSi–N = 9.8 Hz) and –30.15 (d, JSi–N = 12.1 Hz). NaN i-Bu Me3Si O O OO O O O O O O NaN t-Bu Me3Si + -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0 E (d) -29.70 J(10.80) F (d) -30.15 J(12.11) 640 15-crown-5 and 18-crown-6 mix Figure A.2.97. 29Si{1H} NMR (99.36 MHz) of [15N]NaBTA in 2.0 equiv 18-crown-6 and 2.0 equiv 15-crown-5/THF at –100 °C: d –29.65 (d, JSi–N = 11.4 Hz) and –30.15 (d, JSi–N = 12.1 Hz). O O O O O NaN t-Bu Me3Si O O O O O O NaN t-Bu Me3Si + -35.0-34.5-34.0-33.5-33.0-32.5-32.0-31.5-31.0-30.5-30.0-29.5-29.0-28.5-28.0-27.5-27.0-26.5-26.0-25.5-25.0-24.5-24.0 D (d) -29.65 J(11.37) E (d) -30.09 J(12.12) 641 Intramolecular benzene ring complexation for NaPETA dimer ∆G° = –2.3 kcal/mol C1 C2 N Me3Si Me H Na Na N SiMe3 Me H N Me3Si Me H Na Na N SiMe3 Me H ∆G° = –8.1 kcal/mol C1 C3 N Me3Si Me H Na Na N SiMe3 Me H N Me3Si Me H Na Na N SiMe3 Me H ∆G° = –1.6 kcal/mol C4 C3 N Me3Si Me H Na Na N SiMe3 Me H N Me3Si Me H Na Na N SiMe3 Me H 642 Toluene Figure A.2.98. NMR spectra of 0.10 M (R)-NaPETA in toluene at –80 °C. 1H NMR (500 MHz): d 0.19 and 0.20. 29Si{1H} NMR (99.36 MHz): d –12.05 and –13.20. ∆G° = –3.0 kcal/mol C4 C5 N Me3Si Me H Na Na N SiMe3 Me H N Me3Si Me H Na Na N SiMe3 Me H Me Me +2 toluene 0.100.150.200.25 ppm -14.0-13.0-12.0-11.0 ppm 1H spectrum 0.19 ppm 29Si{1H} spectrum –12.05 ppm 0.20 ppm –13.20 ppm 643 Figure A.2.99. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)-NaPETA mixed with 0.060 M (S)-NaPETA in toluene at –80 °C. 0.080.120.160.200.240.280.32 ppm -14.0-13.0-12.0-11.0 ppm 1H spectra 29Si{1H} spectra 0.12 M (R)-NaPETA 0.06 M (R)-NaPETA 0.06 M (S)-NaPETA (R,S) (R,R) (S,S) (R,R) (S,S) (R,R) (R,R) 644 DMEA Figure A.2.100. NMR spectra of 0.30 M (R)-NaPETA in DMEA at –80 °C. 29Si{1H} NMR (99.36 MHz): d –12.70 and –14.58. ∆G° = –9.1 kcal/mol C4 N Me3Si Me H Na Na N SiMe3 Me H + 2 DMEA C6 N Me3Si Me H Na Na N SiMe3 Me H DMEA DMEA -15.2-14.8-14.4-14.0-13.6-13.2-12.8-12.4 ppm 29Si{1H} spectrum –12.70 ppm –14.58 ppm 645 Figure A.2.101. Job plot showing relative integrations of NaPETA-derived enantiomeric homodimers (blue) and R–S heterodimers (green) versus the measured mole fraction of (R)- NaPETA (X(R)-NaPETA) at 0.30 total base molarity in DMEA at –100 °C observed by 29Si NMR spectroscopy. The curves result from a parametric fit to a dimer model. -14.6-14.4-14.2-12.9-12.7-12.5 ppm R : S mole ratio 5 : 0 4 : 1 3 : 2 2 : 3 1 : 4 0 : 5 (R,S) (R,R) (R,R) + (S,S) (S,S) (S,S) (R,R) (R,R) + (S,S) 29Si{1H} spectra 1.0 0.8 0.6 0.4 0.2 0.0 R el at iv e In te gr at io n 1.00.80.60.40.20.0 χ(R)-NaPETA (R,R) + (S,S) (R,S) 646 Et3N Figure A.2.102. NMR spectra of 0.30 M (R)-NaPETA in Et3N at various temperature. 29Si{1H} NMR (99.36 MHz) at –100 °C: d –13.19 and –13.43. ∆G° = –2.3 kcal/mol C4 N Me3Si Me H Na Na N SiMe3 Me H + 2 Et3N C7 N Me3Si Me H Na Na N SiMe3 Me H Et3N Et3N -0.20-0.100.000.10 ppm –50 °C –80 °C –110 °C 1H spectra TMS -14.1-13.8-13.5-13.2-12.9-12.6 ppm 29Si{1H} spectra –50 °C –80 °C –90 °C –100 °C –13.19 ppm –13.43 ppm 647 Figure A.2.103. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)-NaPETA mixed with 0.060 M (S)-NaPETA in Et3N at –100 °C. -0.15-0.10-0.050.000.05 ppm -15.0-14.0-13.0-12.0 ppm 1H spectra TMS 29Si{1H} spectra 0.12 M (R)-NaPETA 0.06 M (R)-NaPETA 0.06 M (S)-NaPETA (R,S) (R,S) (R,R) (S,S) (R,R) (S,S) (R,R) (R,R) 648 MTBE Figure A.2.104. NMR spectra of 0.30 M (R)-NaPETA in MTBE at various temperature. 29Si{1H} NMR (99.36 MHz) at –100 °C: d –13.60. ∆G° = –15.3 kcal/mol C4 N Me3Si Me H Na Na N SiMe3 Me H + 2 MTBE C8 N Me3Si Me H Na Na N SiMe3 Me H MTBE MTBE -0.16-0.12-0.08-0.040.000.04 1H (ppm) -13.6-13.3-13.0-12.7-12.4 29Si (ppm) 1H spectra 29Si{1H} spectra TMS –50 °C –80 °C –100 °C –13.60 ppm 649 Figure A.2.105. Job plot showing relative integrations of NaPETA-derived enantiomeric homodimers (blue) and R–S heterodimers (green) versus the measured mole fraction of (R)- NaPETA (X(R)-NaPETA) at 0.30 total base molarity in MTBE at –100 °C observed by 29Si NMR spectroscopy. The curves result from a parametric fit to a dimer model. -13.25-13.15-13.05-12.95-12.85 ppm 29Si{1H} spectra R : S mole ratio 5 : 0 4 : 1 3 : 2 2 : 3 1 : 4 0 : 5 (R,S) (R,R) (R,R) + (S,S) (S,S) 650 THF N Na(THF)2Me3Si H Me∆G° = 8.8 kcal/mol 1/2 +THF C9 N Me3Si Me H Na Na N SiMe3 Me H THF THF C16 ∆G° = –10.0 kcal/mol C4 C9 N Me3Si Me H Na Na N SiMe3 Me H + 2 THF N Me3Si Me H Na Na N SiMe3 Me H THF THF N Me3Si Me H Na Na N SiMe3 Me H THF THF C10 N Me3Si Me H Na Na N SiMe3 Me H THF THF C9 N Me3Si Me H Na Na N SiMe3 Me H THF THF ∆G° = –0.3 kcal/mol C11 ∆G° = –1.8 kcal/mol N Na Me3Si H Me H N Na Me3Si Me N Na(THF)1Me3Si H Me N Na(THF)2Me3Si H Me N Na(THF)3Me3Si H Me∆G° =–8.1 kcal/mol H N Na(THF)1Me3Si Me H N Na(THF)2Me3Si Me H N Na(THF)3Me3Si Me H N Na(THF)4Me3Si Me ∆G° = –4.2 kcal/mol ∆G° = –0.1 kcal/mol ∆G° = –8.6 kcal/mol ∆G° = –5.9 kcal/mol ∆G° = –2.3 kcal/mol ∆G° = 0.3 kcal/mol ∆G° = 3.4 kcal/mol ∆G° = 3.0 kcal/mol ∆G° = 1.2 kcal/mol ∆G° = –0.8 kcal/mol +THF +THF+THF+THF +THF +THF +THF C12 C14 C16 C18 C13 C15 C17 pe19 C20 651 Figure A.2.106. NMR spectra of 0.10 M (R)-NaPETA in 1.8 M THF pentane cosolvant at various temperature. 29Si{1H} NMR (99.36 MHz) at –110 °C: d –13.88 and –14.47. -15.2-14.6-14.0-13.4-12.8-12.2 ppm 29Si{1H} spectra –10 °C –20 °C –30 °C –40 °C –50 °C –60 °C –70 °C –80 °C –90 °C –100 °C –110 °C –13.88 ppm –14.47 ppm 652 Figure A.2.107. NMR spectra of 0.10 M (R)-NaPETA in 3.6 M THF pentane cosolvant at various temperature. 29Si{1H} NMR (99.36 MHz) at –90 °C: d –14.53; –110 °C: d –20.34. -23-21-19-17-15-13 ppm 29Si{1H} spectra –10 °C –20 °C –30 °C –40 °C –50 °C –60 °C –70 °C –80 °C –90 °C –100 °C –110 °C –14.53 ppm –20.34 ppm 653 Figure A.2.108. 29Si NMR spectra (99.36 MHz) of 0.15 M (R)-NaPETA at varying THF concentrations in pentane at –110 °C. 29Si{1H} NMR (99.36 MHz) for 12.3 M THF: d –14.01 and –21.00. -23-21-19-17-15-13 ppm [THF] (M) 1.8 3.6 5.3 7.0 8.1 10.6 12.3 29Si{1H} spectra –14.01 ppm –21.00 ppm 654 Figure A.2.109. 29Si{1H} NMR (99.36 MHz) of 0.15 M (R)-NaPETA at varying THF concentrations in pentane at –10 °C. -20-19-18-17-16-15-14-13-12 ppm [THF] (M) 1.8 3.6 5.3 7.0 8.1 10.6 12.3 29Si{1H} spectra 655 TMEDA Na N Na N Me3Si SiMe3 Me H HMe TMEDA TMEDA ∆G° = –7.0 kcal/mol +2 TMEDA Na N Na N Me3Si SiMe3 Me H H Me C4 C21 ∆G° = –7.0 kcal/mol +2 TMEDANa N Na N Me3Si SiMe3 Me H H Me Na N Na N Me3Si SiMe3 Me H Me H ∆G° = 5.2 kcal/molN Na N Me3Si SiMe3 Me H HMe Na Me2N NMe2 NMe2Me2N Me2N NMe2 NMe2Me2N C4 C21 C22 N Na Me3Si H Me H N Na Me3Si Me ∆G° = –17.1 kcal/mol H N Na Me3Si Me +TMEDA ∆G° = 3.4 kcal/mol ∆G° = 2.4 kcal/mol ∆G° = –18.1 kcal/mol +TMEDA N Na Me3Si H Me H N Me3Si Me ∆G° = –0.8 kcal/mol ∆G° = 0.0 kcal/mol +TMEDA ∆G° = –3.3 kcal/mol +TMEDA N Me3Si H Me NNa NMe Me MeMe N N Me Me MeMe Me2N NMe2 NMe2 NMe2 Na Me2N NMe2 NMe2 NMe2 C12 C23 C25 C13 C24 C26 N Me3Si H MeN Na N Me3Si SiMe3 Me H HMe 1/2 ∆G° = 1.3 kcal/mol Na Me2N NMe2 NMe2Me2N NNa NMe Me MeMe C21 C23 656 Figure A.2.110. 29Si{1H} NMR (99.36 MHz) of 0.15 M (R)-NaPETA at varying TMEDA concentrations in MTBE at –100 °C. 29Si{1H} NMR at 4.0 equiv TMEDA: d –21.10. -22-20-18-16-14-12 ppm 29Si{1H} spectra 0.0 equiv 1.0 equiv 2.0 equiv 4.0 equiv –13.05 ppm –21.10 ppm 657 PMDTA ∆G° = –15.3 kcal/mol +2 PMDTANa N Na N Me3Si SiMe3 Me H H Me N Na N Me3Si SiMe3 Me H HMe Na Me Me2N NMe2N Me NMe2NMe2N C4 C27 N Na Me3Si H Me H N Na Me3Si Me N Na Me3Si H Me ∆G° = –25.3 kcal/mol H N NaMe3Si Me ∆G° = 3.4 kcal/mol ∆G° = 0.7 kcal/mol ∆G° = –28.0 kcal/mol ∆G° = 1.8 kcal/mol Me2N N N Me MeMe Me2N N Me2N Me H N NaMe3Si Me Me2N N N Me Me Me Me2N N Me NMe2 +PMDTA +PMDTA+PMDTA C12 C28 C13 C29 C30 1/2 ∆G° = –4.5 kcal/molN Na N Me3Si SiMe3 Me H HMe Na Me Me2N NMe2N Me NMe2NMe2N N Na Me3Si H Me Me2N N N Me MeMe C27 C28 658 Figure A.2.111. NMR spectra of 0.15 M (R)-NaPETA in MTBE with various concentrations of PMDTA at –100 °C. 1H NMR (500 MHz) at 2.0 equiv PMDTA: d 0.12. 29Si{1H} NMR (99.36 MHz) at 2.0 equiv PMDTA: d –20.88. -0.28-0.24-0.20-0.16-0.12-0.08 ppm -22-21-20-19-18-17-16-15-14-13 ppm 1H spectra 29Si{1H} spectra 0.0 equiv 0.5 equiv 1.0 equiv 2.0 equiv –13.05 ppm –20.88 ppm 0.12 ppm 0.21 ppm 659 Figure A.2.112. NMR spectra of 0.12 M (R)-NaPETA and 0.060 M (R)-NaPETA mixed with 0.060 M (S)-NaPETA in MTBE with 2.0 equiv PMDTA at –100 °C. -0.35-0.25-0.15-0.050.05 ppm -21.15-21.05-20.95-20.85-20.75 ppm 1H spectra 29Si{1H} spectra TMS 0.12 M (R)-NaPETA 0.06 M (R)-NaPETA 0.06 M (S)-NaPETA 660 HMPA Na N Na N Me3Si SiMe3 Me H HMe HMPA HMPA ∆G° = –16.9 kcal/mol +2 HMPANa N Na N Me3Si SiMe3 Me H H Me C4 C31 N Na Me3Si H Me H N Na Me3Si Me N Na(HMPA)1Me3Si H Me∆G° = –16.9 kcal/mol H N Na(HMPA)1Me3Si Me +HMPA ∆G° = 3.4 kcal/mol ∆G° = 2.5 kcal/mol ∆G° = –17.8 kcal/mol +HMPA N Na(HMPA)2Me3Si H Me H N Na(HMPA)2Me3Si Me ∆G° = –0.8 kcal/mol ∆G° = –6.3 kcal/mol +HMPA ∆G° = –12.0 kcal/mol +HMPA H N Na(HMPA)3Me3Si Me ∆G° = 1.3 kcal/mol + HMPA C12 C32 C34 C13 C33 C35 C36 Na N Na N Me3Si SiMe3 Me H HMe HMPA HMPA 1/2 N Na(HMPA)1Me3Si H Me∆G° = 5.3 kcal/mol C31 C32 661 Figure A.2.113. NMR spectrum of 0.15 M (R)-NaPETA with 1.0 equiv HMPA in MTBE at –100 °C. 29Si{1H} NMR (99.36 MHz): d –20.70. -21.5-20.5-19.5-18.5-17.5-16.5-15.5-14.5-13.5-12.5-11.5-10.5 ppm 29Si{1H} spectrum –20.70 ppm 662 DME Na N Na N Me3Si SiMe3 Me H Me H ∆G° = 2.1 kcal/mol N Na N Me3Si SiMe3 Me H HMe Na MeO OMe OMeMeO MeO OMe OMeMeO C37 C38 N Na Me3Si H Me H N Na Me3Si Me N Na Me3Si H Me ∆G° = –13.6 kcal/mol H N Na Me3Si Me +DME ∆G° = 3.4 kcal/mol ∆G° = 2.2 kcal/mol ∆G° = –14.8 kcal/mol +DME N Me3Si H Me H N Me3Si Me ∆G° = 0.3 kcal/mol ∆G° = –5.5 kcal/mol +DME ∆G° = –7.1 kcal/mol +DME O O Me Me O O Me Me Na MeO OMe MeO OMe Na MeO OMe MeO OMe C12 C39 C41 C13 C40 C42 1/2 ∆G° = 10.3 kcal/mol N Na N Me3Si SiMe3 Me H HMe Na MeO OMe OMeMeO N Na Me3Si H Me O O Me Me C37 C39 663 Figure A.2.114. NMR spectra of 0.10 M (R)-NaPETA in MTBE with various concentrations of DME at –100 °C. 29Si{1H} NMR (99.36 MHz) at 0.0 equiv: d –20.70; 1.0 equiv: d –14.34; 4.0 equiv: d –21.30. -0.40-0.30-0.20-0.100.000.10 ppm -22-20-18-16-14-12 ppm 1H spectra 29Si{1H} spectra TMS –13.05 ppm –14.34 ppm –21.30 ppm 0.0 equiv 1.0 equiv 2.0 equiv 4.0 equiv 664 Diglyme ∆G° = –18.7 kcal/mol +2 diglyme Na N Na N Me3Si SiMe3 Me H H Me N Na N Me3Si SiMe3 Me H HMe Na MeO OMeO OMeOOMe C43 H N Na Me3Si Me H N NaMe3Si Me∆G° = –19.4 kcal/mol ∆G° = –6.4 kcal/molMeO O MeO H N NaMe3Si Me O O O MeO O OMe C13 C44 C45 1/2 ∆G° = 1.8 kcal/mol C44 + diglyme + diglyme Me Me N Na N Me3Si SiMe3 Me H HMe Na MeO OMeO OMeOOMe C43 H N NaMe3Si Me MeO O MeO C4 665 Figure A.2.115. NMR spectra of 0.15 M (R)-NaPETA in MTBE with 2.0 equiv diglyme at –80 °C. 29Si{1H} NMR (99.36 MHz): d –19.72. -21.8-21.4-21.0-20.6-20.2-19.8-19.4-19.0-18.6-18.2-17.8-17.4-17.0 ppm 29Si{1H} spectrum –19.71 ppm 666 12-crown-4 Figure A.2.116. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 12- crown-4 at –110 °C. 29Si{1H} NMR (99.36 MHz) at 0.0 equiv: d –21.00; 1.0 equiv: d –21.31. H N Na Me3Si Me H N Na Me3Si Me∆G° = –21.0 kcal/mol O O OO+12-crown-4 ∆G° = –4.2 kcal/mol N Na Me3Si H Me O O OO C13 C46 C47 -22.0-21.7-21.4-21.1-20.8-20.5 ppm 29Si{1H} spectra –21.00 ppm –21.31 ppm 0.0 equiv 0.5 equiv 1.0 equiv 667 15-crown-5 Figure A.2.117. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 15- crown-5 at –110 °C. 29Si{1H} NMR (99.36 MHz) at 0.0 equiv: d –21.00; 1.0 equiv: d –20.52. H N Na Me3Si Me H N Na Me3Si Me∆G° = –27.7 kcal/mol +15-crown-5 O O O O O C13 C48 -22.5-21.5-20.5-19.5 ppm 29Si{1H} spectra –21.00 ppm –20.25 ppm 0.0 equiv 0.5 equiv 1.0 equiv 668 18-crown-6 Figure A.2.118. NMR spectra of 0.10 M (R)-NaPETA in THF with various concentrations of 18- crown-6 at –110 °C. 29Si{1H} NMR (99.36 MHz) at 0.0 equiv: d –21.00; 2.0 equiv: d –21.33. H N Na Me3Si Me H N Na Me3Si Me∆G° = –22.0 kcal/mol +18-crown-6 O O O O O O C13 C49 -21.8-21.6-21.4-21.2-21.0-20.8 ppm 29Si{1H} spectra –21.00 ppm –21.33 ppm 0.0 equiv 1.0 equiv 2.0 equiv 669 12-crown-4 and 15-crown-5 mix Figure A.2.119. 29Si{1H} NMR (99.36 MHz) of 0.10 M (R)-NaPETA at varying 12-crown-4 and 15-crown-5 in THF at –120 oC. N Na Me3Si H Me O O OO H N Na Me3Si Me O O O O O + C47 C48 -23.0-22.0-21.0-20.0 ppm 29Si{1H} spectra –20.25 ppm –21.31 ppm 1.0 equiv 12-C-4 1.0 equiv 15-C-5 1.0 equiv 15-C-5 1.0 equiv 12-C-4 670 15-crown-5 and 18-crown-6 mix Figure A.2.120. 29Si{1H} NMR (99.36 MHz) of 0.10 M (R)-NaPETA at varying 15-crown-5 and 18-crown-6 in THF at –120 oC. H N Na Me3Si Me O O O O O + H N Na Me3Si Me O O O O O O -22.4-22.0-21.6-21.2-20.8-20.4-20.0 ppm 29Si{1H} spectrum –20.25 ppm –21.33 ppm 1.0 equiv 15-C-5 1.0 equiv 18-C-6 1.0 equiv 18-C-6 1.0 equiv 15-C-5 671 12-crown-4 and 18-crown-6 mix Figure A.2.121. 29Si{1H} NMR (99.36 MHz) of 0.10 M (R)-NaPETA at varying 12-crown-4 and 18-crown-6 in THF at –120 oC. + H N Na Me3Si Me O O O O O O N Na Me3Si H Me O O OO C47 C49 -22.4-22.0-21.6-21.2-20.8-20.4-20.0 ppm 29Si{1H} spectra –20.25 ppm –21.33 ppm 1.0 equiv 15-C-5 1.0 equiv 18-C-6 1.0 equiv 18-C-6 1.0 equiv 15-C-5 672 Synthesis of N,N-dimethylbenzamide D2 Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. To a 0.60 M solution of NaPTA (1.0 mL, 0.60 mmol) solution in a dry 5.0 mL Kimble vial equipped with a magnetic stir bar was added 34.0 μL of dimethylamine (0.50 mmol). The solution was cooled to –78 °C using a dry ice-acetone bath and charged with methyl benzoate (35.0 μL, 0.30 mmol). After stirring at –78 °C for 0.10 hr, the reaction was quenched with 100.0 μL of MeOD and warmed to 23 °C. After drying the solution with anhydrous magnesium sulfate and silica gel in a small pipette, the filtrate was concentrated in vacuo. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded 44.7 mg (99%) of product N,N-dimethylbenzamide (D2) as a colorless liquid. 1H NMR (500 MHz, CDCl3) δ 7.38 (m, 5H), 3.03 (s, 6H). 13C{1H} NMR (126 MHz, CDCl3) δ 171.7, 136.4, 129.6, 128.4, 127.1, 128.0, 39.7, 35.5. OMe O Me2NH NaPTA/toluene –80 °C N O Me Me D2 673 Figure A.2.122. 1H NMR (500 MHz, CDCl3) of N,N-dimethylbenzamide D2 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (m) 7.38 B (s) 3.03 2 .0 3 0 .9 7 2 .5 7 3 .0 3 7 .2 6 7 .3 5 7 .3 6 7 .3 6 7 .3 7 7 .3 7 7 .3 8 7 .3 8 C D C l3 7 .3 9 7 .3 9 7 .4 0 7 .4 0 7 .4 0 7 .4 1 7 .4 1 674 Figure A.2.123. 13C{1H} NMR (125.8 MHz, CDCl3) of N,N-dimethylbenzamide D2 w/ 0.05% TMS at 25 °C. 020406080100120140160180 13C (ppm) A (s) 171.72 B (s) 136.39 C (s) 129.58 D (s) 128.41 E (s) 127.12 F (s) 77.36 0 .0 3 1 .0 2 1 .0 2 0 .5 6 0 .1 9 0 .1 8 7 6 .9 1 C D C l3 7 7 .1 6 C D C l3 7 7 .1 6 C D C l3 7 7 .3 6 7 7 .4 1 C D C l3 1 2 6 .8 6 1 2 7 .1 2 1 2 7 .2 9 1 2 7 .3 2 1 2 8 .2 1 1 2 8 .4 1 1 2 8 .5 8 1 2 9 .3 8 1 2 9 .5 8 1 3 6 .3 9 1 7 1 .7 2 675 Synthesis of N,N-diethylbenzamide D3 Solid NaPTA (138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. The NaPTA stock solution (1.0 mL, 0.60 mmol) was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Add 57.1 μL diethylamine (0.50 mmol) to the solution. Cool the solution to – 78 °C using a dry ice-acetone bath. Then add 35.0 μL of methyl benzoate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at –78 °C for 0.10 hr. Add 100 μL of MeOD to the solution, and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette and then concentrate the filtrate. Flash chromatography (10% ethyl acetate in hexanes) afforded 53.1 mg (91%) of product N,N-diethylbenzamide (D3) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.38 (m, 5H), 3.53 (s, 2H), 3.24 (s, 2H), 1.21 (s, 3H), 1.10 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 171.4, 137.4, 129.2, 128.5, 126.4, 43.3, 39.3, 14.3, 13.0. OMe O Et2NH NaPTA/toluene –80 °C N O Et Et D3 676 Figure A.2.124. 1H NMR (500 MHz, CDCl3) of N,N-diethylbenzamide D3 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (m) 7.36 B (s) 3.53 C (s) 3.24 D (s) 1.21 E (s) 1.10 1 .0 7 1 .0 2 0 .7 0 0 .7 2 2 .0 0 1 .1 0 1 .2 1 1 .2 4 1 .2 6 2 .4 8 3 .2 4 3 .5 3 7 .2 6 C D C l3 7 .3 3 7 .3 4 7 .3 4 7 .3 5 7 .3 5 7 .3 5 7 .3 6 7 .3 6 7 .3 7 7 .3 7 7 .3 8 7 .3 8 7 .3 8 677 Figure A.2.125. 13C{1H} NMR (125.8 MHz, CDCl3) of N,N-diethylbenzamide D3 w/ 0.05% TMS at 25 °C. 020406080100120140160180 13C (ppm) A (s) 171.38 B (s) 137.36 C (s) 129.17 G (s) 128.48 J (s) 126.36 L (s) 77.36 D (s) 43.35 E (s) 39.31 F (s) 14.27 H (s) 13.01 1 5 .7 9 1 4 .7 0 1 4 .2 6 1 4 .2 6 0 .9 3 2 7 .0 3 2 6 .6 7 1 3 .1 9 5 .1 1 4 .8 2 1 3 .0 1 1 4 .2 7 3 9 .3 1 4 3 .3 5 7 6 .9 1 C D C l3 7 7 .1 6 C D C l3 7 7 .1 6 C D C l3 7 7 .3 6 7 7 .4 1 C D C l3 1 2 6 .1 1 1 2 6 .3 6 1 2 6 .5 4 1 2 8 .2 6 1 2 8 .4 8 1 2 8 .6 2 1 2 8 .7 1 1 2 8 .9 9 1 2 9 .1 7 1 3 7 .3 6 1 7 1 .3 8 678 Synthesis of phenyl(piperidin-1-yl)methanone D4 Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. A 5.0 mL Kimble vial equipped with a magnetic stir bar was charged with the NaPTA (1.0 mL, 0.60 mmol) and 49.4 μL of piperidine (0.50 mmol). After cooling the solution to –78 °C using a dry ice-acetone bath, methyl benzoate (35.0 μL, 0.30 mmol) was added. After stirring at –78 °C for 0.10 hr, the reaction was quenched with 100.0 μL and warmed to 23 °C. After filtering the solution through anhydrous magnesium sulfate and silica gel in a small pipette and concentrating in vacuo, flash chromatography (10% ethyl acetate in hexanes) afforded 53.9 mg (95% yield) of phenyl(piperidin-1-yl)methanone (D4) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.38 (m, 5H), 3.67 (s, 2H), 3.36 (s, 2H), 1.67 (q, 2H), 1.58 (m, 4H). 13C{1H} NMR (126 MHz, CDCl3) δ 170.4, 136.6, 129.5, 128.5, 126.9, 48.9, 43.4, 26.3, 24.7. OMe O NaPTA/toluene –80 °C N OHN D4 679 Figure A.2.126. 1H NMR (500 MHz, CDCl3) of phenyl(piperidin-1-yl)methanone D4 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) 1 .0 0 0 .6 9 0 .8 2 A (s) 7.38 B (s) 3.67 C (s) 3.36 D (q) 1.67 E (s) 1.58 0 .9 6 0 .4 0 0 .3 5 0 .4 0 1 .0 0 680 Figure A.2.127. 13C{1H} NMR (125.8 MHz, CDCl3) of phenyl(piperidin-1-yl)methanone D4 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170 13C (ppm) A (s) 170.41 B (s) 136.60 C (s) 129.45 F (s) 128.50 H (s) 126.90 I (s) 24.70 D (m) 48.86 E (m) 43.38 2 .2 6 6 .2 2 5 .5 3 3 .8 7 3 .9 7 2 .0 7 0 .8 7 0 .8 3 2 4 .7 0 2 6 .3 4 4 3 .4 0 4 8 .8 8 7 6 .9 1 C D C l3 7 7 .1 6 C D C l3 7 7 .1 6 C D C l3 7 7 .4 1 C D C l3 1 2 6 .9 0 1 2 8 .2 9 1 2 8 .5 0 1 2 8 .6 5 1 2 9 .2 5 1 2 9 .4 5 1 3 6 .6 0 1 7 0 .4 1 681 Synthesis of phenyl(pyrrolidin-1-yl)methanone D5 Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. 1.0 mL of the NaPTA (0.60 mmol) solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Add 41.0 μL pyrrolidine (0.50 mmol) to the solution. Cool the solution to –78 °C using a dry ice-acetone bath. Then, add 35.0 μL of methyl benzoate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at –78 °C for 0.10 hr. Add 100.0 μL of MeOD to the solution and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded 48.3 mg (92%) of product phenyl(pyrrolidin-1-yl)methanone (D5) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.49 (dq, J = 7.7, 2.4 Hz, 2H), 7.38 (m, 3H), 3.60 (s, 2H), 3.43 (s, 2H), 1.91 (s, 4H). 13C{1H} NMR (126 MHz, CDCl3) δ 169.8, 137.3, 129.8, 127.1, 49.6, 46.2, 45.1, 26.4, 24.6, 24.4. OMe O NaPTA/toluene –80 °C N OHN D5 682 Figure A.2.128. 1H NMR (500 MHz, CDCl3) of phenyl(pyrrolidin-1-yl)methanone D5 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) 1 .0 0 0 .9 8 0 .7 2 0 .4 9 A (dq) 7.49 B (m) 7.38 C (s) 3.60 D (s) 3.43 E (s) 1.91 0 .0 6 0 .9 8 0 .8 8 1 .5 2 1 .0 0 1 .9 1 3 .4 3 3 .6 0 7 .3 3 7 .3 4 7 .3 4 7 .3 4 7 .3 5 7 .3 5 7 .3 6 7 .3 6 7 .3 7 7 .3 7 7 .3 7 7 .3 8 7 .3 8 7 .3 8 7 .3 9 7 .3 9 7 .3 9 7 .4 0 7 .4 0 7 .4 1 7 .4 7 7 .4 7 7 .4 8 7 .4 8 7 .4 8 7 .4 9 7 .4 9 7 .4 9 7 .5 0 7 .5 0 7 .5 1 7 .5 1 7 .5 2 7 .5 2 7 .5 2 7 .5 2 7 .5 3 7 .5 3 7 .5 6 683 Figure A.2.129. 13C{1H} NMR (125.8 MHz, CDCl3) of phenyl(pyrrolidin-1-yl)methanone D5 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170 13C (ppm) 2 4 .4 5 2 6 .4 5 4 5 .0 6 4 6 .2 3 4 9 .6 5 7 7 .1 6 C D C l3 1 2 7 .1 5 1 2 9 .8 4 1 3 7 .3 0 1 6 9 .8 1 684 Synthesis of N-(tert-butyl)benzamide D6 Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138.0 mg, 0.90 mmol) was dissolved in 1.5 mL of toluene at 23 °C. 1.0 mL of the NaPTA (0.60 mmol) solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Add 52.5 μL 2-methylpropan-2-amine (0.50 mmol) to the solution. Cool the solution to –78 °C using a dry ice-acetone bath. Then, add 35.0 μL of methyl benzoate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at –78 °C for 0.10 hr. Add 100.0 μL of MeOD to the solution and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded 46.2 mg (87%) of product N-(tert-butyl)benzamide (D6) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.71 (m, 2H), 7.45 (m, 1H), 7.40 (m, 2H), 5.96 (s, 1H), 1.47 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 167.0, 136.1, 131.2, 128.6, 126.8, 51.7, 29.0. OMe O NaPTA/toluene –80 °C H2N Me Me Me N H O Me Me Me D6 685 Figure A.2.130. 1H NMR (500 MHz, CDCl3) of N-(tert-butyl)benzamide D6 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) A (m) 7.71 B (m) 7.45 C (m) 7.40 D (s) 5.96 E (s) 1.47 4 .5 6 0 .5 1 1 .0 5 0 .5 1 1 .0 0 1 .4 7 1 .8 1 H 2 O 5 .9 6 7 .2 6 C D C l3 7 .3 8 7 .3 8 7 .3 9 7 .3 9 7 .4 0 7 .4 0 7 .4 1 7 .4 1 7 .4 1 7 .4 2 7 .4 4 7 .4 4 7 .4 5 7 .4 5 7 .4 6 7 .4 6 7 .4 7 7 .4 7 7 .4 8 7 .7 0 7 .7 1 7 .7 1 7 .7 2 7 .7 2 7 .7 2 7 .7 3 686 Figure A.2.131. 13C{1H} NMR (125.8 MHz, CDCl3) of N-(tert-butyl)benzamide D6 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) A (s) 167.02 B (s) 136.05 C (s) 131.18 E (s) 128.58 G (s) 126.81 I (s) 51.71 K (s) 28.99 1 0 .0 0 1 .8 5 5 .9 6 6 .0 5 3 .3 0 1 .1 5 1 .1 7 2 8 .8 3 2 8 .9 9 2 9 .1 3 5 1 .7 1 7 6 .9 1 C D C l3 7 7 .1 6 C D C l3 7 7 .1 6 C D C l3 7 7 .3 6 7 7 .4 1 C D C l3 1 2 6 .8 1 1 2 8 .3 6 1 2 8 .5 8 1 3 0 .9 6 1 3 1 .1 8 1 3 6 .0 5 1 6 7 .0 2 687 Synthesis of N-isopropylbenzamide 36 Solid sodium isopropyl(trimethylsilyl)amide (NaPTA, 138 mg, 0.90 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 2.0 mL of the NaPTA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. 35.0 μL of methyl benzoate (D1) (0.30 mmol) was then added to the reaction solution. The reaction was stirred at 25 °C for 0.10 hr. DI water (1.0 mL) was added, and the resulting biphasic mixture was partitioned between water (1.0 mL) and ethyl ether (2.0 mL). The aqueous layer was separated and extracted further with three 2.0 mL portions of ethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate and then concentrated. Purification of the residue by flash chromatography (10% ethyl acetate in hexanes) afforded 48.9 mg (99% yield) N-isopropylbenzamide (36) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.75 (m, 2H), 7.48 (m, 1H), 7.42 (tt, J = 6.7, 1.6 Hz, 2H), 5.91 (s, 1H), 4.29 (dp, J = 7.8, 6.5 Hz, 1H), 1.27 (d, J = 6.5 Hz, 6H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.8, 135.1, 131.4, 128.7, 126.9, 42.0, 23.0. OMe O NaPTA/toluene 23 °C N H O Me Me 36 688 Figure A.2.132. 1H NMR (500 MHz, CDCl3) of N-isopropylbenzamide 36 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) A (m) 7.75 B (m) 7.48 C (tt) 7.42 D (s) 5.91 E (dp) 4.29 F (d) 1.27 5 .2 9 0 .9 9 0 .9 3 1 .9 5 0 .9 3 1 .9 1 689 Figure A.2.133. 13C{1H} NMR (125.8 MHz, CDCl3) of N-isopropylbenzamide 36 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 3 .0 3 4 2 .0 3 1 2 6 .9 3 1 2 8 .6 7 1 3 1 .4 2 1 3 5 .1 1 1 6 6 .8 3 690 Synthesis of (R)-N-(1-phenylethyl)benzamide D7 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Cool the solution to –78 °C using a dry ice- acetone bath. Then, add 35.0 μL of methyl benzoate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at –78 °C for 0.10 hr. Add 100.0 μL of MeOH to the solution and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 62.8 mg (93% yield) (R)-N-(1-phenylethyl)benzamide (D7) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.68 (m, 2H), 7.37 (m, 1H), 7.29 (dd, J = 7.8, 6.1 Hz, 4H), 7.25 (dd, J = 8.5, 6.8 Hz, 2H), 7.18 (m, 1H), 6.49 (d, J = 7.7 Hz, 1H), 5.23 (p, J = 7.1 Hz, 1H), 1.49 (d, J = 6.9 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 166.7, 143.3, 134.7, 131.5, 128.8, 128.6, 127.5, 127.1, 126.8, 126.3. N H O PhPh Me Ph OMe O NaPETA/THF –80 °C, 2 h D7 691 Figure A.2.134. 1H NMR (500 MHz, CDCl3) of (R)-N-(1-phenylethyl)benzamide D7 w/ 0.05% TMS at 25 °C. 0.01.02.03.04.05.06.07.08.09.010.0 1H (ppm) A (m) 7.68 B (m) 7.37 C (dd) 7.29 D (dd) 7.25 E (m) 7.18 F (d) 6.49 G (p) 5.23 H (d) 1.49 2 .9 7 0 .9 7 0 .9 1 1 .0 6 1 .9 4 4 .0 7 1 .0 1 2 .0 7 0 .0 0 0 .7 8 1 .1 6 1 .1 7 1 .4 8 1 .4 9 1 .9 4 5 .2 0 5 .2 2 5 .2 3 5 .2 4 5 .2 6 6 .4 9 6 .5 0 7 .1 6 7 .1 6 7 .1 7 7 .1 7 7 .1 8 7 .1 8 7 .1 9 7 .1 9 7 .2 3 7 .2 3 7 .2 4 7 .2 5 7 .2 6 C D C l3 7 .2 6 7 .2 8 7 .2 9 7 .2 9 7 .3 0 7 .3 0 7 .3 1 7 .3 6 7 .3 6 7 .3 6 7 .3 7 7 .3 7 7 .3 8 7 .3 9 7 .3 9 7 .3 9 7 .6 7 7 .6 7 7 .6 7 7 .6 8 7 .6 8 7 .6 9 692 Figure A.2.135. 13C{1H} NMR (125.8 MHz, CDCl3) of (R)-N-(1-phenylethyl)benzamide D7 w/ 0.05% TMS at 25 °C. 020406080100120140160180 13C (ppm) 2 1 .8 1 4 9 .2 9 7 6 .9 1 C D C l3 7 7 .1 6 C D C l3 7 7 .1 6 C D C l3 7 7 .3 6 7 7 .4 1 C D C l3 1 2 6 .3 4 1 2 6 .8 1 1 2 7 .0 7 1 2 7 .4 7 1 2 8 .5 9 1 2 8 .7 8 1 3 1 .5 0 1 3 4 .6 7 1 4 3 .3 0 1 6 6 .7 1 693 Synthesis of (R)-N-(1-phenylethyl)benzamide D8 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Cool the solution to –78 °C using a dry ice- acetone bath. First, add 125.3 μL of PMDTA (0.60 mmol) to the solution. Then, add 35.0 μL of methyl benzoate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at –78 °C for 2.0 hr. Add 100.0 μL of MeOH to the solution and warm it to 23 °C. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 93.0 mg (76% yield) di-tert-butyl (E)-2-benzylidene-3-phenylpentanedioate (D8) as a oil like product. 1H NMR (500 MHz, CDCl3) δ 7.20 (m, 10H), 6.53 (d, J = 1.5 Hz, 1H), 4.21 (ddd, J = 8.7, 7.3, 1.5 Hz, 1H), 2.88 (dd, J = 15.1, 7.3 Hz, 1H), 2.76 (dd, J = 15.0, 8.7 Hz, 1H), 1.25 (s, 9H), 1.06 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) δ 170.9, 168.2, 140.6, 138.7, 136.5, 130.9, 128.5, 128.4, 128.4, 128.1, 127.7, 127.0, 81.4, 80.8, 46.6, 40.3, 28.1, 27.6. 1.0 equiv PMDTA NaPETA/toluene –80 °C, 2 hPh O-t-Bu O Ph O-t-Bu O Ph O O-t-Bu D8 694 Figure A.2.136. 1H NMR (500 MHz, CDCl3) of di-tert-butyl (E)-2-benzylidene-3- phenylpentanedioate D8 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) A (m) 7.20 B (d) 6.53 C (ddd) 4.21 D (dd) 2.88 E (dd) 2.76 F (s) 1.25 H (s) 1.06 7 .1 7 7 .2 8 0 .7 9 0 .7 8 0 .7 9 0 .8 0 7 .6 8 695 Figure A.2.137. 13C{1H} NMR (125.8 MHz, CDCl3) of di-tert-butyl (E)-2-benzylidene-3- phenylpentanedioate D8 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 7 .6 0 2 8 .0 6 4 0 .3 4 4 6 .6 4 7 7 .1 6 C D C l3 8 0 .7 6 8 1 .3 6 1 2 6 .9 9 1 2 7 .7 0 1 2 8 .0 9 1 2 8 .3 9 1 2 8 .4 2 1 2 8 .5 1 1 3 0 .9 4 1 3 6 .4 5 1 3 8 .6 5 1 4 0 .5 6 1 6 8 .2 2 1 7 0 .9 4 696 Synthesis of (R)-N-(1-phenylethyl)cinnamamide D9 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 44.6 μL of methyl cinnamate (D1) (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 1.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 57.3 mg (73% yield) (R)-N-(1-phenylethyl)cinnamamide (D9) as pale white solid. 1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 15.6 Hz, 1H), 7.50 (m, 2H), 7.38 (m, 7H), 7.31 (m, 1H), 6.42 (d, J = 15.6 Hz, 1H), 5.94 (d, J = 8.0 Hz, 1H), 5.31 (m, 1H), 1.59 (d, J = 6.9 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 143.2, 141.4, 134.9, 129.8, 128.9, 128.8, 127.9, 127.6, 126.4, 120.8. NaPETA/THF 25 °C, 1h Ph N H O Me PhPh OMe O D9 697 Figure A.2.138. 1H NMR (500 MHz, CDCl3) of (R)-N-(1-phenylethyl)cinnamamide D9 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (d) 7.66 B (m) 7.50 C (m) 7.38 D (m) 7.31 E (d) 6.42 F (d) 5.94 G (m) 5.31 H (d) 1.59 2 .8 8 0 .8 0 0 .8 9 0 .9 7 0 .7 2 6 .7 0 1 .8 6 1 .0 0 698 Figure A.2.139. 13C{1H} NMR (125.8 MHz, CDCl3) of (R)-N-(1-phenylethyl)cinnamamide D9 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 1 .7 9 4 9 .0 9 1 2 0 .7 8 1 2 6 .4 3 1 2 7 .5 9 1 2 7 .9 1 1 2 8 .8 7 1 2 8 .9 4 1 2 9 .8 0 1 3 4 .9 5 1 4 1 .4 1 1 4 3 .2 0 1 6 5 .0 6 699 Synthesis of methyl 3-phenyl-3-(((R)-1-phenylethyl)amino)propanoate D10 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of toluene at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 44.6 μL of methyl cinnamate (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 1.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 65.9 mg (77% yield) methyl 3-phenyl-3-(((R)-1- phenylethyl)amino)propanoate (D10) as pale white solid. 1H NMR (500 MHz, CDCl3) δ 7.30 (m, 10H), 4.24 (dd, J = 7.8, 6.1 Hz, 1H), 3.69 (q, J = 6.5 Hz, 1H), 3.65 (s, 3H), 2.78 (dd, J = 15.3, 7.9 Hz, 1H), 2.69 (dd, J = 15.2, 6.1 Hz, 1H), 1.84 (s, 1H), 1.38 (d, J = 6.5 Hz, 1H). 13C{1H} NMR (126 MHz, CDCl3) δ 172.3, 146.0, 142.9, 128.7, 128.5, 127.5, 127.1. 127.0, 126.7, 56.9, 54.7, 51.6, 42.6, 22.4. NaPETA/toluene 25 °C, 1h Ph OMe ONHPh Me Ph OMe O D10 700 Figure A.2.140. 1H NMR (500 MHz, CDCl3) of methyl 3-phenyl-3-(((R)-1- phenylethyl)amino)propanoate D10 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (dd) 4.24 B (q) 3.69 C (s) 3.65 D (dd) 2.78 E (dd) 2.69 F (d) 1.38 G (s) 1.84 H (m) 7.30 2 .9 9 1 .3 9 0 .9 0 0 .9 0 2 .8 5 0 .9 5 1 .0 0 9 .7 7 701 Figure A.2.141. 13C{1H} NMR (125.8 MHz, CDCl3) of methyl 3-phenyl-3-(((R)-1- phenylethyl)amino)propanoate D10 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 2 .4 1 4 2 .6 3 5 1 .6 7 5 4 .7 1 5 6 .8 8 1 2 6 .6 7 1 2 7 .0 0 1 2 7 .0 4 1 2 7 .4 6 1 2 8 .5 0 1 2 8 .6 6 1 4 2 .8 7 1 4 6 .0 4 1 7 2 .3 0 702 Synthesis of (R)-N-(1-phenylethyl)pyridin-2-amine D11 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 25.8 μL of 2-fluoropyridine (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 0.50 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 46.3 mg (78% yield) (R)-N-(1-phenylethyl)pyridin-2-amine (D11) as pale white solid. 1H NMR (500 MHz, CDCl3) δ 8.11 (dd, J = 5.1, 2.0 Hz, 1H), 7.41 (d, J = 7.0 Hz, 2H), 7.34 (1, J = 7.8 Hz, 3H), 7.27 (m, 1H), 6.56 (dd, J = 7.2, 4.9 Hz, 1H), 6.22 (d, J = 8.4 Hz, 1H), 5.17 (d, J = 6.3 Hz, 1H), 4.75 (p, J = 6.7 Hz, 1H), 1.58 (d, J = 6.8 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 158.2, 148.3, 144.8, 137.5, 128.7, 127.1, 125.9, 113.1, 106.7, 52.0, 24.5. NaPETA/THF 25 °C, 1h N F N H N Me Ph D11 703 Figure A.2.142. 1H NMR (500 MHz, CDCl3) of (R)-N-(1-phenylethyl)pyridin-2-amine D11 w/ 0.05% TMS at 25 °C. 704 Figure A.2.143. 13C{1H} NMR (125.8 MHz, CDCl3) of (R)-N-(1-phenylethyl)pyridin-2-amine (D11) w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 4 .5 2 5 2 .0 3 1 0 6 .7 2 1 1 3 .1 1 1 2 5 .9 5 1 2 7 .0 9 1 2 8 .7 4 1 3 7 .5 3 1 4 4 .8 1 1 4 8 .3 3 1 5 8 .1 9 705 Synthesis of (R)-N-(1-phenylethyl)-3-(trimethylsilyl)pyridin-2-amine D12 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 28.3 μL of 2-chloropyridine or 28.6 μL of 2-bromopyridine (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 1.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 50.2 mg (X = Cl, 62% yield) or 54.3 mg (X = Br, 67% yield) (R)-N-(1-phenylethyl)-3-(trimethylsilyl)pyridin-2-amine (D12) as yellow solid. 1H NMR (500 MHz, CDCl3) δ 8.08 (dd, J = 5.0, 2.0 Hz, 1H), 7.47 (dd, J = 7.0, 2.0 Hz, 2H), 7.38 (m, 2H), 7.32 (dd, J = 8.5, 6.8 Hz, 2H), 7.23 (m, 1H), 6.53 (dd, J = 7.0, 5.0 Hz, 1H), 5.34 (p, J = 6.8 Hz, 1H), 4.56 (d, J = 6.9 Hz, 1H), 1.56 (d, J = 6.8 Hz, 3H), 0.32 (s, 9H). 13C{1H} NMR (126 MHz, CDCl3) δ 148.7, 145.3, 143.7, 128.7, 127.0, 126.2, 113.0, 50.6, 23.2, 1.0. NaPETA/THF 25 °C, 1h N H N Me Ph SiMe3 N X (X = Cl) (X = Br) D12 706 Figure A.2.144. 1H NMR (500 MHz, CDCl3) of (R)-N-(1-phenylethyl)-3-(trimethylsilyl)pyridin- 2-amine D12 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (dd) 8.08 B (dd) 7.47 C (m) 7.38 D (dd) 7.32 E (m) 7.23 F (dd) 6.53 G (p) 5.34 H (d) 4.56 I (s) 0.32 J (d) 1.56 8 .2 2 2 .7 6 0 .9 6 1 .0 5 1 .0 4 1 .1 6 2 .2 3 2 .1 9 1 .0 9 1 .0 0 0 .3 2 0 .3 2 0 .3 3 1 .5 5 1 .5 6 1 .5 7 4 .5 5 4 .5 7 5 .3 2 5 .3 3 5 .3 4 5 .3 5 5 .3 6 6 .5 2 6 .5 3 6 .5 3 6 .5 4 7 .2 1 7 .2 2 7 .2 3 7 .2 4 7 .2 4 7 .2 4 7 .3 1 7 .3 2 7 .3 2 7 .3 3 7 .3 4 7 .3 7 7 .3 7 7 .3 7 7 .3 8 7 .3 9 7 .3 9 7 .4 0 7 .4 1 7 .4 5 7 .4 6 7 .4 6 7 .4 7 7 .4 7 8 .0 7 8 .0 8 8 .0 8 8 .0 8 707 Figure A.2.145. 13C{1H} NMR (125.8 MHz, CDCl3) of (R)-N-(1-phenylethyl)-3- (trimethylsilyl)pyridin-2-amine D12 w/ 0.05% TMS at 25 °C. 020406080100120140160180 ppm -0 .9 9 2 3 .2 5 5 0 .6 3 7 7 .1 6 C D C l3 1 1 2 .9 7 1 2 6 .1 9 1 2 6 .9 7 1 2 8 .6 5 1 4 3 .6 8 1 4 5 .2 5 1 4 8 .7 1 708 Synthesis of (R)-N-(1-phenylethyl)octan-1-amine D13 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 51.8 μL of 1-bromooctane (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 24.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (20% ethyl acetate in hexanes) afforded 59.5 mg (85% yield) (R)-N-(1-phenylethyl)octan-1-amine (D13) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.32 (m, 4H), 7.26 (tt, J = 5.9, 2.1 Hz, 1H), 3.77 (q, J = 6.4 Hz, 1H), 2.51 (ddd, J = 11.3, 8.3, 6.1 Hz, 1H), 2.43 (ddd, J = 11.3, 8.3, 6.6 Hz, 1H), 1.46 (m, 2H), 1.38 (dd, J = 6.6, 1.6 Hz, 3H), 1.28 (m, 3H), 1.27 (s, 7H), 0.89 (td, J = 7.0, 1.7 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 146.1, 128.5, 126.9, 126.7, 58.6, 48.1, 32.0, 30.4, 29.7, 29.4, 27.5, 24.5, 22.8, 14.2. NaPETA/THF 25 °C, 24 h n-C6H13 Br n-C6H13 N H Ph Me D13 709 Figure A.2.146. 1H NMR (500 MHz, CDCl3) of (R)-N-(1-phenylethyl)octan-1-amine D13 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (m) 7.32 B (tt) 7.26 C (q) 3.77 D (ddd) 2.51 E (ddd) 2.43 F (m) 1.46 G (dd) 1.38 H (m) 1.29 I (s) 1.27 J (td) 0.89 2 .6 7 7 .1 4 2 .7 9 2 .9 2 1 .7 2 0 .9 4 0 .9 4 0 .9 1 0 .9 2 4 .0 4 0 .8 8 0 .8 8 0 .8 9 0 .8 9 0 .9 1 0 .9 1 1 .2 7 1 .2 8 1 .2 9 1 .3 0 1 .3 2 1 .3 7 1 .3 7 1 .3 8 1 .3 8 1 .4 4 1 .4 4 1 .4 5 1 .4 6 1 .4 6 1 .4 7 1 .4 8 H 2 O 1 .4 8 1 .5 0 2 .4 2 2 .4 3 2 .4 3 2 .4 4 2 .4 4 2 .4 6 2 .4 8 2 .5 0 2 .5 0 2 .5 1 2 .5 1 2 .5 2 3 .7 7 3 .7 7 3 .7 8 7 .2 4 7 .2 5 7 .2 5 7 .2 6 7 .2 6 7 .2 6 7 .2 7 7 .2 7 7 .2 8 7 .2 9 C D C l3 7 .3 1 7 .3 2 7 .3 2 7 .3 3 7 .3 3 7 .3 5 7 .3 5 7 .3 6 710 Figure A.2.147. 13C{1H} NMR (125.8 MHz, CDCl3) of (R)-N-(1-phenylethyl)octan-1-amine D13 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 1 4 .2 4 2 2 .8 0 2 4 .5 1 2 7 .5 2 2 9 .4 0 2 9 .6 6 3 0 .4 4 3 1 .9 7 4 8 .0 7 5 8 .5 6 1 2 6 .6 9 1 2 6 .9 4 1 2 8 .5 3 1 4 6 .0 6 711 Synthesis of 1-(((R)-1-phenylethyl)amino)octan-2-ol D14 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 32.3 μL of 2-hexyloxirane (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 24.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (30% ethyl acetate in hexanes) afforded 63.5 mg (85% yield) 1-(((R)-1-phenylethyl)amino)octan-2-ol (D14) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.31 (m, 5H), 3.78 (m, 1H), 3.56 (m, 1H), 2.61 (ddd, J = 20.9, 12.0, 3.1 Hz, 1H), 2.33 (ddd, J = 40.2, 12.0, 9.2 Hz, 1H), 1.34 (m, 13H), 0.89 (t, J = 6.7 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 145.7, 145.4, 128.6, 127.1, 126.6, 126.5, 70.4, 70.0, 58.8, 57.8, 58.8, 57.8, 53.8, 53.0, 35.2, 35.1, 31.9, 29.5, 25.8, 25.7, 24.6, 24.3, 22.7, 14.2. NaPETA/THF 25 °C, 24 h n-C6H13 N H Ph Me HO n-C6H13 O D14 712 Figure A.2.148. 1H NMR (500 MHz, CDCl3) of 1-(((R)-1-phenylethyl)amino)octan-2-ol D14 w/ 0.05% TMS at 25 °C. 0.51.52.53.54.55.56.57.58.59.5 1H (ppm) A (ddd) 2.61 B (ddd) 2.33 C (m) 3.78 D (m) 3.56 E (m) 7.31 F (t) 0.89 G (m) 1.34 2 .7 1 1 1 .1 8 0 .9 8 1 .0 0 0 .9 2 0 .9 4 4 .8 0 713 Figure A.2.149. 13C{1H} NMR (125.8 MHz, CDCl3) of 1-(((R)-1-phenylethyl)amino)octan-2-ol D14 at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 1 4 .2 0 2 2 .7 3 2 4 .2 7 2 4 .6 5 2 5 .7 0 2 5 .7 6 2 9 .4 9 3 1 .9 0 3 5 .1 6 3 5 .2 0 5 3 .0 5 5 3 .7 9 5 7 .8 1 5 8 .7 8 6 9 .9 5 7 0 .4 3 1 2 6 .5 5 1 2 6 .6 2 1 2 7 .1 3 1 2 8 .6 5 1 4 5 .3 6 1 4 5 .7 4 714 Synthesis of 1-phenyl-2-(((R)-1-phenylethyl)amino)ethan-1-ol D15 Solid sodium (1-phenylethyl)(trimethylsilyl)amide (NaPETA, 193.5 mg, 0.90 mmol) was dissolved in 2.0 mL of THF at 25 °C. 0.80 mL of the NaPETA solution was added to a dry 5.0 mL Kimble vial equipped with a magnetic stir bar. Then, add 34.3 μL of (S)-2-phenyloxirane (0.30 mmol) to the reaction solution. Stir the reaction at 25 °C for 24.0 hr. Add 100.0 μL of H2O to the solution. Filter the solution through anhydrous magnesium sulfate and silica gel in a small pipette, then concentrate the filtrate. Purification of the residue by flash chromatography (30% ethyl acetate in hexanes) afforded 69.6 mg (96% yield) 1-phenyl-2-(((R)-1- phenylethyl)amino)ethan-1-ol (D15) as a white solid. 1H NMR (500 MHz, CDCl3) δ 7.33 (m, 10H), 4.70 (dd, J = 9.1, 3.5 Hz, 1H), 3.83 (q, J = 6.6 Hz, 1H), 2.81 (s, 1H), 2.71 (dd, J = 12.3, 3.5 Hz, 1H), 2.60 (dd, J = 12.2, 9.1 Hz, 1H), 1.42 (d, J = 6.6 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 145.2, 145.1, 142.8, 142.7, 128.7, 128.6, 128.4, 127.5, 127.2, 127.1, 126.6, 126.5, 125.9, 125.8, 72.4, 72.0, 58.6, 57.7, 55.4, 54.9, 24.3, 24.2. NaPETA/THF 25 °C, 24 h Ph O Ph N H Ph Me OH Ph N H Ph Me + OH (5:1) D15 715 Figure A.2.150. 1H NMR (500 MHz, CDCl3) of 1-phenyl-2-(((R)-1-phenylethyl)amino)ethan-1- ol D15 w/ 0.05% TMS at 25 °C. 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 1H (ppm) A (dd) 4.77 B (q) 3.86 C (dd) 2.82 D (dd) 2.60 E (d) 1.42 2 .9 9 1 .0 4 1 .0 8 0 .9 9 1 .0 0 1 .4 2 1 .4 3 2 .5 8 2 .6 0 2 .6 1 2 .6 2 2 .8 0 2 .8 1 2 .8 3 2 .8 3 3 .8 4 3 .8 6 3 .8 7 3 .8 8 4 .7 5 4 .7 6 4 .7 7 4 .7 8 4.64.8 3.7 2.62.8 1.36 716 Figure A.2.151. 13C{1H} NMR (125.8 MHz, CDCl3) of 1-phenyl-2-(((R)-1- phenylethyl)amino)ethan-1-ol D15 w/ 0.05% TMS at 25 °C. 102030405060708090100110120130140150160170180 13C (ppm) 2 4 .2 0 2 4 .3 3 5 4 .8 8 5 5 .4 4 5 7 .7 1 5 8 .6 4 7 2 .0 4 7 2 .4 0 1 2 5 .8 9 1 2 5 .9 2 1 2 6 .5 7 1 2 6 .6 1 1 2 7 .1 7 1 2 7 .5 3 1 2 8 .4 0 1 2 8 .6 3 1 2 8 .6 6 1 4 2 .6 9 1 4 2 .8 4 1 4 5 .0 5 1 4 5 .2 2 717 Figure A.2.152. 29Si NMR spectra of 0.10 M NaPTA in toluene at –80 °C with incremental additions of methyl benzoate in 2:1 toluene:pentane at –80 °C. The equiv of total added substrate for (a) to (e) are as follows: 0.0, 0.5, 1.0, 2.0 and 3.0, respectively. TMSOMe appears because the reaction is proceeding slowly at –80 °C. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Na N Na N i-Pr Me3Si SiMe3 i-Pr toluene toluene Na N Na N i-Pr Me3Si SiMe3 i-Pr PhCOOMe toluene Na N Na N i-Pr Me3Si SiMe3 i-Pr PhCOOMe PhCOOMe + PhCOOMe – toluene + PhCOOMe – toluene -14.1-13.8-13.5-13.2-12.9 29Si (ppm) 18.2018.3518.5018.6518.80 29Si (ppm) 0.1M NaPTA 0.5 equiv sub 1.0 equiv base 1.0 equiv sub 1.0 equiv base 2.0 equiv sub 1.0 equiv base 3.0 equiv sub 1.0 equiv base TMSOMe (a) (b) (c) (d) (e) 718 Figure A.2.153. 29Si NMR spectra recorded at –80 °C of a reaction mixture containing 0.18 M methyl benzoate and 0.060 M [15N]NaPTA in toluene reacting at –80 ºC and 23 ºC. Spectra (a)–(f) were obtained from the same sealed NMR tube. Reaction times for spectra (a)–(c) are 20 m, 50 m, and 100 m, respectively, at –80 ºC. For spectra (d)– (f), the reaction was run at –80 ºC for 100 m and incrementally warmed to 23 °C for 10 m, 50 m, and 250 m, respectively. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Blue ( ) represents the O-silyl- imino ether 38. Red ( ) represents the O-silyl-imino ether 39. O OMe OSiMe3 N i-Pr OSiMe3 N i-Pr 38 39 O N i-Pr Na n 41 toluene 3.0 equiv 1.0 equiv NaPTA 18.118.318.518.7 29Si (ppm) -14.6-14.0-13.4 29Si (ppm) NaPTA TMSOMe (a) (b) (c) (d) (e) (f) –80 ºC 20 m –80 ºC 50 m –80 ºC 100 m –80 ºC 100 m then 23 ºC 10 m –80 ºC 100 m then 23 ºC 50 m –80 ºC 100 m then 23 ºC 250 m 719 Figure A.2.154. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.13 M [15N]NaPTA in toluene reacting at 25 ºC, recorded at –80 ºC. Reaction times for (a)–(c) are as follows: only base (without substrate), 0 m and 20 m. Spectrum (d) is where the tube was quenched with D2O. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Blue ( ) represents [15N]NaPTA complexed TMSOMe. Na N Na N i-Pr Me3Si SiMe3 i-Pr TMSOMe TMSOMe O OMe O N i-Pr Na n Na N Na N i-Pr Me3Si SiMe3 i-Pr toluene TMSOMe toluene 3.0 equiv NaPTA 1.0 equiv D2O TMSOMe + O N D i-Pr 18192021222324 29Si (ppm) -14.2-13.9-13.6-13.3-13.0-12.7 29Si (ppm) NaPTA sub + base 0 s sub + base 10 m sub + base 10 m quench by D 2 O TMSOMe (a) (b) (c) (d) base complexed TMSOMe 720 Figure A.2.155. 29Si NMR spectra recorded at –80 ºC. (a) TMSOMe in toluene. (b) 0.10 M TMSOMe and 0.20 M NaPTA in toluene. (c) 0.050 M methyl benzoate and 0.15 M NaPTA reacting at 23 ºC for 10 m. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). 17181920212223242526 ppm -15.5-14.5-13.5-12.5-11.5 ppm (a) (b) (c) TMSOMe TMSOMe + NaPTA sub + NaPTA after reaction 721 Figure A.2.156. 1H NMR spectra of 0.10 M NaPTA in THF at –80 °C with the addition of methyl benzoate in THF at –80 °C. The added substrate is 0.20 equiv. 7.257.307.357.407.457.507.557.607.657.707.757.807.857.907.95 1H (ppm) 0.020 M sub 0.020 M sub + 0.10 M base 722 Figure A.2.157. 1H NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC and recorded at –80 ºC. Reaction times for (a)–(e) are as follows: 0 s, 30 s, 60 s, 180 s, and 60 m. Spectrum (f) was recorded after the mixture was quenched with CH3OD. 1H spectra are referenced to a TMS internal standard (0.00 ppm). Red( ) represents methyl benzoate. Blue ( ) represents mixture of mixed aggregate 40 and aggregates of imidate 41. Orange ( ) represents product carboxamide. O OMe THF 2.0 equiv NaPTA 1.0 equiv O N i-Pr Na n N Na N Na i-Pr SiMe3i-Pr O THF THF Ph 40 41 quench O N H i-Pr 7.07.27.47.67.88.08.2 1H (ppm) -0.35-0.25-0.15-0.050.050.15 1H (ppm) 0 s 30 s 60 s 180 s 60 m 60 m, quench by CH3OD NaPTA TMSOMe (a) (b) (c) (d) (e) (f) TMS 723 Figure A.2.158. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC, recorded at –80 ºC. Reaction times for (a)–(e) are as follows: only base (without substrate), 0 s, 30 s, 60 s and 180 s. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). Blue ( ) represents mixture of mixed aggregate 40. O OMe THF 2.0 equiv NaPTA 1.0 equiv O N i-Pr Na n N Na N Na i-Pr SiMe3i-Pr O THF THF Ph 40 41 quench O N H i-Pr -19.0-18.0-17.0-16.0-15.0 29Si (ppm) 14.015.016.017.018.019.020.0 29Si (ppm) 0 s 30 s 60 s 180 s only NaPTA (a) (b) (c) (d) (e) TMSOMe 724 Figure A.2.159. 1H NMR spectra of attempts to replicate in situ reaction solutions. All spectra were recorded at –80 ºC. (a) Isolated product N-isopropylbenzamide in THF. (b) Mixture of 0.030 M N-isopropylbenzamide and 0.20 M NaPTA in THF. (c) Mixture of 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC for 10 min. (d) Mixture of 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC for 10 min, then quenched with CH3OD. 1H spectra are referenced to a TMS internal standard (0.00 ppm). 7.17.37.57.77.98.18.3 1H (ppm) (a) (b) (c) (d) 725 Figure A.2.160. 29Si NMR spectra of attempts to replicate in situ reaction solutions. All spectra were recorded at – 80 ºC. (a) 0.10 M [15N]NaPTA in THF. (b) Mixture of 0.050 M methyl benzoate and 0.10 M [15N]NaPTA in THF reacting at 23 ºC for 60 s. (c) Mixture of 0.030 M N-isopropylbenzamide and 0.20 M NaPTA in THF. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). -18.5-17.5-16.5-15.5-14.5 29Si (ppm) (a) (b) (c) 726 Figure A.2.161. 29Si NMR spectra of a reaction mixture containing 0.050 M methyl benzoate, 0.15 M NaPTA, 0.60 M diglyme in toluene reacting at –80 ºC, recorded at –80 ºC. Reaction times for (a)–(b) are as follows: 10 m and 50 m. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). O OMe O N i-Pr Na n 1.0 equiv 3.0 equiv NaPTA toluene 6.0 equiv diglyme -16.0-15.0-14.0-13.0-12.0 ppm 17.717.918.118.318.518.7 ppm (a) (b) 10 m 50 m TMSOMe 727 Figure A.2.162. 29Si NMR spectra of a reaction mixture containing 0.010 M methyl benzoate, 0.10 M NaPTA, 0.20 M PMDTA in toluene reacting at –80 ºC, recorded at –80 ºC. Reaction times for (a)–(e) are as follows: 10 m, 20 m, 50 m, 80 m and 6 h. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). O OMe O N i-Pr Na n 1.0 equiv 10.0 equiv NaPTA toluene 20.0 equiv PMDTA OSiMe3 N i-Pr 17.217.618.018.418.8 29Si (ppm) (a) (b) (c) (d) (e) 10 m 20 m 50 m 80 m 6 h TMSOMe 728 Figure A.2.163. 29Si NMR spectra of a reaction mixtures of methyl benzoate, piperidine and NaPTA in toluene recorded at –80 ºC. (a) 0.12 M NaPTA in toluene. (b) 0.12 M NaPTA and 0.20 M piperidine in toluene. (c) 0.10 M methyl benzoate, 0.12 M piperidine and 0.20 M NaPTA in toluene. Methyl benzoate was titrated to piperidine and NaPTA mixture. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). O OMe 1.0 equiv 1.2 equiv NaPTA 2.0 equiv piperidine toluene O N -15.0-14.4-13.8-13.2-12.6 29Si (ppm) -0.5-0.3-0.10.10.3 29Si (ppm) TMS HPTA (a) (b) (c) NaPTA NaPTA + piperidine NaPTA + piperidine + sub 729 Figure A.2.164. 29Si NMR spectra of a reaction mixture containing 0.10 M methyl benzoate, 0.30 M (R)-NaPETA in MTBE reacting at –23 ºC, recorded at –80 ºC. Reaction times for (a)–(h) are as follows: only TMSOMe, only base, 0 s, 30 s, 70 s, 115 s, 175 s and 240 s. Blue ( ) represents mixture of imino ether. Red ( ) represents mixed aggregate product. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). OMe O 3.0 equiv (R)-NaPETA/MTBE 25 oC O N Me3Si Ph Me N Na N Na (R)-PETA SiMe3(R)-PETA O MTBE MTBE Ph 17.117.417.718.018.3 29Si (ppm) TMSOMe -14.0-13.7-13.4-13.1-12.8-12.5 29Si (ppm) TMSOMe (R)-NaPETA TMSOMe (a) (d) (g) (b) (c) (e) (f) (h) (R)-NaPETA 0 s 30 s 70 s 115 s 175 s 240 s 730 Figure A.2.165. 29Si NMR spectra of a reaction mixture containing 0.10 M methyl benzoate, 0.30 M (R)-NaPETA and 0.60 M PMDTA in MTBE reacting at –23 ºC, recorded at –80 ºC. Reaction times for (a)–(g) are as follows: only TMSOMe, only base, 5 m, 15 m, 45 m, 125 m and 300 m. 29Si spectra are referenced to a TMS internal standard (0.00 ppm). O OMe O N (R)-PETA Na n 1.0 equiv 3.0 equiv (R)-NaPETA MTBE 6.0 equiv PMDTA 16.416.817.217.618.018.418.8 29Si (ppm) -22.0-21.6-21.2-20.8-20.4-20.0 29Si (ppm) TMSOMe(a) (d) (g) (b) (c) (e) (f) (R)-NaPETA 5 m 15 m 45 m 300 m 125 m TMSOMe (R)-NaPETA 731 Rate Studies General procedure for in situ IR analyses IR spectra were recorded with an in situ IR spectrometer fitted with a 30-bounce, silicon-tipped probe. The spectra were acquired at a gain of 1 and a resolution of 4 cm−1. All tracked reactions were conducted under positive flow of argon from a Schlenk line. A representative reaction was carried out as follows: The IR probe was inserted through a teflon adapter and O-ring seal into an oven-dried, cylindrical flask fitted with a magnetic stir bar and a T-joint. The T-joint was capped with a septum for injections and an argon line. After evacuation under full vacuum, heating, and flushing with argon, the flask was charged with the 0.060 M NaPTA in THF/cosolvent mixture of choice 2,2,5,5-Me4THF, 2,5-Me2THF, pentane and cooled to –78 °C in the dry ice acetone and left to stir for 15 min. A set of 256 baseline scans were collected and IR spectra were recorded every 15 seconds from 30 scans. At this point spectral collection was halted and an additional 256 baseline scans were collected. The spectrometer was configured to collect spectra ever 5 seconds from 16 scans. 1 set of scans was collected before addition of 0.005 M methyl picolinate in THF through the septum. The reaction was tracked over the disappearance of methyl picolinate complex (1730 cm–1). 732 Figure A.2.166. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in toluene/pentane cosolvent. The IR spectra presented here are the first collected for this study. (a) Methyl benzoate in neat toluene. (b) Methyl benzoate and NaPTA in neat toluene. (c) Methyl benzoate and NaPTA in 50% toluene. (d) Methyl benzoate and NaPTA in 20% toluene. 14 x 10-3 12 10 8 6 4 2 0 -2 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 12 x 10-3 10 8 6 4 2 0 -2 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 15 x 10-3 10 5 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 15 x 10-3 10 5 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 1728 1711 1713 1712 733 Figure A.2.167. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in Et3N/pentane cosolvent. The IR spectra presented here are the first collected for this study. (a) Methyl benzoate in neat Et3N. (b) Methyl benzoate and NaPTA in neat Et3N. (c) Methyl benzoate and NaPTA in 50% Et3N. (d) Methyl benzoate and NaPTA in 20% Et3N. 14 x 10-3 12 10 8 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 8 x 10-3 6 4 2 0 -2 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 8 x 10-3 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 10 x 10-3 8 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) (b) (a) (d) (c) 1734 1734 1712 1734 1712 1734 1712 734 Figure A.2.168. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –20 °C in MTBE/pentane cosolvent. The IR spectra presented here are the first collected for this study. (a) Methyl benzoate in neat MTBE. (b) Methyl benzoate and NaPTA in neat MTBE. (c) Methyl benzoate and NaPTA in 50% MTBE. (d) Methyl benzoate and NaPTA in 20% MTBE. 12 x 10-3 10 8 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 12 x 10-3 10 8 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 8 x 10-3 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) 8 x 10-3 6 4 2 0 ab so rb an ce 1760 1740 1720 1700 1680 wavenumber (cm-1) (b) (a) (d) (c) 1733 1733 1733 1711 1733 1711 1711 735 Figure A.2.169. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –45 °C in THF/pentane cosolvent. The IR spectra presented here are the first collected for this study. Spectrum A (blue) is methyl benzoate in neat THF. Spectrum B (purple) is methyl benzoate and NaPTA in 10% THF. 30 x 10-3 25 20 15 10 5 0 ab so rb an ce 1800 1760 1720 1680 wavenumber (cm–1) 1727 736 Figure A.2.170. Imino-ether reappearance: (a) Methyl benzoate (0.020 M) was added to a solution of NaPTA (0.060 M) in Et3N at –78 °C. A mixture of Et3N/TMSCl (1:4) was then added at –78 °C, followed by warming to –23 °C and stirring for 10 mins. (b) Methyl benzoate (0.16 M) was added to a solution of NaPTA (0.080 M) in toluene at –78 °C, and the reaction mixture was stirred at this temperature for 5 hrs. (c) The reaction mixture from (b) was warmed to 23 °C and stirred for 10 min. 120 100 80 60 40 20 0 a bs or ba nc e 1680 1670 1660 1650 1640 1630 wavenumber (cm–1 ) (a) 1652 120 100 80 60 40 20 0 a bs or ba nc e 1680 1670 1660 1650 1640 1630 wavenumber (cm–1 ) (b) 1661 120 100 80 60 40 20 0 a bs or ba nc e 1680 1670 1660 1650 1640 1630 wavenumber (cm–1 ) (c) 1661 1652 737 Figure A.2.171. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene with 0.12 M PMDTA at –20 °C. (a) IR spectra of imino ether 39 (first recorded spectrum). The initial recorded spectrum failed to capture the disappearance of methyl benzoate. (b) Plot of concentration of imino ether 39 (M) vs time (s). Figure A.2.172. (a) Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene at – 20 °C at substrate 50% conversion. (b) Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene with 0.12 M PMDTA at –78 °C at 50% conversion. 5 x 10-3 4 3 2 1 0 -1 ab so rb an ce 1760 1720 1680 1640 1600 wavenumber (cm-1) (a) OTMS N i-Pr 1661 5 x 10-3 4 3 2 1 0 [im in o et he r] (M ) 120010008006004002000 time (s) (b) 10 x 10-3 8 6 4 2 ab so rb an ce 1740 1720 1700 1680 1660 1640 1620 wavenumber (cm–1) 6 x 10-3 5 4 3 2 ab so rb an ce 1740 1720 1700 1680 1660 1640 1620 wavenumber (cm-1) 1726 1661 OMe O OTMS N i-Pr 1726 (a) (b) OMe O 738 Figure A.2.173. Addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) in toluene with 10 mol% PMDTA added during reaction at –78 °C. Orange represents IR spectrum recorded at 8 min (before adding 10 mol% PMDTA). Blue represents IR spectrum recorded at 53 min (after adding 10 mol% PMDTA). Green represents IR spectrum recorded at 162 min (after adding 10 mol% PMDTA). Reaction krel = 25. The 1725 cm–1 peak corresponds to non-complexed methyl benzoate, while the 1711 cm–1 peak corresponds to base-complexed methyl benzoate. 0.20 0.15 0.10 0.05 0.00 ab so rb an ce 12 x 1031086420 time (s) 0.25 0.20 0.15 0.10 0.05 0.00 ab so rb an ce 1740 1720 1700 1680 wavenumber (cm–1) add 10% mol PMDTA 8 min (before adding PMDTA) 53 min (AFTER adding PMDTA) 162 min (AFTER adding PMDTA) 8 min 53 min 162 min 1725 1711 k rel = 25 53 min (AFTER adding PMDTA) 162 min (AFTER adding PMDTA) 739 Figure A.2.174. Plot of the concentration of methylbenzoate-NaPTA complex 37 (1712 cm–1) formed from methyl benzoate (0.005 M) and 0.12 M NaPTA in 5.6 M toluene/hexane at –20 °C. The curve depicts an unweighted least-squares fit to y = ae−bx: a = (8.1 ± 0.1) × 10−3; b = (1.5 ± 0.1) × 10−3. 5 4 3 2 1 0 [m et hy l b en zo at e] x 1 03 (M ) 2000150010005000 time (s) 740 Figure A.2.175. Plot of kobsd vs [toluene] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.10 M) at –20 °C measured by IR spectroscopy (1711–1713 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b: a = (1.4 ± 0.1) x 10–3; b = (–3.9 ± 0.1) x 10–5. [toluene] / M kobsd x 103 / sec–1 1.9 1.4 ± 0.2 3.7 1.3 ± 0.1 5.6 1.2 ± 0.1 7.5 2.7 ± 0.2 9.4 1.2 ± 0.1 Table A.2.5. Average pseudo-first-order rate constants (kobsd) at various toluene (pentane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.10 M) at –20 °C. 2.5 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 1086420 [toluene] (M) 741 Figure A.2.176. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) by NaPTA in neat toluene at –20 °C measured by monitoring the loss of 37 (1711–1713 cm–1) by IR spectroscopy. The curve depicts an unweighted least-squares fit to y = ax + b: a = (1.0 ± 0.1) x 10–3; b = (1.5 ± 0.1) x 10–3). [NaPTA] / M kobsd x 103 / sec–1 0.12 1.1 ± 0.1 0.18 1.2 ± 0.1 0.24 1.2 ± 0.2 0.30 1.1 ± 0.1 0.36 1.3 ± 0.1 Table A.2.6. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of NaPTA (0.10 M) to methyl benzoate (0.0050 M) at –20 °C in neat toluene. 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 0.40.30.20.10.0 [NaPTA] (M) 742 Figure A.2.177. Plot of kobsd vs [THF] (M) in pentane (Curve A, red), MTBE (Curve B, blue), and Me4THF (Curve C, green) for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.12 M) at –78 °C measured by IR spectroscopy (1727 cm–1). All fits were to y = ax/1+bx. Curve A: a = (6.3 ± 0.1) × 10–3; b = 91.6 ± 1.0); Curve B: a = (2.6 ± 0.1) × 10–4; b = 0.3 ± 0.1; Curve C: a = (4.8 ± 0.1) × 10–5; b = 0). 0.6 0.4 0.2 0.0 k o bs d x 10 3 / se c–1 121086420 [THF] (M) hexane MTBE Me4THF 743 Red Cosolvent: pentane [THF] / M kobsd x 103 / sec–1 2.5 0.7 ± 0.1 4.9 0.7 ± 0.1 6.2 0.7 ± 0.1 9.9 0.7 ± 0.1 12.3 0.7 ± 0.1 Table A.2.7. Pseudo-first-order rate constants (kobsd) at various THF (pentane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. 744 Blue Cosolvent: MTBE [THF] / M kobsd x 103 / sec–1 0.0 0.02 0.1 0.04 0.2 0.1 0.8 0.2 1.3 0.3 2.4 0.4 4.2 0.5 6.2 0.6 8.6 0.6 11.1 0.7 Table A.2.8. Pseudo-first-order rate constants (kobsd) at various THF concentrations in MTBE cosolvent for the addition of NaPTA (0.060 M) to methyl benzoate (0.0050 M) at –78 °C. 745 Green Cosolvent: 2,2,5,5-Me4THF [THF] / M kobsd x 103 / sec–1 0.2 0.002 1.2 0.05 3.7 0.2 6.2 0.2 8.6 0.4 11.1 0.5 12.3 0.7 Table A.2.9. Pseudo-first-order rate constants (kobsd) at various THF concentrations in Me4THF cosolvent for the addition of NaPTA (0.060 M) to methyl benzoate (0.0050 M) at – 78 °C. 746 Figure A.2.178. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methylbenzoate (0.005 M) in neat THF at –78 °C measured by IR spectroscopy (1727 cm–1). The curve is a least-squares fit to y = axb: a = (6.6 ± 0.1) x 10–2; b = 1.1 ± 0.1). [NaPTA] / M kobsd x 103 / sec–1 0.12 0.7 ± 0.1 0.24 1.4 ± 0.3 0.36 2.3 ± 0.4 0.48 3.0 ± 0.1 0.60 3.9 ± 0.1 Table A.2.10. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of NaPTA to methyl benzoate (0.0050 M) at –78 °C in THF. 30 20 10 0 k o bs d x 1 03 / se c-1 0.60.50.40.30.20.10.0 [NaPTA] (M) 747 Figure A.2.179. Plot of kobsd vs [PMDTA] (M) in toluene cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) at –78 °C measured by IR spectroscopy (1726 cm–1). The curve depicts an unweighted least-squares fit to y = ax + b: a = (1.3 ± 0.1) x 10–2; b = (–1.6 ± 0.1) x 10–3). [PMDTA] / M kobsd x 103 / sec–1 0.12 13.1 ± 1.9 0.18 13.6 ± 1.9 0.24 13.5 ± 1.0 0.30 12.8 ± 0.9 0.36 14.0 ± 1.8 Table A.2.11. Average pseudo-first-order rate constants (kobsd) at various PMDTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C in toluene. 25 20 15 10 5 0 k ob sd x 1 03 / se c-1 0.40.30.20.10.0 [PMDTA] (M) 748 Figure A.2.180. Plot of kobsd vs [NaPTA] (M) in toluene with 2.0 M PMDTA for the aminolysis of methyl benzoate (0.005 M) by NaPTA at –78 °C measured by IR spectroscopy (1726 cm–1). The curve depicts an unweighted least-squares fit to y = axn: a = 0.5 ± 0.1; n = 1.1 ± 0.1. [NaPTA] / M kobsd x 103 / sec–1 0.06 24 ± 3 0.12 48 ± 3 0.18 71 ± 9 0.24 93 ± 9 0.30 128 ± 7 Table A.2.12. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA at –78 °C in toluene with 2.0 M PMDTA. 120 100 80 60 40 20 0 k o bs d x 10 3 / se c-1 0.300.250.200.150.100.050.00 [NaPTA] (M) 749 Figure A.2.181. Plot of kobsd vs [diglyme] (M) in hexane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) at –50 °C measured by IR spectroscopy (1728–1730 cm–1). The curve depicts an unweighted least-squares fit to y = (0.25*a*xn – 0.25*(16*b + a2 *x2n)1/2)2: a = (6.9 ± 0.1) × 10−2; b = (2.3 ± 0.1) × 10−1; n = 1.6 ± 0.3). [diglyme] / M kobsd x 103 / sec–1 0.6 55.9 0.7 54.1 1.0 50.5 1.3 42.7 1.5 23.9 1.8 13.8 2.1 10.8 3.5 6.1 4.9 3.2 6.4 2.6 Table A.2.13. Pseudo-first-order rate constants (kobsd) at various diglyme (hexane cosolvent) concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –78 °C. 60 50 40 30 20 10 0 k o bs d x 10 3 / se c–1 6543210 [diglyme] (M) 750 Figure A.2.182. Plot of kobsd vs [NaPTA] (M) for the aminolysis of methyl benzoate (0.005 M) in 6.3 M diglyme/hexane at –78 °C measured by IR spectroscopy (1730 cm–1). The curve is a least- squares fit to y = axn: a = 2.0 ± 0.1; n = 2.2 ± 0.2. [NaPTA] / M kobsd x 103 / sec–1 0.06 3.0 ± 2 0.09 9.3 0.12 18.1 0.15 29.2 0.18 37.5 0.20 53 ± 4 Table A.2.14. Average pseudo-first-order rate constants (kobsd) at various NaPTA concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA (0.060 M) at –50 °C in 6.3 M diglyme. 50 40 30 20 10 0 k o bs d x 10 3 / se c–1 0.200.150.100.050.00 [NaPTA] (M) 751 Figure A.2.183. Plot of kobsd vs Xdiglyme for the aminolysis of methyl benzoate (0.0050 M) by NaPTA (0.060 M) in fixed 2.0 M diglyme-PMDTA mixtures in hexane at –78 °C measured by IR spectroscopy (1729 cm–1). Xdiglyme kobsd x 103 / sec–1 0.0 29 ± 5 0.05 121 ± 9 0.1 91 ± 8 0.15 46 ± 3 0.2 21 ± 12 0.4 7.1 0.6 3.2 0.8 1.8 1.0 1.1 Table A.2.15. Average pseudo-first-order rate constants (kobsd) for the aminolysis of methyl benzoate (0.0050 M) by NaPTA (0.060 M) in a fixed 2.0 M diglyme-PMDTA mixtures in hexane at –78 °C measured by IR spectroscopy (1729 cm–1). 120 100 80 60 40 20 0 k o bs d x 10 3 / se c-1 1.00.80.60.40.20.0 χdiglyme 752 Figure A.2.184. Plot of kobsd vs free (uncomplexed) crown ether (M) for 12-crown-4 (red), 15- crown-5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.0050 M) by 0.060 M NaPTA in neat THF at –78 °C measured by IR spectroscopy (1733 cm–1). All curves were to fit to y = ax + b. 12-C-4: a = 1.0 ± 0.1; b =(6.0 ± 0.1) x 10–2; 15-C-5: a = (4.3 ± 0.1) x 10–3; b = (1.2 ± 0.1) x 10–3; 18-C-6: a = 0.7 ± 0.1; b = (3.1 ± 0.1) x 10–2. 300 250 200 150 100 50 0 k o bs d x 10 3 / se c–1 0.120.100.080.060.040.020.00 [free crown] (M) 3.0 2.0 1.0 0.0k o bs d x 1 03 / se c–1 0.100.00 [free 15-crown-5] (M) 12-C-4 18-C-6 15-C-5 753 Green [free 15-C-5] / M kobsd x 103 / sec–1 0.00 1.3 ± 0.1 0.03 1.4 0.06 1.5 0.09 1.7 0.12 1.8 ± 0.1 Table A.2.16. Pseudo-first-order rate constants (kobsd) at various free 15-crown-5 concentrations for the addition of NaPTA (0.060 M) to methyl benzoate (0.0050 M) in THF at –78 °C. Red [free 12-C-4] / M kobsd x 103 / sec–1 0.00 63.1 ± 10.3 0.06 128.3 ± 9.1 0.12 189.2 ± 1.5 Table A.2.17. Pseudo-first-order rate constants (kobsd) at various free 12-crown-4 concentrations for the addition of NaPTA (0.060 M) to methyl benzoate (0.0050 M) in THF at –78 °C. 754 Blue [free 18-C-6] / M kobsd x 103 / sec–1 0.0 35 ± 3 0.03 49 ± 4 0.06 75 ± 4 0.09 101 ± 3 Table A.2.18. Pseudo-first-order rate constants (kobsd) at various free 18-crown-6 concentrations for the addition of NaPTA (0.060 M) to methyl benzoate (0.0050 M) in THF at –78 °C. 755 Figure A.2.185. Plot of kobsd vs [NaPTA-12-crown-4] (M) (complexed) for the aminolysis of methyl benzoate (0.0050 M) by NaPTA-12-crown-4 in neat THF at –78 °C measured by IR spectroscopy (1731 cm–1). The curve is a least-squares fit to y = axb: a = 1.7 ± 0.4; b = 1.3 ± 0.1. [NaPTA-12- crown-4] / M kobsd x 103 / sec–1 0.06 34 ± 8 0.12 76 ± 8 0.18 147 ± 16 Table A.2.19. Pseudo-first-order rate constants (kobsd) at various NaPTA-12-crown-4 concentrations for the addition of NaPTA-12-crown-4 to methyl benzoate in THF at –78 °C. 160 140 120 100 80 60 40 20 0 k o bs d x 10 3 / se c-1 0.150.100.050.00 [NaPTA•12-crown-4] (M) 756 Figure A.2.186. Plot of kobsd vs [NaPTA-15-crown-5] (M) (complexed) for the aminolysis of NaPTA-15-crown-5 to methyl benzoate (0.0050 M) in neat THF at –78 °C measured by IR spectroscopy (1730 cm–1). The curve is a least-squares fit to y = axb: a = (4.2 ± 0.1) x 10–2; b = 1.2 ± 0.1. [NaPTA-15- crown-5] / M kobsd x 103 / sec–1 0.06 1.0 ± 0.2 0.12 2.0 ± 0.3 0.18 4.0 ± 0.3 0.24 6.0 ± 0.4 0.30 8.0 ± 1.0 Table A.2.20. Pseudo-first-order rate constants (kobsd) at various NaPTA-15-crown-5 concentrations for the addition of NaPTA-15-crown-5 to methyl benzoate in THF at –78 °C. 8 6 4 2 0 k o bs d x 10 3 / se c-1 0.300.250.200.150.100.050.00 [NaPTA•15-crown-5] (M) 757 Figure A.2.187. Plot of kobsd vs free (uncomplexed) crown ether for 12-crown-4 (red), 15-crown- 5 (green), and 18-crown-6 (blue) for the aminolysis of methyl benzoate (0.005 M) by 0.060 M NaPTA/15-crown-5 complex in neat THF at –78 °C measured by IR spectroscopy (1733 cm–1). All curves were to fit to y = ax + b. 12-C-4: a = 0.7 ± 0.1; b = (4.5 ± 1.0) x 10–3; 15-C-5: a = (1.2 ± 0.1) x 10–3; b = (4.3 ± 0.1) x 10–3; 18-C-6: a = (2.8 ± 0.1) x 10–1; b = (2.4 ± 0.1) x 10–1. 80 60 40 20 0 k o bs d x 10 3 / se c–1 0.120.100.080.060.040.020.00 [free crown] (M) 12-C-4 18-C-6 15-C-5 NaPTA-15-C-5 758 Red [free 12-C-4] / M kobsd x 103 / sec–1 0.00 10.1 0.06 42.0 0.12 86.4 Table A.2.21. Pseudo-first-order rate constants (kobsd) at various free 12-crown-4 concentrations for the addition of NaPTA/15-crown-5 complex (0.060 M) to methyl benzoate (0.0050 M) to complex in THF at –78 °C. Blue [free 18-C-6] / M kobsd x 103 / sec–1 0.00 10.1 0.06 22.1 0.12 34.6 Table A.2.22. Pseudo-first-order rate constants (kobsd) at various free 18-crown-6 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) in THF at –78 °C. 759 Figure A.2.188. Plot of kobsd vs free (uncomplexed) crown (M) for the aminolysis of PhCO2Me (0.005 M) by NaPTA containing 1.0 equiv of 18-crown-6 complex 33a in neat THF at –78 °C measured by IR spectroscopy (1730 cm–1). The curve corresponds to a least-squares fit to y = (axn/(1+bxn)) + c: a = (1.0 ± 0.1) × 10–3; b = (1.5 ± 0.1) × 10–2; c = (8.0 ± 0.1) × 10–3; n = –1.1 ± 0.1). [free 15-C-5] / M kobsd x 103 / sec–1 0.01 48 ± 8 0.025 39 ± 3 0.04 28 ± 5 0.07 20 ± 5 0.13 14.7 ± 0.7 0.19 15 ± 2 0.25 11 ± 3 Table A.2.23. Pseudo-first-order rate constants (kobsd) at various free 15-crown-5 concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) containing 1.0 equiv of 18-crown-6 in THF at –78 °C. 60 50 40 30 20 10 0 k o bs d x 10 3 / se c-1 0.250.200.150.100.050.00 [free 15-crown-5] (M) NaPTA-15-C-5 + 15-C-5 NaPTA-15-C-5 + 18-C-6 + 15-C-5 NaPTA-15-C-5 + 18-C-6 760 Figure A.2.189. Plot of kobsd vs [THF] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) with 1.0 equiv 12-crown-4 at –78 °C measured by IR spectroscopy (1729–1730 cm–1). The red spot indicates the point at which the solution becomes cloudy. [THF] / M kobsd x 103 / sec–1 4.9* 58.0* 7.4 51.3 ± 0.3 8.6 52.3 ± 0.8 9.8 51.5 ± 0.4 11.0 52.7 ± 0.8 12.3 53.5 ± 2.5 Table A.2.24. Pseudo-first-order rate constants (kobsd) at various THF concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/12-crown-4 complex (0.060 M) at –78 °C. Red indicates that the data were collected when the reaction solution became cloudy. 100 80 60 40 20 0 k o bs d x 1 03 / se c-1 121086420 [THF] (M) 761 Figure A.2.190. Plot of kobsd vs [THF] (M) in pentane cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.060 M) with 1.0 equiv 15-crown-5 at –78 °C measured by IR spectroscopy (1729–1730 cm–1). The red point indicates the solution becomes cloudy. [THF] / M kobsd x 103 / sec–1 4.9* 2.4* 7.4 1.2 ± 0.1 8.6 1.2 ± 0.1 9.8 1.1 ± 0.1 11.0 1.2 ± 0.1 12.3 1.3 ± 0.1 Table A.2.25. Pseudo-first-order rate constants (kobsd) at various THF concentrations for the addition of methyl benzoate (0.0050 M) to NaPTA/15-crown-5 complex (0.060 M) at –78 °C. Red indicates that the data were collected when the reaction solution became cloudy. 2.0 1.5 1.0 0.5 0.0 k o bs d x 1 03 / se c-1 121086420 [THF] (M) 762 Figure A.2.191. Plot of kobsd vs [THF] (M) in Me2THF cosolvent for the aminolysis of methyl benzoate (0.005 M) by NaPTA (0.12 M) at –78 °C measured by IR spectroscopy (1727 cm–1). The curve corresponds to a least-squares fit to y = axn/(1+bxn): a = (3.2 ± 0.1) × 10–3; b = (4.5 ± 0.1) × 10–1; n = 2 (set value). Because Me4THF is expensive and difficult to source, we repeated a mistake by assuming 2,5- dimethyltetrahydrofuran (Me2THF) might suffice as an inert polar cosolvent. For the smaller lithium ions, this assumption has withstood scrutiny, but the larger sodium ion is problematic. The rate data for aminolysis of methyl benzoate are shown in Figure 17. Superficially, the rate profile using Me2THF as the cosolvent is indistinguishable from that using hexane (Curve A, Figure A.2.191), which appears to destroy a model arguing cosolvent polarity matters. Previous studies, however, showed that Me2THF was competitive with THF for coordination to sodium, causing intervening THF-Me2THF primary shell mixed solvates. 29Si NMR spectroscopic analysis of titrations of NaPTA in Me2THF shows that it requires nearly equal volumes of THF to fully displace the Me2THF from the coordination sphere of the NaPTA dimer (Figure A.2.191). What if, however, these intervening [A2(THF)2(Me2THF)(ester)]‡ and even [A2(THF)(Me2THF)3(ester)]‡ could impose an approximate zeroth-order apparent THF dependence provided that Me2THF and THF are essentially indistinguishable. That pure Me2THF as cosolvent affords a relative rate 5% that of pure THF would only require that a 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 k o bs d x 10 3 / se c–1 121086420 [THF] (M) 763 [A2(Me2THF)3(ester)]‡ is too congested. DFT computations show that the solvation energies for the bis-Me2THF solvated NaPTA dimer are only 0.9 kcal/mol/solvent lower than THF. 764 Table A.2.26. Reactions of tert-butyl cinnamate with NaPTA with 10 mole percent catalyst. Entry 10% cat krel 1 THF 1 2 PMDTA 2000 3 Diglyme 500 3 Tiglyme 85 3 TMEDA 250 4 TMCDA 300 5 DME 8 6 12-crown-4 1000 7 15-crown-5 700 8 18-crown-6 50 0.10 M substrate, 0.12 M NaPTA, neat toluene, –78 °C Ot-Bu O 10% cat. / toluene –78 oC Ot-Bu ONi-Pr SiMe3 765 Figure A.2.192. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy at 1691 cm–1 for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% THF and 160% THF at –78 °C. 10% THF 160% THF 0.10 0.08 0.06 0.04 0.02 0.00 SM [M ] 500040003000200010000 Time (s) 766 Figure A.2.193. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% PMDTA at –78 °C. 100 x10 -3 80 60 40 20 0 SM [M ] 6000500040003000200010000 Time (s) 767 Figure A.2.194. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy at 1691 cm–1 for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% diglyme at –78 °C. 100 x10 -3 80 60 40 20 0 SM [M ] 6000500040003000200010000 Time (s) 768 Figure A.2.195. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% triglyme at –78 °C. 100 x10 -3 80 60 40 20 0 SM [M ] 20 x10 3151050 Time (s) 769 Figure A.2.196. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy at 1691 cm–1 for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% TMEDA at –78 °C. 100 x10 -3 90 80 70 60 50 40 SM [M ] 2000150010005000 Time (s) 770 Figure A.2.197. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy at 1691 cm–1 for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% TMCDA at –78 °C. 0.10 0.08 0.06 0.04 0.02 0.00 SM [M ] 500040003000200010000 Time (s) 771 Figure A.2.198. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% DME at –78 °C. 0.10 0.08 0.06 0.04 0.02 0.00 SM [M ] 20 x10 3151050 Time (s) 772 Figure A.2.199. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 12-crown-4 at –78 °C. 0.10 0.08 0.06 0.04 0.02 0.00 SM [M ] 6000500040003000200010000 Time (s) 773 Figure A.2.200. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 15-crown-5 at –78 °C. 100 x10 -3 80 60 40 20 0 SM [M ] 6000500040003000200010000 Time (s) 774 Figure A.2.201. Plot of tert-butyl cinnamate concentration versus time measured with IR spectroscopy (1691 cm–1) for the reaction of 0.10 M tert-butyl cinnamate with 0.12 M NaPTA in neat toluene in the presence of 10 mol% 18-crown-6 at –78 °C. 100 x10 -3 80 60 40 20 0 SM [M ] 20 x10 3151050 Time (s) 775 General computational methods All DFT calculations were carried out using Gaussian 16.ref 24 Prompted by a recent benchmarking of modern density functionals, all calculations were conducted at the M06-2X level of theory.ref 25a-c A pruned (99, 590) integration grid (equivalent to Gaussian’s “UltraFine” option) was used for all calculations. The Ahlrichs basis set def2-svp was used for geometry optimizations and the expanded def2-tsvp basis set for single-point energy calculations.ref 25d Ball-and-stick models were rendered using CYLview 1.0b.ref 25e A large number of DFT- computed energies and Cartesian coordinates are archived in the Supporting Information. 776 Anion Scheme A.2.1. DFT-computed energy profile of aminolysis of methyl benzoate by NaPTA via anion pathway. Triple ion Scheme A.2.2. DFT-computed energy profile of aminolysis of methyl benzoate by NaPTA via a triple ion pathway. N i-Pr Me3Si O MeO MeO N i-Pr Me3Si O MeO N i-Pr Me3Si O ∆G° = 1.1 kcal/mol ∆G° = –18.2 kcal/mol E1 T12 E2 IRC IRC N i-Pr Me3Si MeO O Na N SiMe3 i-Pr N i-Pr Me3Si MeO O Na N SiMe3 i-PrN i-Pr Me3Si MeO O Na N SiMe3 i-Pr ∆G° = 7.6 kcal/mol ∆G° = –15.0 kcal/mol E3 T6 E4 N i-Pr Me3Si MeO O Na N SiMe3 i-Pr N i-Pr Me3Si MeO O Na N i-Pr SiMe3∆G° = 1.5 kcal/mol T6 T6-2 IRC IRC 777 Benzene Ph OMe N N SiMe3 i-Pr Na i-Pr Me3Si Na O N N SiMe3 i-Pr Na i-Pr Me3Si Na ∆G° = –6.0 kcal/mol – benzene + PhCOOMe Ph OMe N N SiMe3 i-Pr Na i-Pr Me3Si Na O N N SiMe3 i-Pr Na i-Pr Me3Si Na COOMe ∆G° = 5.4 kcal/mol ∆G° = 6.5 kcal/mol Ph OMe N N SiMe3 i-Pr Na i-Pr Me3Si Na O E5 37 37 E6 E7 N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na Ph OMe N N SiMe3 i-Pr Na i-Pr Me3Si Na O N i-Pr SiMe3 O O Na N i-Pr Me3Si Na Me ∆G° = 32.2 kcal/mol ∆G° = –18.6 kcal/mol Na N i-Pr Me3Si Na O N i-Pr Ph TMSOMe+ ∆G° = –39.2 kcal/mol 37 T5 E8 E9 IRC IRC 778 Scheme A.2.3. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono benzene solvated dimer pathway. N N SiMe3 i-Pr Na i-Pr Me3Si Na COOMe N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na ∆G° = 27.5 kcal/mol ∆G° = –0.1 kcal/mol E5 T14 E10 N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na ∆G° = 2.1 kcal/mol T1 T14 IRC IRC 779 THF Scheme A.2.4. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a tri-THF solvated dimer pathway. IRC IRC N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THF N i-Pr SiMe3 OMeO Na Ni-Pr Me3Si Na THF N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THF THF ∆G° = –1.8 kcal/mol∆G° = –0.3 kcal/mol N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THFN N SiMe3 i-Pr Na i-Pr Me3Si Na THF THF Ph OMe O + ∆G° = 6.0 kcal/mol N i-Pr SiMe3 MeO O Na N i-Pr Me3Si Na THF THF THF ∆G° = –11.3 kcal/mol ∆G° = 14.5 kcal/mol N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na THF THF THF ∆G° = –40.5 kcal/mol + TMSOMe E12 E14 E13 T5 O Na N Na i-Pr SiMe3 N THF THF Ph i-Pr E11 ∆G° = –3.4 kcal/mol O Na N Na i-Pr SiMe3 N THF THF Ph i-Pr E12 O Na N Na i-Pr SiMe3 N THF THF Ph i-Pr T3 T4 T5 – THF + THF THF 780 PMDTA Scheme A.2.5. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono PMDTA solvated monomer pathway. N Na Me3Si i-Pr Me2N N Me2N Me N i-Pr Me3Si MeO O Na N i-Pr Me3Si MeO O N N N Me Me Me Me Me Na N N N Me Me Me Me Me ∆G° = 3.2 kcal/mol ∆G° = 3.9 kcal/mol TMSOMe+Ph N i-Pr O Na N N N Me Me Me Me Me ∆G° = –20.2 kcal/mol N i-Pr Me3Si MeO O Na N N N Me Me Me Me Me Ph OMe O + ∆G° = –8.6 kcal/mol E17 E16 E15 T7 N i-Pr Me3Si MeO O Na N N Me Me Me Me N i-Pr Me3Si MeO O Na N N Me Me Me Me N i-Pr Me3Si MeO O Na N N Me Me Me Me ∆G° = 2.7 kcal/mol ∆G° = 2.8 kcal/mol N i-Pr Me3Si MeO O Na N N N Me Me Me Me Me ∆G° = 3.9 kcal/mol T17T16T15 T7 N N Me Me Me Me – + N N Me Me Me Me – N N Me Me Me Me N Me Me N Me Me + – TMEDA + PMDTA IRC IRC 781 Diglyme Scheme A.2.6. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono diglyme solvated dimer pathway. N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na T8 O O O Me Me N i-Pr SiMe3 OMeO Na Ni-Pr Me3Si Na T18 O O O Me Me ∆G° = 8.7 kcal/mol ∆G° = –1.6 kcal/mol N i-Pr SiMe3 MeO O Na N i-Pr Me3Si Na ∆G° = 14.9 kcal/mol ∆G° = 4.2 kcal/mol N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na ∆G° = –35.7 kcal/mol + TMSOMe E20 E19 E18 T8 O Na N Na i-Pr SiMe3 NPh i-Pr + diglyme – 2 diglyme O O O Me Me N i-Pr SiMe3 OMe O Na N i-Pr Me3Si Na O O O Me Me ∆G° = –16.5 kcal/mol O O O Me Me N N SiMe3 i-Pr Na i-Pr MeO O OMe Me3Si Na O OMeMeO Na MeO O OMe OMe OMeO N i-Pr Me3Si + PhCOOMe – diglyme 2 O OMeMeO OMeMeO O IRC IRC A25 A24 782 12-crown-4 Scheme A.2.7. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 12-crown-4 solvated monomer pathway. Ph OMe O + O O OO NaN i-Pr Me3Si N i-Pr Me3Si MeO O Na O O O O∆G° = 2.1 kcal/mol + PhCOOMe N i-Pr Me3Si MeO O Na O O O O ∆G° = 11.2 kcal/mol ∆G° = –9.9 kcal/mol N i-Pr Me3Si MeO O Na O O O O TMSOMe+Ph N i-Pr O ∆G° = –20.7 kcal/mol E23 O O OO Na E21 T9 E22 IRC IRC 783 15-crown-5 Scheme A.2.8. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 15-crown-5 solvated monomer pathway. N Me3Si i-Pr OMeO Na O O O OO N i-Pr Me3Si MeO O Na O O O OO ∆G° = –11.5 kcal/mol N i-Pr Me3Si OMe O Na O O O OO ∆G° = –2.2 kcal/mol Na O O O O O N Me3Si i-Pr Ph OMe O + N i-Pr Me3Si MeO O E24 Na O O O OO N i-Pr Me3Si MeO O Na O O O OO ∆G° = –15.7 kcal/mol N i-Pr Me3Si MeO O T10 E25 Na O O O O O TMSOMePh N i-Pr O E26 ∆G° = –21.2 kcal/mol Na O O O O O + ∆G° = 6.6 kcal/mol ∆G° = 5.9 kcal/mol T19 T20 T10 IRC IRC 784 18-crown-6 Scheme A.2.9. DFT-computed energy profile of the aminolysis of methyl benzoate by NaPTA, reacting through a mono 18-crown-6 solvated monomer pathway. N i-Pr Me3Si OMe O N Me3Si i-Pr OMeO N i-Pr Me3Si MeO O ∆G° = –2.6 kcal/mol ∆G° = –4.3 kcal/mol Ph OMe O + N i-Pr Me3Si MeO O E27 ∆G° = –19.2 kcal/mol N i-Pr Me3Si MeO O T11 E28 TMSOMePh N i-Pr O E29 ∆G° = –25.1 kcal/mol + ∆G° = 5,7 kcal/mol ∆G° = 10.9 kcal/mol Na O O O O O O Na O O O O O O Na O O O O O O N i-Pr Me3Si MeO O Na O O O O O ONa O O O O O O N i-Pr Me3Si Na O O O O O O Na O O O O O O Na O O O O O O T21 T22 T11 IRC IRC 785 Crown TS comparison Scheme A.2.10. DFT-computed energy comparison of the different crown transition structures of aminolysis of methyl benzoate by NaPTA. N i-Pr Me3Si MeO O Na O O O OO N i-Pr Me3Si MeO O Na O O O O∆G° = –3.9 kcal/mol ∆G° = –4.3 kcal/mol 12-C-4 18-C-6 – 18-C-6 + 12-C-4 – 12-C-4 + 15-C-5 12-C-4 15-C-5 15-C-5 18-C-6 N i-Pr Me3Si MeO O Na O O O O O O 786 CHAPTER 2 REFERENCES AND FOOTNOTES 787 Chapter 2 References and Footnotes 1. (a) Schorigin, P. Synthesen mittels Natrium und Halogenalkylen Ber. 1908, 41, 2711. (b) Gilman, H.; Wright, G. F. The Mechanism of the Wurtz—Fittig Reaction. The Direct Preparation of an Organosodium (Potassium) Compound from an RX Compound. J. Am. Chem. Soc. 1933, 55, 2893. (c) Morton, A. A. The Chemical Behavior of the Organoalkali Compounds. Chem. Rev. 1944, 44, 1. (d) Morton, A. A.; Ward, F. K. The Effect of Triethylamine on the Decomposition of Amylsodium. J. Org. Chem. 1960, 25, 120. (e) Schlosser, M. Organosodium and Organopotassium Compounds. Angew. Chem., Int. Ed. 1964, 3, 287. (f) Lochmann, L.; Pospíšil, J.; Lím, D. On the Interaction of Organolithium Compounds with Sodium and Potassium Alkoxides. A New Method for the Synthesis of Organosodium and Organopotassium Compounds. Tetrahedron Lett. 1966, 7, 257. (g) Schade, C.; Bauer, W.; Von Ragué Schleyer, P. N-Butylsodium: The Preparation, Properties and NMR Spectra of a Hydrocarbon- and Tetrahydrofuran- Soluble Reagent. J. Organomet. Chem. 1985, 295, c25. (h) Williard, P. G.; Hintze, M. J. Mixed Aggregates: Crystal Structures of a Lithium Ketone Enolate/Lithium Amide and of a Sodium Ester Enolate/Sodium Amide. J. Am. Chem. Soc. 1990, 112, 8602. (i) Barr, D.; Dawson, A. J.; Wakefield, B. J. A Simple, High-Yielding Preparation of Sodium Diisopropylamide and Other Sodium Dialkylamides. J. Chem. Soc., Chem. Commun. 1992, 204. 2. (a) Seyferth, D. Alkyl and Aryl Derivatives of the Alkali Metals: Useful Synthetic Reagents as Strong Bases and Potent Nucleophiles. 1. Conversion of Organic Halides to Organoalkali-Metal Compounds. Organometallics 2006, 25, 2. (b) Seyferth, D. Alkyl and Aryl Derivatives of the Alkali Metals: Strong Bases and Reactive Nucleophiles. 2. Wilhelm Schlenk’s Organoalkali-Metal Chemistry. The 788 Metal Displacement and the Transmetalation Reactions. Metalation of Weakly Acidic Hydrocarbons. Superbases. Organometallics 2009, 28, 2. (c) Lochmann, L.; Janata, M. 50 Years of Superbases Made from Organolithium Compounds and Heavier Alkali Metal Alkoxides. Eur. J. Chem. 2014, 12, 537. (d) Robertson, S. D.; Uzelac, M.; Mulvey, R. E. Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry. Chem. Rev. 2019, 119, 8332. (e) Armstrong, D. R.; Kennedy, A. R.; Mulvey, R. E.; Robertson, S. D. Developing a Hetero-Alkali-Metal Chemistry of 2,2,6,6-Tetramethyl-piperidide (TMP): Stoichiometric and Structural Diversity within a Series of Lithium/Sodium, Lithium/Potassium and Sodium/Potassium TMP Compounds Chem. Eur. J. 2011, 17, 8820. (f) Sodium and Potassium Mordini, A. In Comprehensive Organometallic Chemistry III; Mingos, D. M. P.; Crabtree, R. H., Eds; Elsevier, 2007, vol. 9, 3. (g) Benkeser, R. A.; Foster, D. J.; Sauve, D. M.; Nobis, J. F. Metalations With Organosodium Compounds. Chem. Rev. 1957, 57, 867. (h) Sreedharan, R.; Gandhi, T. Masters of Mediation: MN(SiMe3)2 in Functionalization of C(sp3)–H Latent Nucleophiles. Sreedharan, R.; Gandhi, T. Chem. Eur. J. 2024, 30, e202400435. 3. For recent studies illustrating the synthetic potential of organosodium chemistry, see: (a) Gentner, T. X.; Mulvey, R. E. Alkali-Metal Mediation: Diversity of Applications in Main-Group Organometallic Chemistry. Angew. Chem., Int. Ed. 2021, 60, 9247. (b) Anderson, D. E.; Tortajada, A.; Hevia, E. Highly Reactive Hydrocarbon Soluble Alkylsodium Reagents for Benzylic Aroylation of Toluenes Using Weinreb Amides. Angew. Chem., Int. Ed. 2023, 62, e202218498. (c) Harenberg, J. H.; Reddy, R.; Reddy, A.; Karaghiosoff, K.; Knochel, P. Continuous Flow Preparation of Benzylic Sodium Organometallics. Angew. Chem., Int. Ed. 2022, 61, e202203807. (d) Davison, N.; McMullin, C. L.; Zhang, L.; Hu, S.-X.; Waddell, P. G.; Wills, C.; Dixon, C.; Lu, E. Li vs Na: Divergent Reaction Patterns 789 between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation. J. Am. Chem. Soc. 2023, 145, 6562. (e) De, P. B.; Asako, S.; Ilies, L. Recent Advances in the Use of Sodium Dispersion for Organic Synthesis. Synthesis 2021, 53, 3180. (f) Fuentes, M. A.; Zabala, A.; Kennedy, A. R.; Mulvey, R. E. Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand. Chem. - Eur. J. 2016, 22, 14968. g. Asako, S.; Takahashi, I.; Nakajima, H.; Ilies, L.; Takai, K. Halogen-Sodium Exchange Enables Efficient Access to Organosodium Compounds. Commun. Chem. 2021, 4, 76. (h) Mulvey, R. E.; Robertson, S. D. Synthetically Important Alkali-Metal Utility Amides: Lithium, Sodium, and Potassium Hexamethyldisilazides, Diisopropylamides, and Tetramethylpiperidides. Angew. Chem., Int. Ed. 2013, 52, 11470. (i) Harenberg, J. H.; Weidmann, N.; Wiegand, A. J.; Hoefer, C. A.; Annapureddy, R. R.; Knochel, P. (2- Ethylhexyl)sodium: A Hexane-Soluble Reagent for Br/Na-Exchanges and Directed Metalations in Continuous Flow. Angew. Chem., Int. Ed. 2021, 60, 14296. (j) Wong, H. N. C. Is Sodium Finally Coming of Age? Nat. Catal. 2019, 2, 282. (k) Asako, S.; Nakajima, H.; Takai, K. Organosodium Compounds for Catalytic Cross- Coupling. Nat. Catal. 2019, 2, 297. (l) Klett, J. Structural Motifs of Alkali Metal Superbases in Non-coordinating Solvents. Chem. Eur. J. 2021, 27, 888. (m) Anderson, D. E.; Tortajada, A.; Hevia, E. New Frontiers in Organosodium Chemistry as Sustainable Alternatives to Organolithium Reagents. Angew. Chem., Int. Ed. 2024, 63, e202313556. (n) Asako, S.; Kodera, M.; Nakajima, H.; Takai, K. Lithium-Free Synthesis of Sodium 2,2,6,6-Tetramethylpiperidide and Its Synthetic Applications. Adv. Synth. Catal. 2019, 361, 3120. (o) Dilauro, G.; Luccarelli, C.; Quivelli, A. F.; Vitale, P.; Perna, F. M.; Capriati, V. Introducing Water and Deep Eutectic Solvents in Organosodium Chemistry: Chemoselective Nucleophilic Functionalizations in Air. Angew. Chem. Int. Ed. 2023, 62, e202304720. (p) 790 Tortajada, A.; Hevia, E. Perdeuteration of Arenes via Hydrogen Isotope Exchange Catalyzed by the Superbasic Sodium Amide Donor Species NaTMP·PMDETA. J. Am. Chem. Soc. 2022, 144, 20237. (q) Ong, D. Y.; Pang, J. H.; Chiba, S. Synthetic Organic Reactions Mediated by Sodium Hydride. J. Synth. Org. Chem. Japan 2019, 77, 1060. 4. Woltornist, R. A.; Ma, Y.; Algera, R. F.; Zhou, Y.; Zhang, Z.; Collum, D. B. Structure, Reactivity, and Synthetic Applications of Sodium Diisopropylamide. Synthesis 2020, 52, 1478. 5. For recent applications of NaDA, see: (a) Tong, X.; Schneck, F.; Fu, G. C. Catalytic Enantioselective α‑Alkylation of Amides by Unactivated Alkyl Electrophiles. J. Am. Chem. Soc. 2022, 144, 14856. (b) Mason, J. D.; Terwilliger, D. W.; Pote, A. R.; Myers, A. G. Practical Synthesis of Iboxamycin, a Potent Antibiotic Candidate, in Amounts Suitable for Studies in Animal Infection Models. J. Am. Chem. Soc. 2021, 143, 11019. 6. With the superior searching algorithms of Google Scholar compared with the more traditional chemistry databases, we have found allusions to NaDA that we had previously not cited. This includes an report by Hauser et al. that predates the 1960 report by Levine et al. that we believed to be the first report: (a) Thompson, D. F.; Bayless, P. L.; Hauser, C. R. Aroylations of Ethyl Isobutyrate by Alkali Triphenylmethides. Isolation of ß-Esters by Chromatography. Use of a Reagent Having an Amino Group. J. Org. Chem. 1954, 19, 1490. (b) Dice, J.. R.; Scheinman, L.; Berrodin, K. W. α,β-Diphenyl-α-trifluoromethyl-2-pyridineethanol and Related Compounds as Synthetic Estrogens. J. Med. Chem. 1966, 9, 176. (c) Rees, C.; W.; White, A. J. P.; Williams, D. J.; Rakitin, O. A.; Konstantinova, L. S.; 791 Carlos F. Marcos, C. F.; Torroba, T. Synthesis of Bis[1,2]dithiolo[1,4]thiazines and a [1,2]Dithiolo[1,4]thiazine from Tertiary Diisopropylamines. J. Org. Chem. 1999, 64, 5010. (d) Yamataka, H.; Sasaki, D.; Kuwatani, Y.; Mishima, M.; Tsuno, Y. On the Mechanism of Addition of Lithium Pinacolone Enolate to Benzaldehyde: Polar or Electron Transfer? J. Am. Chem. Soc. 1997, 119, 9975. 7. (a) Renny, J. S.; Tomasevich, L. L.; Tallmadge, E. H.; Collum, D. B. Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry. Angew. Chem., Int. Ed. 2013, 52, 11998. (b) For a detailed analysis of the MCV protocols see: Liou, L. R.; McNeil, A. J.; Ramírez, A.; Toombes, G. E. S.; Gruver, J. M.; Collum, D. B. Lithium Enolates of Simple Ketones: Structure Determination Using the Method of Continuous Variation. J. Am. Chem. Soc. 2008, 130, 4859. 8. (a) Woltornist, R. A.; Collum, D. B. Using 15N–29Si Scalar Coupling to Determine Aggregation and Solvation States. J. Am. Chem. Soc. 2020, 142, 6852. (b) Woltornist, R. A.; Collum, D. B. Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum. J. Org. Chem. 2021, 86, 2406. (c) Woltornist, R. A. and Collum, D. B. Ketone Enolization with Sodium Hexamethyldisilazide: Solvent- and Substrate-Dependent E–Z Selectivity and Affiliated Mechanisms. J. Am. Chem. Soc. 2021, 143, 17452. (d) You, Q.; Collum, D. B. Carbon–Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms. J. Am. Chem. Soc. 2023, 145, 23568. 792 9. Ma, Y.; Lui, N. M.; Keresztes, I.; Woltornist, R. A.; Collum, D. B. Sodium Isopropyl(trimethylsilyl)amide (NaPTA): A Stable and Highly Soluble Lithium Diisopropylamide Mimic. J. Org. Chem. 2022, 87, 14223. 10. (a) Avent, A. G.; Antolini, F.; Hitchcock, P. B.; Khvostov, A. V.; Lappert, M. F.; Protchenko, A. V. Reactions Between a Sodium Amide Na[N(SiMe3)R1] (R1 = SiMe3, SiMe2Ph or But) and a Cyanoalkane RCN (R = Ad or But). Dalton Trans. 2006, 919. (b) Antolini, Floria; Hitchcock, Peter B.; Khvostov, Alexei V.; Lappert, Michael F. Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe2Ph)(SiMe3)]-, [N(t-Bu)(SiMe3)]-, [N(Ph)(2-C5H4N)]-, and [N(2- C5H4N)2]-. Eur. J. Inorg. Chem. 2003, 18, 3391. (c) Eppinger, J.; Herdtweck, E.; Anwander, R. Synthesis and Characterisation of Alkali Metal Bis(Dimethylsilyl) Amides: Infinite All-Planar Laddering in the Unsolvated Sodium Derivative. Polyhedron 1998, 17, 1195 (d) Schneider, J.; Popowski, E.; Reinke, H. Darstellung, Charakterisierung Und Reaktionsverhalten von Natrium- Und Kaliumhydridosilylamiden R2(H)Si-N(M)R′ (M = Na, K) - Kristallstruktur von [(Me3C)2(H)Si-N(K)SiMe3]2 ·THF. Zeit. Anorg. Allg. Chem. 2003, 629, 55. (e) Hitchcock, P. B.; Lappert, M. F.; Merle, P. G. Synthesis and Structures of Selected Benzamidinates of Li, Na, Al, Zr and Sn(II) Using the C1-Symmetric Ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]−. Dalton Trans. 2007, 585. 11. (a) Antolini, F.; Hitchcock, P. B.; Khvostov, A. V.; Lappert, M. F. Synthesis and Characterization of N-silylated, C1-symmetric Benzamidinates of Lithium, Sodium, and Tin(II). Can. J. Chem. 2006, 84, 269. (b) Li, J.; Stasch, A.; Schenk, C; Jones, C. Extremely Bulky Amido-Group 14 Element Chloride Complexes: Potential Synthons for Low Oxidation State Main Group Chemistry. Dalt. Trans. 2011, 40, 10448. (c) Chen, J.; Yuan, L. Bis[μ-N-(tert-butyldimethylsilyl)quinolin- 793 8-aminato-1:2κ2N1,N8:N8](N,N,N′,N′-tetramethylethane-1,2-diamine 1κ2N,N′)Lithiumsodium. Acta Crystallogr. E 2012, 68, m1474. (d) Reinhart, E. D.; Studvick, C. M.; Tondreau, A. M.; Popov, I. A.; Boncella, J. M. Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands. Organometallics, 2024, 43, 284. (e) Liddle, S. T.; Clegg, W. Cation-Induced Structural Variations in the Alkali Metal Derivatives of 2-Trimethylsilylaminopyridine: Synthesis and X-ray Structures of Complexes for All Five Metals Li–Cs with 12-Crown-4. J. Chem. Soc., Dalt. Trans. 2001, 402. (f) Liu, H.-Y.; Neale, S. E.; Hill, M. S.; Mahon, M. F.; McMullin, C. L.; Morrison, B. L. Cooperative Dihydrogen Activation at a Na(i)2/Mg(i)2 Ensemble. Chem. Commun. 2023, 59, 3846. (g) M. L.; Junk, P. C. Synthesis and Structure of the First Non ‘Ate’ Heteroleptic Lanthanoid Complexes Bearing Monoanionic 2- Amidopyridine Ligands. New J. Chem. 2003, 27, 1032. 12. (a) Li, J. F.; Huang, S. P.; Weng, L. H.; Liu, D. S. bis-Silyl TMCDA Dianion (Dilithium and Disodium) Reacting with MCl4. Synthesis and Structural Studies of Some Titanium and Zirconium Complexes with Chiral bis(Amide), Amidinate or bis(Amidinate) Ligands. J. Organometal. Chem. 2006, 691, 3003. (b) Gaul, D. A.; Just, O.; Rees, W. S. Synthesis and Characterization of a Series of Zinc Bis[(alkyl)(trimethylsilyl)amide] Compounds. Inorg. Chem. 2000, 39, 5648. (c) Also, see ref 10a and 11. 13. (a) Mannion, J. C.; Dax, S. L.; Macintyre, D. E.; Golder, F. J.; McLeod, J. F. Preparation of Triazines and Related Compounds and Compositions for Treatment of Breathing Control Disorders or Diseases. World Intellectual Property Organization, WO2013181217, 12-05-2013. (b) Kato, M.; Kataoka, K.; Nagasaki, 794 Y.; Motosawa, E.; Tsuruta, T. Preparation of azasilacycloalkanes. Japan, JP06228160, 08-16-1994 14. We also prepared sodium n-butyl(trimethylsilyl)amide and sodium 2- methoxyethyl(trimethylsilyl)amide without further study. 15. Lebedev, A. V.; Lebedeva, A. B.; Sheludyakov, V. D.; Ovcharuk, S. N.; Kovaleva, E. A.; Ustinova, O. L. Russ. J. Gen. Chem. 2006, 76, 469. 16. Poeira, D. L.; Negrão, A. C. R.; Faustino, H.; Coelho, J. A. S.; Gomes, C. S. B.; Gois, P. M. P. Marques, M. M. B. Hypervalent Iodine(III) Reagents with Transferable Primary Amines: Structure and Reactivity on the Electrophilic α- Amination of Stabilized Enolates. Org. Lett. 2022, 24, 776. 17. (a) Eastham, J. F.; Gibson, G. W. Solvent Effects in Organometallic Reactions. II. J. Am. Chem. Soc. 1963, 85, 2171. (b) Bartlett, P. D.; Goebel, C. V.; Weber, W. P. Ethylenation of Secondary and Tertiary Alkyllithiums. II. Its Kinetics and the Nature of the Active Species. J. Am. Chem. Soc. 1969, 91, 7425. (c) Lewis, H. L.; Brown, T. L. Association of Alkyllithium Compounds in Hydrocarbon Media. Alkyllithium-Base Interactions. J. Am. Chem. Soc. 1970, 92, 4664. (d) Popov, A. I. Alkali Metal NMR and Vibrational Spectroscopic Studies on Solvates in Non- aqueous Solvents. Pure Appl. Chem. 1975, 41, 275. 18. Lucht, B. L.; Collum, D. B. Lithium Hexamethyldisilazide: A View of Lithium Ion Solvation Through a Glass-Bottom Boat. Acc. Chem. Res. 1999, 32, 1035. 795 19. (a) Wanat, R. A.; Collum, D. B.; Van Duyne, G.; Clardy, J.; DePue, R. T. Solid- State and Solution Studies of Lithiated 2-Carbomethoxycyclohexanone Dimethylhydrazone and Lithiated Cyclohexanone Phenylimine. J. Am. Chem. Soc. 1986, 108, 3415. (b) Galiano-Roth, A. S.; Michaelides, E. M.; Collum, D. B. 6Li, 13C, and 13N NMR Spectroscopic Studies of Lithium Dialkylamides. Solution Structure of Lithium Isopropylcyclohexylamide (LICA). J. Am. Chem. Soc. 1988, 110, 2658. 20. Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures. Spivey, J. A.; Collum, D. B. J. Am. Chem. Soc. 2024, 145, 17827. 21. The intended mole fraction refers to the mole fraction based on what was added to the samples. The measured mole fraction—the mole fraction within only the ensemble of interest—eliminates the distorting effects of impurities. 22. Job, P. Formation and Stability of Inorganic Complexes in Solution. Ann. Chim. 1928, 9, 113. 23. Pairs of heteroaggregates displaying 2:1 and 1:2 stoichiometries characteristic of trimer are not observed under any conditions. 24. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams- Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; 796 Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision C.01; Gaussian, Inc., Wallingford CT, 2016. 25. (a) Mardirossian, N.; Head-Gordon, M. Thirty Years of Density Functional Theory in Computational Chemistry: An Overview and Extensive Assessment of 200 Density Functionals. Mol. Phys. 2017, 115, 2315. (b) Wang, Y.; Verma, P.; Jin, X.; Truhlar, D. G.; He, X. Revised M06 Density Functional for Main-Group and Transition-Metal Chemistry. Proc. Nat. Acad. Sci. 2018, 115, 10257. (c) Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Function. Theor. Chem. Acc. 2008, 120, 215. (d) Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297. (e) CYLview, 1.0b; C. Y. Legault, Université de Sherbrooke 2009 (http://www.cylview.org; accessed 2024- 7-5). 26. Employing both explicit and implicit solvation models in concert are suggested to lead to large statistical errors: Yang, Z.; Yang, S.; Yu, P.; Li, Y.; Doubleday, C.; Park, J.; Patel, A.; Jeon, B.-s.; Russell, W. K.; Liu, H.-w.; Russell, D. H.; Houk, K. http://www.cylview.org/ 797 N. Influence of Water and Enzyme SpnF on the Dynamics and Energetics of the Ambimodal [6 + 4]/[4 + 2] Cycloaddition. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, E848. 27. We refered to “correlated solvation” to denote deviations from statistical binding, which can be either antagonistic or protagonistic. 28. (a) Yamada, S. Cation-π Interactions in Organic Synthesis. Chem. Rev. 2018, 118, 11353. 60. (b) Jones, G. B.; Chapman, B. J. p-Stacking Effects in Organic Synthesis. Synthesis 1995, 5, 475. (c) Mahadevi, A. S.; Sastry, G. N. Cooperativity in Noncovalent Interactions. Chem. Rev. 2016, 116, 2775. 29. An isodesmic reaction is “a reaction (actual or hypothetical) in which the types of bonds that are made in forming the products are the same as those which are broken in the reactants.” IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. 30. Bao, J. L.; Gagliardi, L.;Truhlar, D. G. Self-Interaction Error in Density Functional Theory: An Appraisal. J. Phys. Chem. Lett. 2018, 9, 2353. 31. See, for example: (a) Przyojski, J. A.; Kiewit, M. L.; Fillman, K. L.; Arman, H. D.; Tonzetich, Z. J. Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring κ1-N1 Coordination. Inorg. Chem. 2015, 54, 9637. (b) Schumann, H.; Hummert, M.; Lukoyanov, A. N.; Fedushkin, I. L. Sodium Cation 798 Migration Above the Diimine π-System of Solvent Coordinated dpp-BIAN Sodium Aluminum Complexes (dpp-BIAN = 1,2-bis[(2,6- diisopropylphenyl)imino]acenaphthene). Chem. - A Eur. J. 2007, 13, 4216. (c) Wang, J.; Gardiner, M. G. C-H Activation (γ-deprotonation) of a Sm(III) bis(trimethylsilyl)amide Complex via Macrocyclic Stabilisation of the Sodium Counter Ion. Chem. Commun. 2005, 1589. (d) Andrikopoulos, P. C.; Armstrong, D. R.; Hevia, E.; Kennedy, A. R.; Mulvey, R. E.; O'Hara, C. T. Stoichiometrically- Controlled Reactivity and Supramolecular Storage of Butylmagnesiate Anions. Chem. Commun. 2005, 1131. 32. An experiment in which a 1:1 binary mixture of two structurally related species suspected to be homoaggregated is a convenient alternative to a full Job plot. It is, in our opinion, an underutilized control experiment. 33. Mack, K. A.; McClory, A.; Zhang, H.; Gosselin, F.; Collum, D. B. Lithium Hexamethyldisilazide-Mediated Enolization of Highly Substituted Aryl Ketones: Structural and Mechanistic Basis of the E/Z Selectivities. J. Am. Chem. Soc. 2017, 139, 12182 and references cited therein. 34. The potential merits of simple trialkylamines in organosodium chemistry were foreshadowed decades ago with studies of amylsodium in triethylamine: (a) Morton, A. A.; Ward, F. K. The Effect of Triethylamine on the Decomposition of Amylsodium. J. Org. Chem. 1960, 25, 120. (b) Gilman, H.; Bebb, R. L. Relative Reactivities of Organometallic Compounds. XX. Metalation. J. Am. Chem. Soc. 1939, 61, 109. 799 35. (a) Seebach and co-workers have suggested that HMPA may activate aggregates without intervening deaggregations by inserting into an aggregate site normally occupied by the anionic fragment: Seebach, D.; Amstutz, R.; Dunitz, J. D. Helv. Chim Acta 1981, 64, 2622. (b) Lithium Dialkylamide Mixed Aggregation: An NMR Spectroscopic Study of the Influence of Hexamethylphosphoramide (HMPA). Romesberg, F. E.; Collum, D. B. J. Am. Chem. Soc. 1994, 116, 9198. (c) Jackman, L. M.; Chen, X. Solvation of Aggregates of Lithium Phenolates by Hexamethylphosphoric Triamide. HMPA Causes Both Aggregation and Deaggregation. J. Am. Chem. Soc. 1992, 114, 403. 36. The computations use the Gaussian standard state of 1.0 atm. If the THF concentration is corrected to neat THF (approximately 13 M), each solvation step benefits from approximately 2.0 kcal/mol of additional stabilization at –78 °C (195 K). Pratt, L. M.; Merry, S.; Nguyen, S. C.; Quan, P.; Thanh, B. T. A Computational Study of Halomethyllithium Carbenoid Mixed Aggregates with Lithium Halides and Lithium Methoxide. Tetrahedron 2006, 62, 10821. 37. (a) Polyamine-Chelated Alkali Metal Compounds; Langer, A. W., Jr., Ed.; American Chemical Society: Washington, DC, 1974. (b) Collum, D. B. Is N,N,N',N'-Tetramethylethylenediamine a Good Ligand for Lithium? Acc. Chem. Res. 1992, 25, 448. 38. Kouklovsky, C.; Langlois, Y.; Aguilar, E.; Fernandez-Garcia, J. M.; Sikervar, V. (1S,2S)-1,2-Diaminocyclohexane. e-EROS Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, NewYork; 2014. 800 39. One could, driven by motivations that are not completely clear, compete two amides with a deficiency of a given crown. 40. (a) 12-Crown-4. Liotta, Charles L.; Berkner, Joachim In e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, New York; 2005. (b) 15- Crown-5. Liotta, Charles L.; Berkner, Joachim In e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, New York; 2005. (c) 18- Crown-6. Liotta, Charles L.; Berkner, Joachim In e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, New York; 2005. 41. Lithium alkyl(trimethylsilyl)amides have been exploited extensively for C–N bond formation. For emblematic cases see: (a) Asao, N.; Yamamoto, Y. Lithium N- Benzyltrimethylsilylamide. e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Inc., 2001. (b) Cundy, D. J.; Donohue, A. C.; McCarthy, T. D. An Asymmetric Synthesis of ADDA and ADDA-glycine Dipeptide Using the β-Lactam Synthon Method. J. Chem. Soc., Perkin Trans. 1 1999, 559. (c) Asao, N.; Uyehara, T.; Yamamoto, Y. Stereodivergent Synthesis of the Enolates of a β-Amino Ester by Using Lithium N-Benzyltrimethylsilylamide. Tetrahedron 1990, 46, 4563. (d) A Chiral Ligand Mediated Aza-conjugate Addition Strategy for the Enantioselective Synthesis of β-Amino Esters that Contain Hydrogenolytically Sensitive Functionality. Archer, R. M.; Hutchby, M.; Winn, C. L.; Fossey, J. S.; Bull, S. D. Tetrahedron 2015, 71, 8838. (e) Jacobsen, M. A.; Williard, P. G. Synthesis of 2,3-Disubstituted Pyrroles from 3,N-Dilithio-N-(tert- Butyldimethylsilyl)-2-buten-1-amine. J. Org. Chem. 2002, 67, 1, 32. (f) Doi, H.; Sakai, T.; Yamada, K.; Tomioka, K. N-Allyl-N-tert-Butyldimethylsilylamine for Chiral Ligand-Controlled Asymmetric Conjugate Addition to tert-Butyl Alkenoates. Chem. Commun. 2004, 1850. (h) Calverley, M. J. Selective N- 801 Monomethylation of Primary Amines via N-trialkylsilyllithioamines. Synth. Commun. 1983, 13, 601. (i) Smith, A. B.,. III; Visnick, M. An Expedient Synthesis of Substituted Indoles. Tetrahedron Lett. 1985, 26, 3757. (j) Sewald, N.; Hiller, K. D.; Korner, M.; Findeisen, M. Tandem Protocol for the Stereoselective Synthesis of Different Polyfunctional ß-Amino Acids and 3-Amino-Substituted Carbohydrates. J. Org. Chem. 1998, 63, 7263. 42. Kour, M.; Gupta, R.; Saini, R.; Bansal, R. K. Diastereoselectivity in the Aza- Michael Reaction of Chiral α-Methylbenzylamines with α,β-Unsaturated Carbonyl Compounds. SynOpen 2018, 02, 122. 43. An analogous silyl transfer is observed for the aminolysis of 2-bromopyridine with NaHMDS: Lis, A. V.; Tsyrendorzhieva, I. P.; Albanov, A. I.; Rakhlin, V. I. Reaction of Sodium Bis(trimethylsilyl)amide with 2-Bromopyridine. Russ. Chem. Bull. 2016, 65, 592. 44. For a similar trimethylsilyl transfer that occurs when benzyne is trapped by metal silazides, see: Ikawa, T.; Masuda, S.; Akai, S. One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols. Chem. Eur. J. 2020, 26, 4320. 45. For an excellent discussion of the limitations of ester aminolyses, see: Zhang, R.; Yao, W.-Z.; Qian, L.; Sang, W.; Yuan, Y.; Du, M.-C.; Cheng, H.; Chen, C.; Qin, X. A Practical and Sustainable Protocol for Direct Amidation of Unactivated Esters Under Transition-Metal-Free and Solvent-Free Conditions. Green Chem. 2021, 23, 3972. 802 46. lit LiHMDS/amine aminolyses and their temperatures (a) Capel, E.; Luis-Barrera, J.; Sorazu, A.; Uria, U.; Prieto, L.; Reyes, E.; Carrillo, L.; Vicario, J. L. Transannular Approach to 2,3-Dihydropyrrolo[1,2-b]isoquinolin- 5(1H)-ones Through Bronsted Acid-Catalyzed Amidohalogenation Transannular Approach to 2,3-Dihydropyrrolo[1,2‑b]isoquinolin- 5(1H)‑ones through Brønsted Acid-Catalyzed Amidohalogenation. J. Org. Chem. 2022, 87, 10062. (b) Vrijdag, J. L.; Delgado, F.; Alonso, N.; De Borggraeve, W. M.; Pérez-Macias, N.; Alcázar, J. Practical Preparation of Challenging Amides from Non-Nucleophilic Amines and Esters. Chem. Commun. 2014, 50, 15094. (c) Li, G.; Ji, C.-L.; Hong, X.; Szostak, M. Highly Chemoselective, Transition-Metal- Free Transamidation of Unactivated Amides and Direct Amidation of Alkyl Esters by N-C/O-C Cleavage. J. Am. Chem. Soc. 2019, 141, 11161. 47. While NaHMDS/ArNH2 mixtures are commonly used to aminolyze aryl esters, the corresponding protocol with aliphatic amines is rarely employed: Wang, J.; Rosingana, M.; Discordia, R. P.; Soundararajan, N.; Polniaszek, R. Aminolysis of Esters or Lactones Promoted by NaHMDS - A General and Efficient Method for the Preparation of N-Aryl Amides. Synlett 2001, 1485. 48. Liu, K. G.; Robichaud, A. J.; AGreenfield, A. A.; Lo, J. R.; Grosanu, C.; Mattes, J. F.; Cai, Y.; Zhang, G. M.; Zhang, J. Y.; Kowal, D. M.; Smith, D. L.; Di, L.; Kerns, E. H.; Schechter, L. E.; Comery, T. A. Identification of 3- Sulfonylindazole Derivatives as Potent and Selective 5-HT6 Antagonists. Bioorg. Med. Chem. 2011, 19, 650. 49. Several general-purpose reviews on determining reaction mechanism: (a) Meek, S. J.; Pitman, C. L.; Miller, A. J. M. Deducing Reaction Mechanism: A 803 Guide for Students, Researchers, and Instructors. J. Chem. Educ. 2016, 93, 275. (b) Simmons, E. M.; Hartwig, J. F. On the Interpretation of Deuterium Kinetic Isotope Effects in C–H Bond Functionalizations by Transition Metal Complexes. Angew. Chem., Int. Ed. 2012, 51, 3066. (c) Collum, D. B.; McNeil, A. J.; Ramírez, A. Lithium Diisopropylamide: Solution Kinetics and Implications for Organic Synthesis. Angew. Chem., Int. Ed. 2007, 46, 3002. (d) Algera, R. F.; Gupta, L.; Hoepker, A. C.; Liang, J.; Ma, Y.; Singh, K. J.; Collum, D. B. Lithium Diisopropylamide: Non-Equilibrium Kinetics and Lessons Learned about Rate Limitation. J. Org. Chem. 2017, 82, 4513. 50. The rate law provides the stoichiometry of the transition structure relative to that of the reactants: Edwards, J. O.; Greene, E. F.; Ross, J. From Stoichiometry and Rate Law to Mechanism. J. Chem. Educ. 1968, 45, 381. 51. Intrinsic reaction coordinate (IRC) calculations are defined as “the minimum energy reaction pathway (MERP) in mass-weighted cartesian coordinates between the transition state of a reaction and its reactants and products.” They show the minima preceding and following transition state. 52. (a) Cini, R.; Caputo, P. A.; Intini, F. P.; Natile, G. Mechanistic and Stereochemical Investigation of Imino Ethers Formed by Alcoholysis of Coordinated Nitriles: X-ray Crystal Structures of cis- and trans-Bis(1-Imino-1- methoxyethane)dichloroplatinum(II). Inorg. Chem. 1995, 34, 1130. (b) Misaki, T.; Kurihara, M.; Tanabe, Y. Si-BEZA - Catalytic Pyridinium Triflate: a Mild and Powerful Agent for the Silylation of Alcohols. Chem. Commun. 2001, 2478. (c) Pump, J.; Rochow, E. G. Die Reaktion von Natrium-bis-trimethylsilyl-amid 804 mit Carbonylchloriden. Chem. Ber. 1964, 97, 627. (d) 1-Aza-2-siloxybutadiene: Structure and Synthetic Application as a Piperidinone Synthon Takasu, K.; Nishida, N.; Ihara, M. Synthesis 2004, 2222. 53. We define the idealized rate law as that obtained by rounding the observed reaction orders to the nearest rational order. 54. Extensive review of structural studies of alkali metal mixed aggregates: Harrison-Marchand, A.; Mongin, F. Mixed Aggregate (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 1. Structural Data Chem. Rev. 2013, 113, 7470. 55. Zhou, Y.; Keresztes, I.; MacMillan, S. N.; Collum, D. B. Disodium Salts of Pseudoephedrine-Derived Myers Enolates: Stereoselectivity and Mechanism of Alkylation. J. Am. Chem. Soc. 2019, 141, 16865. 56. (a) Harada, Y.; Salomon, M.; Petrucci. S. Molecular Dynamics and Ionic Associations of Lithium Hexafluoroarsenate (LiAsF6) in 4-Butyrolactone Mixtures with 2-Methyltetrahydrofuran. J. Phys. Chem. 1985, 89, 2006. (b) Carvajal, C.; Tolle, K. J.; Smid, J.; Szwarc, M. Studies of Solvation Phenomena of Ions and Ion Pairs in Dimethoxyethane and Tetrahydrofuran. J. Am. Chem. Soc. 1965, 87, 5548. 57. Krieck, S.; Schüler, P.; Görls, H.; Westerhausen, M. Straightforward Synthesis of Rubidium Bis(trimethylsilyl)amide and Complexes of the Alkali Metal Bis(trimethylsilyl)amides with Weakly Coordinating 2,2,5,5- Tetramethyltetrahydrofuran. Dalton Trans. 2018, 47, 12562. https://pubs.rsc.org/en/results?searchtext=Author%3APhilipp%20Sch%C3%BCler https://pubs.rsc.org/en/results?searchtext=Author%3AHelmar%20G%C3%B6rls 805 58. Lui, N. M.; Collum, D. B. Sodiated Oppolzer Enolates: Solution Structures, Mechanism of Alkylation, and the Origin of Stereoselectivity. Org. Chem. Front. 2023, 10, 4750. 59. (a) Livingstone, Z.; Hernan-Gomez, A.; Baillie, S. E.; Armstrong, D. R.; Carrella, L. M.; Clegg, W.; Harrington, R. W.; Kennedy, A. R.; Rentschler, E.; Hevia, E. J. Chem. Soc., Dalton Trans. 2016, 45, 6175. (b) Karl, M.; Seybert, G.; Massa, W.; Harms, K.; Agarwal, S.; Maleika, R.; Stelter, W.; Greiner, A.; Neumüller, W. H.; Dehnicke, K. Amidometallate von Seltenerdelementen. Synthese Und Kristallstrukturen von [Na(12-Krone-4)2][M{N(SiMe3)2}3(OSiMe3)] (M = Sm, Yb), [Na(THF)3Sm{N(SiMe3)2}3(C≡C-Ph)], [Na(THF)6][Lu2(μ-NH2)(μ- NSiMe3){N(SiMe3)2}4] Sowie von [NaN(SiMe3)2(THF)]2. Z. Anorg. Allg. Chem. 1999, 625, 1301. 60. Schenk, C.; Henke, F.; Santiso-Quinones, G.; Krossing, I.; Schnepf, A. [Si(SiMe3)3]6Ge18M (M = Cu, Ag, Au): Metalloid Cluster Compounds as Unusual Building Blocks for a Supramolecular Chemistry. Dalton Trans. 2008, 4436. 61. Ashby, E. C.; Dobbs, F. R.; Hopkins, H. P., Jr. Composition of Complex Aluminum Hydrides and Borohydrides, as Inferred from Conductance, Molecular Association, and Spectroscopic Studies. J. Am. Chem. Soc. 1973, 95, 2823. 62. (a) +Na(12-crown-4)2: Gjikaj, M.; Adam, A. Complexation of Alkali Triflates by Crown Ethers: Synthesis and Crystal Structure of [Na(12-crown-4)2 ][SO3CF3], [Na(15-crown-5)][SO3CF3], [Rb(18-crown-6)][SO3CF3], and [Cs(18-crown- 6)][SO3CF3]. Z. Anorg. Allg. Chem. 2006, 632, 2475. (b) +Na(15-crown-5)2: Kather, R.; Lork, E.; Raţ, C.-I.; Silvestru, C.; Beckmann, J. Synthesis and Structure 806 of [Na(15-crown-5)][Ph2P(S)OB(C6F5)3] and [Na(15-crown- 5)2][Ph2P(S)O· · ·HO(S)PPh2]. Main Group Met. Chem. 2017, 40, 47. (c) +Na(18- crown-6)2: Dodonov, V. A.; Kushnerova, O. A.; Baranov, E. V.; Novikov, A. S.; Fedushkin, I. L. Activation and Modification of Carbon Dioxide by Redox-Active Low-Valent Gallium Species. Dalton Trans. 2021, 50, 8899. 63. (a) Huang, R. H.; Eglin, J. L.; Huang, S. Z.; McMills, L. E. H.; Dye, J. L. Complexation of the Cations of Six Alkalides and an Electride by Mixed Crown Ethers. J. Am. Chem. Soc. 1993, 115, 9542. (b) [Cs+(15-Crown-5)(18-Crown- 6)e-]6·(18-Crown-6): Properties of the First Mixed Crown Ether Electride Wagner, M. J.; Dye, J. L. J. Solid State Chem. 1995, 117, 309. (c) Sandwich and Mixed Sandwich Complexes of the Cesium Ion with Crown Ethers in Nitromethane. Kim, J.; Shamsipur, M.; Huang, S. Z.; Huang, R. H.; Dye, J. L. J. Phys. Chem. A 1999, 103, 5615. (d) Maleknia, S.; Brodbelt, J. Gas-Phase Selectivities of Crown Ethers for Alkali Metal Ion Complexation. J. Am. Chem. Soc. 1992, 114, 4295. 64. A sodium arylsilazide triple ion with a +Na(crown)2 counterion has been characterized crystallographically.ref 11a 65. Lukevics et al. appear to be the first to report 15N–29Si coupling in alkali metal silazides: Kupce, E.; Lukevics, E. Silicon-29-nitrogen-15 spin-spin coupling constants in silazanes. Organometallics 1988, 7, 1649. 66. NaDA-PMDTA catalysis Ma, Y.; Woltornist, R. A.; Algera, R. F.; Collum, D. B. Reactions of Sodium Diisopropylamide: Liquid-Phase and Solid–Liquid Phase-Transfer Catalysis by 807 N,N,N′,N″,N″-Pentamethyldiethylenetriamine. J. Am. Chem. Soc. 2021, 143, 13370. 67. We distinguish ligand-based catalysis of stoichiometric bases versus base catalysis in which the ligand and base are stoichiometrically matched. The former requires turnover of the ligand whereas the latter requires turnover of the base. 68. For discussions of the challenges of ligand-catalyzed organolithium reactions, see: Kizirian, J.-C. Chiral Tertiary Diamines in Asymmetric Synthesis. Chem. Rev. 2008, 108, 140. 69. For ligand-catalyzed reactions of sodium salts, see: Davison, N.; McMullin, C. L.; Zhang, L.; Hu, S.-X.; Waddell, P. G.; Wills, C.; Dixon, C.; Lu, E. Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation. J. Am. Chem. Soc. 2023, 145, 6562. (b) Ahlberg, P.; Karlsson, A.; Davidsson, O.; Hilmersson, G.; Loewendahl, M. Mechanism and Solvent Catalysis of the Degenerate 1,12- Metalations of [1.1]Ferrocenophanyllithium and [1.1]Ferrocenophanylsodium Studied by NMR Spectroscopy. J. Am. Chem. Soc. 1997, 119, 1751. 808 CHAPTER 2 CARTESIAN COORDINATES 809 Chapter 2 Cartesian Coordinates DFT Cartesian Coordinate Compound number in SI Table C.2.27. Atomic coordinates and single point energies for 12-crown-4. Table C.2.28. Atomic coordinates and single point energies for 15-crown-5. Table C.2.29. Atomic coordinates and single point energies for 18-crown-6. Table C.2.30. Atomic coordinates and single point energies for benzene. Table C.2.31. Atomic coordinates and single point energies for N1,N1,N3,N3- tetramethylpropane-1,3-diamine. Table C.2.32. Atomic coordinates and single point energies for diglyme. Table C.2.33. Atomic coordinates and single point energies for Me2THF. Table C.2.34. Atomic coordinates and single point energies for DME. Table C.2.35. Atomic coordinates and single point energies for DMEA. Table C.2.36. Atomic coordinates and single point energies for Et3N. Table C.2.37. Atomic coordinates and single point energies for HMPA. Table C.2.38. Atomic coordinates and single point energies for MTBE. Table C.2.39. Atomic coordinates and single point energies for N1,N1,N5,N5- tetramethylpentane-1,5-diamine. Table C.2.40. Atomic coordinates and single point energies for PMDTA. Table C.2.41. Atomic coordinates and single point energies for Me4THF. Table C.2.42. Atomic coordinates and single point energies for THF. Table C.2.43. Atomic coordinates and single point energies for TMCDA. Table C.2.44. Atomic coordinates and single point energies for TMEDA. Table C.2.45. Atomic coordinates and single point energies for toluene. Table C.2.46. Atomic coordinates and single point energies for A1-2. Table C.2.47. Atomic coordinates and single point energies for A33. Table C.2.48. Atomic coordinates and single point energies for A24-2. Table C.2.49. Atomic coordinates and single point energies for A22-2. Table C.2.50. Atomic coordinates and single point energies for A34-2. 810 Table C.2.51. Atomic coordinates and single point energies for A3-2. Table C.2.52. Atomic coordinates and single point energies for A10-2. Table C.2.53. Atomic coordinates and single point energies for A4-2. Table C.2.54. Atomic coordinates and single point energies for A20-2. Table C.2.55. Atomic coordinates and single point energies for A5-2. Table C.2.56. Atomic coordinates and single point energies for A6-2. Table C.2.57. Atomic coordinates and single point energies for A7-2. Table C.2.58. Atomic coordinates and single point energies for A18-2. Table C.2.59. Atomic coordinates and single point energies for A14-2. Table C.2.60. Atomic coordinates and single point energies for A2-2. Table C.2.61. Atomic coordinates and single point energies for A1. Table C.2.62. Atomic coordinates and single point energies for A33. Table C.2.63. Atomic coordinates and single point energies for A24. Table C.2.64. Atomic coordinates and single point energies for A22. Table C.2.65. Atomic coordinates and single point energies for A34. Table C.2.66. Atomic coordinates and single point energies for A3. Table C.2.67. Atomic coordinates and single point energies for A10. Table C.2.68. Atomic coordinates and single point energies for A4. Table C.2.69. Atomic coordinates and single point energies for A20. Table C.2.70. Atomic coordinates and single point energies for A5. Table C.2.71. Atomic coordinates and single point energies for A18. Table C.2.72. Atomic coordinates and single point energies for A14. Table C.2.73. Atomic coordinates and single point energies for A2. Table C.2.74. Atomic coordinates and single point energies for A16. Table C.2.75. Atomic coordinates and single point energies for A27. Table C.2.76. Atomic coordinates and single point energies for A28. Table C.2.77. Atomic coordinates and single point energies for A29. Table C.2.78. Atomic coordinates and single point energies for A30. 811 Table C.2.79. Atomic coordinates and single point energies for A31. Table C.2.80. Atomic coordinates and single point energies for A32. Table C.2.81. Atomic coordinates and single point energies for A15. Table C.2.82. Atomic coordinates and single point energies for A26. Table C.2.83. Atomic coordinates and single point energies for A25. Table C.2.84. Atomic coordinates and single point energies for A35. Table C.2.85. Atomic coordinates and single point energies for A23. Table C.2.86. Atomic coordinates and single point energies for A11. Table C.2.87. Atomic coordinates and single point energies for A12. Table C.2.88. Atomic coordinates and single point energies for A13. Table C.2.89. Atomic coordinates and single point energies for A21. Table C.2.90. Atomic coordinates and single point energies for A36. Table C.2.91. Atomic coordinates and single point energies for A19. Table C.2.92. Atomic coordinates and single point energies for A15. Table C.2.93. Atomic coordinates and single point energies for A17. Table C.2.94. Atomic coordinates and single point energies for B1-2. Table C.2.95. Atomic coordinates and single point energies for B34-2. Table C.2.96. Atomic coordinates and single point energies for B28-2. Table C.2.97. Atomic coordinates and single point energies for B25-2. Table C.2.98. Atomic coordinates and single point energies for B3-2. Table C.2.99. Atomic coordinates and single point energies for B4-2. Table C.2.100. Atomic coordinates and single point energies for B14-2. Table C.2.101. Atomic coordinates and single point energies for B5-2. Table C.2.102. Atomic coordinates and single point energies for B23-2. Table C.2.103. Atomic coordinates and single point energies for B6-2. Table C.2.104. Atomic coordinates and single point energies for B20-2. Table C.2.105. Atomic coordinates and single point energies for B17-2. Table C.2.106. Atomic coordinates and single point energies for B2-2. 812 Table C.2.107. Atomic coordinates and single point energies for B1. Table C.2.108. Atomic coordinates and single point energies for B34. Table C.2.109. Atomic coordinates and single point energies for B28. Table C.2.110. Atomic coordinates and single point energies for B25. Table C.2.111. Atomic coordinates and single point energies for B3. Table C.2.112. Atomic coordinates and single point energies for B4. Table C.2.113. Atomic coordinates and single point energies for B14. Table C.2.114. Atomic coordinates and single point energies for B5. Table C.2.115. Atomic coordinates and single point energies for B23. Table C.2.116. Atomic coordinates and single point energies for B6. Table C.2.117. Atomic coordinates and single point energies for B7. Table C.2.118. Atomic coordinates and single point energies for B8. Table C.2.119. Atomic coordinates and single point energies for B20. Table C.2.120. Atomic coordinates and single point energies for B17. Table C.2.121. Atomic coordinates and single point energies for B2. Table C.2.122. Atomic coordinates and single point energies for B9. Table C.2.123. Atomic coordinates and single point energies for B31. Table C.2.124. Atomic coordinates and single point energies for B32. Table C.2.125. Atomic coordinates and single point energies for B33. Table C.2.126. Atomic coordinates and single point energies for B29. Table C.2.127. Atomic coordinates and single point energies for B30. Table C.2.128. Atomic coordinates and single point energies for B26. Table C.2.129. Atomic coordinates and single point energies for B27. Table C.2.130. Atomic coordinates and single point energies for B15. Table C.2.131. Atomic coordinates and single point energies for B16. Table C.2.132. Atomic coordinates and single point energies for B24. Table C.2.133. Atomic coordinates and single point energies for B35. Table C.2.134. Atomic coordinates and single point energies for B10. 813 Table C.2.135. Atomic coordinates and single point energies for B11. Table C.2.136. Atomic coordinates and single point energies for B12. Table C.2.137. Atomic coordinates and single point energies for B13. Table C.2.138. Atomic coordinates and single point energies for B21. Table C.2.139. Atomic coordinates and single point energies for B22. Table C.2.140. Atomic coordinates and single point energies for B18. Table C.2.141. Atomic coordinates and single point energies for B19. Table C.2.142. Atomic coordinates and single point energies for C47. Table C.2.143. Atomic coordinates and single point energies for C46. Table C.2.144. Atomic coordinates and single point energies for C48. Table C.2.145. Atomic coordinates and single point energies for C49. Table C.2.146. Atomic coordinates and single point energies for C13. Table C.2.147. Atomic coordinates and single point energies for C12. Table C.2.148. Atomic coordinates and single point energies for C1. Table C.2.149. Atomic coordinates and single point energies for C3. Table C.2.150. Atomic coordinates and single point energies for C4. Table C.2.151. Atomic coordinates and single point energies for C2. Table C.2.152. Atomic coordinates and single point energies for C44. Table C.2.153. Atomic coordinates and single point energies for C45. Table C.2.154. Atomic coordinates and single point energies for C43. Table C.2.155. Atomic coordinates and single point energies for C37. Table C.2.156. Atomic coordinates and single point energies for C38. Table C.2.157. Atomic coordinates and single point energies for C39. Table C.2.158. Atomic coordinates and single point energies for C40. Table C.2.159. Atomic coordinates and single point energies for C41. Table C.2.160. Atomic coordinates and single point energies for C42. Table C.2.161. Atomic coordinates and single point energies for C6. Table C.2.162. Atomic coordinates and single point energies for C7. 814 Table C.2.163. Atomic coordinates and single point energies for C31. Table C.2.164. Atomic coordinates and single point energies for C32. Table C.2.165. Atomic coordinates and single point energies for C33. Table C.2.166. Atomic coordinates and single point energies for C34. Table C.2.167. Atomic coordinates and single point energies for C35. Table C.2.168. Atomic coordinates and single point energies for C36. Table C.2.169. Atomic coordinates and single point energies for C8. Table C.2.170. Atomic coordinates and single point energies for C27. Table C.2.171. Atomic coordinates and single point energies for C28. Table C.2.172. Atomic coordinates and single point energies for C29. Table C.2.173. Atomic coordinates and single point energies for C30. Table C.2.174. Atomic coordinates and single point energies for C10. Table C.2.175. Atomic coordinates and single point energies for C9. Table C.2.176. Atomic coordinates and single point energies for C11. Table C.2.177. Atomic coordinates and single point energies for C15. Table C.2.178. Atomic coordinates and single point energies for C17. Table C.2.179. Atomic coordinates and single point energies for C19. Table C.2.180. Atomic coordinates and single point energies for C20. Table C.2.181. Atomic coordinates and single point energies for C14. Table C.2.182. Atomic coordinates and single point energies for C16. Table C.2.183. Atomic coordinates and single point energies for C18. Table C.2.184. Atomic coordinates and single point energies for C22. Table C.2.185. Atomic coordinates and single point energies for C21. Table C.2.186. Atomic coordinates and single point energies for C23. Table C.2.187. Atomic coordinates and single point energies for C24. Table C.2.188. Atomic coordinates and single point energies for C25. Table C.2.189. Atomic coordinates and single point energies for C26. Table C.2.190. Atomic coordinates and single point energies for C5. 815 Table C.2.191. Atomic coordinates and single point energies for methyl Benzoate. Table C.2.192. Atomic coordinates and single point energies for TMSOMe. Table C.2.193. Atomic coordinates and single point energies for 38. Table C.2.194. Atomic coordinates and single point energies for 39. Table C.2.195. Atomic coordinates and single point energies for E23. Table C.2.196. Atomic coordinates and single point energies for E22. Table C.2.197. Atomic coordinates and single point energies for E21. Table C.2.198. Atomic coordinates and single point energies for T9. Table C.2.199. Atomic coordinates and single point energies for E26. Table C.2.200. Atomic coordinates and single point energies for E25. Table C.2.201. Atomic coordinates and single point energies for E24. Table C.2.202. Atomic coordinates and single point energies for T19. Table C.2.203. Atomic coordinates and single point energies for T20. Table C.2.204. Atomic coordinates and single point energies for E29. Table C.2.205. Atomic coordinates and single point energies for E28. Table C.2.206. Atomic coordinates and single point energies for E27. Table C.2.207. Atomic coordinates and single point energies for T11. Table C.2.208. Atomic coordinates and single point energies for T21. Table C.2.209. Atomic coordinates and single point energies for T22. Table C.2.210. Atomic coordinates and single point energies for E2. Table C.2.211. Atomic coordinates and single point energies for E1. Table C.2.212. Atomic coordinates and single point energies for T12. Table C.2.213. Atomic coordinates and single point energies for E8. Table C.2.214. Atomic coordinates and single point energies for 37. Table C.2.215. Atomic coordinates and single point energies for T1. Table C.2.216. Atomic coordinates and single point energies for E10. Table C.2.217. Atomic coordinates and single point energies for E6. Table C.2.218. Atomic coordinates and single point energies for T2. 816 Table C.2.219. Atomic coordinates and single point energies for E7. Table C.2.220. Atomic coordinates and single point energies for E20. Table C.2.221. Atomic coordinates and single point energies for E19. Table C.2.222. Atomic coordinates and single point energies for E18. Table C.2.223. Atomic coordinates and single point energies for T8. Table C.2.224. Atomic coordinates and single point energies for T18. Table C.2.225. Atomic coordinates and single point energies for E17. Table C.2.226. Atomic coordinates and single point energies for E16. Table C.2.227. Atomic coordinates and single point energies for E15. Table C.2.228. Atomic coordinates and single point energies for T7. Table C.2.229. Atomic coordinates and single point energies for T16. Table C.2.230. Atomic coordinates and single point energies for T15. Table C.2.231. Atomic coordinates and single point energies for T17. Table C.2.232. Atomic coordinates and single point energies for E12. Table C.2.233. Atomic coordinates and single point energies for E11. Table C.2.234. Atomic coordinates and single point energies for E14. Table C.2.235. Atomic coordinates and single point energies for E13. Table C.2.236. Atomic coordinates and single point energies for T4. Table C.2.237. Atomic coordinates and single point energies for T5. Table C.2.238. Atomic coordinates and single point energies for T3. Table C.2.239. Atomic coordinates and single point energies for E4. Table C.2.240. Atomic coordinates and single point energies for E3. Table C.2.241. Atomic coordinates and single point energies for T6, T13. Table C.2.242. Atomic coordinates and single point energies for T6-2. 817 Compound number in SI N Me3Si i-Pr 1 (NaPTA) Na N Me3Si tert-Bu Na 2 (NaBTA) N Me3Si Ph(Me)CH Na 3 (NaPETA) N Na N Na SiMe3Me3Si RR S S cis-4 (A2S2) N Me3Si R 5 (ASn) NaSnN Na N Na RMe3Si SiMe3R S S trans-4 (A2S2) N Me3Si Me H Na Na N SiMe3 Me H 6 N Me3Si Me H Na Na N SiMe3 Me H 7 N Me3Si Me H Na Na N SiMe3 Me H 8 9 Sn N Me3Si Me H Na Na N SiMe3 Me H Sn Sn N Me3Si Me H NaSn 10 11 N Na N Na SiMe3i-Pr i-PrMe3Si Me Me N Na N Na SiMe3R RMe3Si S S R = i-Pr-, t-Bu-, or Ph(CH3)CH- S = MTBE, DMEA, Et3N, HMPA 12 N Me3Si Me H Na(HMPA)1 13 N Me3Si Me H Na(HMPA)2 14 15 16 N N SiMe3Me3Si i-Pri-PrN Na N Na i-PrMe3Si SiMe3i-Pr THF THF Na THF THF Na THF THF 17 Na N Na N t-Bu Me3Si t-Bu SiMe3 THF THF 18 N Me3Si t-Bu Na(THF)n+1 N N i-PrMe3Si SiMe3i-Pr 20 NMe2 Na Me2N Me2N Na NMe2 N N i-PrMe3Si SiMe3i-Pr 19 NMe2 Na Me2N Me2N Na NMe2 Me2 N N Me2 N R Me3Si Na 23a; R = i-Pr 23b; R = t-Bu 23c; R = CH(Me)Ph R Me3Si N Na N Me Me MeMe N 21a; R = i-Pr 21b; R = t-Bu 21c; R = CH(Me)Ph N R Me3Si Na L L L L 22; L = NMe2 N Me3Si Me H 25; L = NMe2 N R Me3Si Na L L 24; L = NMe2 S Na L L N N SiMe3 Me3Si Na R Me2N N NMe2 R Na N NMe2Me2N 27a-c not observed Me Me N Na R Me3Si Me2N N Me2N 26a; R = i-Pr 26b; R = t-Bu 26c; R = CH(Me)Ph Me N R Me3Si Na O O O O Me Me Me Me N N SiMe3 Me3Si Na R MeO OMe R Na MeO OMe 28a; R = i-Pr 28b; R = CH(Me)Ph 28c; R = t-Bu 29a; R = i-Pr 29b; R = CH(Me)Ph 29c; R = t-Bu N N SiMe3 Me3Si Na i-Pr MeO O OMe i-Pr Na O OMeMeO Na MeO O OMe OMe OMeO N Me3Si i-Pr 31a30a N Na i-Pr Me3Si MeO O MeO 32a not observed N Na R Me3Si MeO O MeO 32a; R = i-Pr 32b; R = CH(Me)Ph 32c; R = t-Bu N H O i-Pr Ph 36 Ph OMe N N SiMe3 Me3Si Na i-Pr i-Pr Na 37 solvent O OSiMe3 N i-Pr OSiMe3 N i-Pr 38 39 N Na N Na i-Pr SiMe3i-Pr O THF THF Ph O N i-Pr Na n 40 41 B9 C12A16 C3 C4 A2 A4, A34, A3, A10 B5, B3, B4, B14 C8, C6, C7, C31 C32 C34 A5, A5-2 A8, A8-2 B7, B7-2 B10–B13 A14, A14-2 A18, A18-2 A15, B18, C23 A17, B19, C25 A19, B21 C23 A15, B18, C28 A20, B23, C27 A22, B25, C37 A23, B27, C41 A26 A24 A25 A25, B30, C44 36 37 38 39 E12 41 paper SI paper SI paper SI paper SI paper SI paper SI paper SI 818 Table C.2.27. Atomic coordinates and single point energies for 12-crown-4. G = –614.36281 GSP = –615.0754 O -1.05300 -1.59400 -0.43500 O 1.86300 -0.97500 -0.63600 O -1.86300 0.97500 0.63600 O 1.05300 1.59400 0.43500 C -0.10100 -1.70000 0.59600 C 1.22800 -2.07200 -0.03100 C -2.35400 -1.27500 -0.01900 C -2.65100 0.19300 -0.22500 C -1.22800 2.07200 0.03100 C 0.10100 1.70000 -0.59600 C 2.65100 -0.19300 0.22500 C 2.35400 1.27500 0.01900 H -2.50600 -1.53900 1.04400 H -3.06200 -1.87100 -0.61800 H -3.72500 0.38900 -0.04300 H -2.44000 0.43400 -1.28200 H -1.03800 2.81900 0.81500 H -1.88500 2.53400 -0.72800 H 0.40500 2.49000 -1.31100 H 0.01000 0.74500 -1.14700 H 3.06200 1.87100 0.61800 H 2.50600 1.53900 -1.04400 H 2.44000 -0.43400 1.28200 H 3.72500 -0.38900 0.04300 H 1.88500 -2.53400 0.72800 H 1.03800 -2.81900 -0.81500 H -0.40500 -2.49000 1.31100 H -0.01000 -0.74500 1.14700 819 Table C.2.28. Atomic coordinates and single point energies for 15-crown-5. G = –767.95217 GSP = –768.8444 O 2.86000 -1.08200 0.10000 O 1.48700 1.49300 -0.08100 O 0.00000 -1.52500 -0.00000 O -1.48800 1.49400 0.08200 O -2.85900 -1.08300 -0.10000 C 0.64200 2.50100 0.39500 C -0.64300 2.50100 -0.39600 C 2.56900 1.22700 0.76600 C 3.46600 0.17800 0.14200 C 2.10300 -1.36700 -1.05200 C 0.96700 -2.28200 -0.66600 C -0.96500 -2.28200 0.66600 C -2.10100 -1.36700 1.05200 C -2.57000 1.22600 -0.76500 C -3.46600 0.17600 -0.14200 H 1.13500 3.49000 0.30800 H 0.39600 2.34100 1.46200 H -0.39700 2.34000 -1.46200 H -1.13700 3.49000 -0.30900 H -2.20900 0.85200 -1.74200 H -3.16000 2.14800 -0.95000 H -4.37300 0.08500 -0.75900 H -3.77700 0.51000 0.86500 H -2.73600 -1.85900 1.81400 H -1.67200 -0.44800 1.48000 H -1.36300 -3.08600 0.01600 H -0.53600 -2.75900 1.57000 H 0.53800 -2.75900 -1.57000 H 1.36500 -3.08500 -0.01600 H 1.67200 -0.44800 -1.48000 820 H 2.73700 -1.85900 -1.81400 H 3.77700 0.51100 -0.86500 H 4.37300 0.08700 0.75900 H 3.15800 2.14900 0.95000 H 2.20800 0.85300 1.74300 821 Table C.2.29. Atomic coordinates and single point energies for 18-crown-6. G = –921.5379 GSP = –922.6127 O -0.78700 2.74800 -0.23900 O -2.77800 0.69300 0.24100 O 1.98800 2.05700 0.24100 O -1.98800 -2.05700 -0.24100 O 2.77700 -0.69400 -0.24400 O 0.78700 -2.74800 0.24100 C -3.02300 1.95700 -0.29900 C -2.06000 2.95400 0.29500 C 0.18300 3.59500 0.30100 C 1.52900 3.26100 -0.29400 C 3.20600 1.64000 -0.29900 C 3.59000 0.30600 0.29400 C 3.02400 -1.95700 0.29600 C 2.05900 -2.95500 -0.29600 C -1.52900 -3.25900 0.29900 C -0.18300 -3.59600 -0.29400 C -3.58900 -0.30600 -0.29900 C -3.20700 -1.64000 0.29500 H -4.00600 -2.37800 0.07500 H -3.14100 -1.53400 1.39500 H -2.23900 -4.08300 0.08200 H -1.42500 -3.18600 1.39900 H -0.24100 -3.48800 -1.39400 H 0.05800 -4.65600 -0.07200 H 2.05000 -2.83200 -1.39600 H 2.41600 -3.98100 -0.07400 822 H 4.06200 -2.28000 0.07900 H 2.89800 -1.94900 1.39600 H 4.65800 0.10300 0.07400 H 3.47700 0.36000 1.39400 H 3.13600 1.53400 -1.39900 H 4.00500 2.37800 -0.08100 H 1.42600 3.19200 -1.39400 H 2.23900 4.08400 -0.07200 H -0.05800 4.65600 0.08300 H 0.24000 3.48200 1.40000 H -2.41600 3.98100 0.07400 H -2.05300 2.83100 1.39600 H -2.89400 1.94900 -1.39900 H -4.06200 2.28000 -0.08400 H -4.65800 -0.10300 -0.08200 H -3.47200 -0.36000 -1.39900 823 Table C.2.30. Atomic coordinates and single point energies for benzene. G = –231.88383 GSP = –232.1391 C -1.20800 0.69700 0.00000 C 0.00000 1.39500 0.00000 C -1.20800 -0.69700 0.00000 C 1.20800 0.69700 0.00000 C -0.00000 -1.39500 0.00000 C 1.20800 -0.69700 0.00000 H 0.00000 2.48600 0.00000 H 2.15300 1.24300 0.00000 H -2.15300 1.24300 0.00000 H -2.15300 -1.24300 0.00000 H -0.00000 -2.48600 0.00000 H 2.15300 -1.24300 0.00000 824 Table C.2.31. Atomic coordinates and single point energies for N1,N1,N3,N3- tetramethylpropane-1,3-diamine. G = –386.33258 GSP = –386.77508 N -2.48500 -0.02300 -0.32900 N 2.48500 -0.02300 -0.32900 C -1.25900 -0.56000 0.23000 C 0.00000 0.16100 -0.23400 C 1.25900 -0.56000 0.23000 C -3.61100 -0.88100 -0.03900 C -2.74700 1.33700 0.08500 H -3.42100 -1.89500 -0.42100 H -4.51500 -0.49600 -0.53100 H -3.82300 -0.96100 1.05100 H -3.69000 1.68300 -0.36100 H -1.95300 2.01200 -0.25800 H -2.83500 1.43800 1.19100 H -1.19200 -1.61600 -0.07900 H -1.29400 -0.56400 1.34700 H 0.00000 1.19300 0.14700 H 0.00000 0.21700 -1.33400 H 1.19200 -1.61700 -0.07800 H 1.29400 -0.56400 1.34700 C 2.74700 1.33700 0.08500 C 3.61100 -0.88100 -0.03900 H 1.95300 2.01200 -0.25900 H 3.69000 1.68300 -0.36100 H 2.83500 1.43900 1.19100 H 3.82300 -0.96100 1.05100 H 4.51500 -0.49600 -0.53100 H 3.42100 -1.89500 -0.42000 825 Table C.2.32. Atomic coordinates and single point energies for diglyme. G = –461.93744 GSP = –462.4815 O 2.46400 0.65900 -0.39000 O 0.00000 -0.70200 0.25800 O -2.46300 0.65900 -0.39000 C 2.36700 -0.55100 0.29800 C 1.16700 -1.31700 -0.20100 C -1.16700 -1.31700 -0.20200 C -2.36700 -0.55200 0.29700 C 3.48800 1.47700 0.08300 C -3.48800 1.47700 0.08400 H 3.49500 2.39500 -0.51800 H 4.47800 0.98900 -0.00400 H 3.33500 1.75000 1.14400 H 2.25200 -0.38000 1.38700 H 3.28000 -1.16300 0.14900 H 1.22600 -2.36500 0.15900 H 1.19300 -1.33900 -1.30700 H -1.22600 -2.36500 0.15700 H -1.19200 -1.33800 -1.30800 H -2.25300 -0.38100 1.38600 H -3.28000 -1.16300 0.14700 H -3.49500 2.39500 -0.51700 H -3.33700 1.74900 1.14500 H -4.47800 0.98900 -0.00500 826 Table C.2.33. Atomic coordinates and single point energies for Me2THF. G = –310.54588 GSP = –310.9014 C 1.09700 -0.12400 -0.41800 O 0.00000 -0.92400 0.00300 C -1.09800 -0.12300 0.41800 C -0.76100 1.29600 -0.04700 C 0.76100 1.29600 0.04700 H 1.14100 -0.14000 -1.52400 H -1.14600 -0.13900 1.52500 H -1.08100 1.42800 -1.09300 H -1.24900 2.06900 0.56100 H 1.24800 2.06900 -0.56200 H 1.08000 1.42800 1.09300 C 2.38600 -0.69500 0.13900 H 2.52200 -1.73100 -0.19900 H 3.25000 -0.10200 -0.19400 H 2.35300 -0.69100 1.23800 C -2.38500 -0.69600 -0.14200 H -2.52200 -1.73100 0.19700 H -3.25000 -0.10200 0.18700 H -2.34800 -0.69400 -1.24100 827 Table C.2.34. Atomic coordinates and single point energies for DME. G = –308.35021 GSP = –308.7137 O -1.77200 -0.18500 -0.36900 O 1.12700 0.29300 0.31900 C -0.86900 -1.02600 0.28700 C 0.56500 -0.88700 -0.18600 C -1.74400 1.15700 0.04100 H -1.20000 -2.05600 0.08900 H -0.89400 -0.86100 1.38200 H 0.58000 -0.88600 -1.29400 H 1.14900 -1.76600 0.15600 H -2.60700 1.65600 -0.41800 H -0.81900 1.66800 -0.26500 H -1.83100 1.24000 1.14000 C 2.44200 0.49800 -0.10200 H 2.80200 1.43200 0.34800 H 2.51000 0.58400 -1.20200 H 3.10400 -0.32800 0.21900 828 Table C.2.35. Atomic coordinates and single point energies for DMEA. G = –213.37362 GSP = –213.6199 N 0.45700 -0.00300 -0.31600 C 1.66600 -0.75200 -0.06000 C 0.60200 1.37500 0.09400 C -0.69800 -0.65100 0.27800 C -2.02400 -0.03200 -0.14200 H 1.91600 -0.81000 1.02300 H 2.51600 -0.28600 -0.57800 H 1.56000 -1.78000 -0.43700 H 1.48700 1.81400 -0.38800 H 0.72400 1.48400 1.19600 H -0.27000 1.96800 -0.21300 H -0.62400 -0.65900 1.39100 H -0.68100 -1.70500 -0.04000 H -2.17000 0.97000 0.28400 H -2.86000 -0.65800 0.19800 H -2.06900 0.04900 -1.23800 829 Table C.2.36. Atomic coordinates and single point energies for Et3N. G = –291.84636 GSP = –292.1794 N 0.00000 -0.00000 0.02900 C 0.88100 1.08200 0.44400 C -1.37700 0.22200 0.44400 C 0.49600 -1.30400 0.44400 C -0.00400 -2.43900 -0.43900 H 0.31500 2.02300 0.39400 C 2.11400 1.21600 -0.43900 H 1.18000 0.96200 1.51000 C -2.11000 1.22300 -0.43900 H -1.42400 0.54100 1.51000 H -1.90900 -0.73900 0.39400 H 0.24400 -1.50300 1.51000 H 1.59500 -1.28400 0.39400 H -1.09900 -2.52900 -0.41100 H 0.41600 -3.40000 -0.11100 H 0.29300 -2.25900 -1.48100 H 1.81000 1.38500 -1.48100 H 2.73900 0.31200 -0.41200 H 2.73800 2.06000 -0.11100 H -1.64000 2.21600 -0.41200 H -3.15200 1.34100 -0.11000 H -2.10400 0.87500 -1.48100 830 Table C.2.37. Atomic coordinates and single point energies for HMPA. G = –819.40278 GSP = –820.1001 O -0.00100 -0.31300 -1.96300 P -0.00000 -0.04800 -0.50000 N 1.39800 -0.66000 0.20600 N -1.40000 -0.65600 0.20700 N 0.00200 1.53700 0.07000 C 2.14600 -1.68800 -0.49300 C 1.68200 -0.54800 1.62000 C -2.15300 -1.68000 -0.49300 C -1.68100 -0.54600 1.62100 C -1.20600 2.33100 -0.07900 C 1.21300 2.32800 -0.08100 H 1.95500 -2.69300 -0.07500 H 3.22700 -1.48800 -0.41200 H 1.86100 -1.68000 -1.55100 H 1.16700 0.32300 2.04400 H 2.76600 -0.40800 1.77400 H 1.37900 -1.44900 2.18500 H -1.96500 -2.68700 -0.07700 H -1.86900 -1.67200 -1.55100 H -3.23300 -1.47600 -0.41100 H -1.16300 0.32400 2.04600 H -1.37900 -1.44800 2.18500 H -2.76400 -0.40200 1.77700 H -1.23700 3.10800 0.70200 H -2.09300 1.69500 0.02200 H -1.24800 2.83100 -1.06300 H 2.09800 1.68900 0.01700 H 1.24800 3.10400 0.70000 H 1.25400 2.82800 -1.06500 831 Table C.2.38. Atomic coordinates and single point energies for MTBE. G = –272.48016 GSP = –272.7971 O -0.77700 0.01200 -0.80200 C -2.01500 0.00600 -0.15400 C 0.40000 -1.20400 0.95400 C 1.53300 -0.11900 -0.99900 C 0.52100 1.30700 0.79400 C 0.39400 -0.00100 0.00700 H -2.20300 -0.93400 0.39500 H -2.78400 0.10500 -0.93000 H -2.13300 0.84800 0.55200 H 0.45200 2.16300 0.10700 H 1.49100 1.34800 1.31000 H -0.26400 1.40600 1.55700 H 1.49400 0.72500 -1.70100 H 1.42600 -1.04900 -1.57300 H 2.50800 -0.11900 -0.49200 H -0.36600 -1.11300 1.73800 H 1.37700 -1.28800 1.45100 H 0.21500 -2.12800 0.38700 832 Table C.2.39. Atomic coordinates and single point energies for N1,N1,N5,N5- tetramethylCntane-1,5-diamine. G = –464.806631 GSP = –465.33512 N 2.82400 0.53300 0.06700 C -0.00000 -0.43600 -0.00000 N -2.82400 0.53300 -0.06700 C 2.37600 -0.43900 -0.91400 C 1.18800 -1.27700 -0.45200 C -1.18800 -1.27700 0.45200 C -2.37600 -0.43900 0.91400 C 3.30800 -0.07900 1.28200 C 3.79900 1.43800 -0.49500 H 3.64200 0.70100 1.98200 H 4.16400 -0.76900 1.10400 H 2.51000 -0.64800 1.77800 H 4.73600 0.92400 -0.80700 H 4.06700 2.20900 0.24200 H 3.38100 1.94200 -1.37800 H 3.21100 -1.11400 -1.21600 H 2.08000 0.12000 -1.81700 H 1.49400 -1.96200 0.35700 H 0.88800 -1.92800 -1.29000 H -0.88800 -1.92800 1.29000 H -1.49400 -1.96200 -0.35700 H -2.08000 0.11900 1.81700 H -3.21100 -1.11400 1.21600 C -3.79900 1.43800 0.49500 C -3.30800 -0.07800 -1.28300 H -3.38100 1.94200 1.37800 H -4.73600 0.92300 0.80700 H -4.06800 2.20900 -0.24200 H -2.50900 -0.64700 -1.77800 H -3.64200 0.70100 -1.98200 H -4.16400 -0.76900 -1.10500 H -0.31500 0.23400 -0.81700 H 0.31500 0.23400 0.81700 833 Table C.2.40. Atomic coordinates and single point energies for PMDTA. G = –520.052747 GSP = –520.644062 N -2.79700 0.40400 0.10200 N -0.00000 -0.82600 0.19900 N 2.79700 0.40400 0.10200 C -2.34500 -0.71400 -0.71700 C -1.23000 -1.55200 -0.09600 H -2.01900 -0.36100 -1.71700 H -3.19700 -1.39200 -0.88600 H -1.00600 -2.35800 -0.81200 H -1.62600 -2.03900 0.81900 C 1.23000 -1.55200 -0.09600 C 2.34500 -0.71300 -0.71700 H 1.00600 -2.35800 -0.81200 H 1.62600 -2.03900 0.81900 H 2.01900 -0.36100 -1.71700 H 3.19600 -1.39200 -0.88700 C 0.00000 -0.31100 1.56100 H 0.90100 0.29200 1.73300 H -0.00000 -1.14000 2.30200 H -0.90000 0.29200 1.73300 C -4.23300 0.57000 0.10100 C -2.12600 1.64000 -0.24200 H -4.72400 -0.34700 0.45600 H -4.64200 0.81600 -0.90400 H -4.51200 1.38600 0.78400 H -2.36200 2.41900 0.49800 H -2.42400 2.01500 -1.24600 H -1.04100 1.48000 -0.24900 C 2.12600 1.64000 -0.24100 C 4.23300 0.56900 0.10100 H 1.04100 1.48000 -0.24800 H 2.42400 2.01600 -1.24500 H 2.36200 2.41900 0.49900 H 4.72400 -0.34800 0.45500 834 H 4.51300 1.38500 0.78400 H 4.64200 0.81600 -0.90400 835 Table C.2.41. Atomic coordinates and single point energies for Me4THF. G = –310.545875 GSP = –310.901391 C 1.18800 -0.01100 -0.08000 O 0.00000 -0.00100 -0.87300 C -1.18800 0.01100 -0.08000 C -0.70100 0.29900 1.35100 C 0.70100 -0.30200 1.35100 H -0.65800 1.38600 1.52100 H -1.36600 -0.13400 2.11200 H 1.36600 0.13000 2.11200 H 0.65800 -1.38800 1.51900 C 2.11100 -1.09300 -0.62400 H 2.38800 -0.86800 -1.66400 H 3.03000 -1.16200 -0.02300 H 1.60000 -2.06600 -0.60600 C -2.11000 1.09500 -0.62300 H -2.38600 0.87100 -1.66300 H -3.02800 1.16400 -0.02200 H -1.59700 2.06700 -0.60400 C 1.84700 1.36500 -0.18100 H 2.81100 1.38300 0.34800 H 2.01600 1.61300 -1.23800 H 1.19600 2.14000 0.25000 C -1.84800 -1.36400 -0.18300 H -2.81300 -1.38200 0.34600 H -2.01800 -1.61000 -1.24000 H -1.19900 -2.14100 0.24700 836 Table C.2.42. Atomic coordinates and single point energies for THF. G = –232.06028 GSP = –232.329645 C -1.13100 -0.46100 0.13800 O -0.01000 -1.18800 -0.30000 C 1.11100 -0.48600 0.17600 C 0.78900 0.99600 -0.07400 C -0.75600 1.02600 -0.02500 H -2.00100 -0.76800 -0.45700 H -1.34100 -0.68800 1.20200 H 1.25000 -0.67200 1.25900 H 2.00100 -0.84600 -0.35400 H 1.25600 1.65400 0.67000 H 1.15000 1.30100 -1.06500 H -1.14000 1.63300 0.80600 H -1.17000 1.43800 -0.95500 837 Table C.2.43. Atomic coordinates and single point energies for TMCDA. G = –502.860215 GSP = –503.424539 N -1.95200 -0.17800 -0.07000 N 1.03400 -1.15200 -0.43500 C -2.97900 0.72500 -0.54900 C -2.44400 -0.93500 1.06300 H -2.69500 1.17700 -1.50600 H -3.19300 1.54700 0.17200 H -3.91000 0.16500 -0.70900 H -2.56300 -0.30900 1.97500 H -1.77400 -1.77000 1.30600 H -3.42500 -1.36400 0.81700 C 0.19000 -2.27900 -0.78500 C 2.40400 -1.58500 -0.26600 H 0.16300 -3.04800 0.02100 H 0.57600 -2.76300 -1.69400 H -0.83200 -1.93500 -0.97700 H 2.68000 -2.21600 -1.12200 H 2.56800 -2.18400 0.65700 H 3.09900 -0.73300 -0.25200 C -0.69900 0.51900 0.22500 C 0.47900 -0.37600 0.67900 C -0.23700 1.38200 -0.96500 C 1.48300 0.58100 1.35100 C 1.25000 1.76200 -0.89300 C 1.72700 1.88100 0.55500 H -0.89000 1.20100 1.08900 H -0.84900 2.29600 -1.00100 H -0.43100 0.81800 -1.89000 H 1.41900 2.71000 -1.42500 838 H 1.84000 0.99200 -1.40500 H 1.18900 2.71500 1.03600 H 2.79300 2.15200 0.58200 H 1.06200 0.83000 2.33600 H 2.42300 0.05700 1.56100 H 0.14200 -1.07300 1.47600 839 Table C.2.44. Atomic coordinates and single point energies for TMEDA. G = –347.097574 GSP = –347.494517 N -1.51000 0.12800 -0.15700 N 1.63900 -0.08400 -0.35200 C -0.65000 -1.02700 0.03700 C 0.75000 -0.75400 0.57700 H 0.70300 -0.22300 1.55500 H 1.18500 -1.74100 0.79700 H -0.52800 -1.52300 -0.93800 H -1.14100 -1.76100 0.72000 C -1.84000 0.79600 1.08200 C -2.70000 -0.23300 -0.89300 H -0.93500 1.19000 1.56600 H -2.35400 0.12300 1.80400 H -2.50400 1.64700 0.87800 H -2.42600 -0.67200 -1.86200 H -3.31200 0.66000 -1.08200 H -3.33100 -0.97200 -0.34800 C 1.35600 1.33100 -0.49300 C 3.02600 -0.29700 -0.00500 H 1.54300 1.89000 0.45300 H 0.30900 1.47400 -0.78200 H 2.00400 1.76300 -1.27000 H 3.25700 -1.37200 0.01400 H 3.29300 0.13000 0.98900 H 3.67500 0.17700 -0.75500 840 Table C.2.45. Atomic coordinates and single point energies for toluene. G = –271.124619 GSP = –271.423661 C 0.00000 0.91300 0.00000 C 1.20300 0.20100 0.00000 C -1.19900 0.18900 0.00000 C 1.21100 -1.19400 0.00000 C -1.19700 -1.20300 0.00000 C 0.01100 -1.90100 0.00000 H 2.14800 0.74800 0.00000 H 2.16200 -1.73000 0.00000 C -0.02000 2.42000 0.00000 H -2.15000 0.72900 0.00000 H -2.14300 -1.74700 0.00000 H 0.01600 -2.99300 0.00000 H 0.99800 2.83200 0.00000 H -0.54400 2.80700 0.88700 H -0.54400 2.80700 -0.88700 841 Table C.2.46. Atomic coordinates and single point energies for A1-2. G = –1488.306458 GSP = –1489.283821 Na -0.07500 -0.43900 -1.42700 Na 0.11400 -0.36200 1.40900 N 1.83100 -0.40400 -0.10200 N -1.78700 -0.46400 0.08400 Si 2.60300 1.09400 0.21600 C 4.27000 0.94500 1.10700 C 1.46900 2.10000 1.37600 C 2.91300 2.14900 -1.33100 C 2.66900 -1.50000 -0.56900 C 2.98500 -2.49400 0.55400 H 3.63900 -3.31700 0.22200 H 2.04700 -2.93600 0.93400 H 3.47800 -1.97400 1.38800 C 2.02700 -2.25200 -1.74400 H 3.65100 -1.14200 -0.95200 H 2.65300 -3.08300 -2.10100 H 1.87100 -1.57500 -2.60300 H 1.05900 -2.69000 -1.43900 H 4.15000 0.47100 2.09300 H 4.73000 1.93400 1.25900 H 4.98100 0.33400 0.52800 H 1.45500 1.67200 2.39600 H 0.43100 2.18900 1.01300 H 1.84500 3.12800 1.48600 H 3.53800 1.59000 -2.04500 H 3.43000 3.09300 -1.10100 H 1.96800 2.39700 -1.84100 C -2.32400 -1.60300 0.80400 C -1.56600 -2.88100 0.41800 C -3.82600 -1.84100 0.62100 H -1.73600 -3.09500 -0.65000 H -1.89200 -3.75500 1.00300 H -0.47700 -2.76800 0.56100 842 H -2.18700 -1.49300 1.91400 H -4.15600 -2.75400 1.14000 H -4.05700 -1.94100 -0.45100 H -4.41100 -0.99900 1.01700 Si -2.60800 1.00600 -0.21100 C -1.46600 2.00800 -1.37000 C -2.91900 2.06100 1.34000 C -4.26200 0.94800 -1.14300 H -0.42600 2.08600 -1.01100 H -1.83600 3.03900 -1.48100 H -1.46000 1.57900 -2.38900 H -1.97900 2.30800 1.86100 H -3.55700 1.51300 2.05200 H -3.42700 3.00900 1.10200 H -4.53100 1.96000 -1.48800 H -5.09200 0.57700 -0.52500 H -4.18800 0.29800 -2.02900 843 Table C.2.47. Atomic coordinates and single point energies for A33. G = –1952.085157 GSP = –1953.56659 Na 1.48400 0.19000 0.30100 Na -1.36000 -0.16700 0.32900 N 0.29300 -1.81000 0.47200 N -0.16800 1.83500 0.45100 Si 0.25500 -2.89800 -0.84600 C 1.88600 -3.80900 -1.22600 C -0.17800 -1.93700 -2.42100 C -1.00500 -4.31100 -0.62200 C 0.46500 -2.41400 1.78800 C 1.86800 -2.17600 2.36400 H 2.01600 -2.67800 3.33400 H 2.04500 -1.09700 2.52500 H 2.63000 -2.54300 1.66000 C -0.58900 -1.90400 2.77800 H 0.33900 -3.52000 1.76000 H -0.47400 -2.33700 3.78500 H -1.60000 -2.14800 2.41500 H -0.51200 -0.80700 2.87700 H 2.63900 -3.12500 -1.64700 H 1.73000 -4.62100 -1.95400 H 2.30700 -4.25900 -0.31200 H -0.19100 -2.60400 -3.29700 H 0.57100 -1.15200 -2.61600 H -1.16200 -1.44600 -2.36400 H -0.61900 -5.07500 0.07100 844 H -1.21600 -4.81700 -1.57800 H -1.95600 -3.94500 -0.20600 C -0.13300 2.49800 1.74900 C 1.04100 2.00800 2.60400 C -1.44400 2.32200 2.52800 H 0.95100 0.92200 2.78500 H 1.08200 2.50000 3.58800 H 1.99500 2.20100 2.08700 H 0.01300 3.59900 1.65300 H -1.43200 2.84200 3.50000 H -1.62700 1.25000 2.72500 H -2.28600 2.70800 1.93600 Si -0.47100 2.86700 -0.88000 C -0.66100 1.82200 -2.44900 C 0.91900 4.12000 -1.23900 C -2.02800 3.94500 -0.68000 H 0.25200 1.23700 -2.64500 H -0.83600 2.46300 -3.32800 H -1.50100 1.11200 -2.38700 H 1.78500 3.62200 -1.70200 H 1.26300 4.60200 -0.31000 H 0.58700 4.91500 -1.92600 H -2.22400 4.54800 -1.58100 H -1.90100 4.64400 0.16300 H -2.92400 3.34000 -0.47000 C 4.08600 -0.90500 -0.47700 C 3.57200 -0.25600 -1.60300 C 4.43700 -0.16500 0.65500 C 3.40400 1.13200 -1.59500 C 4.27300 1.22200 0.66200 C 3.75100 1.87100 -0.46000 C -4.16500 0.68600 0.45500 C -4.01000 0.68200 -0.93300 C -4.07300 -0.51100 1.17200 C -3.82100 -1.71000 0.49800 C -3.76000 -0.51700 -1.60400 C -3.66400 -1.71300 -0.89000 H 4.20000 -1.99000 -0.47700 H 3.29500 -0.83600 -2.48600 H 2.99400 1.63800 -2.47000 H 4.54400 1.79900 1.54700 H 4.83100 -0.67300 1.53600 H -3.45500 -2.64700 -1.41400 H -3.63300 -0.51800 -2.68800 H -4.07400 1.61700 -1.49300 H -4.18900 -0.50700 2.25700 845 H -4.35200 1.62400 0.98000 H 3.60300 2.95200 -0.44800 H -3.74200 -2.64500 1.05600 846 Table C.2.48. Atomic coordinates and single point energies for A24-2. G = –2412.237025 GSP = –2414.27809 Na -1.48100 0.50100 -0.31000 Na 1.33900 0.15000 -0.73300 N 0.24700 2.15300 -0.11700 N -0.34900 -1.50400 -0.64900 Si -0.09000 2.81800 1.41900 C -0.51900 4.67100 1.37000 C 1.24500 2.65800 2.77200 C -1.60700 1.92900 2.15300 C 0.79700 3.04400 -1.12600 C 2.25700 3.44500 -0.85400 H 2.67400 4.07800 -1.65500 H 2.88000 2.54000 -0.75300 H 2.33800 4.00200 0.09300 C 0.68500 2.44100 -2.53200 H 0.23100 4.00500 -1.17400 H 0.97600 3.16600 -3.30900 H -0.34900 2.11600 -2.72800 H 1.34100 1.56100 -2.66000 H 0.34300 5.27800 1.05200 H -0.82200 5.02300 2.36900 H -1.34500 4.88200 0.67300 H 2.20200 3.09400 2.44400 H 1.41800 1.60100 3.03200 H 0.93800 3.17800 3.69400 847 H -2.50300 2.08800 1.52900 H -1.83700 2.29400 3.16600 H -1.42900 0.84400 2.23700 C -0.81500 -2.09300 -1.89200 C -0.78600 -1.06300 -3.02900 C -2.23600 -2.66600 -1.78700 H -1.47700 -0.22900 -2.80600 H -1.09900 -1.50000 -3.99000 H 0.22000 -0.63400 -3.15700 H -0.17100 -2.94400 -2.22400 H -2.59500 -3.06900 -2.74800 H -2.92800 -1.87400 -1.45200 H -2.27300 -3.47500 -1.04300 Si 0.24100 -2.48000 0.61500 C 0.49300 -1.36700 2.13700 C 1.93800 -3.26600 0.23200 C -0.84200 -3.93100 1.20300 H 0.98200 -0.40900 1.88400 H 1.10000 -1.86500 2.91000 H -0.47700 -1.12100 2.59700 H 2.68000 -2.48600 -0.01200 H 1.86900 -3.94300 -0.63500 H 2.33300 -3.85000 1.07900 H -0.40700 -4.40500 2.09800 H -0.92900 -4.70700 0.42700 H -1.86100 -3.59600 1.45700 O 2.72100 -0.58000 -2.52100 O 3.54500 0.16100 -0.03000 C 3.98900 0.00700 -2.33300 C 4.52200 -0.28900 -0.94500 H 3.85300 1.09300 -2.44700 H 4.70100 -0.33800 -3.10400 H 5.47300 0.25300 -0.78800 H 4.72300 -1.36300 -0.79800 C 2.75800 -1.92800 -2.93300 H 3.12400 -2.00400 -3.97100 H 1.73500 -2.31700 -2.87400 H 3.40000 -2.53700 -2.27600 C 3.97300 0.42400 1.28900 C 4.20600 -0.84500 2.08900 H 4.87900 1.05800 1.26300 H 3.17100 1.01300 1.75800 O 5.28200 -1.61400 1.61300 C 6.54100 -1.17000 2.03000 H 6.61800 -1.15600 3.13300 H 6.78100 -0.15700 1.65800 848 H 7.29000 -1.86800 1.63500 H 3.30800 -1.47400 2.01500 H 4.35300 -0.58100 3.15500 O -3.71200 -0.09000 0.35800 O -2.97200 1.77400 -1.53700 C -2.91900 3.16000 -1.28500 H -3.40800 3.72100 -2.10000 H -1.85800 3.43300 -1.22100 H -3.40500 3.42000 -0.32800 C -4.26200 1.21100 -1.52000 C -4.68500 0.80700 -0.12100 H -4.75800 1.68800 0.54800 H -5.67400 0.32300 -0.17500 H -5.00000 1.90600 -1.95800 H -4.22200 0.30800 -2.14800 C -3.91300 -0.59100 1.66100 C -5.31000 -1.17000 1.87800 H -3.74100 0.19800 2.41600 H -3.13300 -1.35700 1.79500 O -5.76100 -1.96400 0.82300 H -6.04400 -0.35900 1.98800 H -5.30000 -1.73100 2.83500 C -5.02200 -3.14200 0.63700 H -3.98700 -2.93300 0.32200 H -5.51400 -3.72000 -0.15400 H -5.00000 -3.75000 1.56100 849 Table C.2.49. Atomic coordinates and single point energies for A22-2. G = –2105.052815 GSP = –2106.737680 Na -1.52400 0.27300 0.26900 Na 1.36000 -0.31800 0.08300 N -0.45200 -1.81500 0.07900 N 0.30100 1.77600 0.24100 Si -1.15300 -2.48600 -1.32600 C -2.12600 -4.08700 -0.99900 C 0.03200 -2.90700 -2.76100 C -2.36000 -1.21900 -2.07500 C -0.04000 -2.67200 1.17000 C 1.28800 -3.40600 0.90300 H 1.60400 -4.03300 1.75400 H 2.09500 -2.68300 0.68800 H 1.19100 -4.05500 0.01900 C 0.06000 -1.87300 2.47800 H -0.78400 -3.48100 1.36900 H 0.35300 -2.50400 3.33300 H -0.90800 -1.40600 2.71600 H 0.79800 -1.05600 2.39000 H -2.62000 -4.43500 -1.91900 H -2.90400 -3.94400 -0.23300 H -1.46200 -4.89500 -0.65300 H 0.47000 -1.98300 -3.17400 H -0.49800 -3.41200 -3.58400 H 0.85500 -3.56300 -2.43500 H -3.20000 -1.04500 -1.38300 850 H -2.76900 -1.57400 -3.03300 H -1.85600 -0.25900 -2.27900 C 0.27000 2.26700 1.60900 C -0.85800 3.28100 1.86600 C 1.59900 2.85700 2.10100 H -0.69400 4.19000 1.26600 H -0.90700 3.57700 2.92700 H -1.83200 2.85900 1.57800 H 0.06100 1.40800 2.28900 H 1.54700 3.16400 3.15700 H 1.86800 3.74600 1.50500 H 2.40400 2.11400 2.00100 Si 0.85300 2.66600 -1.10400 C 0.22500 1.77600 -2.66100 C 2.75100 2.72900 -1.35700 C 0.34600 4.50000 -1.24800 H 3.15300 1.71400 -1.51400 H 3.26800 3.18000 -0.49500 H 3.00500 3.32700 -2.24800 H 0.69400 4.90900 -2.21000 H 0.81100 5.09800 -0.44800 H -0.74100 4.66200 -1.18900 O 3.36000 -0.84300 -0.99500 O 3.16600 -0.37500 1.72200 C 4.53500 -0.60900 -0.26200 C 4.16900 0.23500 0.94200 H 5.27900 -0.06700 -0.87700 H 4.98700 -1.57400 0.04000 H 3.75700 1.19400 0.59600 H 5.06800 0.44400 1.54900 C 3.55200 -1.65800 -2.12600 C 3.64100 -1.34400 2.62400 H 2.77600 -1.74100 3.16900 H 4.34600 -0.89200 3.34200 H 4.14000 -2.18100 2.10700 H 4.24300 -1.18000 -2.84000 H 2.57700 -1.80500 -2.60200 H 3.95900 -2.64100 -1.83400 O -3.55800 -0.69800 1.04600 O -3.34700 1.73000 0.01600 C -3.58200 -1.84800 1.85300 C -4.63300 0.18100 1.24000 C -4.62800 1.16900 0.09400 C -3.20100 2.70300 -0.98900 H -4.48600 -2.45000 1.65200 H -3.56100 -1.58400 2.92500 851 H -2.68800 -2.43100 1.59800 H -4.52800 0.71000 2.20600 H -5.59400 -0.36500 1.24900 H -5.39200 1.95000 0.26900 H -4.87400 0.65100 -0.85200 H -2.16000 3.04600 -0.95000 H -3.87800 3.55700 -0.81300 H -3.41300 2.27500 -1.98500 H -0.86800 1.85900 -2.76600 H 0.46900 0.70000 -2.61800 H 0.68200 2.18400 -3.57600 852 Table C.2.50. Atomic coordinates and single point energies for A34-2. G = –1915.080675 GSP = –1916.53946 Na 1.50200 -0.04200 -0.33600 Na -1.38900 -0.10900 0.00700 N 0.10100 -1.89900 -0.24300 N 0.05300 1.75700 -0.05700 Si 0.05900 -2.82000 1.19600 C -0.57500 -4.59300 0.96200 C -1.12800 -2.00100 2.44600 C 1.73300 -2.98900 2.08600 C -0.04800 -2.53300 -1.54000 C -1.45700 -2.32800 -2.11900 H -1.60500 -2.84800 -3.08000 H -1.64400 -1.25300 -2.29700 H -2.21100 -2.69800 -1.40500 C 0.98700 -2.01500 -2.54800 H 0.10300 -3.63300 -1.49000 H 0.88700 -2.48800 -3.53700 H 2.00500 -2.20800 -2.17700 H 0.86500 -0.92500 -2.69400 H -1.55800 -4.60800 0.46600 H -0.67900 -5.09600 1.93600 H 0.11700 -5.19500 0.35200 H -2.16600 -2.12400 2.09500 H -0.93800 -0.92200 2.58000 H -1.06400 -2.46000 3.44400 H 2.41000 -3.62900 1.49900 853 H 1.61800 -3.44800 3.08100 H 2.23000 -2.01400 2.22400 C -0.39600 2.65000 -1.10700 C -1.10500 1.86900 -2.22000 C 0.75200 3.44400 -1.75000 H -0.41500 1.11600 -2.63700 H -1.43800 2.52000 -3.04300 H -1.99400 1.33900 -1.84200 H -1.13100 3.40500 -0.73700 H 0.39400 4.14000 -2.52600 H 1.45700 2.73700 -2.22100 H 1.30300 4.02100 -0.99500 Si 0.40600 2.32600 1.51500 C 1.47100 0.99900 2.37000 C -1.12200 2.56400 2.63000 C 1.34500 3.97200 1.65800 H 0.99900 0.00400 2.32800 H 1.62700 1.23400 3.43400 H 2.47000 0.91700 1.91000 H -1.70900 1.63400 2.71600 H -1.78500 3.34500 2.22100 H -0.84000 2.87300 3.64900 H 1.52400 4.22000 2.71700 H 0.76400 4.79800 1.21800 H 2.32000 3.93900 1.14800 N -3.80700 0.34200 -0.08400 N 3.82300 0.49300 -0.78000 C 3.96900 0.40900 -2.22600 H 5.01300 0.61100 -2.54600 H 3.31500 1.15300 -2.70400 H 3.67800 -0.58300 -2.59500 C 4.09100 1.85400 -0.33500 H 3.99400 1.92200 0.75700 H 3.36400 2.54400 -0.78500 H 5.11500 2.18000 -0.61300 C 4.68400 -0.46000 -0.07900 C 4.35800 -1.91500 -0.37900 H 4.55800 -0.27800 1.00100 H 5.75100 -0.25200 -0.31200 H 3.29200 -2.12800 -0.19700 H 4.94300 -2.57200 0.27900 H 4.59500 -2.19100 -1.41600 C -3.91300 1.78300 0.11400 C -4.28100 -0.37500 1.09100 C -4.45200 -0.11400 -1.32000 C -5.95700 0.12600 -1.42600 854 H -3.61300 2.31200 -0.80200 H -3.23600 2.09800 0.92100 H -4.93900 2.10200 0.38200 H -5.33500 -0.14500 1.34100 H -3.66900 -0.10500 1.96500 H -4.19000 -1.45900 0.92900 H -3.94200 0.38300 -2.16100 H -4.24100 -1.19000 -1.42200 H -6.20400 1.19700 -1.38200 H -6.51400 -0.38900 -0.63100 H -6.32300 -0.25800 -2.38800 855 Table C.2.51. Atomic coordinates and single point energies for A3-2. G = –2072.018856 GSP = –2073.65095 Na -1.51200 0.07500 -0.12400 Na 1.34600 0.41400 -0.11600 N -0.33700 2.05600 -0.14200 N 0.14300 -1.59500 -0.16900 Si -0.39400 2.65400 1.45500 C -1.21100 4.35200 1.65400 C 1.31700 2.80900 2.29200 C -1.39800 1.40800 2.48700 C -0.14400 2.95500 -1.26400 C 1.30300 2.93700 -1.78500 H 1.47000 3.65500 -2.60300 H 1.55300 1.93400 -2.18100 H 2.00400 3.17200 -0.97000 C -1.09800 2.61900 -2.41500 H -0.35300 4.01200 -0.98900 H -0.96700 3.28900 -3.28000 H -2.14200 2.69300 -2.07500 H -0.92000 1.58500 -2.75600 H -0.61900 5.14500 1.17100 H -1.30700 4.61400 2.72000 H -2.21700 4.36500 1.20700 H 1.92400 3.56100 1.76100 H 1.87600 1.85700 2.26900 H 1.24900 3.11800 3.34700 H -2.45700 1.43300 2.17900 856 H -1.36200 1.63400 3.56400 H -1.02600 0.37600 2.37000 C 0.17400 -2.23800 -1.47400 C -0.09400 -1.22700 -2.59300 C -0.81300 -3.40400 -1.63400 H -1.13100 -0.84900 -2.53400 H 0.03200 -1.67200 -3.59200 H 0.57900 -0.35600 -2.52600 H 1.18100 -2.67000 -1.68600 H -0.78900 -3.82600 -2.65200 H -1.84000 -3.05600 -1.42700 H -0.59100 -4.21800 -0.92900 Si 0.45800 -2.55000 1.22000 C 0.97500 -1.43400 2.68600 C 1.85400 -3.81500 0.93200 C -0.99600 -3.55500 1.92900 H 1.24600 -0.40400 2.40300 H 1.84400 -1.86400 3.20800 H 0.16400 -1.35400 3.42600 H 2.77700 -3.33300 0.57200 H 1.56400 -4.56600 0.18100 H 2.09600 -4.35400 1.86200 H -0.67300 -4.13500 2.80900 H -1.42800 -4.25900 1.20200 H -1.79900 -2.87600 2.26000 N 3.75200 0.19000 -0.33200 N -3.89600 -0.28600 -0.14400 C -4.06500 -0.45000 -1.59200 C -3.92900 -1.52700 0.63200 H -3.64800 -1.25900 1.66400 H -3.12000 -2.17900 0.26100 C -5.23800 -2.31400 0.65600 C -4.68000 0.79800 0.44000 C -4.29500 2.16100 -0.11700 H -4.49100 0.78300 1.52600 H -5.76900 0.63600 0.31700 H -3.21100 2.33600 -0.00900 H -4.82900 2.95700 0.42100 H -4.54800 2.25500 -1.18300 C 3.63500 -0.62100 -1.54100 C 4.01600 -0.54300 0.90500 C 4.42100 1.48100 -0.47300 C 5.93600 1.52200 -0.26700 H 2.92800 -0.11700 -2.22800 H 3.14400 -1.56400 -1.24700 C 4.90900 -0.91100 -2.33700 857 H 4.16800 1.86700 -1.47400 H 3.96100 2.18300 0.24600 H 6.46900 0.84000 -0.94400 H 6.20300 1.25700 0.76600 H 6.30500 2.54100 -0.45000 H -3.48800 0.34000 -2.10600 C -5.49500 -0.41900 -2.13500 H -3.58500 -1.40400 -1.86500 H 4.12100 0.20500 1.70800 C 5.20400 -1.50600 0.93000 H 3.11600 -1.13200 1.15200 H 6.15500 -1.01200 0.69000 H 5.05600 -2.33300 0.21900 H 5.29100 -1.95200 1.93100 H 5.33900 0.01500 -2.74500 H 4.66900 -1.56500 -3.18800 H 5.67700 -1.40800 -1.73100 H -5.95700 0.56800 -1.99600 H -6.14000 -1.16500 -1.65300 H -5.48100 -0.62700 -3.21400 H -6.08600 -1.68500 0.96500 H -5.15600 -3.14400 1.37200 H -5.46800 -2.74900 -0.32700 858 Table C.2.52. Atomic coordinates and single point energies for A10-2. G = –3127.169958 GSP = –3129.52539 Na 1.47800 0.57700 -0.76400 Na -1.35800 0.62300 -0.07900 N 0.06100 -1.24900 -0.51100 N 0.11600 2.41600 -0.36400 Si -0.08900 -2.16200 0.91800 C -0.53700 -3.98800 0.62500 C -1.42500 -1.42700 2.07600 C 1.47900 -2.16100 1.99100 C -0.21500 -1.83300 -1.80800 C -1.71100 -1.79900 -2.16500 H -1.93400 -2.29600 -3.12400 H -2.05800 -0.75400 -2.23900 H -2.29900 -2.28600 -1.37100 C 0.56900 -1.11800 -2.91900 H 0.09000 -2.90400 -1.86000 H 0.38400 -1.56000 -3.91000 H 1.65300 -1.15700 -2.72600 H 0.26200 -0.05700 -2.97200 H -1.44100 -4.10300 0.00700 H -0.70500 -4.51100 1.57900 H 0.28200 -4.50500 0.10100 H -2.38900 -1.30500 1.55500 H -1.12600 -0.43000 2.44600 H -1.58500 -2.05700 2.96700 859 H 2.27200 -2.78600 1.55200 H 1.27900 -2.52600 3.01100 H 1.87500 -1.13600 2.07100 C -0.37600 3.29300 -1.41300 C -1.67700 2.75500 -2.02500 C 0.66200 3.49100 -2.52800 H -1.49500 1.75300 -2.45900 H -2.05700 3.39800 -2.83400 H -2.46300 2.66400 -1.25800 H -0.62300 4.31300 -1.03400 H 0.31100 4.17600 -3.31700 H 0.88900 2.51700 -2.99800 H 1.59800 3.88700 -2.11000 Si 0.78900 3.12500 1.03200 C 1.66900 1.75400 2.01900 C -0.49200 3.91100 2.19700 C 2.09500 4.46900 0.70400 H 0.97900 0.93000 2.26800 H 2.06500 2.14700 2.97000 H 2.52000 1.32600 1.45900 H -1.20500 3.14700 2.54900 H -1.07100 4.68000 1.66100 H -0.03500 4.38700 3.07900 H 2.48300 4.89900 1.64200 H 1.67300 5.29500 0.10900 H 2.94400 4.05100 0.13900 O -3.53400 0.55300 0.05600 P -4.85900 -0.14900 0.11000 N -5.02000 -1.58000 0.95500 N -5.31900 -0.59000 -1.43800 N -5.96100 0.85600 0.87400 C -5.17100 -1.59500 2.40200 C -4.52600 -2.83700 0.41400 C -6.49100 -1.39300 -1.72200 C -4.81700 0.15900 -2.57800 C -5.68200 2.27300 1.02400 C -7.35800 0.49200 0.97800 H -5.48700 -0.61000 2.76300 H -4.22100 -1.86000 2.89500 H -5.93100 -2.34000 2.69000 H -4.41100 -2.76900 -0.67300 H -5.23800 -3.64700 0.64500 H -3.54700 -3.10300 0.85100 H -6.78700 -1.97100 -0.83700 H -6.26900 -2.10400 -2.53500 H -7.34900 -0.77400 -2.04100 860 H -3.95600 0.76600 -2.27600 H -5.59400 0.82500 -2.99500 H -4.49500 -0.53400 -3.37100 H -7.47200 -0.60000 0.96300 H -7.96500 0.92000 0.15800 H -7.77100 0.86200 1.93100 H -4.60400 2.44800 0.94600 H -6.02700 2.61700 2.01300 H -6.19800 2.87600 0.25400 H 5.90600 1.87200 0.62800 H 5.47900 -0.65700 3.33100 H 6.23900 -3.24700 -0.52100 H 8.11800 0.63500 -0.70900 H 2.58000 -2.14500 -0.81400 H 5.05700 0.33500 -2.72200 P 4.76500 -0.44700 -0.15200 H 6.67800 1.07700 -2.67700 C 3.50300 -2.74200 -0.80500 C 5.65200 -2.93500 0.36300 C 6.09900 0.17200 -2.42600 N 4.52300 -2.09600 0.01100 N 6.16600 -0.08000 -0.99800 C 4.65600 -0.57300 2.60200 C 5.58300 1.43700 1.58200 C 7.50500 -0.25200 -0.47600 O 3.59900 0.16800 -0.86800 N 5.14100 0.06400 1.38900 H 3.84000 -2.91300 -1.84500 H 6.32300 -2.40400 1.05300 H 7.47900 -0.37000 0.61500 H 4.26600 -1.57200 2.38000 H 6.43200 1.46600 2.28600 H 4.77000 2.06100 1.99100 H 3.84400 0.01800 3.06100 H 5.29500 -3.84200 0.87400 H 8.01000 -1.13300 -0.91300 H 3.26600 -3.72000 -0.35900 H 6.51500 -0.67000 -3.00800 861 Table C.2.53. Atomic coordinates and single point energies for A4-2. G = –2033.304438 GSP = –2034.90028 Na -1.36300 0.41500 -0.20500 Na 1.36300 -0.41600 -0.20600 N 0.53200 1.76400 -0.13900 N -0.53200 -1.76400 -0.13900 Si 1.10900 2.32200 1.37200 C 2.49200 3.61600 1.21600 C 1.83100 0.83000 2.31400 C -0.18900 3.07300 2.54700 C 0.46700 2.68100 -1.26300 C 0.11300 1.94000 -2.55600 H 0.14100 2.60300 -3.43400 H -0.91000 1.52300 -2.49800 H 0.80600 1.10300 -2.73300 C -0.53000 3.83300 -1.06600 H 1.45700 3.16200 -1.45000 H -0.57200 4.50000 -1.94200 H -0.26400 4.44200 -0.19000 H -1.54100 3.42300 -0.89500 H 3.30100 3.26000 0.55900 H 2.92900 3.85400 2.19800 H 2.11100 4.55600 0.78500 H 2.11000 1.10600 3.34300 H 2.73700 0.43900 1.82100 H 1.10300 0.00400 2.39400 862 H -0.68400 3.94400 2.09100 H 0.26500 3.40200 3.49600 H -0.96900 2.33400 2.79300 C -0.46700 -2.68100 -1.26300 C 0.53000 -3.83300 -1.06700 C -0.11300 -1.94000 -2.55600 H 1.54100 -3.42400 -0.89500 H 0.57200 -4.50000 -1.94200 H 0.26400 -4.44200 -0.19000 H -1.45700 -3.16200 -1.45100 H 0.91000 -1.52300 -2.49800 H -0.80600 -1.10300 -2.73300 H -0.14100 -2.60200 -3.43400 Si -1.10900 -2.32300 1.37200 C -1.83100 -0.83100 2.31400 C 0.18800 -3.07400 2.54700 C -2.49200 -3.61700 1.21600 H -2.73700 -0.43900 1.82100 H -1.10300 -0.00500 2.39400 H -2.11100 -1.10700 3.34200 H -0.26500 -3.40400 3.49500 H 0.96900 -2.33500 2.79300 H 0.68400 -3.94500 2.09000 H -2.11200 -4.55600 0.78400 H -3.30100 -3.26000 0.55800 H -2.93000 -3.85500 2.19800 O 3.52000 -1.03600 -0.19400 O -3.52000 1.03600 -0.19400 C -3.91000 2.07900 0.66900 H -4.55600 1.71800 1.48500 H -4.42500 2.88800 0.12700 H -2.99000 2.48900 1.11000 C -4.54300 0.26000 -0.84200 C -5.34700 -0.52800 0.19200 C -3.76800 -0.69600 -1.74400 C -5.44800 1.16800 -1.67200 H -4.67700 -1.15100 0.80200 H -6.06200 -1.18700 -0.31900 H -5.92200 0.13200 0.85600 C 3.91000 -2.07900 0.66800 C 4.54300 -0.25900 -0.84200 C 5.34700 0.52800 0.19200 H 4.42400 -2.88800 0.12600 H 2.99100 -2.48800 1.11000 H 4.55600 -1.71800 1.48500 C 3.76900 0.69600 -1.74400 863 C 5.44800 -1.16700 -1.67200 H 5.92200 -0.13200 0.85700 H 4.67700 1.15200 0.80300 H 6.06200 1.18800 -0.31800 H 6.06800 -1.81800 -1.03800 H 6.12700 -0.55700 -2.28400 H 4.84300 -1.79600 -2.34100 H 4.45500 1.36800 -2.27600 H 3.06900 1.31200 -1.15300 H 3.19400 0.12900 -2.49200 H -3.19400 -0.12800 -2.49200 H -4.45500 -1.36700 -2.27700 H -3.06900 -1.31100 -1.15300 H -6.06700 1.81900 -1.03900 H -6.12600 0.55800 -2.28500 H -4.84300 1.79700 -2.34200 864 Table C.2.54. Atomic coordinates and single point energies for A20-2. G = –2528.454521 GSP = –2530.60395 Na -1.43600 0.79800 0.01100 Na 1.33100 -0.61200 0.28200 N 0.83900 1.73700 0.13300 N -0.96700 -1.47800 0.36700 Si 1.42000 2.37900 1.61500 C 3.01300 3.43800 1.52400 C 1.74700 0.95300 2.83300 C 0.28300 3.55200 2.60500 C 0.90200 2.54700 -1.07700 C 2.29600 2.62700 -1.72300 H 2.29300 3.30200 -2.59400 H 2.60300 1.62700 -2.07300 H 3.05200 2.99000 -1.01500 C -0.05700 2.01900 -2.15300 H 0.60400 3.60800 -0.88500 H 0.05100 2.56600 -3.10300 H -1.11200 2.11800 -1.85400 H 0.16600 0.95700 -2.34900 H 3.88700 2.94000 1.07800 H 3.29300 3.75900 2.54000 H 2.82300 4.35100 0.93600 H 2.35400 0.13600 2.41100 H 0.80900 0.52000 3.21000 H 2.29600 1.33500 3.70800 H 0.11100 4.50700 2.08400 H 0.77300 3.78900 3.56400 H -0.69600 3.10500 2.83500 865 C -1.00700 -2.48900 -0.66900 C -0.55200 -1.89600 -2.00900 C -2.37500 -3.15000 -0.88600 H -1.23600 -1.08200 -2.30100 H -0.54900 -2.64400 -2.81700 H 0.46500 -1.47000 -1.94900 H -0.31800 -3.33800 -0.45200 H -2.32300 -3.92800 -1.66500 H -3.12800 -2.40900 -1.19800 H -2.73000 -3.62500 0.03800 Si -1.36700 -1.69600 2.01300 C -1.84400 0.02600 2.68600 C 0.03200 -2.35800 3.13300 C -2.81200 -2.84300 2.50200 H -1.09500 0.79600 2.43900 H -1.94800 0.02200 3.78200 H -2.81200 0.34200 2.26400 H 0.98200 -1.81500 3.00900 H 0.22100 -3.42400 2.92500 H -0.25700 -2.27800 4.19300 H -2.96400 -2.77100 3.59200 H -2.58800 -3.89600 2.27400 H -3.76500 -2.58500 2.01700 N 2.81400 -2.80800 -0.48000 N 4.26300 -0.65700 0.89700 C 2.37500 -3.57000 -1.63900 H 2.64300 -3.03400 -2.56200 H 1.28800 -3.70700 -1.62000 H 2.85200 -4.57200 -1.67100 C 4.26700 -2.69300 -0.53300 C 4.89500 -1.93500 0.62200 H 4.54600 -2.20200 -1.47600 H 4.72900 -3.70400 -0.55700 H 5.97300 -1.82000 0.38700 H 4.83900 -2.53500 1.54500 C 2.37500 -3.44600 0.75200 H 2.81200 -4.46000 0.87600 H 1.28000 -3.53500 0.75400 H 2.66300 -2.83500 1.61900 C 4.87700 -0.02700 2.05100 H 4.69200 -0.63700 2.94900 H 4.43700 0.96500 2.21900 H 5.97600 0.09000 1.94800 C 4.14900 0.24100 -0.24700 C 5.45200 0.74900 -0.87000 H 3.54900 -0.26300 -1.02400 866 H 3.54900 1.10000 0.08000 N 6.06100 -0.19000 -1.80200 C 7.48300 0.03100 -1.94900 C 5.39700 -0.17500 -3.08800 H 5.50200 0.80300 -3.60600 H 4.32200 -0.37600 -2.97500 H 5.81700 -0.95600 -3.73900 H 7.98300 -0.06700 -0.97500 H 7.72100 1.03700 -2.36000 H 7.91100 -0.72000 -2.62800 H 6.17300 0.95500 -0.06400 H 5.25700 1.72700 -1.36500 N -4.07700 0.81300 -0.31800 N -2.82700 3.40300 -0.77300 C -2.30500 3.61700 0.56000 C -2.38100 4.43700 -1.68300 H -2.64100 4.57800 1.00700 H -1.20800 3.61400 0.52100 H -2.61700 2.80800 1.23800 H -1.28400 4.50100 -1.66400 H -2.79200 5.43500 -1.42100 H -2.69300 4.19400 -2.71000 C -4.26600 3.25700 -0.81300 C -4.78500 2.05500 -0.03700 H -4.71900 2.24100 1.04800 H -5.86800 1.97800 -0.27000 H -4.78300 4.16200 -0.42400 H -4.56300 3.16400 -1.87000 C -3.95000 0.54000 -1.74400 H -3.49900 -0.45200 -1.87800 H -3.30300 1.29600 -2.21300 H -4.92300 0.53200 -2.27400 C -4.67600 -0.30600 0.41500 C -6.03000 -0.79900 -0.12000 H -4.78900 0.01200 1.46300 H -3.95500 -1.13900 0.40500 N -5.88800 -1.82700 -1.14100 H -6.58000 0.05100 -0.55500 H -6.65700 -1.16200 0.72200 C -6.95100 -1.80100 -2.11900 C -5.75000 -3.14100 -0.55200 H -6.76800 -2.56700 -2.88700 H -6.98500 -0.82200 -2.62000 H -7.95200 -1.99800 -1.67700 H -4.95800 -3.13700 0.20900 H -5.46800 -3.87700 -1.32000 867 H -6.69100 -3.48200 -0.06500 868 Table C.2.55. Atomic coordinates and single point energies for A5-2. G = –1720.378668 GSP = –1721.618703 Na 1.32400 0.87100 0.30300 Na -1.26100 -0.33400 0.59200 O 3.57500 1.01400 0.35100 C 4.18000 -0.19200 0.83000 C 4.48900 1.75000 -0.46400 C 5.35200 -0.43600 -0.11000 C 5.81600 0.99500 -0.38700 H 4.52500 -0.03900 1.86700 H 3.41300 -0.98100 0.81700 H 4.55500 2.78200 -0.09200 H 4.09800 1.77600 -1.49600 H 6.42000 1.36600 0.45400 H 6.40900 1.09700 -1.30500 H 5.00000 -0.91600 -1.03600 H 6.12800 -1.07200 0.33500 N 0.81400 -1.39900 0.45200 N -0.77000 1.91000 0.32500 Si 1.24000 -2.10800 -1.04300 Si -1.44700 2.32400 -1.18700 C -3.02200 3.38400 -1.09600 C -0.25800 3.27300 -2.32900 C -1.91500 0.71100 -2.08600 C 0.96600 -2.14500 1.68600 C -0.76600 2.91500 1.37600 C -0.12100 -3.21200 1.89200 869 H -1.12000 -2.74100 1.93100 H 0.01900 -3.78000 2.82600 H -0.12400 -3.92700 1.05400 C 0.98300 -1.19900 2.89200 H 0.04000 -0.62600 2.95200 H 1.80700 -0.47200 2.80500 H 1.10500 -1.73700 3.84500 H 1.93600 -2.69400 1.71700 H -2.72300 0.17800 -1.55500 H -1.05600 0.02600 -2.17200 H -2.27200 0.90900 -3.10800 H -2.83400 4.32700 -0.55800 H -3.83600 2.86300 -0.56900 H -3.38200 3.64500 -2.10400 H -0.70900 3.54200 -3.29700 H 0.64700 2.67600 -2.53300 H 0.06600 4.20400 -1.83600 C 0.59200 2.98400 2.08900 C -1.87200 2.65400 2.40800 H 0.82700 2.01000 2.55400 H 0.60900 3.73900 2.88900 H 1.39100 3.23900 1.37200 H -0.94700 3.94100 0.98200 H -1.71500 1.66500 2.87500 H -2.85300 2.64200 1.91000 H -1.89500 3.41000 3.21000 C 1.86500 -0.72600 -2.19400 C 2.62700 -3.40000 -0.90400 C -0.16800 -2.98200 -1.98400 H -1.00400 -2.29100 -2.18400 H -0.56200 -3.82700 -1.39500 H 0.17100 -3.38100 -2.95300 H 3.52100 -2.99500 -0.40200 H 2.93300 -3.75700 -1.90000 H 2.29400 -4.27600 -0.32500 H 1.13100 0.09100 -2.29900 H 2.79700 -0.29300 -1.79300 H 2.07600 -1.09600 -3.20900 O -3.33400 -1.16200 0.70000 C -4.47500 -0.29900 0.73000 C -3.64900 -2.39200 0.04900 C -5.60400 -1.07100 0.04200 C -4.83800 -2.06100 -0.84000 H -5.42500 -2.94600 -1.11500 H -4.49300 -1.57200 -1.76400 H -6.20600 -1.61600 0.78500 870 H -6.27600 -0.41300 -0.52200 H -4.70600 -0.03900 1.77400 H -4.21800 0.62900 0.19300 H -2.75700 -2.73200 -0.49600 H -3.91200 -3.15500 0.80300 Table C.2.56. Atomic coordinates and single point energies for A6-2. 871 G = –2184.530824 GSP = –2186.29512 Na 1.12900 -0.15800 -0.14300 Na -1.68100 0.45800 -0.48100 N -0.02100 1.89600 0.26300 N -0.66400 -1.58700 -0.82400 Si 0.10300 2.21800 1.93700 Si -1.26400 -2.58900 0.41900 C -2.48600 -3.94300 -0.12500 C 0.08000 -3.51500 1.40000 C -2.17600 -1.48500 1.67600 C -0.00900 3.00100 -0.67600 C -0.41700 -2.14400 -2.14200 C -1.22500 3.93300 -0.55500 H -2.15600 3.35800 -0.71000 H -1.20000 4.75100 -1.29300 H -1.27900 4.38300 0.44800 C 0.08600 2.49100 -2.11800 H -0.82400 1.93000 -2.40300 H 0.94300 1.80900 -2.21800 H 0.19800 3.31200 -2.84400 H 0.88800 3.65200 -0.52900 H -3.08600 -1.04800 1.22800 H -1.54000 -0.65400 2.02500 H -2.48800 -2.05000 2.56700 H -2.04400 -4.57400 -0.91300 H -3.42400 -3.52600 -0.52400 H -2.74200 -4.60000 0.72100 C 0.74100 -1.42100 -2.83900 872 C -1.65900 -2.06700 -3.04200 H 0.50800 -0.34500 -2.91100 H 0.91900 -1.80000 -3.85800 H 1.67800 -1.52900 -2.27200 H -0.12700 -3.22100 -2.10200 H -1.95100 -1.00900 -3.17000 H -2.50300 -2.59500 -2.57600 H -1.48700 -2.49800 -4.04100 C 1.00300 0.75900 2.76000 C 1.12300 3.77200 2.34000 C -1.54800 2.41600 2.86900 H -2.15000 1.49500 2.79400 H -2.14100 3.24200 2.44600 H -1.39400 2.62400 3.94000 H 2.13000 3.71500 1.89500 H 1.24400 3.89100 3.42800 H 0.64400 4.68600 1.95600 O -3.90700 0.67100 -0.64900 C -4.68400 -0.42700 -1.13800 C -4.64100 1.42500 0.31600 C -6.06500 -0.27300 -0.50000 C -5.74200 0.48400 0.79000 H -6.60300 1.01700 1.21400 H -5.34900 -0.20400 1.55300 H -6.71800 0.33700 -1.14200 H -6.55700 -1.23900 -0.33100 H -4.70600 -0.39100 -2.23600 H -4.19000 -1.36400 -0.83400 H -3.95000 1.74200 1.11100 H -5.06200 2.32600 -0.16200 H 4.06600 -1.06200 2.49700 H 2.44900 -1.67800 2.93300 C 3.26600 -1.76600 2.20400 H 4.57700 -3.42500 2.79900 C 3.80100 -3.18700 2.06000 O 2.77700 -1.41000 0.91300 H 2.97700 -3.90800 2.17000 H 5.28500 -2.68200 0.55700 C 4.30500 -3.17900 0.61700 C 3.23700 -2.33600 -0.07400 H 4.39900 -4.18000 0.17800 H 3.61400 -1.76200 -0.93200 H 2.38200 -2.95200 -0.40400 H 0.98500 0.82800 3.85800 H 2.05800 0.74600 2.44100 H 0.61300 -4.22300 0.74300 873 H -0.33000 -4.08600 2.24800 H 4.56100 2.76300 -3.23500 H 2.63400 0.80500 -3.27200 C 3.85300 2.45900 -2.45400 H 4.30800 0.35900 -2.83200 C 3.44600 0.99400 -2.55600 H 2.95900 3.09800 -2.52000 C 4.43400 2.50900 -1.04000 H 5.46000 2.11100 -1.03700 O 2.99400 0.64600 -1.25300 H 4.45600 3.51800 -0.61000 C 3.49000 1.57700 -0.28200 H 2.62600 2.11700 0.13900 H 3.98200 1.01100 0.52400 H 0.56100 -0.21500 2.48700 H 0.81700 -2.79300 1.78600 874 Table C.2.57. Atomic coordinates and single point energies for A7-2. G = –2416.593591 GSP = –2418.62177 Na -1.47200 -0.22100 -0.17400 Na 1.42200 0.11700 0.02400 N -0.11800 1.36900 -1.30600 N 0.13200 -1.71800 0.75600 Si -0.49300 0.99800 -2.93200 Si 0.48200 -3.11700 -0.16100 C 1.59500 -4.41100 0.69200 C -1.02900 -4.14500 -0.70500 C 1.33900 -2.60400 -1.77500 C 0.20300 2.74500 -0.98700 C -0.13000 -1.83200 2.17700 C 1.58300 3.18100 -1.50800 C 0.12500 2.99200 0.52500 H 0.91400 2.42000 1.04100 H -0.84800 2.65100 0.91400 H 0.26200 4.05600 0.78000 H 2.23700 -1.99200 -1.59400 H 0.66100 -2.01200 -2.40800 H 1.64100 -3.48900 -2.35700 H 1.13300 -4.75900 1.63100 H 2.59600 -4.02700 0.94200 H 1.72300 -5.29200 0.04300 C -1.04000 -0.68900 2.65000 C 1.15900 -1.83500 3.01200 H -0.58800 0.28200 2.37300 875 H -1.20200 -0.69500 3.73900 H -2.02900 -0.74300 2.16300 H -0.66700 -2.77600 2.44600 H 1.74000 -0.92800 2.78400 H 1.78300 -2.69900 2.74500 H 0.96300 -1.87100 4.09700 C -1.72700 -0.45700 -2.97500 C -1.33600 2.43400 -3.85600 C 0.95800 0.49300 -4.05900 H 1.48100 -0.39100 -3.66200 H 1.69000 1.31300 -4.13300 H 0.61900 0.25400 -5.08000 H -2.21400 2.81800 -3.31300 H -1.67000 2.10900 -4.85400 H -0.64300 3.27900 -3.99900 O 3.58000 -0.22000 -0.56200 C 4.18600 -1.21600 0.26400 C 4.30300 -0.05200 -1.77900 C 5.54200 -1.49900 -0.37700 C 5.23800 -1.25500 -1.85600 H 6.13000 -1.06200 -2.46600 H 4.70500 -2.11900 -2.28200 H 6.29500 -0.78000 -0.01900 H 5.90600 -2.51200 -0.16300 H 4.24000 -0.82800 1.29200 H 3.54400 -2.11300 0.27100 H 3.58500 0.01100 -2.60900 H 4.87000 0.89500 -1.73400 H -4.62600 -0.01400 -0.60200 H -4.97400 -1.57400 -1.40100 C -4.67500 -1.10200 -0.45100 H -6.16500 -0.66000 1.12400 C -5.61600 -1.51500 0.70500 O -3.37500 -1.54000 -0.08600 H -6.36200 -2.24100 0.35300 H -4.30200 -1.42500 2.45200 C -4.66700 -2.16500 1.72400 C -3.51500 -2.61100 0.83300 H -5.12900 -2.99300 2.27800 H -2.55000 -2.74800 1.33800 H -3.76600 -3.54400 0.29600 H -1.90500 -0.78500 -4.01100 H -2.70500 -0.16100 -2.55800 H -1.50100 -4.64800 0.15400 H -0.73000 -4.92800 -1.42100 H -5.17300 3.20500 2.14000 876 H -2.96500 1.59500 2.55200 C -4.27400 3.05200 1.53000 H -4.44900 0.89600 1.84300 C -3.66500 1.66400 1.70700 H -3.53700 3.82500 1.80000 C -4.53200 3.07800 0.02400 H -5.44200 2.50300 -0.21500 O -2.96100 1.40200 0.50000 H -4.64600 4.08800 -0.39000 C -3.29300 2.36200 -0.50500 H -2.44300 3.05000 -0.64200 H -3.45500 1.83500 -1.45700 H 2.91800 3.25600 4.40700 H 2.23000 3.72900 2.82800 C 2.85400 2.98400 3.34500 H 1.19000 1.54800 3.12900 C 2.28800 1.58800 3.12500 H 2.66200 0.88100 3.88600 C 4.21200 2.85900 2.65600 H 4.65600 3.82300 2.37500 O 2.75200 1.19300 1.83500 H 4.92200 2.33100 3.31000 C 3.86200 2.00300 1.44000 H 3.55700 2.62700 0.58400 H 4.68500 1.35200 1.11100 H -1.78900 -3.50800 -1.18700 H -1.38300 -1.34300 -2.41700 H -0.52300 3.45800 -1.44900 H 2.35200 2.47000 -1.16000 H 1.86200 4.19600 -1.17800 H 1.60600 3.16400 -2.60900 877 Table C.2.58. Atomic coordinates and single point energies for A18-2. G = –2494.058258 GSP = –2496.15461 Na -1.56500 0.03200 0.07400 Na 1.46800 0.16000 0.17800 N -0.06200 1.98200 -0.00900 N 0.03500 -1.71400 0.41300 Si 0.23700 2.75200 1.49500 C 1.04500 4.48000 1.48100 C 1.42000 1.63500 2.49200 C -1.25900 3.05500 2.63900 C -0.58800 2.73900 -1.13700 C 0.41300 3.70700 -1.79000 H -0.07200 4.31000 -2.57500 H 1.23200 3.14100 -2.26300 H 0.85500 4.39400 -1.05800 C -1.08500 1.80300 -2.24600 H -1.46500 3.36600 -0.84500 H -1.44900 2.36300 -3.12200 H -1.90600 1.14900 -1.91800 H -0.25200 1.15900 -2.57700 H 1.99600 4.52600 0.93200 H 1.24000 4.79300 2.52000 H 0.36500 5.22500 1.03900 H 1.54700 2.02600 3.51200 H 2.42200 1.61200 2.03000 H 1.05400 0.59800 2.59200 H -1.98400 3.74900 2.18500 878 H -0.91500 3.51100 3.58100 H -1.78900 2.12600 2.89500 C 0.83700 -2.45700 -0.54800 C 0.46200 -2.09600 -1.99100 C 0.79500 -3.98400 -0.41000 H -0.52600 -2.51500 -2.23900 H 1.19000 -2.49600 -2.71600 H 0.40700 -1.00300 -2.12600 H 1.91400 -2.18800 -0.46000 H 1.43100 -4.47300 -1.16500 H -0.23700 -4.35000 -0.53700 H 1.14300 -4.30800 0.58500 Si -0.45800 -2.31700 1.93300 C -1.59200 -0.99100 2.69200 C 0.88500 -2.65200 3.24800 C -1.50700 -3.91200 1.96200 H -1.13200 0.01100 2.67300 H -1.81800 -1.22400 3.74300 H -2.55700 -0.93700 2.16200 H 0.41800 -3.04100 4.16800 H 1.44000 -1.73900 3.51700 H 1.61700 -3.40300 2.91000 H -2.00400 -4.00900 2.94100 H -0.89700 -4.81500 1.81200 H -2.28900 -3.90500 1.18700 N 4.18400 -1.59500 0.12500 N 3.73700 1.08900 -0.54400 C 3.72900 -1.34600 1.48100 C 4.33900 -3.02400 -0.07600 H 4.42600 -1.75800 2.24400 H 2.74600 -1.81500 1.63200 H 3.63000 -0.26900 1.66900 H 4.39700 -3.27800 -1.14300 H 3.45900 -3.53600 0.33300 H 5.23800 -3.43000 0.43700 C 3.52500 2.52200 -0.38100 C 3.32700 0.66000 -1.87300 H 3.88500 2.84200 0.60900 H 2.45000 2.73700 -0.44500 H 4.04700 3.12700 -1.15000 H 3.32200 -0.43700 -1.93000 H 3.96000 1.06600 -2.68900 H 2.30400 1.02800 -2.06100 C 5.37900 -0.82100 -0.18500 C 5.10200 0.71200 -0.14300 C 6.07500 -1.20100 -1.49800 879 C 7.48400 -0.58200 -1.54600 C 7.54400 0.77500 -0.82700 C 6.19600 1.48100 -0.91600 H 6.13500 -1.01100 0.61500 H 5.47400 -0.85800 -2.35300 H 6.16400 -2.28900 -1.59400 H 7.78800 -0.46400 -2.59600 H 8.20800 -1.27400 -1.09000 H 8.33900 1.40200 -1.25600 H 7.80400 0.63400 0.23500 H 5.18000 1.02200 0.91400 H 5.90800 1.56600 -1.97700 H 6.26700 2.50700 -0.53000 H -3.91500 -2.92500 -1.12900 H -3.60800 -1.84300 -3.40300 H -4.83000 -0.17400 2.58500 H -4.45300 2.78900 0.41800 H -5.67000 -2.22300 -1.97400 H -7.11400 0.66900 0.96000 H -7.53400 -1.53900 -0.67400 H -8.54100 0.79500 -0.91400 C -3.31400 -2.07500 -0.75100 C -3.08200 -1.01300 -2.89100 C -3.73200 1.96400 0.25200 C -4.52100 0.80500 2.18800 C -5.93100 -1.16100 -2.09900 C -7.49800 0.55400 -1.16700 C -7.34600 -0.91100 -1.56100 C -6.58000 0.87300 0.02000 C -5.26200 0.05600 0.01700 C -4.85000 -0.27900 -1.42300 N -3.49800 -0.84500 -1.50800 N -4.18100 0.68500 0.78100 H -3.53900 1.88900 -0.82600 H -5.46300 -0.90300 0.52500 H -4.80500 0.67400 -1.98000 H -5.33900 1.53100 2.37200 H -3.27300 -0.08600 -3.45200 H -3.56800 -1.91100 0.30600 H -2.25300 -2.36700 -0.78100 H -2.00300 -1.21500 -2.93300 H -8.09300 -1.20400 -2.31200 H -3.64300 1.13800 2.75600 H -6.34400 1.94800 0.02600 H -2.78900 2.25100 0.73700 H -7.23600 1.18300 -2.03400 880 H -5.91300 -0.96600 -3.18200 881 Table C.2.59. Atomic coordinates and single point energies for A14-2. G = –2182.529942 GSP = –2184.29153 Na -1.51000 -0.03500 -0.15200 Na 1.52800 0.13900 -0.04100 N -0.10100 1.96900 -0.11200 N 0.12200 -1.77000 -0.08300 Si 0.23800 2.60200 1.44300 C 1.00300 4.34500 1.56600 C 1.49300 1.45200 2.30200 C -1.23100 2.73800 2.65100 C -0.77600 2.82100 -1.08400 C 0.10900 3.90700 -1.72300 H -0.48800 4.58100 -2.35900 H 0.88200 3.44900 -2.36000 H 0.61300 4.51700 -0.96300 C -1.37100 1.99800 -2.23400 H -1.63300 3.37200 -0.62800 H -1.82200 2.64000 -3.00700 H -2.15400 1.30100 -1.89900 H -0.57700 1.39800 -2.71000 H 1.93400 4.45700 0.99000 H 1.23000 4.56600 2.62100 H 0.29600 5.11400 1.21700 H 2.47100 1.49600 1.79300 H 1.16800 0.39900 2.35900 H 1.66000 1.78600 3.33700 H -1.95500 3.50000 2.32200 882 H -0.87700 3.03800 3.65000 H -1.75900 1.77800 2.75500 C 0.93000 -2.33400 -1.14500 C 0.41800 -1.91200 -2.52700 C 1.07200 -3.86200 -1.12900 H -0.52600 -2.43300 -2.74900 H 1.13500 -2.16000 -3.32800 H 0.22300 -0.82700 -2.55800 H 1.98100 -1.94900 -1.09700 H 1.71800 -4.21700 -1.94900 H 0.08200 -4.33300 -1.24200 H 1.50600 -4.21200 -0.17900 Si -0.24700 -2.53200 1.39700 C -1.42700 -1.36000 2.32300 C 1.18300 -2.86200 2.61800 C -1.16800 -4.20200 1.34700 H -1.01600 -0.34100 2.42400 H -1.62500 -1.73300 3.33900 H -2.40100 -1.28200 1.81400 H 1.86500 -2.00000 2.69400 H 1.77400 -3.74200 2.31900 H 0.78600 -3.06800 3.62500 H -1.56200 -4.44100 2.34800 H -0.50800 -5.02900 1.04700 H -2.01800 -4.18400 0.64700 N 4.02000 -1.19300 0.30600 N 3.42300 1.30700 -1.13100 C 4.75900 -0.77200 -0.87500 C 4.75800 0.73300 -1.09600 H 4.31800 -1.28700 -1.74400 H 5.82000 -1.10700 -0.81900 H 5.31700 0.95300 -2.03100 H 5.31900 1.22100 -0.28600 C 4.07200 -2.64100 0.41800 C 4.52800 -0.58300 1.52100 H 3.69100 -3.10400 -0.50200 H 3.44700 -2.97300 1.25500 H 5.11000 -3.00100 0.58300 H 4.39800 0.50700 1.49900 H 5.60500 -0.80400 1.68100 H 3.96700 -0.96700 2.38500 C 3.43800 2.73100 -0.84400 C 2.74800 1.04100 -2.39100 H 2.40500 3.09700 -0.79600 H 3.99200 3.30900 -1.61300 H 3.91200 2.91100 0.13300 883 H 2.71500 -0.04000 -2.59100 H 3.25200 1.53600 -3.24800 H 1.71300 1.41200 -2.33300 H -5.39700 0.90000 2.40300 H -3.34900 -2.24200 -0.08500 H -4.96200 2.43600 0.50200 H -3.85200 -1.56600 -3.70200 H -5.15600 -1.21600 0.45700 H -5.49500 -0.97200 -1.94300 C -4.40600 0.44400 2.19700 C -3.24900 -2.26000 -1.18000 N -4.06500 0.52200 0.78500 N -3.38600 -0.91700 -1.72700 C -3.98900 1.91400 0.37100 C -3.13400 -0.91700 -3.15900 C -4.70200 -0.35300 -1.46800 C -5.04700 -0.21700 0.00700 H -3.65300 0.97000 2.79800 H -3.69500 1.99600 -0.68300 H -3.22600 0.10400 -3.55600 H -2.24500 -2.64600 -1.39600 H -4.01200 -2.95500 -1.59200 H -4.43500 -0.60500 2.52400 H -6.04900 0.26300 0.07700 H -3.22900 2.43300 0.96800 H -2.11700 -1.27200 -3.36300 H -4.74900 0.63200 -1.95900 884 Table C.2.60. Atomic coordinates and single point energies for A2-2. G = –2030.568133 GSP = –2032.136900 Na -1.44500 -0.32700 -0.17600 Na 1.44400 0.32700 -0.17400 N 0.37200 -1.76700 -0.18500 N -0.37300 1.76700 -0.18500 Si 0.45600 -2.61000 1.30200 C -0.04400 -4.44100 1.20800 C -0.70900 -1.79900 2.57300 C 2.19200 -2.59500 2.08500 C 0.73400 -2.48700 -1.39600 C -0.49500 -3.07200 -2.10600 H -0.22700 -3.66000 -2.99900 H -1.16100 -2.25000 -2.42500 H -1.05900 -3.71800 -1.41700 C 1.49000 -1.58900 -2.38300 H 1.41400 -3.34700 -1.19300 H 1.72500 -2.10500 -3.32600 H 2.44100 -1.24600 -1.94900 H 0.88000 -0.70200 -2.63100 H -1.09800 -4.55400 0.90700 H 0.08200 -4.93500 2.18500 H 0.56900 -4.99100 0.47700 H -1.70500 -2.26500 2.52700 H -0.83600 -0.71300 2.42100 H -0.33400 -1.93300 3.60000 H 2.94200 -2.96100 1.36500 H 2.25300 -3.22200 2.98900 H 2.47100 -1.56600 2.37000 885 C -0.73300 2.48700 -1.39700 C -1.48800 1.59000 -2.38500 C 0.49600 3.07400 -2.10400 H -0.87800 0.70300 -2.63200 H -1.72200 2.10700 -3.32800 H -2.44000 1.24700 -1.95200 H -1.41300 3.34700 -1.19400 H 0.23000 3.66200 -2.99800 H 1.16200 2.25200 -2.42300 H 1.05900 3.71900 -1.41400 Si -0.45700 2.61000 1.30300 C 0.70700 1.79800 2.57300 C -2.19300 2.59500 2.08500 C 0.04400 4.44100 1.20900 H 0.83100 0.71100 2.42200 H 0.33300 1.93400 3.60000 H 1.70400 2.26100 2.52500 H -2.47300 1.56600 2.37000 H -2.94400 2.96100 1.36500 H -2.25500 3.22200 2.98900 H -0.08300 4.93400 2.18600 H -0.56900 4.99100 0.47700 H 1.09800 4.55300 0.91000 C -3.65200 -2.16300 0.36500 C -3.96200 -1.09200 1.20900 C -3.81000 -2.01600 -1.01400 C -4.41600 0.11400 0.67400 C -4.26100 -0.80500 -1.54300 C -4.57000 0.27800 -0.71000 C 3.81000 2.01700 -1.01100 C 3.65100 2.16100 0.36800 C 4.26300 0.80600 -1.54200 C 4.57100 -0.27700 -0.70900 C 3.96100 1.09000 1.21000 C 4.41600 -0.11500 0.67500 H -3.28500 -3.10400 0.77800 H -3.84200 -1.19400 2.28900 H -4.64700 0.94700 1.34000 C -5.04100 1.59500 -1.26800 H -4.37000 -0.69400 -2.62500 H -3.57000 -2.84500 -1.68100 H 4.64800 -0.95000 1.34000 H 3.84000 1.19000 2.29100 C 5.04400 -1.59300 -1.26900 H 3.28300 3.10200 0.78200 H 4.37400 0.69800 -2.62300 886 H 3.57100 2.84600 -1.67700 H 6.05300 -1.83200 -0.90400 H 5.06900 -1.57500 -2.36600 H 4.37600 -2.40900 -0.95500 H -5.06700 1.57800 -2.36500 H -4.37100 2.41000 -0.95400 H -6.04900 1.83600 -0.90200 887 Table C.2.61. Atomic coordinates and single point energies for A1. G = –1488.306458 GSP = –1489.283817 Na -0.05900 -0.09100 1.48100 Na -0.12000 -0.09400 -1.38300 N -1.85000 -0.46700 0.08600 N 1.61300 0.46100 0.02000 Si -2.85700 0.90200 -0.12600 Si 2.77700 -0.75900 -0.26800 C 1.89400 -2.08900 -1.31600 C 3.38000 -1.67500 1.28800 C 4.33600 -0.27700 -1.23700 C -4.43400 0.58300 -1.12600 C -1.83600 2.20700 -1.06500 C -3.40200 1.69900 1.51100 C -2.47200 -1.73400 0.43900 C 1.92500 1.81500 0.44500 C -2.61300 -2.65800 -0.77600 H -3.10400 -3.61300 -0.52800 H -1.61400 -2.88500 -1.18900 H -3.20000 -2.15800 -1.56100 C -1.68400 -2.45700 1.54000 H -3.49900 -1.59900 0.84800 H -2.11500 -3.43600 1.79800 H -1.66800 -1.85800 2.46800 H -0.64500 -2.63800 1.20500 C 2.93800 1.89800 1.59600 H 2.61200 1.28700 2.45400 H 3.08300 2.93200 1.94500 H 3.91900 1.51100 1.27300 C 2.38700 2.71100 -0.71200 H 0.99400 2.29600 0.83300 H 2.55000 3.75200 -0.39100 H 1.63500 2.71200 -1.51700 H 3.32900 2.32600 -1.13200 H 4.07300 0.17500 -2.20600 888 H 4.95900 -1.16400 -1.43300 H 4.95500 0.44800 -0.68700 H 0.95300 -2.43200 -0.85000 H 2.52700 -2.98200 -1.43400 H 1.67500 -1.73200 -2.33900 H -4.19100 0.24900 -2.14700 H -5.05400 1.49000 -1.20200 H -5.04800 -0.20100 -0.65700 H -1.69000 1.92900 -2.12400 H -0.84500 2.37200 -0.60700 H -2.34700 3.18200 -1.07300 H 2.53000 -2.09700 1.85000 H 3.92400 -0.99900 1.96600 H 4.05400 -2.51000 1.03700 H -3.92400 0.96000 2.14000 H -4.08000 2.55400 1.36500 H -2.52900 2.06200 2.08000 889 Table C.2.62. Atomic coordinates and single point energies for A33. G = –1952.087511 GSP = –1953.569542 Na 1.51700 -0.00000 -0.00000 Na -1.36000 0.00100 0.00100 N 0.11800 1.75800 0.42600 N 0.11600 -1.75800 -0.42500 Si -0.10700 2.84500 -0.86900 C -1.44100 4.18300 -0.63100 C -0.64200 1.78400 -2.36000 C 1.43300 3.78200 -1.48900 C 0.37000 2.14000 1.80300 C 1.26000 3.37800 1.97400 H 1.49500 3.57100 3.03200 H 0.75800 4.27400 1.57200 H 2.20400 3.25200 1.42200 C -0.92700 2.33100 2.60200 H 0.91600 1.31200 2.31800 H -0.73700 2.57900 3.65800 H -1.53300 1.41100 2.57200 H -1.52100 3.14400 2.15200 H -2.39600 3.73500 -0.31200 H -1.61900 4.74500 -1.56200 H -1.14600 4.90900 0.14300 H -1.66500 1.38700 -2.25800 H 0.03700 0.92500 -2.50400 H -0.62400 2.37200 -3.29000 H 1.87400 4.42300 -0.71000 H 1.18200 4.42400 -2.34900 890 H 2.20600 3.07000 -1.82100 C 0.36900 -2.13900 -1.80100 C -0.92800 -2.32900 -2.60100 C 1.25800 -3.37800 -1.97300 H -1.52300 -3.14200 -2.15200 H -0.73800 -2.57700 -3.65800 H -1.53300 -1.40800 -2.57100 H 0.91600 -1.31200 -2.31600 H 1.49300 -3.57100 -3.03100 H 0.75500 -4.27400 -1.57200 H 2.20200 -3.25300 -1.42100 Si -0.11000 -2.84500 0.87000 C -0.64600 -1.78400 2.36000 C 1.43000 -3.78200 1.49000 C -1.44400 -4.18300 0.63000 H 0.03200 -0.92400 2.50500 H -0.62700 -2.37300 3.29000 H -1.66900 -1.38800 2.25800 H 2.20300 -3.07000 1.82300 H 1.87100 -4.42200 0.71100 H 1.17900 -4.42500 2.34900 H -1.62100 -4.74600 1.56000 H -1.14900 -4.90800 -0.14500 H -2.39800 -3.73400 0.31300 C 3.99700 1.39500 -0.07400 C 3.99800 0.76100 1.17200 C 3.99900 0.63200 -1.24600 C 3.99900 -0.63500 1.24500 C 3.99600 -0.76500 -1.17300 C 3.99500 -1.39800 0.07300 C -3.98600 -1.24700 -0.63200 C -3.99400 -1.16900 0.76200 C -3.99100 -0.07600 -1.39500 C -3.99200 1.17100 -0.76400 C -3.99200 0.07800 1.39300 C -3.98500 1.24900 0.63000 H 3.97900 2.48400 -0.13500 H 3.98500 1.35700 2.08500 H 3.99200 -1.13100 2.21700 H 3.98100 -1.36100 -2.08600 H 3.99200 1.12800 -2.21800 H -3.96600 2.22200 1.12400 H -3.98500 0.13900 2.48300 H -3.98700 -2.08300 1.35900 H -3.98400 -0.13600 -2.48500 H -3.96700 -2.22000 -1.12600 891 H 3.97600 -2.48700 0.13300 H -3.98400 2.08500 -1.36100 892 Table C.2.63. Atomic coordinates and single point energies for A24. G = –2412.240524 GSP = –2414.280832 Na 1.41300 0.63300 0.24900 Na -1.33800 -0.27400 0.45200 N -0.54500 1.93100 0.32600 N 0.54600 -1.54100 -0.04200 Si -0.36100 2.90400 -1.05700 C 0.00500 4.75500 -0.78200 C -1.77900 2.87200 -2.33500 C 1.14800 2.23700 -2.01800 C -1.30400 2.31600 1.49900 C -0.52100 3.23200 2.45000 H -1.09200 3.46500 3.36400 H -0.27700 4.18100 1.94600 H 0.41800 2.73900 2.74400 C -2.67600 2.93500 1.18500 H -1.51900 1.40800 2.11400 H -3.25900 3.13900 2.09900 H -3.25700 2.26000 0.53600 H -2.55300 3.89100 0.65000 H -0.83100 5.27300 -0.28500 H 0.18100 5.26200 -1.74500 H 0.90100 4.89900 -0.15700 H -2.75400 3.08100 -1.86800 H -1.83500 1.88200 -2.81600 H -1.61800 3.61500 -3.13300 H 2.08500 2.40400 -1.46100 893 H 1.25200 2.74800 -2.98800 H 1.05700 1.15700 -2.23200 C 0.56700 -1.90800 -1.43800 C -0.68400 -1.37100 -2.15200 C 0.68500 -3.41300 -1.71000 H -1.58100 -1.85300 -1.72200 H -0.67200 -1.57200 -3.23500 H -0.77200 -0.28000 -2.01300 H 1.43100 -1.43200 -1.97100 H 0.69600 -3.63800 -2.78900 H -0.16500 -3.94100 -1.25000 H 1.60900 -3.82100 -1.26900 Si 1.25100 -2.39100 1.25400 C 0.92600 -1.31400 2.79200 C 3.14300 -2.66700 1.18600 C 0.58300 -4.14100 1.63100 H 1.41200 -0.32400 2.72500 H 1.30800 -1.79700 3.70500 H -0.15100 -1.12500 2.94100 H 3.67200 -1.83800 0.69000 H 3.38500 -3.58500 0.62700 H 3.55800 -2.79300 2.20100 H 0.82500 -4.44500 2.66200 H 1.04100 -4.88000 0.95500 H -0.50600 -4.21300 1.49500 O -2.60700 -1.03600 2.32300 O -3.58600 -0.28800 -0.09800 C -3.84300 -0.36900 2.24800 C -4.53100 -0.57800 0.91000 H -3.61800 0.69800 2.38300 H -4.51200 -0.69500 3.06500 H -5.39600 0.10700 0.83700 H -4.91600 -1.60300 0.79400 C -2.69200 -2.44200 2.35200 H -3.43800 -2.77300 3.09500 H -1.70500 -2.82200 2.63900 H -2.95600 -2.85800 1.36400 C -4.10000 0.05300 -1.36700 C -4.71200 -1.12900 -2.09800 H -4.83000 0.87800 -1.26100 H -3.25100 0.44300 -1.94600 O -5.89300 -1.60800 -1.50600 C -7.04100 -0.87400 -1.82600 H -7.21100 -0.85100 -2.91800 H -6.99300 0.16900 -1.46400 H -7.89600 -1.36600 -1.34700 894 H -3.99100 -1.96000 -2.08900 H -4.89100 -0.84700 -3.15400 O 3.67400 0.41200 -0.49500 O 2.83300 1.72800 1.73200 C 3.02300 3.08800 1.42000 H 3.70000 3.56700 2.14900 H 2.03700 3.56500 1.46100 H 3.43700 3.22300 0.40500 C 4.00700 0.95400 1.78300 C 4.66800 0.80400 0.42300 H 5.13300 1.75300 0.09300 H 5.46000 0.03900 0.49600 H 4.73100 1.38200 2.50100 H 3.70000 -0.03600 2.15000 C 4.07600 0.39900 -1.84700 C 5.35500 -0.39600 -2.09000 H 4.22500 1.43200 -2.21800 H 3.23000 -0.03000 -2.40200 O 5.36700 -1.64300 -1.46600 H 6.22600 0.15200 -1.70300 H 5.49000 -0.48900 -3.18700 C 4.39800 -2.53600 -1.95000 H 3.37800 -2.24600 -1.64300 H 4.61800 -3.52300 -1.52600 H 4.43700 -2.60500 -3.05400 895 Table C.2.64. Atomic coordinates and single point energies for A22. G = –2105.045705 GSP = –2106.731319 Na -1.58300 0.00200 0.00200 Na 1.49800 -0.00200 -0.00300 N -0.03400 1.78100 -0.32200 N -0.03800 -1.78200 0.32200 Si 0.22400 2.71000 1.07300 C 0.85600 4.50300 0.92000 C 1.50600 1.84700 2.20500 C -1.32800 2.88600 2.17500 C 0.03700 2.04000 -1.73800 C -0.99300 1.20000 -2.51300 H -0.91800 1.35600 -3.60100 H -2.01700 1.46100 -2.20000 H -0.83700 0.12300 -2.33300 C -0.11100 3.51100 -2.15100 H 1.02300 1.71900 -2.16300 H -0.06000 3.63200 -3.24400 H 0.67700 4.13300 -1.70100 H -1.07900 3.90800 -1.80500 H 1.82700 4.58300 0.40700 H 0.98400 4.91900 1.93300 H 0.13700 5.14300 0.38600 H 2.49800 1.83700 1.72600 H 1.22700 0.80500 2.44100 H 1.60200 2.37300 3.16800 H -1.94800 3.73700 1.85000 896 H -1.04300 3.07300 3.22300 H -1.96900 1.99000 2.15400 C 0.03700 -2.03800 1.73800 C -0.11100 -3.50800 2.15400 C -0.98900 -1.19600 2.51500 H -1.08100 -3.90500 1.81200 H -0.05500 -3.62800 3.24700 H 0.67400 -4.13200 1.70200 H 1.02500 -1.71800 2.16000 H -0.91400 -1.35200 3.60200 H -2.01500 -1.45400 2.20300 H -0.83200 -0.12000 2.33500 Si 0.21600 -2.71200 -1.07300 C 1.49900 -1.85400 -2.20700 C -1.33900 -2.88300 -2.17200 C 0.84200 -4.50700 -0.92000 H -1.97500 -1.98300 -2.15200 H -1.96300 -3.73000 -1.84400 H -1.05600 -3.07400 -3.22000 H 0.96600 -4.92400 -1.93300 H 0.12200 -5.14400 -0.38400 H 1.81400 -4.59000 -0.40900 O 3.45200 1.26000 -0.44700 O 3.45100 -1.26600 0.44200 C 4.63900 0.51900 -0.54600 C 4.63700 -0.52500 0.54600 H 5.52000 1.17500 -0.42000 H 4.70600 0.03500 -1.53800 H 4.69900 -0.04100 1.53900 H 5.51900 -1.18000 0.42500 C 3.44800 2.44800 -1.19900 C 3.44400 -2.45500 1.19300 H 2.47500 -2.93900 1.02100 H 3.56200 -2.24700 2.27100 H 4.25600 -3.12800 0.86500 H 4.25700 3.12300 -0.86800 H 2.47800 2.93100 -1.03300 H 3.57200 2.23900 -2.27600 O -3.54400 1.34000 -0.00100 O -3.54400 -1.33300 0.00600 C -3.51600 2.68800 -0.40500 C -4.73300 0.67900 -0.34000 C -4.73600 -0.67100 0.33600 C -3.52000 -2.68100 0.41000 H -4.20400 3.29500 0.20800 H -3.80100 2.78600 -1.46800 897 H -2.48500 3.03800 -0.27600 H -4.79600 0.55500 -1.43800 H -5.61500 1.25700 -0.00800 H -5.61600 -1.24800 -0.00400 H -4.80800 -0.54700 1.43300 H -2.48800 -3.03000 0.29100 H -4.20200 -3.28800 -0.21100 H -3.81600 -2.78000 1.47000 H 2.49200 -1.84500 -1.73000 H 1.22100 -0.81100 -2.44400 H 1.59200 -2.38100 -3.17000 898 Table C.2.65. Atomic coordinates and single point energies for A34. G = –1915.078184 GSP = –1916.537352 Na -1.61500 -0.06100 0.01700 Na 1.24400 -0.01900 0.07400 N -0.24400 1.75900 -0.34300 N -0.18100 -1.81600 0.48800 Si 0.11800 2.76500 0.98800 C 1.59500 3.95100 0.77900 C 0.60400 1.59400 2.41400 C -1.30100 3.82600 1.68300 C -0.38600 2.21900 -1.71400 C -1.07400 3.58300 -1.87500 H -1.20800 3.84800 -2.93500 H -0.46900 4.37600 -1.40600 H -2.06200 3.58600 -1.39200 C 0.95800 2.25000 -2.45900 H -1.02400 1.49600 -2.27600 H 0.84600 2.54900 -3.51300 H 1.43200 1.25500 -2.44000 H 1.63700 2.96300 -1.96500 H 2.49100 3.40200 0.44600 H 1.83800 4.45200 1.73000 H 1.39500 4.73500 0.03200 H 1.61400 1.17000 2.28500 H -0.10100 0.75200 2.51700 H 0.61600 2.12900 3.37600 H -1.72800 4.49600 0.92100 899 H -0.95000 4.44800 2.52200 H -2.11500 3.18600 2.06100 C -0.37900 -2.24800 1.85900 C 0.95200 -2.45900 2.59500 C -1.25500 -3.49800 2.01900 H 1.52200 -3.26500 2.10400 H 0.81000 -2.72900 3.65400 H 1.55700 -1.53800 2.55700 H -0.90600 -1.44200 2.42200 H -1.44200 -3.73500 3.07800 H -0.76700 -4.37300 1.56000 H -2.22400 -3.35600 1.51800 Si 0.05000 -2.85500 -0.84300 C 0.72100 -1.75600 -2.25100 C -1.53100 -3.64400 -1.55800 C 1.27800 -4.29600 -0.64700 H 0.09000 -0.86400 -2.40600 H 0.75200 -2.30000 -3.20800 H 1.75100 -1.40700 -2.05600 H -2.24200 -2.86000 -1.86900 H -2.03700 -4.27900 -0.81400 H -1.31700 -4.26700 -2.44200 H 1.42400 -4.81400 -1.60800 H 0.91700 -5.04100 0.07900 H 2.26100 -3.94500 -0.29700 N 3.66300 -0.12900 0.17900 N -3.99600 -0.30600 -0.19300 C -4.35100 -0.30700 -1.60600 H -5.44900 -0.35300 -1.75400 H -3.90300 -1.18300 -2.09600 H -3.96900 0.59400 -2.10400 C -4.35400 -1.57700 0.42200 H -4.04600 -1.58200 1.47800 H -3.83500 -2.40000 -0.09000 H -5.44600 -1.76500 0.37700 C -4.61400 0.80800 0.52900 C -4.17700 2.17400 0.02400 H -4.33100 0.70400 1.58900 H -5.72100 0.71800 0.48800 H -3.07800 2.25000 -0.01000 H -4.54300 2.95900 0.70100 H -4.57200 2.39400 -0.97800 C 3.96700 -1.55200 0.12000 C 4.13400 0.45000 1.42800 C 4.12400 0.61000 -1.00100 C 5.63500 0.66700 -1.21800 900 H 3.63500 -1.96800 -0.84300 H 3.42400 -2.07800 0.92000 H 5.04700 -1.76600 0.23800 H 5.22800 0.34200 1.56400 H 3.64400 -0.05100 2.27600 H 3.88200 1.52000 1.46600 H 3.64600 0.15200 -1.88300 H 3.71900 1.63300 -0.92700 H 6.07000 -0.33700 -1.32600 H 6.14900 1.18000 -0.39300 H 5.85300 1.22300 -2.14000 901 Table C.2.66. Atomic coordinates and single point energies for A3. G = –2072.015793 GSP = –2073.647972 Na 1.46500 -0.05800 -0.13000 Na -1.34600 0.25100 0.07300 N 0.24200 1.88800 -0.43900 N -0.12400 -1.68900 0.43900 Si 0.26000 2.86900 0.95800 C -1.18900 4.08700 1.17800 C 1.82400 3.90800 1.27000 C 0.10900 1.66800 2.43300 C 0.15200 2.37500 -1.80400 C -1.29000 2.31900 -2.33100 H -1.37600 2.66600 -3.37300 H -1.93800 2.94700 -1.69700 H -1.67600 1.28600 -2.29800 C 0.71700 3.78300 -2.03500 H 0.74100 1.70400 -2.47100 H 0.68000 4.06500 -3.09900 H 1.76100 3.84700 -1.69800 H 0.13500 4.53000 -1.47100 H -1.20800 4.85700 0.39200 H -1.12300 4.60600 2.14800 H -2.15400 3.55600 1.14700 H 1.90300 4.73800 0.55200 H 2.73900 3.30100 1.17400 H 1.81000 4.34200 2.28200 H -0.89700 1.21500 2.49500 902 H 0.26700 2.19700 3.38500 H 0.83700 0.83800 2.39800 C -0.21300 -2.12300 1.82300 C 1.16800 -2.41100 2.43000 C -1.12400 -3.33500 2.06800 H 1.64500 -3.24700 1.89300 H 1.11100 -2.67300 3.49900 H 1.82100 -1.52800 2.33300 H -0.64000 -1.29700 2.43500 H -1.20500 -3.57200 3.14000 H -0.72600 -4.22800 1.55800 H -2.13600 -3.15300 1.67800 Si -0.08300 -2.74200 -0.90300 C 0.49800 -1.67400 -2.37400 C -1.74700 -3.50200 -1.44300 C 1.10100 -4.23200 -0.82300 H -0.06300 -0.72500 -2.44400 H 0.36700 -2.19900 -3.33200 H 1.57200 -1.42100 -2.30300 H -2.48200 -2.72600 -1.71400 H -2.18600 -4.11000 -0.63700 H -1.61900 -4.15500 -2.32100 H 1.13300 -4.75100 -1.79500 H 0.77800 -4.96700 -0.06900 H 2.12600 -3.92500 -0.56800 N -3.75000 0.15700 0.02900 N 3.85900 -0.32800 -0.18200 C 4.21400 0.29000 1.10000 C 4.04000 -1.77900 -0.24300 H 3.60700 -2.11100 -1.20200 H 3.40900 -2.22500 0.54400 C 5.46200 -2.32600 -0.12300 C 4.36100 0.37900 -1.35800 C 3.87500 1.82100 -1.42400 H 3.99400 -0.16800 -2.24200 H 5.46800 0.35500 -1.41700 H 2.78300 1.88200 -1.29300 H 4.13100 2.26400 -2.39600 H 4.33400 2.44700 -0.64500 C -3.74500 -0.99200 0.93200 C -4.03100 -0.12700 -1.37600 C -4.29500 1.40500 0.55200 C -5.79700 1.64400 0.38800 H -3.00000 -0.81000 1.73100 H -3.34800 -1.84500 0.35800 C -5.05800 -1.38100 1.61200 903 H -4.02200 1.45700 1.62000 H -3.76200 2.23900 0.06200 H -6.40000 0.85200 0.85100 H -6.07100 1.70600 -0.67600 H -6.07300 2.60200 0.85300 H 3.57600 1.18000 1.24700 C 5.67100 0.71500 1.29400 H 3.92800 -0.42300 1.89000 H -4.09400 0.84400 -1.89400 C -5.26600 -0.97000 -1.69300 H -3.15400 -0.64200 -1.81200 H -6.18700 -0.52200 -1.29600 H -5.16800 -1.98400 -1.27800 H -5.37500 -1.07100 -2.78200 H -5.40400 -0.58800 2.29100 H -4.90100 -2.28600 2.21700 H -5.85800 -1.58800 0.88800 H 5.96000 1.50200 0.58400 H 6.37100 -0.12100 1.17300 H 5.80100 1.12300 2.30600 H 6.14600 -1.84900 -0.84000 H 5.45900 -3.40500 -0.33000 H 5.86700 -2.18700 0.88900 904 Table C.2.67. Atomic coordinates and single point energies for A10. G = –3127.162014 GSP = –3129.518898 Na -1.46800 0.31700 0.61500 Na 1.38200 0.58700 -0.08400 N 0.17100 -1.31500 0.65800 N -0.32000 2.13900 -0.30800 Si 0.03300 -2.22400 -0.77100 C -0.30500 -4.09400 -0.63700 C 1.56900 -2.06900 -1.91000 C -1.39500 -1.48200 -1.78600 C 0.81800 -1.76300 1.87400 C -0.07700 -2.68600 2.71300 H 0.39200 -2.96500 3.67100 H -0.29500 -3.60900 2.15200 H -1.03400 -2.18600 2.92600 C 2.18400 -2.43200 1.65000 H 1.02200 -0.87900 2.52000 H 2.68700 -2.68100 2.59900 H 2.84300 -1.76400 1.07200 H 2.06700 -3.36700 1.07600 H 0.53800 -4.63000 -0.17400 H -0.46700 -4.52900 -1.63600 H -1.19800 -4.29500 -0.02700 H 2.48800 -2.22600 -1.32200 H 1.63300 -1.05600 -2.34600 H 1.56100 -2.78500 -2.74900 H -2.36000 -1.61300 -1.27000 905 H -1.47600 -1.95400 -2.77800 H -1.24100 -0.40100 -1.95300 C -0.63900 2.41200 -1.69300 C 0.03900 3.66300 -2.27000 C -2.15700 2.49200 -1.93500 H -0.32300 4.56900 -1.75500 H -0.16400 3.78500 -3.34600 H 1.12800 3.60600 -2.12200 H -0.28000 1.56600 -2.32300 H -2.40800 2.60200 -3.00400 H -2.57700 3.35300 -1.38800 H -2.65400 1.58500 -1.54900 Si -0.24900 3.30500 0.93000 C -0.24300 2.33100 2.57000 C -1.70600 4.52400 1.05800 C 1.32900 4.37500 0.97500 H -1.22700 1.87300 2.77400 H -0.01300 2.98400 3.42600 H 0.50800 1.52100 2.56500 H -2.65800 3.97400 1.13300 H -1.76700 5.18400 0.17800 H -1.61000 5.16600 1.94900 H 1.35900 5.01900 1.86900 H 1.40100 5.02300 0.08800 H 2.22500 3.73200 0.98900 O 3.54900 0.51200 -0.10500 P 4.93100 -0.07400 -0.11700 N 5.22900 -1.49000 -0.94400 N 5.38900 -0.43800 1.44900 N 5.96300 1.00300 -0.87800 C 5.21200 -1.50100 -2.39900 C 5.14300 -2.81200 -0.34700 C 6.75000 -0.82800 1.75000 C 4.62200 0.03700 2.58800 C 5.65000 2.42200 -0.88200 C 7.33000 0.68800 -1.23800 H 5.22900 -0.47500 -2.78700 H 4.30600 -2.00100 -2.77600 H 6.09600 -2.03700 -2.78500 H 5.08000 -2.73900 0.74400 H 6.03400 -3.40400 -0.61800 H 4.25000 -3.35200 -0.70700 H 7.22600 -1.27800 0.86800 H 6.75600 -1.58100 2.55500 H 7.36600 0.02900 2.08000 H 3.60600 0.29400 2.27200 906 H 5.08600 0.92700 3.05000 H 4.56000 -0.75600 3.35000 H 7.47400 -0.39800 -1.29000 H 8.05600 1.10600 -0.51700 H 7.56200 1.11100 -2.23000 H 4.59000 2.56900 -0.64600 H 5.84700 2.84500 -1.88000 H 6.26200 2.97700 -0.14900 H -6.00800 1.99800 -0.50700 H -5.54500 -0.32100 -3.37600 H -6.59800 -3.16700 0.07100 H -8.13500 0.82200 0.90200 H -3.00400 -2.30500 0.89900 H -4.95800 0.41800 2.71000 P -4.87000 -0.39800 0.12400 H -6.54800 1.22900 2.76300 C -3.87700 -2.88600 0.57700 C -5.94400 -2.74900 -0.71700 C -6.02200 0.30400 2.47700 N -4.80300 -2.04600 -0.16700 N -6.18500 0.06300 1.05400 C -4.74400 -0.31600 -2.61800 C -5.72200 1.60600 -1.49000 C -7.55800 -0.07400 0.61700 O -3.61400 0.03300 0.82300 N -5.25800 0.23100 -1.37100 H -4.35300 -3.33800 1.46600 H -6.54300 -2.07800 -1.34700 H -7.60600 -0.17200 -0.47500 H -4.38700 -1.34100 -2.47100 H -6.59800 1.65300 -2.15800 H -4.93200 2.25200 -1.90600 H -3.90600 0.28900 -3.00200 H -5.59700 -3.58400 -1.34700 H -8.05400 -0.95100 1.07100 H -3.52600 -3.70000 -0.07600 H -6.43700 -0.52400 3.07900 907 Table C.2.68. Atomic coordinates and single point energies for A4. G = –2033.299782 GSP = –2034.896306 Na -1.44300 0.16400 -0.44100 Na 1.37500 -0.06700 -0.26600 N -0.23900 -1.71000 0.22000 N 0.10400 1.89200 -0.58200 Si 0.10800 -3.03600 -0.80200 C 1.30100 -4.35900 -0.12400 C 0.93100 -2.33100 -2.36800 C -1.39000 -4.01300 -1.45500 C -0.62200 -1.84500 1.61600 C -1.48200 -3.07200 1.95300 H -1.79000 -3.06900 3.01100 H -0.92300 -4.00400 1.77000 H -2.39000 -3.10100 1.33300 C 0.59200 -1.81100 2.55700 H -1.24500 -0.96900 1.91100 H 0.30300 -1.84000 3.62000 H 1.18300 -0.89300 2.39600 H 1.24500 -2.67500 2.35100 H 2.25100 -3.91700 0.21300 H 1.53300 -5.10100 -0.90500 H 0.87000 -4.90500 0.72900 H 1.87800 -1.79900 -2.17100 H 0.25500 -1.63300 -2.88600 H 1.16700 -3.14100 -3.07600 H -1.96900 -4.47200 -0.63900 908 H -1.07000 -4.81900 -2.13300 H -2.07000 -3.35200 -2.01800 C 0.39200 2.52500 -1.85800 C -0.86900 3.08800 -2.53200 C 1.05900 1.54000 -2.82500 H -1.58400 2.26600 -2.71600 H -0.65000 3.57300 -3.49700 H -1.36100 3.82300 -1.88000 H 1.09800 3.38600 -1.75600 H 1.26700 1.99200 -3.80700 H 0.39300 0.67600 -2.98900 H 2.01500 1.16000 -2.42800 Si 0.02300 2.83900 0.84000 C -0.93600 1.86400 2.15900 C -0.80700 4.54300 0.66500 C 1.70600 3.22900 1.64700 H -1.94300 1.56800 1.81800 H -1.06400 2.46700 3.07100 H -0.39500 0.94800 2.44800 H -1.87000 4.47300 0.38700 H -0.30100 5.14800 -0.10500 H -0.74500 5.09600 1.61500 H 1.56900 3.72500 2.62200 H 2.31100 3.90200 1.01800 H 2.28800 2.30800 1.81400 O 3.54900 0.51500 -0.18800 O -3.61400 0.69500 -0.32100 C -3.91700 2.05900 -0.13500 H -4.72400 2.39100 -0.80700 H -3.00300 2.61800 -0.37900 H -4.19800 2.28200 0.90800 C -4.57300 -0.28800 0.11100 C -4.51500 -0.41400 1.63300 C -4.10800 -1.58000 -0.55000 C -5.97600 0.08000 -0.36400 H -3.50500 -0.71200 1.95200 H -5.22600 -1.17800 1.97900 H -4.77400 0.53400 2.12800 C 3.88800 1.83500 -0.55400 C 4.58500 -0.32200 0.35500 C 4.91700 0.13100 1.77600 H 4.49500 1.85500 -1.47400 H 4.42800 2.35800 0.25200 H 2.94300 2.36400 -0.73200 C 5.82100 -0.29800 -0.54100 C 3.97000 -1.71600 0.37400 909 H 5.33000 1.14900 1.79400 H 5.66400 -0.54000 2.22200 H 4.01200 0.10900 2.40100 H 3.05500 -1.73200 0.98800 H 4.67000 -2.44700 0.80200 H 3.71300 -2.03900 -0.64600 H 6.32000 0.68100 -0.52300 H 5.54500 -0.53700 -1.57800 H 6.54500 -1.04900 -0.19300 H -4.73500 -2.42600 -0.23600 H -3.06800 -1.81400 -0.27100 H -4.16400 -1.48900 -1.64500 H -6.66300 -0.75200 -0.15700 H -5.97600 0.26700 -1.44800 H -6.36500 0.97000 0.15000 910 Table C.2.69. Atomic coordinates and single point energies for A20. G = –2528.462636 GSP = –2530.611447 Na -1.60800 0.90700 0.23900 Na 1.21000 -0.33600 0.17800 N 0.49100 1.97900 0.01700 N -0.86500 -1.28600 0.92300 Si 1.05800 2.55600 -1.47600 C 0.88900 4.39400 -1.96400 C 0.10900 1.58600 -2.80700 C 2.92600 2.25200 -1.77700 C 0.62000 2.59600 1.31900 C 1.27500 1.64300 2.32600 H 1.28200 2.04700 3.35200 H 2.31500 1.45800 2.01600 H 0.74400 0.67800 2.35300 C 1.36600 3.93500 1.35500 H -0.39400 2.81200 1.74000 H 1.43300 4.33400 2.38000 H 0.86800 4.68900 0.72700 H 2.39200 3.80500 0.97100 H -0.11000 4.81500 -1.77900 H 1.09600 4.48900 -3.04300 H 1.62300 5.02000 -1.43500 H -0.92200 1.97300 -2.87500 H 0.04100 0.51500 -2.55600 H 0.56000 1.67200 -3.80800 H 3.52300 2.89200 -1.10600 H 3.23700 2.46500 -2.81300 911 H 3.18700 1.20700 -1.55100 C -0.96900 -2.49300 0.12800 C 0.12400 -3.52300 0.45600 C -0.93800 -2.16400 -1.36800 H 1.11500 -3.06000 0.31300 H 0.06800 -4.42500 -0.17700 H 0.05400 -3.83600 1.50900 H -1.93600 -3.02500 0.30000 H -1.09000 -3.05600 -1.99800 H 0.03100 -1.71600 -1.64700 H -1.72200 -1.43100 -1.61100 Si -1.37500 -1.37200 2.55400 C -2.15200 0.29900 3.04400 C -0.04600 -1.70200 3.88100 C -2.66600 -2.73300 2.88500 H -1.44400 1.13500 2.91000 H -2.46300 0.30900 4.10000 H -3.04600 0.51400 2.43400 H 0.73700 -0.92900 3.88900 H 0.44200 -2.67500 3.71300 H -0.49900 -1.72600 4.88500 H -3.06300 -2.64000 3.90800 H -2.20400 -3.73000 2.80300 H -3.51600 -2.70900 2.18600 N 2.57400 -1.84300 -1.96300 N 3.55700 -0.99100 0.96600 C 2.42400 -1.11600 -3.21500 H 2.57700 -0.04100 -3.06500 H 1.40700 -1.26300 -3.60800 H 3.14200 -1.47200 -3.98400 C 3.91700 -1.67700 -1.41000 C 3.99300 -2.05800 0.06300 H 4.22700 -0.63000 -1.53200 H 4.65500 -2.27700 -1.98300 H 5.01900 -2.39200 0.30400 H 3.33600 -2.92100 0.24700 C 2.29600 -3.25000 -2.21100 H 2.96200 -3.65400 -3.00200 H 1.25400 -3.37800 -2.53300 H 2.43900 -3.85200 -1.30500 C 3.32800 -1.53100 2.30100 H 2.54800 -2.30600 2.25800 H 2.97200 -0.73500 2.97000 H 4.23700 -1.98400 2.74600 C 4.46600 0.16700 1.00300 C 5.96500 -0.13600 1.07500 912 H 4.26400 0.81900 0.14200 H 4.19400 0.75600 1.88900 N 6.55900 -0.45100 -0.21400 C 7.81400 -1.15600 -0.06900 C 6.70800 0.71600 -1.05800 H 7.40700 1.46400 -0.62400 H 5.74100 1.21300 -1.22400 H 7.09700 0.41500 -2.04100 H 7.66000 -2.09000 0.49200 H 8.58400 -0.55700 0.46500 H 8.21400 -1.41500 -1.05900 H 6.12700 -0.99200 1.75000 H 6.48300 0.72900 1.54800 N -3.99100 0.37700 -0.46100 N -3.03300 3.06100 0.49800 C -3.26400 3.45400 1.88000 C -2.24600 4.07100 -0.19000 H -3.80700 4.42100 1.94000 H -2.30600 3.56000 2.40700 H -3.85300 2.69300 2.40800 H -1.28400 4.20600 0.32000 H -2.77100 5.04900 -0.23500 H -2.03100 3.73900 -1.21600 C -4.29600 2.81900 -0.19200 C -4.85600 1.42500 0.05600 H -4.97900 1.26500 1.14000 H -5.87200 1.38100 -0.39200 H -5.05700 3.57300 0.09900 H -4.13400 2.95300 -1.27100 C -3.90800 0.40000 -1.91700 H -3.44600 -0.52700 -2.27700 H -3.28500 1.24200 -2.25800 H -4.90000 0.47200 -2.40000 C -4.27800 -0.93500 0.11300 C -5.61000 -1.58600 -0.25700 H -4.25400 -0.82200 1.20700 H -3.43700 -1.60300 -0.12400 N -5.70500 -2.02600 -1.63800 H -6.42700 -0.86800 -0.07300 H -5.78300 -2.43600 0.44500 C -7.07000 -2.33000 -2.00400 C -4.82800 -3.14200 -1.92500 H -7.12200 -2.60900 -3.06600 H -7.70800 -1.44700 -1.85200 H -7.49700 -3.16800 -1.40900 H -3.77800 -2.88200 -1.73200 913 H -4.91300 -3.41600 -2.98700 H -5.07300 -4.04000 -1.31600 914 Table C.2.70. Atomic coordinates and single point energies for A5. G = –1952.458075 GSP = –1953.95987 Na 1.19000 -0.51000 -0.82100 Na -1.03600 0.71100 0.50500 O 3.22100 -1.31500 -0.31700 C 3.71800 -2.54200 0.19300 C 4.15300 -0.29200 0.03500 C 4.24700 -2.17100 1.57400 C 4.81900 -0.75700 1.34800 H 2.89500 -3.26900 0.20200 H 4.52400 -2.92000 -0.46200 H 3.58500 0.64500 0.12900 H 4.89400 -0.18500 -0.77400 H 4.58200 -0.08500 2.18300 H 5.91100 -0.78100 1.24000 H 4.99200 -2.88300 1.94900 H 3.41000 -2.14400 2.28700 N -1.05300 -1.26100 -0.74200 N 1.10500 1.59600 0.17300 Si -0.78800 -2.82000 -0.10000 Si 1.38400 2.62000 -1.16900 C 0.02400 3.89600 -1.54800 C 3.00400 3.60300 -1.04500 C 1.53600 1.52800 -2.73000 C -1.72900 -1.02400 -2.00800 C 1.62300 1.97700 1.47400 C -2.93700 -1.93100 -2.27600 H -3.43600 -1.67300 -3.22300 915 H -3.67100 -1.83600 -1.45800 H -2.63800 -2.98800 -2.33400 C -2.19200 0.43700 -2.10100 H -2.65400 0.66900 -3.07300 H -1.34700 1.13100 -1.96500 H -2.93900 0.64000 -1.31200 H -1.04100 -1.18000 -2.87400 H 0.65600 0.88200 -2.89800 H 2.43600 0.89000 -2.67500 H 1.64100 2.14600 -3.63400 H -0.07700 4.61000 -0.71600 H -0.95600 3.41100 -1.68700 H 0.24500 4.47100 -2.46100 H 3.17900 4.18600 -1.96200 H 3.86900 2.93700 -0.89800 H 2.98200 4.31000 -0.20100 C 1.61300 0.78500 2.43400 C 0.86900 3.15400 2.11400 H 0.58000 0.44000 2.62500 H 2.06100 1.03000 3.41000 H 2.16500 -0.06300 1.99900 H 2.68900 2.30300 1.41000 H -0.19900 2.89800 2.23800 H 0.92100 4.04600 1.47200 H 1.27300 3.42100 3.10400 C 0.28400 -2.60100 1.45600 C 0.17700 -3.97200 -1.27600 C -2.28500 -3.82900 0.50200 H -2.86500 -3.26200 1.24800 H -1.94300 -4.75800 0.98600 H -2.96800 -4.10900 -0.31400 H 1.10800 -3.49500 -1.62700 H -0.41700 -4.20900 -2.17400 H 0.44700 -4.92600 -0.79600 H 1.21000 -2.03100 1.27400 H 0.57500 -3.57800 1.87400 H -0.27900 -2.06500 2.23900 O -3.10500 1.02400 1.33500 C -3.95800 2.16300 1.20600 C -3.86600 -0.19000 1.30300 C -5.38400 1.62000 1.27200 C -5.21000 0.20800 0.70900 H -6.01800 -0.48000 0.99000 H -5.14700 0.23500 -0.38900 H -5.72800 1.57200 2.31600 H -6.09400 2.23600 0.70600 916 H -3.72700 2.87800 2.00800 H -3.75600 2.65000 0.23700 H -3.30400 -0.92300 0.70300 H -3.98000 -0.57400 2.33100 917 Table C.2.71. Atomic coordinates and single point energies for A18. G = –2494.052964 GSP = –2496.149081 Na 1.68100 0.00100 -0.01800 Na -1.50100 -0.16400 -0.03300 N 0.21800 -1.94400 0.08400 N 0.03200 1.77900 -0.15400 Si 0.22500 -2.43200 -1.56000 C 0.98800 -4.11500 -2.01100 C 1.21100 -1.15000 -2.55400 C -1.51700 -2.50700 -2.34400 C -0.14600 -2.92600 1.09500 C 0.91800 -3.99800 1.39600 H 0.53300 -4.74200 2.11200 H 1.81300 -3.53900 1.84400 H 1.23000 -4.53000 0.48800 C -0.48700 -2.25500 2.43100 H -1.05000 -3.50900 0.79100 H -0.99200 -2.94600 3.12500 H -1.12700 -1.36900 2.29300 H 0.43500 -1.90600 2.92300 H 2.03200 -4.19900 -1.67100 H 0.97900 -4.23800 -3.10600 H 0.42200 -4.95600 -1.58000 H 2.29000 -1.23700 -2.34500 H 0.89700 -0.12200 -2.32100 H 1.07400 -1.29400 -3.63600 H -2.12100 -3.29100 -1.85900 918 H -1.46400 -2.74600 -3.41800 H -2.06800 -1.55600 -2.24500 C -0.40600 2.71200 -1.18300 C -0.62800 2.00500 -2.52700 C 0.54500 3.89200 -1.45900 H 0.34100 1.75900 -2.98800 H -1.18500 2.63500 -3.23900 H -1.17200 1.05400 -2.40500 H -1.37700 3.19200 -0.91100 H 0.10400 4.58800 -2.19100 H 1.49800 3.53200 -1.87600 H 0.76900 4.45800 -0.54600 Si -0.04100 2.27500 1.48500 C 1.03100 1.08500 2.50600 C -1.79700 2.19700 2.23800 C 0.56100 4.01900 1.94800 H 0.80800 0.03300 2.27700 H 0.86400 1.22600 3.58500 H 2.10300 1.25900 2.31400 H -2.26200 1.20200 2.12500 H -2.46000 2.92900 1.74700 H -1.78000 2.43500 3.31300 H 0.52700 4.13700 3.04400 H -0.07500 4.80600 1.51200 H 1.59700 4.20100 1.62200 N -3.95700 -0.79300 1.27800 N -4.03900 0.24500 -1.37700 C -3.61000 -2.11100 0.75600 C -3.98200 -0.84500 2.73400 H -4.40900 -2.85600 0.96100 H -2.68900 -2.46800 1.22900 H -3.44500 -2.06900 -0.32800 H -4.03100 0.16000 3.17000 H -3.06100 -1.31700 3.09700 H -4.84200 -1.43900 3.11200 C -4.05200 0.15500 -2.83000 C -3.73900 1.59800 -0.94200 H -4.26000 -0.88100 -3.13700 H -3.06800 0.43500 -3.22900 H -4.80600 0.81700 -3.30000 H -3.50500 1.61600 0.13100 H -4.55400 2.32500 -1.13500 H -2.86000 1.95700 -1.48700 C -5.26600 -0.40500 0.73900 C -5.26800 -0.32700 -0.81000 C -5.91600 0.84300 1.35000 919 C -7.42000 0.85400 1.01100 C -7.72100 0.17700 -0.33600 C -6.55900 0.37200 -1.30500 H -5.96400 -1.23900 0.98600 H -5.43200 1.75500 0.97400 H -5.79800 0.85700 2.43900 H -7.77600 1.89500 0.99200 H -7.98500 0.34900 1.80900 H -8.64900 0.57900 -0.76600 H -7.89300 -0.90200 -0.19300 H -5.30100 -1.36500 -1.18100 H -6.37400 1.45300 -1.41400 H -6.82000 -0.00100 -2.30500 H 4.06600 3.18200 -0.34800 H 4.31900 2.32500 -2.65200 H 3.86700 -0.40300 3.02500 H 4.37500 -2.91600 0.38100 H 6.01600 2.49500 -0.53200 H 6.66500 -0.99300 2.01600 H 7.45700 1.48800 1.05800 H 8.55700 -0.77300 0.61800 C 3.49600 2.26700 -0.09300 C 3.67300 1.47700 -2.34400 C 3.71600 -2.06500 0.11800 C 3.73200 -1.28400 2.38000 C 6.32300 1.47400 -0.80100 C 7.61700 -0.45200 0.14700 C 7.53900 1.06700 0.04200 C 6.41900 -0.98700 0.94300 C 5.12600 -0.15600 0.74000 C 5.11700 0.51100 -0.64700 N 3.82200 1.12900 -0.94300 N 3.89300 -0.91000 0.98700 H 3.91000 -1.79100 -0.92800 H 5.13400 0.65400 1.48900 H 5.24100 -0.29200 -1.39200 H 4.44600 -2.06900 2.70300 H 3.91200 0.60800 -2.97600 H 3.68900 2.02500 0.96100 H 2.42500 2.49700 -0.19200 H 2.62800 1.75900 -2.54000 H 8.45700 1.48700 -0.39400 H 2.71300 -1.66600 2.53900 H 6.23200 -2.03400 0.66400 H 2.67400 -2.41000 0.18400 H 7.61900 -0.87800 -0.87100 920 H 6.60800 1.50800 -1.86400 921 Table C.2.72. Atomic coordinates and single point energies for A14. G = –2182.539871 GSP = –2184.299664 Na -1.49700 0.06600 0.10300 Na 1.51500 0.12000 0.02300 N -0.12200 1.96800 -0.03500 N 0.02400 -1.76900 0.45900 Si 0.03700 2.59300 1.54700 C 0.34700 4.46200 1.73900 C 1.52600 1.73200 2.35500 C -1.41900 2.19600 2.72100 C -0.93300 2.63400 -1.04500 C -2.32900 3.05800 -0.55600 H -2.95000 3.45800 -1.37400 H -2.24200 3.84800 0.20900 H -2.86300 2.20900 -0.10200 C -0.27100 3.85900 -1.70100 H -1.11200 1.91900 -1.87900 H -0.93500 4.31800 -2.45100 H 0.66700 3.59100 -2.20600 H -0.03700 4.62000 -0.94100 H 1.23900 4.78200 1.17800 H 0.50900 4.71100 2.80000 H -0.50500 5.06200 1.38500 H 2.43400 1.87700 1.74900 H 1.34800 0.65100 2.48600 H 1.72400 2.14000 3.35800 H -2.37300 2.59800 2.34600 922 H -1.25100 2.60000 3.73300 H -1.52800 1.10200 2.82100 C -0.16000 -1.98700 1.88600 C 1.16300 -2.17200 2.64800 C -1.07300 -3.17200 2.25100 H 1.62900 -3.12500 2.35300 H 1.01500 -2.18600 3.74000 H 1.87100 -1.36500 2.40600 H -0.63500 -1.07900 2.33200 H -1.32200 -3.18400 3.32500 H -0.56900 -4.12300 2.01800 H -2.00900 -3.15200 1.67600 Si 0.29900 -3.07900 -0.61000 C 1.16300 -2.37300 -2.15200 C -1.24600 -4.04000 -1.21300 C 1.38500 -4.54100 -0.03100 H 0.62500 -1.51100 -2.57600 H 1.27300 -3.12600 -2.94700 H 2.17500 -2.02900 -1.87800 H -2.01500 -3.43200 -1.71200 H -1.72600 -4.54000 -0.35600 H -0.94300 -4.82900 -1.92000 H 1.63600 -5.16400 -0.90500 H 0.84000 -5.18600 0.67500 H 2.32500 -4.24300 0.44900 N 4.00300 -0.84000 0.18800 N 3.19300 1.60100 -1.15000 C 4.66000 -0.39100 -1.03400 C 4.55700 1.11300 -1.25600 H 4.20900 -0.93600 -1.87900 H 5.73900 -0.66500 -1.02600 H 5.01000 1.36000 -2.23900 H 5.16600 1.63300 -0.50200 C 4.15300 -2.27700 0.32600 C 4.53200 -0.17200 1.36600 H 3.74100 -2.78800 -0.55500 H 3.60300 -2.62300 1.21100 H 5.21900 -2.57100 0.43300 H 4.33100 0.90600 1.33000 H 5.62800 -0.32500 1.47100 H 4.04300 -0.57200 2.26500 C 3.12900 3.00900 -0.80000 C 2.42000 1.32400 -2.35000 H 2.08200 3.27600 -0.60700 H 3.53300 3.66100 -1.60400 H 3.70900 3.19300 0.11700 923 H 2.49000 0.25900 -2.61500 H 2.77400 1.91600 -3.22000 H 1.36300 1.56700 -2.16300 H -4.11400 0.51000 -3.76300 H -4.80700 1.20600 -0.16300 H -2.33200 -1.28500 -3.47500 H -4.68800 -1.30600 2.58600 H -5.13100 -0.43800 -1.52200 H -4.79500 -2.03900 0.27300 C -3.67800 0.97200 -2.85300 C -4.84500 0.71400 0.81600 N -3.13000 -0.02000 -1.94500 N -3.79500 -0.28200 0.94200 C -2.02200 -0.72200 -2.56900 C -3.75000 -0.78000 2.30900 C -3.93700 -1.38800 -0.00500 C -4.15400 -0.93700 -1.44800 H -2.88400 1.66500 -3.16500 H -1.57500 -1.43800 -1.86700 H -2.91500 -1.47900 2.43300 H -4.69600 1.48900 1.58000 H -5.85500 0.27400 0.95800 H -4.45900 1.56000 -2.35200 H -4.22600 -1.84100 -2.08500 H -1.24200 -0.00200 -2.85900 H -3.60400 0.05900 3.00300 H -3.03200 -2.01800 0.06300 924 Table C.2.73. Atomic coordinates and single point energies for A2. G = –2030.572269 GSP = –2032.140810 Na -1.42000 -0.32500 0.01200 Na 1.39300 0.43000 -0.10300 N 0.47900 -1.64900 0.46300 N -0.53300 1.79300 -0.39600 Si 0.57300 -2.94200 -0.65800 C 2.22200 -3.89400 -0.71900 C 0.28900 -2.23800 -2.39500 C -0.69700 -4.34200 -0.41700 C 0.60100 -1.96300 1.88000 C 1.22700 -0.79600 2.65100 H 1.30600 -0.99700 3.73100 H 0.60500 0.10800 2.52900 H 2.23800 -0.57000 2.27800 C -0.74600 -2.31000 2.53200 H 1.26400 -2.84300 2.05800 H -0.63500 -2.61800 3.58400 H -1.24900 -3.11800 1.98100 H -1.41100 -1.42700 2.51600 H 3.06000 -3.27300 -1.06700 H 2.13000 -4.74900 -1.40700 H 2.49400 -4.29900 0.27000 H 1.03100 -1.45800 -2.64100 H -0.71300 -1.79000 -2.50400 H 0.37800 -3.02800 -3.15700 H -0.52200 -4.87300 0.53300 H -0.61900 -5.08500 -1.22800 925 H -1.72800 -3.95900 -0.40300 C -0.64400 2.40800 -1.71100 C -1.02500 1.37200 -2.76800 C 0.63400 3.12800 -2.16600 H -0.25400 0.58500 -2.82000 H -1.12600 1.81500 -3.77200 H -1.98100 0.89200 -2.51100 H -1.44800 3.18000 -1.73200 H 0.49600 3.65300 -3.12500 H 1.44600 2.39300 -2.29600 H 0.96300 3.86200 -1.41400 Si -0.61900 2.81600 0.97900 C 1.07600 3.19500 1.76700 C -1.67100 2.01400 2.34500 C -1.41600 4.50300 0.63500 H 1.61100 2.27800 2.07300 H 0.97700 3.82600 2.66400 H 1.71600 3.72800 1.04600 H -1.44100 0.94700 2.50500 H -2.73500 2.09000 2.07000 H -1.53900 2.52100 3.31400 H -1.48100 5.09100 1.56300 H -2.43700 4.39100 0.23700 H -0.83800 5.09100 -0.09500 C -3.85200 -2.37400 0.32400 C -4.12200 -1.38600 1.27200 C -3.74800 -2.02200 -1.02300 C -4.27100 -0.05700 0.87700 C -3.90400 -0.69000 -1.41400 C -4.15300 0.31800 -0.47000 C 3.81800 0.81500 -1.77900 C 3.90200 2.02700 -1.08600 C 3.96700 -0.39500 -1.10100 C 4.20200 -0.42400 0.28400 C 4.13300 2.01300 0.28900 C 4.27900 0.79800 0.96400 H -3.72700 -3.41300 0.63400 H -4.21200 -1.65200 2.32700 H -4.48500 0.70700 1.62600 C -4.22600 1.76600 -0.87400 H -3.83300 -0.42800 -2.47100 H -3.54600 -2.78800 -1.77400 H 4.46000 0.79900 2.04100 H 4.19600 2.95000 0.84300 C 4.32700 -1.73100 1.01700 H 3.78400 2.97300 -1.61400 926 H 3.90100 -1.33500 -1.65300 H 3.63700 0.81400 -2.85600 H 4.73600 -1.58300 2.02500 H 4.97600 -2.43200 0.47300 H 3.33700 -2.20300 1.10900 H -4.52300 1.87600 -1.92500 H -3.23000 2.22700 -0.75200 H -4.93600 2.32000 -0.24600 927 Table C.2.74. Atomic coordinates and single point energies for A16. G = –744.119976 GSP = –744.61314 Na 0.48200 2.37900 -0.43900 N 0.52100 0.29300 0.00700 Si -1.09200 -0.23000 0.07800 C -2.15300 1.32100 -0.30400 C -1.62700 -1.55100 -1.17800 C -1.66300 -0.87100 1.77100 H -1.35700 -1.25300 -2.20300 H -2.71300 -1.73500 -1.14400 H -1.12400 -2.50900 -0.96800 H -1.08200 -1.76000 2.06200 H -2.72700 -1.15800 1.76400 H -1.51300 -0.10900 2.55000 H -3.22700 1.08300 -0.28200 H -1.95300 1.72200 -1.31500 H -2.00500 2.12100 0.44500 C 1.63900 -0.57800 0.27600 C 2.10500 -1.33400 -0.97600 C 2.81400 0.21500 0.85700 H 2.94600 -2.01500 -0.76600 H 2.42400 -0.61000 -1.74400 H 1.27800 -1.92300 -1.40000 H 1.38600 -1.35100 1.03800 H 3.14100 0.97700 0.12400 H 3.68400 -0.42000 1.08400 H 2.50400 0.73000 1.77900 928 Table C.2.75. Atomic coordinates and single point energies for A27. G = –1358.527839 GSP = –1359.72034 Na 0.52200 0.35000 -0.50400 N -1.67900 0.62700 -0.18100 Si -2.96900 -0.37700 0.28200 C -2.82100 -1.01600 2.07800 C -4.66300 0.49000 0.23900 C -3.16600 -1.96200 -0.76800 H -4.67000 1.36400 0.90900 H -5.46000 -0.19500 0.56900 H -4.92100 0.84400 -0.77100 H -3.38200 -1.69800 -1.81600 H -3.97700 -2.61200 -0.40300 H -2.23500 -2.55400 -0.77500 H -3.73900 -1.56100 2.35000 H -2.71300 -0.17000 2.77600 H -1.97900 -1.70500 2.25200 C -1.97100 1.80600 -0.96900 C -0.81600 2.82100 -0.93400 C -2.29900 1.49000 -2.43900 H -1.09700 3.77500 -1.40600 H 0.06200 2.45200 -1.50300 H -0.50200 3.00700 0.10200 H -2.85200 2.36100 -0.57200 H -1.45000 0.95400 -2.90000 H -2.50500 2.39600 -3.03400 H -3.17500 0.82700 -2.50800 O 2.89800 0.42700 -0.88400 O 1.21500 -1.74700 -1.34900 O 1.30000 -1.03900 1.31800 O 1.52100 1.70200 1.17800 C 2.74900 2.19100 0.70500 929 C 3.61100 1.07600 0.14200 C 3.44400 -0.81900 -1.24300 C 2.41800 -1.58300 -2.05800 C 0.53300 -2.14400 0.89500 C 1.20700 -2.72600 -0.32700 C 1.52900 1.02600 2.42000 C 0.67700 -0.21600 2.28900 H 1.11900 1.68300 3.20500 H 2.55700 0.74300 2.70500 H -0.33500 0.07400 1.94900 H 0.60200 -0.73900 3.26000 H -0.48900 -1.81900 0.62900 H 0.45700 -2.90800 1.69000 H 0.65700 -3.61800 -0.67000 H 2.23600 -3.03000 -0.06900 H 2.16700 -1.01600 -2.96600 H 2.83800 -2.55500 -2.37100 H 4.37300 -0.69200 -1.83000 H 3.69500 -1.38400 -0.32700 H 3.84900 0.34500 0.93700 H 4.56300 1.48900 -0.23800 H 2.50700 2.91100 -0.09000 H 3.30500 2.72800 1.49400 930 Table C.2.76. Atomic coordinates and single point energies for A28. G = –1590.596713 GSP = –1592.05197 Na 0.30800 -0.13100 -0.09300 N -1.80100 0.70800 0.29700 Si -3.32800 0.42500 -0.40400 C -4.67000 -0.04100 0.87400 C -4.07100 1.91000 -1.34500 C -3.31700 -1.00500 -1.66300 H -4.16000 2.79500 -0.69500 H -5.07900 1.67300 -1.72300 H -3.44100 2.18800 -2.20500 H -2.36900 -1.04100 -2.22300 H -4.13700 -0.86100 -2.38300 H -3.48200 -1.98500 -1.18600 H -5.65600 -0.19900 0.40800 H -4.78100 0.75000 1.63300 H -4.39100 -0.96700 1.40300 C -1.74200 1.94500 1.06000 C -0.93500 1.79000 2.35600 C -1.16500 3.10000 0.22200 H -0.84400 2.74200 2.90500 H 0.08200 1.41900 2.14000 H -1.42400 1.06000 3.02000 H -2.75000 2.29400 1.39200 H -0.18100 2.79800 -0.17000 H -1.05400 4.03700 0.79600 H -1.81200 3.29600 -0.64500 O 2.40800 -1.41600 -0.65300 O -0.09800 -1.91700 -1.68500 O 0.03000 -2.43100 1.03100 931 O 1.66300 -0.39300 1.88700 C 2.99400 -0.66500 1.52400 C 3.09000 -1.79200 0.51800 C 2.24600 -2.46500 -1.57100 C 1.05400 -2.14700 -2.45400 C -1.13000 -2.75100 0.29500 C -0.71000 -3.06300 -1.12300 C 1.06700 -1.28100 2.81300 C -0.24500 -1.79600 2.26100 H 0.88400 -0.75200 3.76300 H 1.74200 -2.13100 3.01600 H -0.95200 -0.96200 2.09100 H -0.69500 -2.50500 2.98300 H -1.81700 -1.88900 0.30200 H -1.64800 -3.62700 0.72900 H -1.59100 -3.34600 -1.72100 H -0.00600 -3.91300 -1.11500 H 1.24100 -1.21900 -3.01400 H 0.89900 -2.95800 -3.18700 H 3.15300 -2.60100 -2.18900 H 2.07000 -3.41100 -1.02600 H 2.62800 -2.70800 0.93000 H 4.15500 -2.00500 0.30200 H 3.38400 0.25300 1.06700 H 3.60500 -0.90800 2.41100 O 1.92900 1.56300 -0.32400 C 2.32400 2.67300 0.47900 C 2.24600 1.79000 -1.69500 C 2.54500 3.81700 -0.50300 C 3.08400 3.06800 -1.72300 H 3.22900 4.58300 -0.11800 H 1.58200 4.29400 -0.73900 H 4.15000 2.83200 -1.58400 H 2.97500 3.62300 -2.66400 H 2.77900 0.90700 -2.07800 H 1.30600 1.91400 -2.26000 H 1.53600 2.86800 1.21900 H 3.25800 2.42500 1.01700 932 Table C.2.77. Atomic coordinates and single point energies for A29. G = –1512.136234 GSP = –1513.50246 Na 0.52700 -0.03700 0.08000 N -1.75400 -0.01200 0.33000 Si -2.23600 -1.40100 -0.51200 C -3.44600 -2.60100 0.34900 C -2.97400 -1.13400 -2.25500 C -0.66400 -2.44600 -0.80000 H -3.90700 -0.54800 -2.21500 H -3.20300 -2.08900 -2.75600 H -2.26000 -0.58100 -2.88700 H 0.03700 -1.93100 -1.47900 H -0.91400 -3.41400 -1.26100 H -0.16400 -2.64500 0.16300 H -3.49700 -3.56000 -0.19200 H -4.46700 -2.19300 0.40100 H -3.11500 -2.80600 1.38000 C -2.63200 1.06500 0.70100 C -4.09500 0.67000 0.96000 C -2.59900 2.22100 -0.31400 H -4.56500 0.29700 0.03400 H -4.69100 1.52400 1.31900 H -4.14600 -0.13300 1.71100 H -2.29400 1.50600 1.67100 H -3.21800 3.08100 -0.00400 H -2.96800 1.85900 -1.28900 H -1.56100 2.56100 -0.45400 O 1.39800 -1.42400 1.83300 O 2.62300 -1.11200 -0.55800 933 O 1.11300 1.26200 2.11300 O 0.90700 2.20500 -0.39700 O 1.04100 0.29400 -2.27700 C 0.53300 2.52200 1.89200 C 1.15100 3.11400 0.64300 H 2.23800 3.26900 0.77400 H 0.67900 4.09000 0.43000 C 1.04700 2.66200 -1.71100 C 0.51100 1.55500 -2.61000 H 2.10400 2.91000 -1.92900 H 0.45000 3.57800 -1.88200 H 0.69900 1.79900 -3.67200 H -0.57200 1.46300 -2.44500 C 2.39900 0.09100 -2.56500 C 2.79600 -1.22900 -1.94700 H 2.15700 -2.03700 -2.34800 H 3.84900 -1.46100 -2.19400 H 2.57400 0.06900 -3.65600 H 3.02500 0.88900 -2.12600 C 2.66100 -1.99600 1.62800 C 2.81000 -2.30900 0.15600 C 1.18200 -0.85800 3.10800 C 0.35600 0.39600 2.93800 H 2.15200 -0.59300 3.56500 H 0.66400 -1.57400 3.76800 H 0.17000 0.85300 3.92700 H -0.60700 0.15500 2.44400 H 0.70300 3.19500 2.75400 H -0.55300 2.41900 1.73100 H 2.78700 -2.92300 2.21600 H 3.45100 -1.28300 1.92900 H 2.06100 -3.05800 -0.15900 H 3.81900 -2.72200 -0.02700 934 Table C.2.78. Atomic coordinates and single point energies for A30. G = –1744.202046 GSP = –1745.83228 Na -0.52300 -0.38600 0.07900 N 1.76000 0.04500 -0.34500 Si 2.58200 0.97500 0.81300 C 3.88700 0.08000 1.89600 C 3.54200 2.50400 0.18000 C 1.31100 1.66500 2.05000 H 4.41900 2.20600 -0.41600 H 3.90800 3.11800 1.02000 H 2.91200 3.14200 -0.46100 H 0.64100 2.37500 1.54200 H 1.81600 2.19900 2.87100 H 0.66900 0.88700 2.49100 H 4.23600 0.74100 2.70600 H 4.76900 -0.21000 1.30300 H 3.49300 -0.83800 2.36100 C 2.38400 -0.43100 -1.55800 C 3.79500 -1.02100 -1.38100 C 2.45300 0.63300 -2.67200 H 4.50800 -0.23100 -1.08800 H 4.17000 -1.47800 -2.31100 H 3.80900 -1.78300 -0.58600 H 1.76800 -1.26100 -1.97600 H 2.85300 0.22200 -3.61500 H 3.10200 1.46600 -2.35900 H 1.45800 1.05700 -2.87600 O -1.19500 -0.77800 2.44100 O -3.00000 -0.50000 0.43000 935 O 0.13400 -2.80900 1.22500 O -0.31800 -2.29600 -1.41100 O -1.81500 -0.15600 -2.04100 C 1.07500 -3.19900 0.25700 C 0.32600 -3.48200 -1.02300 H -0.41400 -4.29000 -0.87300 H 1.04500 -3.80200 -1.80000 C -0.83400 -2.27900 -2.70800 C -1.10900 -0.82500 -3.05700 H -1.74300 -2.90900 -2.77600 H -0.10200 -2.67900 -3.43500 H -1.64300 -0.75700 -4.02400 H -0.14800 -0.29900 -3.14400 C -3.16800 -0.50600 -1.91200 C -3.68100 0.11200 -0.63600 H -3.47500 1.19600 -0.64600 H -4.77100 -0.05400 -0.54900 H -3.75100 -0.13700 -2.77600 H -3.29200 -1.60200 -1.84900 C -2.56600 -0.76000 2.73000 C -3.26000 0.07600 1.68400 C -0.44400 -1.69800 3.20100 C 0.70000 -2.19400 2.35200 H -1.08200 -2.55600 3.47800 H -0.06700 -1.22700 4.12600 H 1.31300 -2.90700 2.93800 H 1.34700 -1.35600 2.03900 H 1.62200 -4.10700 0.57700 H 1.78700 -2.37200 0.08600 H -2.76100 -0.33600 3.73300 H -2.96900 -1.78800 2.70200 H -2.87900 1.11000 1.71300 H -4.34600 0.09400 1.89200 O -1.34600 2.06800 -0.02500 C -0.52600 2.48000 -1.12600 C -1.84200 3.20100 0.67600 C -0.13600 3.91800 -0.81100 C -1.39800 4.43200 -0.11800 H 0.13700 4.49000 -1.70800 H 0.71900 3.93400 -0.11900 H -2.15900 4.69900 -0.86700 H -1.22800 5.30600 0.52400 H 0.33300 1.79100 -1.17600 H -1.11300 2.41300 -2.05900 H -2.94000 3.13400 0.75800 H -1.42200 3.20300 1.69600 936 937 Table C.2.79. Atomic coordinates and single point energies for A31. G = –1744.194864 GSP = –1745.82351 Na -0.44100 0.02500 0.02900 N 2.01800 0.28800 0.19300 Si 3.43500 -0.65000 0.06100 C 3.87900 -1.25300 -1.70700 C 5.07300 0.11200 0.67900 C 3.31300 -2.26200 1.07700 H 5.39200 0.97200 0.06900 H 5.87400 -0.64300 0.62800 H 4.99000 0.45100 1.72300 H 3.19200 -2.04300 2.15000 H 4.25200 -2.82600 0.95800 H 2.49400 -2.93500 0.77800 H 4.83300 -1.80500 -1.70800 H 3.98500 -0.40100 -2.39700 H 3.11400 -1.92400 -2.13000 C 2.05500 1.71400 -0.07600 C 2.60900 2.10400 -1.45600 C 2.77900 2.55700 0.99500 H 3.67800 1.84800 -1.53400 H 2.51100 3.18600 -1.64700 H 2.06800 1.56500 -2.24800 H 1.01600 2.09300 -0.07900 H 2.61000 3.63700 0.84000 H 3.86400 2.38400 0.97000 H 2.43200 2.29200 2.00600 O -0.59000 1.32000 -1.89900 O -0.47700 -1.51700 -1.72700 O -1.23000 2.09100 0.56000 O -1.13200 0.24000 2.48100 O -0.80200 -2.14100 0.98000 C -0.82700 2.50800 1.84200 938 C -0.21200 1.31200 2.55200 H -0.00700 1.58200 3.60500 H 0.74000 1.02900 2.06300 C -0.69000 -0.98000 3.03700 C 0.08200 -1.83300 2.04600 H -1.59400 -1.52400 3.34800 H -0.06600 -0.79900 3.93000 H 0.41900 -2.76000 2.54700 H 0.96900 -1.28500 1.67500 C -0.37600 -3.10000 0.03800 C 0.36100 -2.49000 -1.14200 H 1.29500 -2.01200 -0.81100 H 0.60900 -3.28800 -1.86800 H 0.26600 -3.86100 0.51600 H -1.28500 -3.60100 -0.32700 C -0.73700 0.46000 -3.00200 C 0.12100 -0.76600 -2.76100 C -1.57000 2.31400 -1.76000 C -1.30300 3.05200 -0.45800 H -2.56900 1.84400 -1.73000 H -1.53600 3.03200 -2.60000 H -1.69900 2.89300 2.40200 H -0.06500 3.30600 1.77500 H -0.42300 0.96400 -3.93400 H -1.79500 0.15200 -3.10400 H 1.13500 -0.44900 -2.45400 H 0.19100 -1.36600 -3.68700 H -0.34800 3.60600 -0.52800 H -2.11600 3.77800 -0.27100 O -2.83400 -0.14800 -0.36300 C -3.72500 0.53300 0.52300 C -3.38900 -1.40200 -0.73300 C -4.89400 -1.20500 -0.62400 H -3.04500 -2.17900 -0.02800 H -3.02200 -1.65700 -1.73600 H -5.45000 -2.14900 -0.55500 H -5.26700 -0.64300 -1.49500 C -4.97100 -0.35200 0.64300 H -4.89500 -0.99800 1.53000 H -5.89700 0.23100 0.72800 H -3.96400 1.51700 0.08200 H -3.22000 0.69900 1.48400 939 Table C.2.80. Atomic coordinates and single point energies for A32. G = –1665.722998 GSP = –1667.265100 Na -0.44200 -0.07500 0.15000 N 1.54700 -0.61700 -0.93400 Si 3.01900 0.00900 -0.37400 C 3.36100 -0.33400 1.47500 C 4.55600 -0.64500 -1.28800 C 3.18000 1.91700 -0.46400 H 4.60500 -1.74500 -1.25800 H 5.47400 -0.25200 -0.82200 H 4.56300 -0.34300 -2.34700 H 3.01400 2.28300 -1.49100 H 4.18300 2.24700 -0.14800 H 2.44200 2.40000 0.19500 H 4.28500 0.15700 1.81900 H 3.45600 -1.41600 1.66300 H 2.52800 0.04300 2.08800 C 1.53600 -1.50200 -2.08100 C 1.27900 -2.97000 -1.70200 C 0.48900 -1.09300 -3.12700 H 1.41100 -3.65100 -2.55900 H 0.24200 -3.07600 -1.34400 H 1.96500 -3.27900 -0.89700 H 2.51000 -1.50200 -2.61700 H -0.51000 -1.07800 -2.66100 H 0.46600 -1.79100 -3.98000 H 0.69400 -0.08400 -3.51400 O -2.97200 0.62100 0.25700 O -1.28800 1.30600 -1.83400 O -1.89400 -1.86400 -0.51200 O -0.91700 -1.83800 2.05400 940 O -0.00300 2.26200 0.40800 O 0.00100 0.65900 2.42900 C -0.07000 2.88900 1.65700 C 0.51800 1.93800 2.68100 C 0.23400 -0.29900 3.43300 C 0.27100 -1.66200 2.78200 C -0.93400 -3.02500 1.30400 C -2.10600 -2.95000 0.35700 C -3.80000 -0.41100 -0.23000 C -3.03800 -1.35700 -1.15000 C -3.11200 1.87400 -0.36300 C -2.56400 1.88300 -1.78600 C -0.18500 2.18700 -1.92700 C -0.07200 3.09500 -0.71900 H -1.12200 3.12700 1.90700 H 0.50700 3.83200 1.66400 H 0.25400 2.28500 3.69700 H 1.62000 1.92000 2.59300 H -0.56700 -0.24800 4.19300 H 1.20400 -0.12100 3.93000 H 0.38100 -2.44100 3.56000 H 1.13700 -1.71800 2.09800 H -1.04000 -3.91000 1.96100 H 0.00400 -3.12200 0.72900 H -3.03100 -2.81000 0.94400 H -2.19500 -3.89100 -0.21500 H -3.70400 -2.17500 -1.48300 H -2.67500 -0.82600 -2.04100 H -4.17400 -0.96100 0.64800 H -4.67900 -0.00100 -0.75900 H -2.55200 2.57800 0.26800 H -4.17200 2.19200 -0.37100 H -2.56500 2.91600 -2.17900 H -3.22300 1.29400 -2.44500 H -0.24400 2.79000 -2.85100 H 0.69800 1.52800 -1.95400 H -0.93500 3.78600 -0.63700 H 0.84200 3.71000 -0.80800 941 Table C.2.81. Atomic coordinates and single point energies for A37. G = –1130.487967 GSP = –1131.414299 N -1.74700 0.22300 -0.46000 Na 0.41700 -0.07600 -0.61800 Si -2.41200 -1.01300 0.48900 C -3.06700 -0.54000 2.21700 C -3.82200 -1.98400 -0.33400 C -0.99800 -2.25900 0.83300 H -3.36300 -1.42900 2.79700 H -3.94800 0.11600 2.13900 H -2.30400 0.00500 2.79600 H -4.14400 -2.83700 0.28400 H -3.51400 -2.36600 -1.32000 H -4.70100 -1.33700 -0.49000 H -1.33100 -3.09500 1.46700 H -0.14900 -1.78400 1.35800 H -0.62900 -2.69200 -0.11400 C -2.54900 1.09700 -1.27800 C -3.27000 2.18900 -0.47300 C -1.68600 1.75300 -2.36300 H -3.88100 2.84700 -1.11300 H -2.53300 2.81000 0.06200 H -3.93000 1.73700 0.28300 H -3.34700 0.53900 -1.82100 H -2.26300 2.42200 -3.02000 H -1.21600 0.97800 -2.99000 H -0.88700 2.35000 -1.88900 N 2.52700 -1.23900 -0.68100 N 1.52400 1.52900 0.74700 C 2.34700 -1.79600 -2.01700 C 2.71900 -2.32300 0.27500 H 1.48700 -2.48100 -2.02600 942 H 3.24000 -2.35900 -2.35700 H 2.15900 -0.99200 -2.74500 H 3.63500 -2.90600 0.04800 H 1.85400 -2.99900 0.24600 H 2.80200 -1.93600 1.29800 C 0.76100 2.76300 0.61100 C 1.13200 0.84200 1.97000 H -0.31000 2.51600 0.58200 H 1.02900 3.26900 -0.32700 H 0.95500 3.46100 1.45200 H 1.61500 -0.14300 2.03600 H 0.04200 0.69200 1.96400 H 1.40400 1.42300 2.87500 C 2.95600 1.78000 0.68600 C 3.83700 0.53600 0.58500 C 3.65600 -0.30400 -0.68000 H 3.52300 0.37900 -1.53600 H 4.59200 -0.87100 -0.87500 H 4.87900 0.88900 0.59400 H 3.74100 -0.08800 1.48600 H 3.14300 2.41100 -0.19800 H 3.28000 2.37400 1.56900 943 Table C.2.82. Atomic coordinates and single point energies for A26. G = –1206.102402 GSP = –1207.125810 Na 0.56700 0.13600 -0.95000 N -1.07300 -0.02300 0.55000 Si -2.46100 0.06200 -0.41600 C -1.90100 0.39000 -2.22000 C -3.51200 -1.52500 -0.48700 C -3.68900 1.45100 0.02100 H -2.92500 -2.36700 -0.88800 H -4.41000 -1.40300 -1.11400 H -3.84800 -1.81000 0.52300 H -4.02300 1.34100 1.06500 H -4.58500 1.43900 -0.62000 H -3.21600 2.44200 -0.07000 H -2.77300 0.54700 -2.87300 H -1.35300 -0.47300 -2.63900 H -1.27200 1.29100 -2.32200 C -1.18600 -0.55000 1.88900 C -0.70900 -2.00900 1.97100 C -0.40200 0.29300 2.90200 H -0.78500 -2.42900 2.98800 H 0.34500 -2.06100 1.64600 H -1.29900 -2.63500 1.28500 H -2.23800 -0.55400 2.26300 H 0.67600 0.25600 2.66200 H -0.52600 -0.06800 3.93600 H -0.72300 1.34400 2.85300 O 1.04200 2.43000 -0.60400 O 2.91300 0.29700 -0.52900 O 1.46000 -1.95800 -0.86100 944 C -0.12600 3.13400 -0.22000 H 0.14100 4.13600 0.15700 H -0.68200 2.55800 0.53800 H -0.75300 3.24500 -1.11300 C 1.96300 2.31100 0.45100 C 3.19700 1.60500 -0.07500 H 2.25300 3.31100 0.82600 H 1.50400 1.75500 1.29100 H 3.98100 1.58300 0.70200 H 3.58000 2.16000 -0.94300 C 2.96700 -0.70600 0.46100 C 2.69600 -2.03900 -0.20100 H 3.96300 -0.72500 0.93900 H 2.20500 -0.52700 1.24300 H 2.66900 -2.82200 0.57900 H 3.50100 -2.28600 -0.91700 C 0.86000 -3.19600 -1.14700 H 0.69400 -3.77300 -0.22200 H 1.48000 -3.78800 -1.84200 H -0.11400 -2.99100 -1.60800 945 Table C.2.83. Atomic coordinates and single point energies for A25. G = –1668.064074 GSP = –1669.61721 Na 0.41400 0.06900 -0.15600 N -1.86200 -0.01000 -0.75100 Si -3.14200 -0.13000 0.35000 C -2.43600 -0.52900 2.08700 C -4.23900 1.42200 0.58500 C -4.40700 -1.50400 -0.04800 H -3.65300 2.31300 0.86100 H -4.99700 1.26400 1.36900 H -4.76900 1.66300 -0.35000 H -4.92800 -1.30500 -0.99900 H -5.17300 -1.57400 0.74100 H -3.92500 -2.49100 -0.13800 H -2.86900 0.08800 2.89000 H -1.34600 -0.36500 2.06200 H -2.61600 -1.58400 2.35200 C -2.07500 -0.34600 -2.13900 C -2.99700 0.62300 -2.90100 C -0.73300 -0.45200 -2.87500 H -3.13900 0.31900 -3.95100 H -2.57400 1.64000 -2.89200 H -3.98900 0.67000 -2.42500 H -2.56000 -1.35100 -2.25700 H -0.20900 0.51800 -2.84000 H -0.85200 -0.74900 -3.92900 H -0.09700 -1.20100 -2.37700 O 2.52800 -1.36800 -1.28100 O 2.80400 1.06700 -0.04400 O 0.63800 2.25200 -1.23700 C 2.40000 -2.33600 -2.28900 946 H 2.51300 -1.88800 -3.29200 H 1.40100 -2.77300 -2.19100 H 3.15900 -3.13100 -2.16900 C 3.81200 -0.83100 -1.17600 C 3.82100 0.10300 0.01900 H 4.56600 -1.62600 -1.01300 H 4.09700 -0.30600 -2.10900 H 4.81500 0.58000 0.11300 H 3.61400 -0.48000 0.92800 C 2.96700 2.05300 -1.03300 C 1.78700 2.98700 -0.94700 H 3.91000 2.60900 -0.87300 H 2.99100 1.60200 -2.04100 H 1.92400 3.82000 -1.66400 H 1.71900 3.40800 0.07500 C -0.54600 3.01500 -1.19200 H -0.62800 3.66500 -2.08300 H -0.55800 3.65300 -0.29000 H -1.37700 2.29600 -1.14700 O 0.29800 -2.47400 -0.02800 O 1.28700 -0.82400 2.02100 O 0.40700 1.76800 1.67000 C -0.98100 -3.06600 -0.05700 H -1.53500 -2.88800 0.87900 H -0.89500 -4.15500 -0.22700 H -1.53900 -2.59000 -0.87100 C 1.13600 -2.94500 0.99100 C 0.95400 -2.16700 2.27900 H 2.17000 -2.80800 0.63900 H 0.96600 -4.02100 1.18100 H 1.61200 -2.58700 3.06400 H -0.09100 -2.23200 2.63700 C 1.16600 0.02300 3.13700 C 1.35800 1.44700 2.65400 H 1.92700 -0.22600 3.90200 H 0.16800 -0.10200 3.59900 H 2.34500 1.53800 2.18100 H 1.30300 2.14600 3.50700 C -0.78300 2.33300 2.16600 H -0.63200 3.39500 2.43100 H -1.15500 1.79300 3.05200 H -1.53900 2.25000 1.37500 947 Table C.2.84. Atomic coordinates and single point energies for A35. G = –1052.520905 GSP = –1053.789241 Na -0.76600 -0.34100 -0.99600 N 0.96700 0.59100 -0.04500 Si 2.31100 -0.33900 -0.48900 C 1.64700 -1.75400 -1.59600 C 3.62900 0.56800 -1.51400 C 3.27700 -1.19600 0.91300 H 3.18300 1.01700 -2.41500 H 4.43800 -0.11000 -1.82900 H 4.08800 1.38200 -0.93100 H 3.74900 -0.44600 1.56900 H 4.07800 -1.84500 0.52400 H 2.61400 -1.81200 1.54100 H 1.21600 -1.36100 -2.53400 H 0.88600 -2.37100 -1.08500 H 2.45400 -2.44300 -1.89000 C 1.09800 1.86900 0.60800 C -0.01900 2.82300 0.16700 C 1.08700 1.75100 2.14100 H 0.04800 3.81000 0.65300 H -1.00200 2.38500 0.41900 H 0.01800 2.96500 -0.92400 H 2.05400 2.38200 0.34700 H 0.12100 1.33300 2.47500 H 1.23000 2.72300 2.64100 H 1.87800 1.06500 2.47700 O -1.64200 -1.59700 0.76700 O -2.96900 0.21100 -0.86100 C -0.60200 -2.02000 1.63200 C -2.40400 -0.55400 1.32200 C -3.52200 -0.20500 0.36900 948 C -3.92900 0.68000 -1.77600 H 0.11800 -1.20000 1.78900 H -0.09100 -2.86000 1.14600 H -1.02200 -2.36300 2.59300 H -1.76100 0.33000 1.50000 H -2.84000 -0.86200 2.29000 H -4.13200 0.60700 0.80400 H -4.17200 -1.08400 0.20700 H -4.66400 -0.10700 -2.01700 H -3.40700 0.97900 -2.69300 H -4.46400 1.55500 -1.36900 949 Table C.2.85. Atomic coordinates and single point energies for A23. G = –1360.871115 GSP = –1362.07408 Na -0.89000 -0.17600 -0.04400 N 1.24300 -0.11600 0.70200 Si 2.48800 0.80100 0.01100 C 1.71100 2.19200 -1.04500 C 3.61700 1.68800 1.26500 C 3.72900 -0.14100 -1.10100 H 3.01700 2.28600 1.97100 H 4.32100 2.36500 0.75400 H 4.21400 0.97600 1.85600 H 4.29700 -0.85800 -0.48500 H 4.45800 0.53800 -1.57300 H 3.24000 -0.72200 -1.90000 H 1.54800 3.08000 -0.41100 H 0.73400 1.89000 -1.45500 H 2.35700 2.50100 -1.88200 C 1.53300 -0.96800 1.83600 C 0.40400 -0.91800 2.87300 C 1.76700 -2.43600 1.43900 H 0.62100 -1.53800 3.75800 H -0.53400 -1.28900 2.42200 H 0.22500 0.11700 3.19900 H 2.45300 -0.64800 2.37800 H 0.83700 -2.84800 1.00900 H 2.05300 -3.06400 2.30000 H 2.55700 -2.50700 0.67600 O -0.61400 -1.10900 -2.25500 O -1.57900 -2.35200 0.00900 C 0.27300 -0.39600 -3.08500 950 C -0.04300 -2.32000 -1.80900 C -1.08600 -3.11800 -1.06500 C -2.37000 -3.08300 0.90900 H 1.22300 -0.18900 -2.56500 H -0.19900 0.55700 -3.35200 H 0.48300 -0.96400 -4.00900 H 0.81300 -2.09600 -1.14600 H 0.31100 -2.91800 -2.67000 H -0.61800 -4.04600 -0.68900 H -1.91900 -3.39500 -1.73900 H -3.23600 -3.54000 0.39800 H -2.72900 -2.39100 1.68000 H -1.77800 -3.87900 1.39400 O -1.98600 1.13100 1.64800 O -1.74600 1.79200 -0.94700 C -3.34400 1.40200 1.86400 C -2.11700 2.20500 -2.23500 C -1.19900 2.25400 1.31000 C -1.61400 2.85000 -0.02600 H -3.47500 2.23200 2.58100 H -3.80000 0.49900 2.28800 H -3.87000 1.65500 0.92600 H -2.29100 1.30400 -2.83600 H -1.32200 2.81200 -2.70200 H -3.04600 2.80100 -2.20500 H -2.57600 3.39300 0.04600 H -0.84500 3.56900 -0.36200 H -1.26200 3.02800 2.09700 H -0.16400 1.87300 1.25700 951 Table C.2.86. Atomic coordinates and single point energies for A11. G = –1563.55874 GSP = –1564.74100 Na 0.87700 -0.13600 -1.82400 N 2.39800 0.44100 -0.36500 Si 3.41700 -0.86500 -0.01100 C 2.65200 -2.38400 -0.88300 C 5.21200 -0.80100 -0.64500 C 3.56400 -1.26900 1.84400 H 5.23300 -0.54500 -1.71600 H 5.71900 -1.77000 -0.51400 H 5.80400 -0.04100 -0.11300 H 4.04500 -0.43400 2.37700 H 4.17500 -2.16900 2.01900 H 2.57700 -1.42900 2.30600 H 3.21700 -3.30400 -0.67100 H 2.66600 -2.26100 -1.98200 H 1.61100 -2.55900 -0.56300 C 2.44600 1.70500 0.32200 C 3.73000 2.50300 0.05700 C 1.23000 2.55800 -0.06200 H 3.72500 3.48500 0.55900 H 3.84500 2.65900 -1.02800 H 4.61100 1.94600 0.40700 H 2.38400 1.57300 1.43100 H 1.26300 2.77900 -1.14500 H 1.19600 3.51900 0.47800 H 0.30000 2.00400 0.14600 O -1.22400 -0.34400 -1.43600 P -2.11600 -0.14800 -0.24000 N -1.62000 -0.99300 1.10300 N -3.66800 -0.63600 -0.60900 N -2.21200 1.45200 0.21100 C -0.24800 -0.87200 1.58000 C -2.50800 -1.72900 1.97700 952 C -3.87800 -1.80200 -1.44500 C -4.85200 -0.08800 0.01300 C -2.37100 2.46600 -0.81400 C -2.23000 1.93800 1.57400 H -3.48700 -1.87300 1.50600 H -2.65600 -1.21300 2.94400 H -2.08200 -2.72200 2.19200 H 0.40300 -0.34800 0.85900 H 0.18000 -1.87500 1.73900 H -0.20600 -0.32800 2.54100 H -4.59900 0.80700 0.59500 H -5.34000 -0.81500 0.68900 H -5.58900 0.20000 -0.75600 H -2.93700 -2.07400 -1.93700 H -4.62300 -1.57800 -2.22600 H -4.24500 -2.66600 -0.86100 H -3.17200 2.47100 1.79400 H -1.39300 2.63700 1.74400 H -2.13100 1.10500 2.28000 H -2.28800 2.00800 -1.80800 H -1.58100 3.23000 -0.72100 H -3.35200 2.96600 -0.73300 953 Table C.2.87. Atomic coordinates and single point energies for A12. G = –2382.979306 GSP = –2384.85243 Na -0.53500 0.88600 -0.60000 N -2.21600 2.02900 0.34400 Si -2.96300 3.06300 -0.76300 C -2.08300 2.80300 -2.43700 C -4.80700 2.73900 -1.14300 C -2.85400 4.91700 -0.34400 H -4.95300 1.70300 -1.48900 H -5.18600 3.41300 -1.92900 H -5.43500 2.88000 -0.24900 H -3.39500 5.13700 0.59100 H -3.28800 5.54600 -1.13700 H -1.80500 5.22000 -0.19700 H -2.54600 3.38700 -3.24800 H -2.12700 1.74200 -2.74000 H -1.02300 3.10500 -2.37800 C -2.29900 2.15000 1.77300 C -3.72200 1.99200 2.33300 C -1.38100 1.10900 2.42900 H -3.75100 2.05600 3.43400 H -4.14100 1.01800 2.02700 H -4.38300 2.77500 1.93100 H -1.94200 3.14400 2.13700 H -1.68900 0.10100 2.09700 H -1.40200 1.14300 3.53100 H -0.34100 1.26900 2.09700 O 1.62100 0.86000 -0.15200 P 3.10800 0.69200 -0.06100 954 N 4.01600 1.50300 -1.21700 N 3.50800 -0.92400 -0.18400 N 3.71000 1.30800 1.36500 C 3.82200 2.94400 -1.30200 C 4.25400 0.87200 -2.50400 C 2.68100 -1.85600 -0.93000 C 4.83200 -1.39900 0.15200 C 2.90100 1.18800 2.56600 C 5.06000 1.78500 1.57900 H 4.47600 -0.19400 -2.37400 H 5.12500 1.34500 -2.98300 H 3.39100 0.97100 -3.18700 H 3.60400 3.35400 -0.30700 H 2.98300 3.20600 -1.97000 H 4.73700 3.42200 -1.68500 H 5.34500 -0.68600 0.81000 H 5.46200 -1.56000 -0.74300 H 4.76000 -2.36000 0.68700 H 1.68000 -1.43600 -1.10000 H 2.56200 -2.78900 -0.35000 H 3.13800 -2.11900 -1.90300 H 5.60600 1.13900 2.29000 H 5.04400 2.80500 2.00200 H 5.60900 1.80900 0.63100 H 1.86900 0.93600 2.29600 H 2.88400 2.14900 3.10400 H 3.29900 0.41600 3.24700 H 0.72600 -0.95700 1.07300 H -3.57200 -3.79600 -0.86500 H 1.66600 -2.26100 1.82500 H -2.34800 -2.73700 2.30000 C 0.64400 -1.87000 1.67800 H 0.22600 -1.61100 2.66800 C -2.80100 -4.14500 -1.56300 H -3.00400 -3.70500 -2.55700 C -3.14600 -2.28300 1.70000 H -3.51500 -1.39800 2.24300 H -2.88900 -5.23900 -1.65200 H -3.97900 -3.00600 1.61500 N -0.16800 -2.86100 0.99300 N -1.48200 -3.80700 -1.06500 P -1.19500 -2.37500 -0.23200 N -2.64300 -1.88300 0.40400 O -0.57400 -1.29600 -1.07600 H -0.54700 -4.09700 2.67400 C -0.20000 -4.16300 1.62600 955 H 0.81300 -4.60400 1.63900 C -0.38600 -4.31000 -1.87500 H -0.39400 -3.88500 -2.89500 C -3.53700 -1.04200 -0.38900 H -3.57200 -0.02000 0.02400 H -0.44900 -5.40700 -1.95100 H -4.54500 -1.49100 -0.42500 H -0.86600 -4.83600 1.07500 H 0.57300 -4.05400 -1.40400 H -3.15600 -0.95800 -1.41600 956 Table C.2.88. Atomic coordinates and single point energies for A13. G = –3202.38209 GSP = –3204.128842 Na -0.04600 -0.44000 0.04400 N 0.45700 -1.69300 1.91700 Si 0.75800 -3.26100 1.36500 C 0.91500 -3.18500 -0.53000 C 2.37400 -4.12000 1.92400 C -0.63300 -4.51600 1.74000 H 3.24200 -3.47100 1.71900 H 2.52500 -5.07000 1.38300 H 2.37900 -4.34300 3.00200 H -0.80300 -4.62700 2.82300 H -0.42800 -5.51600 1.32500 H -1.56600 -4.13900 1.29200 H 1.20400 -4.15900 -0.95700 H 1.68000 -2.44000 -0.81100 H -0.02800 -2.86900 -1.00000 C 0.07300 -1.39500 3.26900 C 0.88100 -2.14200 4.34400 C 0.18200 0.11000 3.54700 H 0.59400 -1.83800 5.36400 H 1.95600 -1.93800 4.20400 H 0.73500 -3.23100 4.26600 H -0.99700 -1.66200 3.46900 H 1.24200 0.41400 3.49300 H -0.20200 0.37500 4.54700 H -0.37100 0.68000 2.78500 O 1.86500 0.16500 -0.89400 957 P 3.31800 -0.05300 -1.10000 N 3.77100 -1.48700 -1.82800 N 3.92200 1.10000 -2.15400 N 4.15300 0.03000 0.34100 C 3.17600 -1.81800 -3.11200 C 4.31000 -2.62000 -1.10100 C 5.07900 0.93700 -3.00400 C 3.30400 2.41000 -2.19900 C 3.56200 -0.47200 1.57500 C 5.56900 0.31400 0.40100 H 5.12800 -3.08100 -1.68000 H 3.53900 -3.38800 -0.91400 H 4.71200 -2.30000 -0.13200 H 2.79400 -0.90800 -3.59500 H 2.33500 -2.52400 -2.99400 H 3.93200 -2.27300 -3.77300 H 3.01100 2.66100 -3.23300 H 4.00200 3.19300 -1.84800 H 2.40000 2.42100 -1.57400 H 5.48100 -0.07900 -2.90700 H 5.87600 1.65800 -2.74400 H 4.81200 1.10500 -4.06200 H 6.17600 -0.60000 0.54600 H 5.77700 0.99000 1.24700 H 5.90500 0.81200 -0.51700 H 2.50200 -0.75600 1.44500 H 3.61900 0.30200 2.36000 H 4.11000 -1.35900 1.94100 H -1.23200 1.79300 -1.77700 H 1.41100 1.60900 1.46800 H -0.74900 3.20400 -2.77400 H -3.42500 3.65700 0.98400 C -1.47500 2.83400 -2.03000 H -2.47800 2.85200 -2.48900 C 1.79100 2.63000 1.35100 H 2.73900 2.57200 0.79500 C -2.93000 3.71700 1.96300 H -3.15500 2.79200 2.52300 H 1.99600 3.05500 2.35200 H -3.35300 4.57200 2.51300 N -1.47200 3.65200 -0.82800 N 0.84000 3.43700 0.60800 P -0.77600 3.02300 0.55200 N -1.49800 3.91300 1.78500 O -0.97000 1.54000 0.61400 H -2.96100 5.03800 -1.36400 958 C -1.91600 5.01700 -1.00700 H -1.30000 5.54800 -1.75600 C 1.26300 4.79200 0.33200 H 2.25100 4.77500 -0.15400 C -0.78000 4.05300 3.04400 H -0.80300 3.12900 3.65100 H 1.34900 5.40900 1.24800 H -1.24000 4.86300 3.63000 H -1.86200 5.56000 -0.05600 H 0.56100 5.28600 -0.35200 H 0.26800 4.32200 2.86100 H -2.56000 0.29600 -3.23800 H -1.99300 -3.35000 -2.32300 C -3.64700 0.17900 -3.31200 H -3.89500 -0.17600 -4.32700 H -4.12900 1.16700 -3.17300 H -4.73100 0.98000 -0.65300 C -2.75300 -3.85600 -1.71500 H -2.25600 -4.65900 -1.14700 H -3.50600 -4.30900 -2.38500 C -4.14800 0.80700 0.26100 H -4.80300 1.00400 1.12400 N -4.09100 -0.77900 -2.32400 O -1.67200 -0.98000 -1.45900 H -3.30100 1.51700 0.29300 N -3.37000 -2.90500 -0.80500 H -5.80000 -1.46100 -3.33900 C -5.49900 -1.09800 -2.34100 N -3.68700 -0.57100 0.32100 H -6.12900 -0.22100 -2.09900 P -3.09600 -1.28100 -1.07400 C -4.42600 -3.45700 0.02100 H -4.02000 -4.22700 0.69700 H -5.20900 -3.93300 -0.59900 C -3.03000 -0.90500 1.58700 H -3.78400 -0.99300 2.38700 H -5.72500 -1.88700 -1.61300 H -2.47700 -1.85200 1.50700 H -4.88700 -2.66900 0.62700 H -2.29600 -0.13000 1.86200 959 Table C.2.89. Atomic coordinates and single point energies for A21. G = –1264.221683 GSP = –1265.29702 Na 0.38200 0.05600 -0.68300 N -1.47300 0.11100 0.59700 Si -2.64400 0.17600 -0.63000 C -1.74400 0.22000 -2.32300 C -3.85000 -1.29600 -0.71800 C -3.76500 1.71500 -0.60700 H -3.31400 -2.25100 -0.83800 H -4.56300 -1.19500 -1.55200 H -4.43800 -1.36200 0.21200 H -4.27800 1.79900 0.36400 H -4.53900 1.67800 -1.39000 H -3.17800 2.63600 -0.75000 H -2.48100 0.29400 -3.13600 H -1.15800 -0.69700 -2.51700 H -1.07900 1.09600 -2.42400 C -1.95900 -0.03500 1.95400 C -1.88300 -1.48900 2.44500 C -1.20500 0.86400 2.94100 H -2.25000 -1.60800 3.47800 H -0.83400 -1.83300 2.41200 H -2.47400 -2.14600 1.79000 H -3.03100 0.25900 2.05600 H -0.14500 0.56000 2.99900 H -1.62200 0.80400 3.95900 H -1.24300 1.91200 2.60800 N 1.16100 2.30900 -0.53700 N 2.76900 -0.12400 0.33000 N 0.93700 -2.26700 -0.71700 C -0.03300 3.14400 -0.49900 C 2.17900 2.86800 -1.40600 960 H 0.17900 4.14300 -0.06600 H -0.80200 2.63400 0.10100 H -0.42400 3.28700 -1.51700 H 1.73900 3.08500 -2.38900 H 2.99900 2.15100 -1.55800 H 2.60500 3.81100 -1.00400 C 1.63100 2.08000 0.82600 C 2.87600 1.20700 0.93100 H 1.86900 3.04500 1.32400 H 0.79100 1.63800 1.38400 H 3.14800 1.12900 2.00500 H 3.71700 1.72400 0.44600 C 4.10000 -0.62900 0.03300 H 4.73200 -0.69000 0.94300 H 4.60000 0.03300 -0.68900 H 4.05300 -1.63200 -0.40900 C 2.03000 -1.04600 1.19200 C 1.68400 -2.38600 0.53900 H 2.59600 -1.24600 2.12900 H 1.08200 -0.56700 1.49200 H 1.07300 -2.93800 1.27000 H 2.59300 -2.99700 0.38800 C -0.29200 -3.05100 -0.70800 C 1.74900 -2.54300 -1.88900 H 2.15400 -3.57600 -1.89400 H 2.59100 -1.83800 -1.94500 H 1.14200 -2.41300 -2.79700 H -0.93700 -2.69700 0.10800 H -0.09800 -4.13700 -0.59600 H -0.83600 -2.89400 -1.65000 961 Table C.2.90. Atomic coordinates and single point energies for A36. G = –1784.266803 GSP = –1785.93317 Na 0.01700 -0.26100 -0.19600 N 2.29900 -0.57200 0.39100 Si 3.82100 -0.02300 -0.18300 C 3.90200 0.71600 -1.93900 C 4.56600 1.34000 0.92700 C 5.14300 -1.39900 -0.28100 H 3.93700 2.24500 0.89400 H 5.58500 1.62500 0.62000 H 4.61000 1.01200 1.97700 H 5.26900 -1.93700 0.67100 H 6.12400 -0.98300 -0.56100 H 4.86400 -2.14200 -1.04700 H 4.97200 0.86500 -2.15300 H 3.41300 1.69400 -2.05300 H 3.50800 0.03800 -2.71200 C 2.54500 -1.32100 1.62800 C 1.67200 -0.86900 2.80300 C 2.41000 -2.83800 1.43600 H 1.82000 -1.51300 3.68700 H 0.60200 -0.88800 2.53500 H 1.92400 0.16200 3.09200 H 3.58600 -1.18300 2.00200 H 1.36200 -3.10400 1.22200 H 2.71700 -3.40200 2.33300 H 3.02200 -3.17000 0.58500 N -0.11400 -2.10600 -2.06400 N -2.30200 -2.43400 0.18500 N -1.76100 -0.48600 2.66000 962 C 1.27700 -2.19900 -2.50200 C -1.00700 -1.98900 -3.20500 H -0.64000 -1.21200 -3.89000 H -2.01900 -1.70500 -2.88300 H -1.07100 -2.93500 -3.78400 C -0.42200 -3.29700 -1.27800 C -1.85800 -3.41900 -0.79500 H -0.22200 -4.20500 -1.89100 H 0.28800 -3.33900 -0.44000 H -1.97900 -4.44500 -0.38300 H -2.53300 -3.36500 -1.66100 C -3.75200 -2.47900 0.27500 H -4.18600 -2.34400 -0.72500 H -4.13500 -1.67700 0.91900 H -4.11500 -3.44900 0.68000 C -1.68000 -2.71700 1.47600 C -2.12000 -1.89100 2.67900 H -1.86200 -3.78400 1.74400 H -0.59100 -2.60000 1.37800 H -1.59900 -2.34700 3.53500 H -3.20600 -2.02800 2.88100 C -1.71100 0.03400 4.01300 C -2.60700 0.33600 1.82200 H -0.92100 -0.47300 4.58600 H -2.67700 -0.09800 4.54800 H -1.48700 1.10900 3.99800 H -2.20400 1.35900 1.79300 H -3.65600 0.38400 2.19800 H -2.62100 -0.03700 0.78900 N -0.25400 3.10500 1.21900 N 0.04500 1.99200 -1.51300 N -2.95200 1.31400 -1.39900 C -0.92600 4.03400 2.09900 C 0.58500 2.18800 1.96900 C 0.49600 3.79600 0.19000 C 1.03200 2.87800 -0.90200 C 0.71100 1.13400 -2.47600 C -1.03400 2.73100 -2.15100 C -2.24900 1.89300 -2.52900 C -4.05800 0.50100 -1.85400 H -3.69500 -0.29400 -2.52200 H -4.82100 1.09000 -2.40800 H -4.55200 0.02700 -0.99400 H -2.93000 2.55500 -3.11300 H -1.96100 1.07600 -3.20900 H -1.36300 3.53000 -1.47600 963 H -0.66600 3.23300 -3.07200 H 1.22800 1.71500 -3.27000 H -0.01600 0.46700 -2.95200 H 1.46300 0.51700 -1.96700 H 1.51200 3.51900 -1.67500 H 1.83000 2.23900 -0.49300 H -0.15200 4.57500 -0.24200 H 1.37100 4.33600 0.61900 H -1.60300 4.68400 1.52500 H -0.21800 4.68200 2.65900 H -1.52900 3.48100 2.83700 H 1.13300 1.49200 1.31400 H -0.03000 1.57800 2.64300 H 1.34300 2.72600 2.58000 H 1.51300 -1.36800 -3.18000 H 1.46600 -3.14800 -3.04400 H 1.93900 -2.12100 -1.62500 C -3.40700 2.33400 -0.47200 H -2.55200 2.77500 0.06000 H -4.07100 1.88000 0.27600 H -3.97900 3.13700 -0.98700 964 Table C.2.91. Atomic coordinates and single point energies for A19. G = –1247.012083 GSP = –1248.06271 Na -0.45800 -0.03900 -0.87000 N -2.52500 0.28500 -0.24800 Si -3.01700 -1.11900 0.55900 C -1.56100 -2.35900 0.42200 C -3.37300 -0.96500 2.42500 C -4.53900 -1.99300 -0.17000 H -2.52800 -0.48900 2.94800 H -3.56000 -1.94500 2.89300 H -4.26300 -0.33900 2.60100 H -5.42600 -1.34300 -0.11000 H -4.77300 -2.92400 0.36900 H -4.37800 -2.23600 -1.23200 H -1.79400 -3.30400 0.93500 H -0.63400 -1.97300 0.88300 H -1.35100 -2.61100 -0.63300 C -3.40700 1.38900 -0.52300 C -3.46400 2.39900 0.63300 C -2.97700 2.11200 -1.80500 H -4.15500 3.23400 0.43200 H -2.45600 2.81700 0.80600 H -3.77800 1.90200 1.56200 H -4.45700 1.05700 -0.69900 H -1.94700 2.49400 -1.68100 H -3.62600 2.96800 -2.05100 H -2.98200 1.41100 -2.65200 N 1.69600 -0.92800 -1.40400 N 1.21400 1.37200 0.16700 C 1.73200 -2.34700 -1.73600 C 1.69300 -0.13400 -2.62800 H 1.51200 -2.96300 -0.85600 H 2.70900 -2.65700 -2.16000 H 0.95500 -2.55700 -2.48400 965 H 2.63600 -0.24600 -3.20000 H 1.55700 0.93200 -2.39900 H 0.86600 -0.45200 -3.28200 C 0.60000 0.94900 1.42500 C 1.00000 2.79800 -0.03200 H 0.96400 1.52300 2.29800 H 0.79400 -0.11600 1.61000 H -0.49300 1.07800 1.35500 H 1.34600 3.10100 -1.03200 H 1.52200 3.42000 0.72200 H -0.07600 3.01500 0.03800 C 2.80100 -0.49500 -0.53800 C 2.61600 0.97800 -0.03800 C 3.13800 -1.43300 0.62500 C 4.51500 -1.05600 1.21100 C 4.82100 0.44600 1.08300 C 3.52700 1.24800 1.17500 H 2.97500 1.62100 -0.85700 H 3.01000 0.95100 2.10100 H 3.72700 2.32600 1.25800 H 5.52700 0.75700 1.86600 H 5.31500 0.65800 0.12100 H 4.54400 -1.35200 2.27000 H 5.30100 -1.63700 0.70600 H 2.35600 -1.38400 1.39600 H 3.17500 -2.47700 0.29000 H 3.71900 -0.47900 -1.16900 966 Table C.2.92. Atomic coordinates and single point energies for A15. G = –1091.251484 GSP = –1092.13447 Na 0.45600 0.01500 -0.09600 N -1.67600 0.50400 -0.14000 Si -2.61800 -0.89200 0.04100 C -1.38400 -2.35000 0.13200 C -3.67100 -1.06600 1.62100 C -3.80900 -1.24500 -1.39800 H -3.06600 -0.84400 2.51400 H -4.07500 -2.08600 1.72200 H -4.52500 -0.37100 1.61900 H -4.57100 -0.45200 -1.47000 H -4.33900 -2.20200 -1.26900 H -3.27000 -1.27300 -2.35700 H -1.89300 -3.31700 0.26300 H -0.70200 -2.22900 0.99300 H -0.78400 -2.41800 -0.79200 C -2.22400 1.78600 -0.49900 C -3.12000 2.39500 0.59100 C -1.09700 2.77200 -0.82000 H -3.49100 3.39600 0.31600 H -2.54900 2.47100 1.53100 H -3.99000 1.75100 0.78300 H -2.85100 1.72600 -1.42000 H -0.48500 2.92200 0.08800 H -1.46900 3.75700 -1.14400 H -0.45000 2.36800 -1.61700 N 2.33100 -1.58200 -0.08800 N 2.49300 1.35800 0.15900 C 2.21900 1.57900 1.57300 C 2.63500 2.62800 -0.54000 C 2.36800 -1.69600 -1.54000 C 2.19100 -2.89600 0.52400 967 C 3.51400 -0.90800 0.43600 C 3.67400 0.52900 -0.04500 H 4.43800 -1.46200 0.16200 H 3.45600 -0.93500 1.53500 H 3.90900 0.53700 -1.12000 H 4.56000 0.96500 0.46600 H 2.77300 2.45000 -1.61500 H 3.50300 3.20800 -0.16600 H 1.72700 3.23000 -0.40700 H 3.06300 2.08500 2.08600 H 2.02700 0.62700 2.09000 H 1.32100 2.20400 1.68100 H 2.35000 -0.70300 -2.01400 H 1.48500 -2.25100 -1.88600 H 3.27300 -2.23100 -1.89400 H 3.06300 -3.54600 0.30400 H 1.28200 -3.38700 0.15400 H 2.10300 -2.79300 1.61500 968 Table C.2.93. Atomic coordinates and single point energies for A17. G = –1438.364893 GSP = –1439.64081 Na 0.43900 0.03900 -0.02300 N -1.83500 0.02900 0.44200 Si -2.64300 0.38600 -1.00500 C -1.30600 0.82600 -2.30000 C -3.75700 -0.97800 -1.75300 C -3.79100 1.91600 -1.07700 H -3.27000 -1.96400 -1.79100 H -4.08500 -0.71500 -2.77300 H -4.66700 -1.08800 -1.13900 H -4.71700 1.76700 -0.50200 H -4.08100 2.11500 -2.12200 H -3.30100 2.82200 -0.68800 H -1.74500 0.92000 -3.30600 H -0.48200 0.09700 -2.37000 H -0.87300 1.80600 -2.04000 C -2.50900 -0.36200 1.65600 C -3.78500 0.43200 1.97900 C -2.85100 -1.86300 1.69400 H -4.18100 0.18300 2.97700 H -4.57500 0.21000 1.24200 H -3.58700 1.51400 1.94100 H -1.83500 -0.18000 2.52500 H -3.56200 -2.10200 0.88700 H -3.29600 -2.17400 2.65400 H -1.94800 -2.47100 1.52000 N 1.46200 -1.59400 1.63000 N 0.89900 -2.08200 -1.40000 C 1.52900 -2.07200 -2.71000 C -0.47500 -2.56500 -1.52000 969 C 0.71700 -1.54900 2.88100 C 2.87500 -1.39400 1.89500 C 1.22200 -2.86900 0.96000 C 1.67500 -2.91900 -0.49200 H 0.14300 -3.07700 1.01100 H 1.72600 -3.69400 1.50900 H 1.63400 -3.98000 -0.82300 H 2.73100 -2.61600 -0.56600 H -1.04900 -2.36300 -0.60500 H -0.50000 -3.64900 -1.75800 H -0.98100 -2.02200 -2.32800 H 1.54800 -3.08200 -3.16900 H 2.56700 -1.71700 -2.63300 H 0.98100 -1.40000 -3.38700 H 1.02000 -2.37000 3.56400 H -0.35800 -1.63000 2.68000 H 0.90100 -0.59500 3.39400 H 3.26700 -2.14300 2.61500 H 3.45800 -1.46800 0.97000 C 2.32000 1.50600 -1.96000 H -0.70000 3.62400 -0.51300 H 1.57700 3.73700 -0.62500 C -0.62300 3.24600 0.51800 N 2.84100 1.17700 -0.64200 C 1.77400 3.22000 0.32600 H -0.64300 4.11500 1.20900 H 3.83200 3.01000 -0.22700 H -1.48300 2.58900 0.71300 C 3.02700 2.36300 0.18500 C 4.09900 0.46800 -0.77200 N 0.58900 2.46000 0.67000 H 4.84200 1.04400 -1.36200 H 1.98500 4.01700 1.07300 H 3.37600 2.02800 1.17600 H 4.53200 0.28000 0.22000 C 0.65200 1.89400 2.00500 H -0.25600 1.29300 2.17200 H 0.72000 2.67600 2.79100 H 1.52900 1.23500 2.10100 H 3.94100 -0.49900 -1.27200 H 1.32200 1.95300 -1.88300 H 2.22900 0.58700 -2.55600 H 2.98500 2.20800 -2.50700 H 3.04200 -0.39200 2.31900 970 Table C.2.94. Atomic coordinates and single point energies for B1-2. G = –1566.780054 GSP = –1567.84458 N 1.83900 0.30700 0.08300 N -1.83900 0.30800 -0.08200 Na 0.06000 0.28300 -1.40400 Na -0.06000 0.28300 1.40400 Si 2.58200 -1.16700 -0.38500 Si -2.58100 -1.16700 0.38500 C 2.59700 1.47500 0.53100 C -2.59700 1.47400 -0.53100 C 3.02800 -2.34800 1.03300 C 4.12200 -1.06400 -1.49500 C 1.32200 -2.11200 -1.47700 C -1.32200 -2.11100 1.47700 C -4.12200 -1.06500 1.49600 H -0.31100 -2.19900 1.04400 H -1.67500 -3.14100 1.64000 H -1.23900 -1.66400 2.48600 H -3.90700 -0.49900 2.41600 H -4.43500 -2.07900 1.79200 H -4.98200 -0.58700 1.00300 C -3.02800 -2.34800 -1.03300 H -2.15500 -2.54400 -1.67700 H -3.81800 -1.91900 -1.66800 H -3.39100 -3.31600 -0.65400 H 0.31100 -2.19900 -1.04300 H 1.67500 -3.14100 -1.63900 H 1.23900 -1.66600 -2.48500 H 3.81700 -1.91800 1.66900 H 3.39300 -3.31600 0.65400 H 2.15500 -2.54500 1.67600 H 4.98200 -0.58600 -1.00300 H 3.90700 -0.49900 -2.41600 H 4.43600 -2.07800 -1.79100 C 3.11900 2.28500 -0.67100 971 C 3.79100 1.11500 1.43500 C 1.68800 2.41000 1.35300 H 2.27200 2.61900 -1.29400 H 3.68800 3.17600 -0.36100 H 3.77200 1.65700 -1.29400 H 3.44600 0.53000 2.30200 H 4.30700 2.01400 1.80700 H 4.53100 0.50800 0.89100 H 0.77100 2.65900 0.79300 H 2.18900 3.35600 1.60300 H 1.41200 1.94600 2.31900 C -1.68800 2.40900 -1.35400 C -3.11800 2.28500 0.67100 C -3.79200 1.11500 -1.43500 H -0.77100 2.65800 -0.79500 H -2.18900 3.35600 -1.60300 H -1.41300 1.94500 -2.32000 H -2.27100 2.61900 1.29400 H -3.77100 1.65700 1.29400 H -3.68800 3.17700 0.36200 H -3.44700 0.52900 -2.30100 H -4.30800 2.01400 -1.80600 H -4.53100 0.50800 -0.89000 972 Table C.2.95. Atomic coordinates and single point energies for B34-2. G = –2030.558701 GSP = –2032.12827 N -0.41500 1.85900 0.17000 N 0.33600 -1.79500 0.13900 Na -1.44400 -0.22200 0.21800 Na 1.40300 0.28600 0.14900 Si -0.52400 2.52800 -1.40500 Si 0.66500 -2.37800 -1.44100 C -0.37000 2.68700 1.37400 C 0.18600 -2.69700 1.28100 C 1.17200 2.94900 -2.17900 C -1.55400 4.10700 -1.67000 C -1.36800 1.26600 -2.56400 C 1.44200 -0.96500 -2.45500 C 1.93100 -3.78900 -1.62700 H 0.91300 -0.00300 -2.37800 H 1.45100 -1.22800 -3.52400 H 2.49100 -0.80800 -2.15700 H 2.90200 -3.50000 -1.19500 H 2.08900 -4.00000 -2.69700 H 1.61700 -4.72800 -1.14800 C -0.86600 -2.94200 -2.42800 H -1.61200 -2.13200 -2.49600 H -1.35200 -3.80600 -1.94800 H -0.59900 -3.23500 -3.45600 H -1.19400 0.20900 -2.30600 973 H -1.02400 1.39300 -3.60300 H -2.45600 1.44000 -2.55800 H 1.66000 3.75300 -1.60500 H 1.07000 3.29300 -3.22100 H 1.85500 2.08300 -2.18400 H -1.15900 4.98200 -1.13200 H -2.60000 3.96300 -1.35700 H -1.55800 4.35400 -2.74400 C -1.73300 3.34200 1.67400 C 0.68800 3.80500 1.29200 C -0.03000 1.80900 2.58800 H -2.50300 2.56000 1.75300 H -1.71600 3.91300 2.61600 H -2.02500 4.02500 0.86500 H 1.67600 3.37400 1.07100 H 0.75800 4.37800 2.23100 H 0.44600 4.51400 0.48500 H -0.79400 1.02500 2.71700 H 0.01100 2.39400 3.52000 H 0.94900 1.31300 2.46700 C -0.45900 -1.94400 2.45600 C 1.54800 -3.21000 1.78800 C -0.70200 -3.91800 0.97000 H 0.13200 -1.04800 2.69900 H -0.51800 -2.57000 3.36100 H -1.49100 -1.63300 2.21800 H 2.16200 -2.35600 2.11000 H 2.08700 -3.73700 0.98800 H 1.43800 -3.89800 2.64200 H -1.67600 -3.58200 0.58200 H -0.87500 -4.53800 1.86400 H -0.23800 -4.55900 0.20500 H 4.77100 -1.11200 -1.17700 C 4.47200 -0.39900 -0.40600 C 4.31600 0.95200 -0.72600 H 4.48900 1.29700 -1.74700 C 3.92900 1.86300 0.26000 H 3.80300 2.91700 0.00800 C 3.70100 1.42100 1.56700 H 3.40200 2.13300 2.33800 C 3.84500 0.06700 1.88200 H 3.65400 -0.28000 2.89900 C 4.23000 -0.84300 0.89400 H 4.33300 -1.90200 1.13600 H -3.63100 -2.79700 -0.92700 C -3.84200 -1.87900 -0.37700 974 C -3.95600 -0.66600 -1.06400 H -3.83700 -0.64200 -2.14900 C -4.20500 0.51600 -0.36100 H -4.27900 1.46600 -0.89300 C -4.35100 0.48300 1.02800 H -4.55000 1.40500 1.57500 C -4.24000 -0.72800 1.71400 H -4.34800 -0.75100 2.80000 C -3.98500 -1.90800 1.01200 H -3.88800 -2.85300 1.54900 975 Table C.2.96. Atomic coordinates and single point energies for B28-2. G = –2490.702224 GSP = –2492.83203 N -0.11600 -2.20000 -0.14600 N -0.17000 1.60300 -0.26200 Na 1.10500 -0.28600 -0.91800 Na -1.40300 -0.32900 0.63800 Si 1.18700 -3.01000 0.61200 Si -0.18100 2.41300 1.25200 C -1.13200 -2.93000 -0.90400 C -0.24700 2.36000 -1.51500 C 2.10900 -1.78500 1.73900 C 2.56600 -3.59100 -0.57800 C 0.82700 -4.54600 1.68400 C 0.47400 1.23800 2.59900 C 0.85300 3.99700 1.48600 H 0.01300 0.23700 2.59600 H 0.27100 1.67700 3.58800 H 1.56300 1.09700 2.52000 H 1.93100 3.81800 1.35400 H 0.70600 4.35700 2.51700 H 0.55400 4.81100 0.80800 C -1.93100 2.87000 1.86600 H -2.54600 1.95700 1.90000 H -2.43500 3.58500 1.19700 H -1.91000 3.30000 2.88000 H 0.11100 -4.34200 2.49500 H 1.76400 -4.89800 2.14500 H 0.42300 -5.37800 1.08600 H 2.30900 -0.82500 1.23700 976 H 3.08600 -2.21200 2.01700 H 1.57500 -1.55000 2.67100 H 2.88700 -2.73100 -1.18700 H 2.23600 -4.38600 -1.26400 H 3.44500 -3.96100 -0.02600 C -2.21000 -3.51500 0.03200 C -0.56700 -4.08900 -1.74900 C -1.83700 -1.97900 -1.88500 H -2.68100 -2.70400 0.61300 H -3.00300 -4.04400 -0.52100 H -1.75200 -4.22100 0.74200 H 0.21600 -3.71400 -2.42500 H -1.35200 -4.56900 -2.35400 H -0.11900 -4.86400 -1.10900 H -2.33100 -1.14300 -1.36200 H -2.61700 -2.49500 -2.46800 H -1.10800 -1.54600 -2.58700 C -0.55800 1.41800 -2.69500 C 1.10200 3.03000 -1.85100 C -1.32300 3.46600 -1.50300 H 0.27300 0.71600 -2.88300 H -0.69900 1.98200 -3.63100 H -1.46600 0.82800 -2.50700 H 1.87800 2.25500 -1.94800 H 1.40900 3.72000 -1.05200 H 1.06000 3.59200 -2.79900 H -2.32000 3.06000 -1.27100 H -1.38100 3.98500 -2.47400 H -1.08900 4.22500 -0.74000 O 3.33000 0.47100 -0.75900 O 2.36800 -0.76600 -2.91100 C 4.07700 0.55500 -1.94600 C 3.76500 -0.66100 -2.78600 H 5.16200 0.59200 -1.74100 H 3.79900 1.47300 -2.49700 H 4.17300 -1.57300 -2.31400 H 4.23700 -0.54900 -3.77900 C 1.96300 -1.78400 -3.79500 H 2.32100 -2.77000 -3.45400 H 2.34300 -1.59100 -4.81300 H 0.86600 -1.78900 -3.81500 H -3.93300 -2.23600 2.36600 C -3.61100 -1.29700 2.85400 H -1.62900 -2.11600 4.42300 H -5.40600 -0.28200 2.27300 O -3.88800 0.01200 0.89700 977 O -2.22600 -1.12900 2.70100 C -4.31400 -0.11800 2.23100 C -1.48700 -2.15000 3.32900 H -3.88100 -1.35800 3.92400 H -1.79200 -3.13900 2.94900 H -0.42900 -1.99500 3.09000 H -4.08400 0.80700 2.79200 C 3.48500 1.55900 0.13200 C 4.49500 1.25300 1.22100 O 4.54100 2.37400 2.05100 C 5.34700 2.20200 3.18000 H 2.50000 1.75600 0.57800 H 3.78500 2.47100 -0.41200 H 5.49200 1.03500 0.78600 H 4.17600 0.35200 1.78000 H 6.39600 1.99200 2.90100 H 4.98500 1.37200 3.81200 H 5.31500 3.13100 3.76200 C -4.60100 1.00800 0.19800 C -4.10700 1.03100 -1.22900 O -4.67800 2.13700 -1.86000 C -4.35900 2.21900 -3.22100 H -4.72300 1.33300 -3.77200 H -3.26900 2.30300 -3.37400 H -4.84500 3.11500 -3.62600 H -3.00200 1.10400 -1.21300 H -4.37800 0.08900 -1.74600 H -5.68500 0.79600 0.22800 H -4.43200 2.00000 0.65400 978 Table C.2.97. Atomic coordinates and single point energies for B25-2. G = –2183.525021 GSP = –2185.29866 N -0.37400 -1.87700 0.19800 N 0.37400 1.87600 0.19800 Na -1.40800 0.30500 0.10200 Na 1.40800 -0.30400 0.10400 Si -1.22300 -2.57000 -1.11600 Si 1.22300 2.57000 -1.11700 C 0.00500 -2.68100 1.36200 C -0.00400 2.68000 1.36200 C -1.21400 -1.35400 -2.57800 C -3.09100 -2.84700 -0.81700 C -0.60800 -4.22800 -1.83000 C 1.21200 1.35500 -2.57800 C 0.60700 4.22900 -1.82800 H 1.71000 0.39900 -2.34400 H 1.77100 1.79700 -3.41800 H 0.19800 1.12500 -2.93600 H -0.44600 4.18300 -2.14300 H 1.21100 4.49700 -2.71100 H 0.70200 5.05300 -1.10400 C 3.09100 2.84700 -0.81700 H 3.54000 1.89600 -0.48600 H 3.29700 3.60200 -0.04400 H 3.60500 3.15500 -1.74200 H 0.44500 -4.18100 -2.14600 H -1.21200 -4.49600 -2.71100 979 H -0.70100 -5.05200 -1.10500 H -1.71300 -0.39800 -2.34300 H -1.77100 -1.79600 -3.41800 H -0.20000 -1.12200 -2.93400 H -3.54100 -1.89700 -0.48500 H -3.29800 -3.60400 -0.04600 H -3.60400 -3.15400 -1.74300 C 1.26600 -3.52100 1.07400 C -1.10300 -3.64500 1.83100 C 0.33500 -1.76900 2.55500 H 2.09500 -2.85300 0.79000 H 1.58500 -4.10900 1.95000 H 1.08400 -4.21400 0.23900 H -2.02800 -3.08500 2.03300 H -0.81200 -4.18400 2.74600 H -1.32600 -4.39600 1.05800 H 1.19800 -1.11600 2.34200 H 0.59400 -2.35400 3.45200 H -0.52400 -1.12500 2.79500 C -0.33400 1.76700 2.55500 C -1.26600 3.52000 1.07500 C 1.10400 3.64300 1.83200 H -1.19800 1.11400 2.34100 H -0.59400 2.35100 3.45200 H 0.52500 1.12300 2.79500 H -2.09500 2.85200 0.79100 H -1.08400 4.21300 0.24000 H -1.58400 4.10800 1.95100 H 2.02900 3.08300 2.03400 H 0.81300 4.18200 2.74700 H 1.32600 4.39500 1.05900 O -3.10700 1.36000 -1.14200 O -3.47600 0.24800 1.26400 C -4.28100 1.67700 -0.44200 C -4.61100 0.53200 0.48600 C -2.72300 2.35600 -2.06000 H -5.12300 1.83900 -1.13900 H -4.13300 2.60700 0.13800 H -4.90600 -0.36100 -0.09500 H -5.46300 0.81900 1.13000 C -3.70900 -0.72600 2.25300 H -4.03700 -1.67800 1.80000 H -4.47500 -0.38100 2.96900 H -2.76500 -0.89400 2.78500 H -2.59300 3.32600 -1.55100 H -3.47500 2.45900 -2.86200 980 H -1.76200 2.05700 -2.49600 H 4.13300 -2.60700 0.13500 C 4.28100 -1.67600 -0.44400 H 2.58900 -3.32300 -1.55300 H 5.46500 -0.82000 1.12700 O 3.47700 -0.24900 1.26400 O 3.10600 -1.35800 -1.14300 C 4.61200 -0.53300 0.48400 C 2.72100 -2.35400 -2.06200 H 5.12200 -1.83800 -1.14300 H 1.76000 -2.05300 -2.49700 C 3.71200 0.72600 2.25200 H 2.76800 0.89300 2.78600 H 3.47300 -2.45800 -2.86300 H 4.03900 1.67700 1.79800 H 4.90600 0.36100 -0.09600 H 4.47900 0.38100 2.96700 981 Table C.2.98. Atomic coordinates and single point energies for B3-2. G = –1993.552939 GSP = –1995.09938 N -0.45100 -1.81300 0.00600 N 0.25600 1.88600 -0.05900 Na -1.47400 0.26400 0.08900 Na 1.32100 -0.19700 -0.16800 Si -0.29100 -2.44500 1.58900 Si 0.88300 2.47800 1.42300 C -0.41900 -2.63900 -1.19500 C -0.13900 2.78200 -1.14500 C 1.51800 -2.74500 2.13300 C -1.16800 -4.07600 2.02400 C -1.04800 -1.18000 2.80000 C 1.84300 1.06400 2.27200 C 2.14600 3.90300 1.35500 H 1.23500 0.16900 2.47000 H 2.21700 1.40900 3.24800 H 2.72900 0.75800 1.68900 H 3.02900 3.62900 0.75700 H 2.49200 4.13500 2.37600 H 1.73000 4.82900 0.93100 C -0.42700 3.03200 2.69000 H -1.18200 2.24400 2.85000 H -0.95700 3.93200 2.34100 H 0.02400 3.26600 3.66800 H -0.86000 -0.12700 2.53500 982 H -0.65600 -1.31800 3.82000 H -2.13700 -1.33200 2.84600 H 1.94600 -3.59600 1.57900 H 1.58300 -2.98100 3.20700 H 2.16900 -1.87400 1.95200 H -0.74700 -4.93900 1.48500 H -2.24500 -4.02800 1.80100 H -1.05400 -4.27300 3.10200 C -1.66600 -3.53600 -1.32100 C 0.82500 -3.54800 -1.25300 C -0.39700 -1.73200 -2.43600 H -2.57400 -2.91500 -1.27300 H -1.67600 -4.09700 -2.26900 H -1.71200 -4.25900 -0.49600 H 1.74200 -2.94400 -1.13400 H 0.89500 -4.10300 -2.20200 H 0.80800 -4.28300 -0.43300 H -1.29200 -1.08800 -2.45100 H -0.38200 -2.31200 -3.37200 H 0.49100 -1.07600 -2.44100 C -1.04700 2.03100 -2.13400 C 1.08400 3.27300 -1.94300 C -0.93100 4.01200 -0.65900 H -0.55800 1.10700 -2.47600 H -1.28400 2.64100 -3.02000 H -2.00900 1.77000 -1.66000 H 1.60400 2.40800 -2.38600 H 1.79000 3.79500 -1.28100 H 0.80300 3.95800 -2.75900 H -1.80400 3.68600 -0.07300 H -1.28500 4.63000 -1.50000 H -0.31300 4.65400 -0.01300 C 4.14100 1.09100 -0.72600 N 3.62100 -0.25700 -0.92400 C 3.44700 -0.53500 -2.34200 C 4.40200 -1.28400 -0.22700 C -4.36600 1.82900 0.10000 N -3.88100 0.47200 -0.09900 C -4.24000 -0.08500 -1.40600 C -4.25900 -0.39700 1.00700 H 2.72700 0.17800 -2.77200 H 3.05200 -1.55200 -2.48300 H 4.38800 -0.44200 -2.91800 H 5.06700 1.27800 -1.30300 H 4.35900 1.25700 0.33800 H 3.38400 1.82800 -1.03500 983 H -5.35500 -0.50100 1.12100 H -3.86500 0.01600 1.94800 H -3.82100 -1.39700 0.85900 H -5.46600 1.88200 0.21900 H -4.07900 2.45700 -0.75700 H -3.90800 2.25700 1.00400 C -5.73300 -0.26600 -1.68000 H -3.72700 -1.05600 -1.49700 H -3.80500 0.57200 -2.17600 H -6.20000 -0.96000 -0.96700 H -5.87400 -0.68300 -2.68600 H -6.27500 0.68900 -1.63700 C 5.85200 -1.44900 -0.67800 H 3.86600 -2.24100 -0.33900 H 4.37600 -1.04000 0.84800 H 5.92100 -1.74700 -1.73400 H 6.33800 -2.23300 -0.08100 H 6.42900 -0.52300 -0.54300 984 Table C.2.99. Atomic coordinates and single point energies for B4-2. G = –2150.486844 GSP = –2152.206901 N 0.33600 1.83900 0.04800 N -0.22900 -1.87800 0.06100 Na 1.43700 -0.20300 -0.05800 Na -1.38800 0.15800 0.02700 Si 0.42200 2.48200 1.63500 Si -0.64700 -2.46600 1.61600 C 0.22000 2.66800 -1.14800 C -0.01400 -2.76700 -1.07900 C -1.27200 2.82400 2.44700 C 1.38900 4.09800 1.91700 C 1.32400 1.22400 2.75600 C -1.50200 -1.05300 2.57200 C -1.89300 -3.90400 1.73100 H -0.91000 -0.12700 2.61100 H -1.67400 -1.35800 3.61600 H -2.49500 -0.81200 2.15300 H -2.85000 -3.65200 1.24600 H -2.10300 -4.11900 2.79100 H -1.52500 -4.83500 1.27300 C 0.82800 -2.99800 2.69600 H 1.56100 -2.18000 2.79400 H 1.35000 -3.85900 2.24900 H 0.51200 -3.28600 3.71100 H 1.20500 0.17100 2.45200 H 0.96400 1.28900 3.79500 985 H 2.40100 1.45200 2.77100 H -1.82300 3.59400 1.88300 H -1.15200 3.18900 3.48000 H -1.90700 1.92400 2.49100 H 0.92600 4.96800 1.42400 H 2.42800 4.01800 1.56000 H 1.42100 4.31000 2.99800 C 1.49900 3.48600 -1.41900 C -0.96500 3.65000 -1.07600 C 0.01400 1.76500 -2.37400 H 2.36600 2.80900 -1.46700 H 1.43700 4.03900 -2.37100 H 1.68200 4.21200 -0.61600 H -1.90200 3.10100 -0.88500 H -1.08500 4.22700 -2.00700 H -0.82600 4.36500 -0.25100 H 0.87600 1.08900 -2.49700 H -0.09000 2.34700 -3.30300 H -0.89400 1.14600 -2.27200 C 0.75900 -2.02000 -2.17800 C -1.35200 -3.21800 -1.69500 C 0.81200 -4.02000 -0.72700 H 0.23500 -1.09000 -2.44900 H 0.87000 -2.62600 -3.09000 H 1.77700 -1.77000 -1.83300 H -1.91300 -2.33100 -2.03400 H -1.96400 -3.74200 -0.94600 H -1.21100 -3.88700 -2.55900 H 1.77600 -3.72100 -0.28600 H 1.01200 -4.64000 -1.61500 H 0.28700 -4.64900 0.00800 C -4.27800 -1.14400 -0.26300 N -3.76700 0.19800 -0.54300 C -3.72700 0.57600 -1.95400 C -4.15300 1.24700 0.39900 C 4.15200 -1.66100 -0.18900 N 3.81900 -0.28400 -0.55000 C 4.06300 0.10100 -1.93700 C 4.10300 0.73500 0.46100 H -2.94500 -0.03000 -2.44700 H -3.37700 1.62000 -2.00300 C -5.01200 0.42200 -2.77100 C -5.77800 -1.29000 -0.00100 H -3.73800 -1.54700 0.61100 H -3.98000 -1.78500 -1.10700 C 5.47200 1.41600 0.42700 986 H 3.95200 0.25900 1.44500 H 3.33000 1.52300 0.38300 C 5.56400 -1.93600 0.33100 H 3.95300 -2.28500 -1.07600 H 3.43600 -2.00300 0.58200 C 5.45600 -0.16600 -2.51200 H 3.82400 1.17400 -2.01900 H 3.32800 -0.41900 -2.57600 H 6.24900 0.32600 -1.93300 H 5.50500 0.20900 -3.54500 H 5.67100 -1.24300 -2.54400 C -5.43500 2.03300 0.11500 H -3.32600 1.97800 0.47000 H -4.21800 0.77800 1.39500 H -5.34600 2.60700 -0.81800 H -5.61000 2.75200 0.92700 H -6.31600 1.38200 0.03700 H -4.83900 0.77700 -3.79700 H -5.84800 0.99400 -2.34800 H -5.31400 -0.63300 -2.83500 H -6.38800 -0.92700 -0.83900 H -6.07900 -0.74200 0.90400 H -6.01900 -2.35000 0.16400 H 6.33800 -1.63500 -0.38800 H 5.68000 -3.01100 0.53000 H 5.74700 -1.40500 1.27600 H 5.60300 1.99200 -0.50000 H 6.30000 0.69900 0.50800 H 5.54800 2.12400 1.26500 987 Table C.2.100. Atomic coordinates and single point energies for B14-2. G = –3205.638026 GSP = –3208.08161 N -0.22300 -1.91700 0.29700 N 0.57700 1.74200 0.10500 Na -1.18900 0.18000 -0.17000 Na 1.53300 -0.35100 0.61700 Si -1.26200 -2.41100 1.55900 Si 0.48500 2.47100 1.64700 C 0.21800 -2.82700 -0.75400 C 0.58600 2.49500 -1.14200 C -0.46200 -3.37300 2.99200 C -2.81300 -3.40900 1.05200 C -2.02000 -0.85000 2.35200 C 1.20100 1.24000 2.92100 C 1.45600 4.08100 1.96800 H 0.72700 0.24400 2.91100 H 1.07500 1.63300 3.94200 H 2.28300 1.09600 2.75900 H 2.53400 3.96300 1.78000 H 1.32900 4.38000 3.02100 H 1.09600 4.91500 1.34500 C -1.28400 2.90500 2.22600 H -1.98200 2.06700 2.06800 H -1.66800 3.76500 1.65400 H -1.31300 3.17200 3.29500 H -1.27900 -0.07800 2.60600 988 H -2.53600 -1.11700 3.28900 H -2.77200 -0.40000 1.68100 H -0.08900 -4.35500 2.66500 H -1.17600 -3.53800 3.81500 H 0.39600 -2.80900 3.39300 H -2.57800 -4.38000 0.58800 H -3.40300 -2.82200 0.32700 H -3.44900 -3.60700 1.93100 C -0.85900 -2.97700 -1.84800 C 0.58300 -4.23100 -0.23400 C 1.47800 -2.26200 -1.43700 H -1.08400 -1.98800 -2.28300 H -0.54000 -3.64800 -2.66300 H -1.78700 -3.37600 -1.41400 H 1.34400 -4.14700 0.55800 H 0.97900 -4.87500 -1.03600 H -0.29800 -4.73500 0.19300 H 1.27300 -1.24500 -1.80900 H 1.78400 -2.87700 -2.30000 H 2.32900 -2.22200 -0.73500 C 0.38700 1.54200 -2.33400 C 1.93900 3.20100 -1.36500 C -0.53400 3.55500 -1.20800 H 1.16000 0.75900 -2.31700 H 0.45900 2.07300 -3.29600 H -0.60400 1.05400 -2.31500 H 2.74700 2.45300 -1.32300 H 2.12200 3.93800 -0.57000 H 1.98200 3.72300 -2.33500 H -1.51300 3.07900 -1.03400 H -0.56100 4.06900 -2.18200 H -0.39000 4.32100 -0.42900 O 3.71400 -0.51400 0.75100 P 4.90100 -0.25400 -0.13000 N 5.08500 1.39600 -0.35200 N 6.24200 -0.98800 0.55200 N 4.91600 -0.82900 -1.69700 C 4.15600 -0.16900 -2.74900 C 5.22400 -2.21900 -1.98900 C 6.11700 1.95500 -1.20200 C 4.62200 2.28900 0.70000 C 6.22200 -1.43200 1.93400 C 7.55800 -0.88700 -0.04200 H 6.38400 1.24900 -1.99800 H 7.03300 2.21100 -0.63800 H 5.74200 2.87700 -1.67500 989 H 3.69500 1.90000 1.13800 H 4.40000 3.27300 0.26100 H 5.37800 2.42500 1.49600 H 7.47900 -0.64300 -1.11000 H 8.08600 -1.85200 0.04500 H 8.18000 -0.11700 0.44900 H 5.18700 -1.47700 2.28900 H 6.79700 -0.75100 2.58700 H 6.67000 -2.43600 2.01200 H 3.85200 0.83600 -2.43300 H 3.24900 -0.74500 -2.99700 H 4.77000 -0.08300 -3.66100 H 5.74500 -2.68100 -1.14300 H 5.87200 -2.28000 -2.87900 H 4.30500 -2.79500 -2.19100 H -7.21100 -0.95600 -2.35600 H -7.33300 -0.71700 -0.58800 C -6.82100 -1.28700 -1.37600 H -7.46400 1.91500 -1.64000 H -7.15700 1.54700 0.08400 C -6.77500 2.08700 -0.79200 H -6.79000 3.16500 -0.56100 H -7.08600 -2.34900 -1.24600 H -4.85600 -1.75300 -3.23100 N -5.38700 -1.12000 -1.27600 C -4.60000 -1.94600 -2.17400 N -5.42400 1.66700 -1.09700 P -4.73800 0.23800 -0.55300 N -5.29700 0.15800 1.01500 H -4.81200 2.18400 1.33300 C -4.79600 2.39500 -2.18500 H -4.78500 -3.01100 -1.96100 H -4.75300 3.47000 -1.94300 H -5.35900 2.28000 -3.12900 H -3.53400 -1.74200 -2.02300 C -5.11200 1.29600 1.90400 H -5.65600 -1.91700 0.99900 H -6.05100 1.52000 2.43800 C -5.59100 -1.08500 1.70800 H -6.55100 -0.99400 2.24500 O -3.25900 0.28300 -0.81400 H -3.77300 2.03300 -2.33100 H -4.32900 1.08500 2.65100 H -4.80400 -1.32400 2.44200 990 Table C.2.101. Atomic coordinates and single point energies for B5-2. G = –2111.7675 GSP = –2113.4524 N -0.23900 1.96800 -0.24300 N 0.04200 -1.81100 -0.26200 Na 1.35700 0.17300 -0.21500 Na -1.47400 -0.00400 -0.23500 Si -0.47100 2.53100 1.35900 Si 0.62000 -2.66300 1.11000 C 0.10400 2.85800 -1.35000 C -0.24800 -2.50900 -1.51800 C -1.67800 1.34300 2.23700 C -1.25500 4.24200 1.64300 C 1.12500 2.56200 2.40500 C 0.49800 -1.52200 2.62900 C -0.29700 -4.25000 1.63500 H 0.75200 -0.46800 2.42900 H 1.16600 -1.87700 3.43100 H -0.52600 -1.52800 3.03400 H -1.37400 -4.07500 1.78900 H 0.12200 -4.61800 2.58500 H -0.19200 -5.05800 0.89500 C 2.45500 -3.19200 1.03600 H 3.07900 -2.36000 0.67700 H 2.61200 -4.04200 0.35400 H 2.81900 -3.49300 2.03200 H 1.63200 1.58300 2.40200 H 0.92800 2.82700 3.45600 991 H 1.83500 3.29800 1.99600 H -2.68800 1.44900 1.80600 H -1.74700 1.58900 3.30800 H -1.39200 0.28200 2.18000 H -2.25600 4.30800 1.18800 H -0.64700 5.06700 1.24400 H -1.36600 4.40700 2.72700 C 1.34400 3.72100 -1.04100 C -1.06000 3.79700 -1.72300 C 0.40900 2.03200 -2.60900 H 2.19200 3.07800 -0.75000 H 1.65100 4.33600 -1.90200 H 1.14500 4.40100 -0.19700 H -1.95300 3.19800 -1.95900 H -0.81700 4.42000 -2.60000 H -1.30900 4.46700 -0.89000 H 1.26100 1.35000 -2.45500 H 0.66000 2.67500 -3.46700 H -0.46500 1.42200 -2.88200 C -0.31700 -1.50000 -2.67500 C -1.61100 -3.23100 -1.46400 C 0.82800 -3.54500 -1.89700 H -1.11900 -0.75700 -2.51900 H -0.52800 -1.99600 -3.63500 H 0.63400 -0.95400 -2.77600 H -2.41600 -2.50400 -1.26900 H -1.62200 -3.97300 -0.65300 H -1.83900 -3.75100 -2.40900 H 1.82200 -3.06800 -1.91200 H 0.63600 -3.98900 -2.88600 H 0.85900 -4.36600 -1.16400 C -4.75800 -0.04400 -0.32700 C -4.24100 1.13400 -1.14600 H -3.65000 1.81600 -0.51400 H -3.59900 0.77500 -1.96700 H -5.07200 1.69900 -1.58800 C -5.61900 0.44900 0.83400 H -5.02600 1.08300 1.51100 H -6.45800 1.04300 0.44800 H -6.03900 -0.38600 1.41200 C -5.53200 -1.01700 -1.21500 H -6.40000 -0.51300 -1.66200 H -4.88400 -1.38700 -2.02300 H -5.90600 -1.87900 -0.64400 O -3.56500 -0.67800 0.15700 C -3.67500 -1.69100 1.13000 992 H -2.67600 -2.14400 1.21900 H -4.38400 -2.47800 0.82700 H -3.97400 -1.28300 2.10900 H 4.87200 2.31700 -0.05300 H 6.06000 1.26100 0.76500 C 5.50300 1.42300 -0.16900 H 6.23500 1.61300 -0.96600 H 4.18200 0.97300 2.18500 H 3.38300 1.37300 -1.86100 C 4.64300 0.21300 -0.53000 C 3.89600 -0.00900 1.77700 O 3.56200 0.07400 0.40900 C 3.95300 0.43200 -1.87000 H 3.00400 -0.36900 2.30700 H 4.68900 0.49000 -2.68300 C 5.47400 -1.06900 -0.57800 H 5.98200 -1.27000 0.37600 H 4.70600 -0.73300 1.95600 H 6.25000 -0.97700 -1.35000 H 3.27400 -0.40800 -2.08800 H 4.83500 -1.92900 -0.82300 993 Table C.2.102. Atomic coordinates and single point energies for B23-2. G = –2606.920076 GSP = –2609.15998 N 0.21900 -1.12700 -1.41500 N -0.70800 1.33100 1.50600 Na 0.95800 0.93200 -0.25000 Na -1.25500 -0.87700 0.45300 Si 1.48800 -2.27000 -1.58900 Si -0.19900 0.71400 3.02500 C -0.66300 -0.85900 -2.55800 C -1.44900 2.59800 1.42700 C 2.20100 -2.74600 0.10500 C 2.98100 -1.68400 -2.63600 C 1.06800 -3.95800 -2.38300 C 1.04200 -0.67900 2.66000 C 0.63700 1.87000 4.29700 H 0.60800 -1.46100 2.01700 H 1.36700 -1.17600 3.58800 H 1.94700 -0.31600 2.14700 H 1.40300 2.54000 3.87900 H 1.11200 1.25200 5.07600 H -0.11400 2.50100 4.79900 C -1.51200 -0.13900 4.12500 H -1.92600 -1.02700 3.62800 H -2.35100 0.52500 4.38100 H -1.04900 -0.47500 5.06800 H 0.25500 -4.48600 -1.86200 H 1.96200 -4.60200 -2.34500 H 0.77900 -3.86600 -3.44100 H 2.50200 -1.88200 0.71200 H 3.09000 -3.38200 -0.04200 994 H 1.47500 -3.32500 0.69700 H 3.24400 -0.63900 -2.40700 H 2.76500 -1.74500 -3.71300 H 3.87200 -2.30300 -2.43900 C -1.73300 -1.95800 -2.73700 C 0.08500 -0.72100 -3.89900 C -1.41200 0.45300 -2.31400 H -2.37100 -2.00800 -1.84000 H -2.38500 -1.75300 -3.60400 H -1.26900 -2.94300 -2.88200 H 0.92400 -0.01500 -3.79800 H -0.58200 -0.36500 -4.70100 H 0.50400 -1.68600 -4.22100 H -2.01500 0.41000 -1.39500 H -2.10400 0.70700 -3.13300 H -0.70900 1.28900 -2.20200 C -1.86400 2.89500 -0.02000 C -0.60100 3.81100 1.86700 C -2.72200 2.59500 2.29700 H -0.97000 2.90000 -0.66600 H -2.34000 3.88700 -0.09700 H -2.57000 2.15900 -0.42800 H 0.27900 3.90400 1.21500 H -0.25300 3.71300 2.90300 H -1.17600 4.74800 1.79000 H -3.33800 1.70900 2.07700 H -3.33400 3.49700 2.13200 H -2.46200 2.56300 3.36800 N 3.50700 1.57000 0.39700 N 1.72700 3.06100 -1.63900 C 3.98000 2.48200 -0.65100 C 3.08300 2.57300 -1.87700 C 2.93000 2.31300 1.51100 H 4.96100 2.14400 -1.01500 H 4.15800 3.48700 -0.22700 H 3.00100 1.56700 -2.32300 H 3.59400 3.21900 -2.62600 C 1.00100 3.06300 -2.90300 C 1.72000 4.41400 -1.10100 H 0.99800 2.05700 -3.34200 H 1.46500 3.75900 -3.63100 H -0.04000 3.37400 -2.74100 H 2.20800 4.46300 -0.12100 H 0.68100 4.75100 -0.97700 H 2.23700 5.12200 -1.78300 H 2.02700 2.85400 1.20000 995 H 3.64900 3.04200 1.94000 H 2.63100 1.62200 2.30600 H -1.97500 -4.85200 0.70200 H -2.26500 -3.37200 -0.26900 H -3.68800 -3.81800 1.99200 C -1.64900 -3.80500 0.52700 H -4.46200 -3.53300 -0.01300 H -0.61100 -3.81400 0.16900 C -3.12300 -2.89100 2.21700 H -1.24000 -4.58800 3.08100 H -4.87500 -1.64800 2.17400 C -4.80700 -2.53600 -0.31300 N -3.95500 -1.51100 0.26800 N -1.74200 -3.00400 1.74400 C -3.86100 -1.65500 1.71600 C -0.88700 -3.58300 2.77300 H -4.77300 -2.49200 -1.40900 H -3.11100 -2.81000 3.31400 H 0.13800 -3.68500 2.39000 H -5.86300 -2.42600 0.01300 H -0.85600 -2.93000 3.65500 H -3.34000 -0.76400 2.10400 C 4.58100 0.70500 0.89100 C 5.02500 -0.34400 -0.11900 N 6.25800 -1.00300 0.27100 C 6.72200 -1.88400 -0.77900 H 4.20300 0.20500 1.79500 H 5.46700 1.30100 1.19700 H 5.20000 0.13100 -1.09700 H 4.20000 -1.06900 -0.27300 H 6.83800 -1.32300 -1.71800 H 6.02200 -2.72700 -0.97100 H 7.70000 -2.30800 -0.51000 C 6.13500 -1.71700 1.52500 H 5.93600 -1.02500 2.35500 H 7.08000 -2.23200 1.74800 H 5.32400 -2.47800 1.50600 C -4.44200 -0.16500 -0.03400 C -4.75000 0.06700 -1.51100 N -4.65100 1.46500 -1.87400 C -5.47300 2.33500 -1.06100 C -4.90900 1.65300 -3.28300 H -5.15100 2.30800 -0.01000 H -6.55300 2.07000 -1.10600 H -5.36200 3.37100 -1.41100 H -5.95500 1.40000 -3.56400 996 H -4.23800 1.01300 -3.87600 H -4.72200 2.69900 -3.56400 H -4.02000 -0.49200 -2.11800 H -5.75800 -0.34200 -1.75600 H -5.34800 0.05300 0.57500 H -3.66900 0.55500 0.28000 997 Table C.2.103. Atomic coordinates and single point energies for B6-2. G = –2030.933174 GSP = –2032.52122 N 0.86600 1.65500 -0.35600 N -0.88500 -1.66000 -0.36500 Na 1.24100 -0.66000 -0.35900 Na -1.25900 0.65100 -0.42400 Si 1.47700 2.07500 1.18600 Si -1.56900 -2.06400 1.15100 C 0.88500 2.56600 -1.49900 C -0.85700 -2.58100 -1.49900 C 0.29900 3.08600 2.28800 C 3.14200 3.00200 1.27000 C 1.83200 0.45100 2.12800 C -1.94600 -0.42900 2.06500 C -3.24200 -2.98200 1.16400 H -1.07900 0.24800 2.14200 H -2.27600 -0.63700 3.09400 H -2.76500 0.12000 1.57100 H -4.01900 -2.43100 0.60900 H -3.59200 -3.09600 2.20300 H -3.17900 -3.99000 0.72700 C -0.45500 -3.07400 2.31900 H 0.52900 -2.59300 2.44200 H -0.28200 -4.08500 1.91900 H -0.90600 -3.18000 3.31900 H 0.98200 -0.24900 2.15700 H 2.09600 0.67000 3.17500 998 H 2.69400 -0.07500 1.68400 H 0.15200 4.09700 1.87700 H 0.69000 3.19400 3.31200 H -0.69200 2.60800 2.35400 H 3.10300 3.99900 0.80500 H 3.95000 2.43900 0.77600 H 3.43200 3.14300 2.32400 C 2.26400 2.55700 -2.18600 C 0.53600 4.01900 -1.12300 C -0.15200 2.11900 -2.54800 H 2.49700 1.53700 -2.53600 H 2.30500 3.23600 -3.05300 H 3.04400 2.86100 -1.47300 H -0.44400 4.05000 -0.62100 H 0.49300 4.67200 -2.00900 H 1.28200 4.44100 -0.43300 H -0.00600 1.05800 -2.80600 H -0.07000 2.70300 -3.47700 H -1.18300 2.25900 -2.17800 C 0.22400 -2.14400 -2.50700 C -2.20600 -2.57700 -2.24400 C -0.52400 -4.03000 -1.09500 H 0.08900 -1.08500 -2.78100 H 0.18000 -2.73600 -3.43400 H 1.23800 -2.28200 -2.09400 H -2.42500 -1.55900 -2.60600 H -3.01500 -2.88000 -1.56200 H -2.21000 -3.26000 -3.10900 H 0.43500 -4.05600 -0.55200 H -0.44500 -4.69200 -1.97200 H -1.29800 -4.44600 -0.43200 C -4.94500 1.93200 0.99600 C -4.03100 2.49500 -0.09400 O -3.37800 1.35700 -0.62900 C -4.35700 0.32900 -0.73400 C -5.29200 0.51900 0.47500 H -5.83200 2.55900 1.15600 H -4.39900 1.87100 1.94800 H -3.26400 3.19000 0.27300 H -4.61300 2.99500 -0.88800 H -3.82600 -0.63400 -0.74900 H -4.90300 0.44500 -1.68600 H -5.10600 -0.24300 1.24400 H -6.34400 0.43500 0.17400 C 5.38600 -0.50100 0.39900 C 4.30500 -0.32000 -0.65800 999 O 3.37100 -1.37500 -0.41500 C 3.96300 -2.40600 0.37900 C 5.43700 -2.02600 0.51700 H 5.06500 -0.05000 1.35100 H 6.34300 -0.05000 0.10900 H 4.71700 -0.42400 -1.67700 H 3.76500 0.63700 -0.59400 H 3.80700 -3.37500 -0.11500 H 3.45900 -2.42900 1.36000 H 6.02100 -2.45000 -0.31400 H 5.87500 -2.38100 1.45800 1000 Table C.2.104. Atomic coordinates and single point energies for B20-2. G = –2572.536378 GSP = –2574.72062 N 0.35600 2.03800 0.65100 N -0.54200 -1.78100 0.84900 Na 1.34200 -0.42100 0.31600 Na -1.48400 0.52000 0.43700 Si 1.17800 2.72600 -0.68300 Si -1.27000 -2.77200 -0.34500 C 0.07300 2.83500 1.85600 C -0.19600 -2.30000 2.18000 C 1.34400 1.35500 -1.99300 C 2.94400 3.38400 -0.33500 C 0.43400 4.19400 -1.66100 C -1.40600 -1.70500 -1.90900 C -0.40200 -4.37600 -0.92200 H -1.98000 -0.78400 -1.72800 H -1.90400 -2.25100 -2.72600 H -0.40800 -1.40400 -2.26800 H 0.44300 -4.18900 -1.60200 H -1.12900 -4.99100 -1.47600 H -0.03200 -4.98600 -0.08300 C -3.03200 -3.44700 0.00900 H -3.53400 -3.66500 -0.95000 H -3.68400 -2.77400 0.58600 H -2.97600 -4.39600 0.56400 H -0.59100 4.02800 -2.02500 H 1.07000 4.36600 -2.54500 H 0.43100 5.12600 -1.07700 1001 H 2.10900 0.60600 -1.74800 H 1.62800 1.78400 -2.96700 H 0.39000 0.81900 -2.13800 H 3.50500 2.76000 0.37800 H 2.89900 4.39900 0.09400 H 3.53100 3.45300 -1.26600 C -0.15000 4.33400 1.57400 C 1.20600 2.74500 2.89600 C -1.20900 2.32400 2.53800 H -0.94500 4.48100 0.82700 H -0.43800 4.87000 2.49200 H 0.76800 4.80700 1.19200 H 1.32800 1.70900 3.24300 H 0.99700 3.37300 3.77700 H 2.15700 3.08100 2.45400 H -2.08000 2.45900 1.87800 H -1.41400 2.86200 3.47600 H -1.10800 1.25800 2.78700 C -0.14900 -1.14600 3.19100 C 1.19600 -2.96500 2.19500 C -1.19400 -3.34400 2.71800 H 0.48600 -0.32500 2.81500 H 0.24800 -1.46900 4.16600 H -1.15600 -0.73800 3.35500 H 1.98500 -2.24100 1.92700 H 1.23700 -3.79100 1.47000 H 1.44100 -3.36800 3.19100 H -2.22100 -2.95000 2.70600 H -0.94900 -3.63500 3.75200 H -1.17600 -4.25800 2.10400 N 3.08400 -1.63400 -1.35800 N 3.98000 -0.61100 1.23100 C 4.42300 -1.02700 -1.19300 C 4.40800 -0.00800 -0.03300 C 3.02700 -2.93000 -0.69200 C 2.62200 -1.80100 -2.72800 C 3.52500 0.37400 2.19300 C 4.94800 -1.50600 1.83500 H 2.57400 -0.84300 -3.25900 H 1.60600 -2.22100 -2.70000 H 3.25500 -2.50000 -3.31200 H 2.76900 1.03200 1.73900 H 4.33800 1.02200 2.58400 H 3.06400 -0.13700 3.05400 H 5.30600 -2.24900 1.10900 H 4.47100 -2.05100 2.66400 1002 H 5.83000 -0.97300 2.24500 H 3.37500 -2.84500 0.34100 H 3.64900 -3.68500 -1.21800 H 1.99100 -3.28800 -0.66400 H -3.54800 3.59300 -1.31300 H -3.44800 2.78800 0.28000 C -2.99800 2.83600 -0.71500 H -5.35300 2.22800 0.95300 H -1.95700 3.16500 -0.59600 C -4.36800 0.91500 -1.29600 C -4.96600 1.56200 1.73600 N -4.04200 0.58600 1.18200 N -3.02200 1.52700 -1.35900 C -4.49200 -0.02600 -0.07400 C -2.43800 1.67300 -2.68700 H -4.44200 2.18000 2.48200 C -3.69000 -0.39200 2.19900 H -3.29600 0.13700 3.08100 H -5.83400 1.09000 2.23700 H -2.90600 -1.07100 1.82800 H -4.55200 -1.00300 2.53800 C 5.72900 0.80500 0.03900 C 4.99800 -0.30100 -2.41400 C 6.86700 0.13300 -0.72200 C 6.50000 -0.01300 -2.20600 H 7.06600 -0.85700 -0.28100 H 7.79800 0.70800 -0.61400 H 7.09800 -0.82000 -2.65600 H 6.76500 0.90700 -2.74600 H 4.86700 -0.89500 -3.32700 H 4.44000 0.63900 -2.56400 H 5.13600 -1.84300 -0.96100 H 5.55800 1.80600 -0.38700 H 6.00600 0.97100 1.09100 H 3.60900 0.70200 -0.29900 C -5.90000 -0.63500 0.01000 C -4.74100 0.12500 -2.56000 C -6.26100 -1.39900 -1.25900 C -6.13900 -0.48200 -2.47000 H -6.88600 0.32800 -2.39100 H -6.36300 -1.02800 -3.39900 H -5.57400 -2.25400 -1.37500 H -7.27700 -1.81300 -1.18300 H -5.96200 -1.29700 0.88700 H -6.63600 0.17300 0.16500 H -3.78400 -0.85000 -0.27500 1003 H -5.12400 1.72400 -1.19900 H -4.68100 0.78000 -3.43900 H -4.00700 -0.68500 -2.70700 H -2.33600 0.70900 -3.19900 H -1.43100 2.09700 -2.57000 H -3.01800 2.36100 -3.33500 1004 Table C.2.105. Atomic coordinates and single point energies for B17-2. G = –2260.99758 GSP = –2262.84693 N 0.13400 1.97300 0.06200 N 0.02600 -1.85200 0.13700 Na 1.57800 -0.03800 0.05000 Na -1.47000 0.08100 0.10000 Si 0.44300 2.58500 -1.51300 Si -0.16900 -2.80200 -1.27400 C -0.53200 2.83100 1.05300 C 0.15700 -2.45900 1.46400 C 1.77500 1.53100 -2.36200 C 1.12800 4.35500 -1.70300 C -1.01700 2.54900 -2.74100 C -0.11100 -1.62200 -2.76600 C 1.13800 -4.13300 -1.67800 H -0.44500 -0.60100 -2.51900 H -0.72800 -1.98600 -3.60300 H 0.92200 -1.53700 -3.13900 H 2.15600 -3.72000 -1.74400 H 0.90000 -4.58500 -2.65500 H 1.14900 -4.94700 -0.93700 C -1.78500 -3.83600 -1.40500 H -2.63200 -3.41000 -0.84700 H -1.62300 -4.85100 -1.00900 H -2.09300 -3.94500 -2.45700 H -1.44100 1.53400 -2.81400 H -0.68400 2.84000 -3.75000 H -1.82400 3.23400 -2.44200 1005 H 2.76500 1.71800 -1.91800 H 1.83500 1.82200 -3.42300 H 1.58900 0.44800 -2.34600 H 2.02000 4.52100 -1.08000 H 0.39000 5.13200 -1.45000 H 1.41600 4.50800 -2.75600 C -1.85400 3.42000 0.51200 C 0.34100 4.01700 1.51800 C -0.87800 2.02900 2.32000 H -2.48700 2.61900 0.09200 H -2.42600 3.94500 1.29600 H -1.65800 4.14200 -0.29600 H 1.29900 3.65800 1.92100 H -0.16500 4.59900 2.30500 H 0.56200 4.69700 0.68700 H -1.59900 1.22300 2.11400 H -1.33300 2.67800 3.08500 H 0.02000 1.57000 2.75300 C -0.03000 -1.36900 2.52700 C 1.55400 -3.06200 1.70300 C -0.88100 -3.56800 1.72200 H 0.72800 -0.57800 2.40200 H 0.06400 -1.76300 3.55200 H -1.01800 -0.90000 2.43100 H 2.31000 -2.26300 1.68400 H 1.80700 -3.79600 0.92400 H 1.61700 -3.56200 2.68400 H -1.89000 -3.21200 1.46300 H -0.87700 -3.89700 2.77300 H -0.67400 -4.45000 1.09500 N 3.93000 -0.63100 -0.97600 N 3.67800 0.53900 1.75100 C 4.78000 0.46500 -0.51000 C 4.15700 1.30300 0.60700 C 4.21400 -1.87000 -0.26300 C 4.09400 -0.87000 -2.40400 H 4.96200 1.15300 -1.35000 H 5.77800 0.08300 -0.21200 H 3.29400 1.85400 0.19600 H 4.89500 2.07500 0.92200 C 2.81700 1.35700 2.58700 C 4.76800 -0.00600 2.54100 H 3.85600 0.03500 -2.97700 H 3.40700 -1.66800 -2.72000 H 5.12800 -1.18800 -2.65100 H 1.96200 1.71600 1.99600 1006 H 3.35300 2.24000 3.00000 H 2.44100 0.76100 3.43100 H 5.45500 -0.59100 1.91700 H 4.36600 -0.67100 3.31900 H 5.35500 0.79600 3.03400 H 4.09200 -1.72800 0.81400 H 5.24800 -2.22300 -0.46200 H 3.50900 -2.65000 -0.57800 H -5.26800 1.22800 -2.51400 H -4.67000 2.19500 -1.12900 H -5.58300 0.41700 -0.07800 C -4.38000 1.45300 -1.88700 H -4.26900 1.65300 1.11200 H -3.60900 1.90100 -2.52400 C -4.88500 -0.36400 -0.41000 H -4.20800 -1.02600 -2.91000 H -5.24200 -1.55000 1.31900 C -4.27300 1.01700 2.00600 N -3.61500 -0.25500 1.74700 N -3.85600 0.25600 -1.24300 C -4.36000 -1.09900 0.81300 C -3.38300 -0.68400 -2.25100 H -3.72300 1.55300 2.79200 H -5.49200 -1.07500 -1.00500 H -2.61800 -0.21100 -2.88000 C -3.44100 -0.97000 3.00300 H -2.79500 -0.39200 3.67900 H -5.32100 0.88300 2.34900 H -2.93400 -1.56900 -1.78100 H -2.96800 -1.94400 2.82500 H -3.70600 -1.93600 0.51400 H -4.41400 -1.14100 3.50900 1007 Table C.2.106. Atomic coordinates and single point energies for B2-2. G = –2109.042681 GSP = –2110.69947 N -0.57900 -1.81800 0.13300 N 0.63300 1.70000 0.01200 Na 1.35500 -0.55100 0.04600 Na -1.35100 0.45900 0.17200 Si -0.93000 -2.43500 -1.42600 Si 0.49900 2.36900 -1.56100 C -0.97700 -2.49700 1.36300 C 1.35000 2.38700 1.08600 C -2.65000 -1.92200 -2.08900 C -0.89500 -4.31700 -1.71200 C 0.38400 -1.79200 -2.65400 C -0.96500 1.53500 -2.45100 C 0.09200 4.22500 -1.70300 H -0.95900 0.43500 -2.41200 H -0.95300 1.80500 -3.51800 H -1.92700 1.88900 -2.04800 H -0.85100 4.45800 -1.18200 H -0.03500 4.49700 -2.76300 H 0.87400 4.87800 -1.28600 C 2.01200 2.09500 -2.68900 H 2.27000 1.02400 -2.74800 H 2.89600 2.62900 -2.30700 H 1.82200 2.44900 -3.71500 H 0.77100 -0.78300 -2.43700 H -0.01500 -1.75900 -3.68000 H 1.23800 -2.48800 -2.66000 H -3.42500 -2.52600 -1.58800 1008 H -2.74400 -2.09800 -3.17200 H -2.88500 -0.86000 -1.90400 H -1.65800 -4.85700 -1.13100 H 0.08700 -4.74800 -1.46200 H -1.08800 -4.51900 -2.77800 C -0.17300 -3.79100 1.59600 C -2.47600 -2.85200 1.38100 C -0.69700 -1.58200 2.56700 H 0.90300 -3.55800 1.58800 H -0.42200 -4.26300 2.56000 H -0.36700 -4.52000 0.79900 H -3.07500 -1.94700 1.19400 H -2.79200 -3.28900 2.34200 H -2.71400 -3.57900 0.58800 H 0.37700 -1.34200 2.62000 H -0.98200 -2.05800 3.51800 H -1.25700 -0.63300 2.49300 C 1.66300 1.39600 2.22000 C 0.50400 3.51400 1.70900 C 2.69000 2.99000 0.62200 H 0.73800 0.90800 2.56200 H 2.12500 1.89600 3.08600 H 2.37300 0.61500 1.89000 H -0.40900 3.08500 2.14900 H 0.20800 4.24400 0.94200 H 1.05000 4.04800 2.50400 H 3.30400 2.20900 0.14600 H 3.25900 3.42300 1.46100 H 2.53000 3.78900 -0.11800 H -3.64500 3.29700 -1.03800 C -3.70000 2.56800 -0.22800 C -4.46400 1.41100 -0.38600 H -5.00300 1.24100 -1.32100 C -4.56200 0.46200 0.64300 C -3.85500 0.70000 1.83000 H -3.91900 -0.02600 2.64300 C -3.07900 1.85300 1.98800 H -2.53500 2.01600 2.92100 C -3.00000 2.79300 0.95900 H -2.38900 3.68800 1.07600 H 4.66400 0.49300 -1.28000 C 4.36500 -0.35700 -0.66300 C 3.68100 -1.42800 -1.24900 H 3.45400 -1.40500 -2.31700 C 3.28100 -2.51600 -0.47100 H 2.73200 -3.34600 -0.91900 1009 C 3.57600 -2.52700 0.89600 H 3.27000 -3.37300 1.51200 C 4.26600 -1.46100 1.47100 H 4.49400 -1.47900 2.54000 C 4.67500 -0.36100 0.70200 C 5.41700 0.77900 1.34600 H 5.73300 1.52200 0.60300 H 4.77900 1.29100 2.08300 H 6.30900 0.41400 1.87500 C -5.41400 -0.76600 0.46400 H -6.43400 -0.48900 0.16400 H -4.99900 -1.41300 -0.32300 H -5.47100 -1.35100 1.39000 1010 Table C.2.107. Atomic coordinates and single point energies for B1. G = –1566.779371 GSP = –1567.84387 N 1.81400 0.31800 0.08900 N -1.81400 -0.31800 0.08900 Na -0.00000 -0.00000 -1.33500 Na -0.00000 0.00100 1.47500 Si 2.76200 -1.02500 -0.40100 Si -2.76300 1.02500 -0.40100 C 2.39600 1.58400 0.53300 C -2.39500 -1.58400 0.53400 C 3.38500 -2.13800 1.00700 C 4.25700 -0.68900 -1.52700 C 1.64700 -2.14900 -1.47900 C -1.64800 2.14900 -1.47900 C -4.25700 0.68800 -1.52700 H -0.68300 2.41300 -1.01400 H -2.16600 3.10100 -1.67200 H -1.45500 1.70900 -2.47500 H -3.94700 0.15900 -2.44100 H -4.71600 1.64300 -1.83100 H -5.04100 0.08700 -1.04300 C -3.38500 2.13800 1.00700 H -2.54600 2.47500 1.63700 H -4.09200 1.60000 1.65600 H -3.89700 3.03400 0.62300 H 0.68200 -2.41200 -1.01400 H 2.16500 -3.10100 -1.67100 H 1.45500 -1.70900 -2.47500 H 4.09200 -1.60000 1.65600 H 3.89600 -3.03400 0.62300 H 2.54500 -2.47400 1.63800 H 5.04100 -0.08900 -1.04300 H 3.94700 -0.16000 -2.44100 H 4.71500 -1.64400 -1.83100 C 2.76800 2.47100 -0.67100 1011 C 3.64800 1.40300 1.41200 C 1.37400 2.36600 1.38500 H 1.87100 2.67400 -1.27900 H 3.20000 3.43600 -0.36200 H 3.49900 1.95200 -1.30700 H 3.41200 0.76900 2.28200 H 4.03100 2.36800 1.78100 H 4.46000 0.91600 0.85100 H 0.41200 2.47000 0.85500 H 1.72900 3.38000 1.62300 H 1.20500 1.86800 2.35800 C -1.37300 -2.36500 1.38500 C -2.76600 -2.47100 -0.67000 C -3.64800 -1.40300 1.41300 H -0.41100 -2.46700 0.85600 H -1.72600 -3.37900 1.62300 H -1.20500 -1.86600 2.35800 H -1.87000 -2.67400 -1.27800 H -3.49800 -1.95300 -1.30700 H -3.19800 -3.43700 -0.36100 H -3.41200 -0.76900 2.28200 H -4.03000 -2.36800 1.78200 H -4.45900 -0.91700 0.85100 1012 Table C.2.108. Atomic coordinates and single point energies for B34. G = –2030.55932 GSP = –2032.12883 N 0.61000 -1.84000 0.25700 N -0.54000 1.65200 -0.43200 Na 1.39100 0.33500 0.02400 Na -1.36000 -0.49500 0.01900 Si 0.77800 -2.69000 -1.22200 Si -0.54600 2.87600 0.76900 C 0.62100 -2.50000 1.56100 C -0.85000 1.95000 -1.83300 C -0.90700 -3.16300 -1.99100 C 1.78600 -4.30400 -1.26800 C 1.68600 -1.59500 -2.49300 C 0.18600 2.15900 2.37000 C 0.46600 4.44600 0.37500 H -0.43800 1.33800 2.75700 H 0.20700 2.94300 3.14300 H 1.21700 1.78100 2.27400 H 1.48300 4.20100 0.03300 H 0.55100 5.08300 1.27000 H -0.00600 5.05300 -0.41400 C -2.23200 3.55100 1.35800 H -2.81200 2.75800 1.85700 H -2.84500 3.96000 0.54100 H -2.07700 4.35500 2.09500 H 1.43300 -0.52400 -2.44800 H 1.47600 -1.92700 -3.52200 H 2.77200 -1.68600 -2.33200 1013 H -1.44700 -3.84200 -1.31000 H -0.79400 -3.67700 -2.95900 H -1.55200 -2.28400 -2.16400 H 1.38000 -5.09700 -0.62200 H 2.83300 -4.13000 -0.97400 H 1.79000 -4.68700 -2.30100 C 2.01400 -3.05200 1.91800 C -0.39100 -3.66000 1.65000 C 0.25500 -1.47900 2.64900 H 2.75300 -2.23800 1.85800 H 2.04000 -3.47700 2.93500 H 2.31600 -3.83800 1.21300 H -1.40300 -3.29600 1.41500 H -0.40900 -4.11700 2.65300 H -0.14400 -4.45100 0.92500 H 0.97900 -0.64800 2.65400 H 0.25300 -1.93000 3.65400 H -0.74900 -1.05400 2.47700 C -1.31700 0.67000 -2.54800 C 0.39300 2.47400 -2.58000 C -1.98000 2.98300 -2.00700 H -0.57900 -0.13700 -2.43600 H -1.46600 0.83000 -3.62700 H -2.28300 0.33100 -2.13700 H 1.20200 1.72500 -2.54300 H 0.76100 3.39400 -2.10300 H 0.18300 2.69200 -3.63900 H -2.88200 2.64100 -1.47500 H -2.23400 3.12800 -3.06900 H -1.69400 3.96300 -1.59600 H -4.77500 0.35900 -1.55100 C -4.43300 -0.14700 -0.64700 C -4.23400 -1.53000 -0.65200 H -4.41700 -2.10700 -1.55900 C -3.79300 -2.17500 0.50600 H -3.63600 -3.25500 0.50100 C -3.55100 -1.43600 1.66800 H -3.20900 -1.94200 2.57300 C -3.73800 -0.05100 1.66800 H -3.53700 0.52800 2.57200 C -4.17800 0.59400 0.50900 H -4.31100 1.67700 0.50600 H 3.92400 0.80100 -2.21800 C 3.93300 0.92900 -1.13400 C 4.31500 -0.13300 -0.30900 H 4.60200 -1.09000 -0.74600 1014 C 4.32000 0.02800 1.07800 H 4.62100 -0.80000 1.72100 C 3.93500 1.24600 1.64200 H 3.93200 1.36900 2.72600 C 3.55000 2.30700 0.81800 H 3.23800 3.25500 1.26000 C 3.54900 2.15000 -0.57000 H 3.23800 2.97400 -1.21300 1015 Table C.2.109. Atomic coordinates and single point energies for B28. G = –2490.699978 GSP = –2492.83049 N -0.67400 -1.52000 0.95100 N 0.87200 1.36300 -1.06900 Na 1.00100 -1.02000 -0.64900 Na -0.95200 0.77300 0.37900 Si -2.06700 -2.44600 0.59100 Si 1.79600 2.67500 -0.45400 C 0.06100 -1.69700 2.20400 C 0.67400 1.22200 -2.51800 C -2.56600 -2.13400 -1.21500 C -3.62600 -2.04600 1.62700 C -1.90100 -4.34200 0.73300 C 2.29000 2.42100 1.36200 C 3.45300 3.08200 -1.31900 H 1.42100 2.22400 2.00600 H 2.76000 3.35400 1.71300 H 3.02500 1.61400 1.51000 H 4.16500 2.24200 -1.28500 H 3.92500 3.92600 -0.79100 H 3.33500 3.37800 -2.37200 C 0.89200 4.35900 -0.36800 H 0.13200 4.30200 0.42800 H 0.39200 4.64900 -1.30400 H 1.59300 5.16400 -0.09500 H -1.04700 -4.71800 0.14600 H -2.81200 -4.83800 0.36200 H -1.75100 -4.66600 1.77500 H -2.62000 -1.06300 -1.46400 H -3.55500 -2.57700 -1.42000 H -1.84900 -2.59700 -1.90700 H -3.76300 -0.96000 1.75200 1016 H -3.57000 -2.48400 2.63500 H -4.53400 -2.44800 1.14600 C 1.05600 -2.87400 2.12200 C -0.84400 -1.93100 3.42900 C 0.87200 -0.42500 2.48400 H 1.81400 -2.67700 1.34700 H 1.58600 -3.03400 3.07600 H 0.52600 -3.80300 1.86200 H -1.59700 -1.13100 3.50200 H -0.26100 -1.95100 4.36300 H -1.37700 -2.89200 3.35000 H 1.50800 -0.15700 1.62400 H 1.52600 -0.52100 3.36700 H 0.19200 0.42300 2.66700 C -0.56000 0.34400 -2.79000 C 1.89400 0.55100 -3.19000 C 0.41500 2.55300 -3.25500 H -0.46600 -0.66300 -2.35000 H -0.73100 0.19900 -3.86900 H -1.46400 0.80700 -2.36100 H 2.07900 -0.45300 -2.77400 H 2.79700 1.15600 -3.02300 H 1.75400 0.43600 -4.27800 H -0.47400 3.05300 -2.84100 H 0.24100 2.38800 -4.32900 H 1.26700 3.24100 -3.15700 O 3.17700 -1.62800 -0.45300 O 1.51600 -2.88300 -2.15200 C 3.66400 -2.72400 -1.18300 C 2.49400 -3.63600 -1.47600 H 4.43700 -3.27600 -0.61900 H 4.10400 -2.37400 -2.13400 H 2.07700 -4.05200 -0.54000 H 2.84000 -4.47600 -2.10500 C 0.50900 -3.67000 -2.73800 H -0.07900 -4.20500 -1.97300 H 0.94500 -4.40500 -3.43700 H -0.15300 -2.99800 -3.29800 H -3.30300 3.63300 1.50600 C -2.32700 3.55700 0.98900 H -0.56400 4.03600 2.93100 H -3.13000 3.73900 -1.00200 O -3.00800 1.73700 -0.47100 O -1.48700 2.66400 1.68200 C -2.48700 3.04800 -0.42900 C -1.15800 3.10700 2.97600 1017 H -1.88300 4.56800 0.95900 H -2.06900 3.28700 3.57300 H -0.56200 2.32500 3.46100 H -1.49600 3.00200 -0.90800 C 4.08300 -0.57100 -0.21100 C 4.63700 -0.65000 1.19900 O 5.45300 0.46500 1.38500 C 5.89100 0.62000 2.70400 H 3.52600 0.37000 -0.33500 H 4.90300 -0.57800 -0.94900 H 5.20200 -1.59400 1.34800 H 3.79200 -0.65700 1.91600 H 6.47700 -0.25400 3.04300 H 5.03900 0.75800 3.39500 H 6.52800 1.51200 2.74500 C -4.32900 1.62100 0.01600 C -4.99700 0.42600 -0.62700 O -6.29600 0.35700 -0.11700 C -7.00400 -0.75500 -0.58200 H -6.49900 -1.69900 -0.30700 H -7.11700 -0.73300 -1.68200 H -8.00000 -0.73800 -0.12300 H -4.99700 0.54900 -1.72900 H -4.43000 -0.49200 -0.39500 H -4.34000 1.49800 1.11400 H -4.90900 2.52800 -0.22900 1018 Table C.2.110. Atomic coordinates and single point energies for B25. G = –2183.524354 GSP = –2185.29792 N 0.92600 1.65500 -0.48600 N -0.71500 -1.69900 0.41100 Na 1.42300 -0.60200 0.07800 Na -1.14400 0.58900 -0.02200 Si 0.74500 3.05900 0.47600 Si -1.56100 -2.69300 -0.69800 C 1.48100 1.73300 -1.83900 C -0.53800 -2.09800 1.81000 C 0.36000 2.58200 2.27600 C -0.74200 4.16300 -0.02000 C 2.21800 4.26500 0.60000 C -1.30500 -2.08100 -2.47600 C -1.13600 -4.55600 -0.72100 H -1.71200 -1.06300 -2.58800 H -1.86700 -2.73200 -3.16400 H -0.25700 -2.05900 -2.80800 H -0.06400 -4.74400 -0.88500 H -1.69000 -5.04900 -1.53600 H -1.41800 -5.06100 0.21600 C -3.47400 -2.67400 -0.57400 H -3.84600 -1.69100 -0.90500 H -3.85400 -2.86700 0.44000 H -3.91000 -3.43000 -1.24700 H 3.12300 3.76400 0.97700 H 1.97100 5.08200 1.29600 1019 H 2.47100 4.72300 -0.36900 H -0.52200 1.92900 2.36300 H 0.15400 3.50000 2.85000 H 1.19200 2.06500 2.77700 H -1.63200 3.54000 -0.21700 H -0.54000 4.73700 -0.93600 H -0.99900 4.88300 0.77500 C 3.02200 1.78000 -1.80800 C 0.98000 2.95100 -2.64000 C 1.07700 0.48900 -2.64800 H 3.40500 0.88600 -1.29000 H 3.45900 1.80500 -2.82000 H 3.36800 2.66700 -1.25800 H -0.12100 2.95100 -2.67600 H 1.36400 2.94400 -3.67300 H 1.30200 3.89400 -2.17300 H 1.49600 -0.43900 -2.22400 H 1.43700 0.54400 -3.68700 H -0.01800 0.38900 -2.67100 C -0.25300 -0.85400 2.66700 C 0.65100 -3.07000 1.96900 C -1.77700 -2.77400 2.43000 H 0.62900 -0.29600 2.30800 H -0.06300 -1.11300 3.72100 H -1.11700 -0.17000 2.63300 H 1.58200 -2.60700 1.60000 H 0.47200 -3.98400 1.38200 H 0.81600 -3.35900 3.02000 H -2.64800 -2.10300 2.36300 H -1.61400 -3.01600 3.49200 H -2.02800 -3.71000 1.90900 O 2.91200 -2.19200 -0.76600 O 3.51300 -0.38000 1.12700 C 4.03700 -2.41400 0.04500 C 4.56100 -1.07500 0.50400 C 2.37000 -3.37600 -1.30200 H 4.82600 -2.94700 -0.51700 H 3.75700 -3.03500 0.91700 H 4.93600 -0.49700 -0.36200 H 5.40300 -1.22800 1.20500 C 3.90000 0.88200 1.61800 H 4.32300 1.50200 0.81000 H 4.64400 0.77400 2.42600 H 3.00300 1.37900 2.00200 H 2.11300 -4.08600 -0.49700 H 3.08300 -3.85200 -1.99700 1020 H 1.45200 -3.10900 -1.84000 H -4.67300 1.99500 -0.43200 C -4.24500 0.97400 -0.40300 H -3.73000 2.30200 -2.61700 H -4.71500 0.59900 1.67400 O -2.80600 1.40000 1.50000 O -3.09600 0.91600 -1.21200 C -3.83800 0.57800 1.00400 C -3.31900 1.28000 -2.55100 H -5.01900 0.27400 -0.77000 H -2.35400 1.25000 -3.07100 C -3.23200 2.64900 1.98900 H -2.34300 3.18300 2.34500 H -4.01500 0.57700 -3.03900 H -3.93900 2.51600 2.82500 H -3.43600 -0.44700 0.98300 H -3.71200 3.25800 1.20500 1021 Table C.2.111. Atomic coordinates and single point energies for B3. G = –1993.552871 GSP = –1995.09949 N 0.23800 1.91400 -0.07000 N -0.17100 -1.80200 0.52600 Na 1.41500 -0.07400 0.13800 Na -1.39000 0.16200 0.08000 Si -0.00900 2.77100 1.39100 Si 0.21100 -2.98800 -0.65000 C 0.11300 2.52000 -1.39100 C -0.47000 -2.16400 1.91400 C -1.83400 2.72500 1.97500 C 0.44800 4.61500 1.47800 C 1.04200 1.97500 2.76300 C 1.01300 -2.12200 -2.14200 C 1.47800 -4.32400 -0.14900 H 0.33500 -1.40200 -2.62500 H 1.28700 -2.87200 -2.90000 H 1.94000 -1.58700 -1.87400 H 2.42000 -3.86900 0.19500 H 1.71000 -4.96200 -1.01700 H 1.11700 -4.98400 0.65400 C -1.25000 -3.95900 -1.39700 H -1.95200 -3.28700 -1.91800 H -1.81900 -4.50500 -0.63000 H -0.89100 -4.69400 -2.13500 H 1.08600 0.87600 2.70900 1022 H 0.66200 2.23200 3.76500 H 2.07400 2.35400 2.69300 H -2.47800 3.22000 1.22800 H -1.97100 3.25100 2.93300 H -2.22000 1.70100 2.11800 H -0.14300 5.24000 0.79100 H 1.51300 4.77600 1.25200 H 0.26300 4.98200 2.50000 C 1.22700 3.54600 -1.67200 C -1.24700 3.22000 -1.59200 C 0.23100 1.42500 -2.46100 H 2.20900 3.07100 -1.51800 H 1.18200 3.93100 -2.70400 H 1.15600 4.40100 -0.98700 H -2.07000 2.50900 -1.40100 H -1.36600 3.61900 -2.61200 H -1.36300 4.05700 -0.88600 H 1.20600 0.91500 -2.38500 H 0.14500 1.82900 -3.48200 H -0.55900 0.66400 -2.33900 C -1.29500 -1.04800 2.57800 C 0.83000 -2.33100 2.72800 C -1.29100 -3.46000 2.05900 H -0.76900 -0.08200 2.52300 H -1.48800 -1.25200 3.64200 H -2.27800 -0.95000 2.08500 H 1.41500 -1.39600 2.70300 H 1.44800 -3.13000 2.29300 H 0.63600 -2.57800 3.78500 H -2.23900 -3.37300 1.50600 H -1.52700 -3.67100 3.11400 H -0.74500 -4.32800 1.66100 C -3.99300 -1.44600 -0.15100 N -3.63000 -0.15600 -0.72500 C -3.35400 -0.28900 -2.14900 C -4.59100 0.90600 -0.41800 C 4.28900 -1.48800 0.13400 N 3.79300 -0.15100 -0.15200 C 4.18500 0.34400 -1.47400 C 4.11200 0.78300 0.91900 H -2.50400 -0.97700 -2.29500 H -3.08600 0.68900 -2.57500 H -4.21100 -0.69800 -2.71900 H -4.84200 -1.92400 -0.67800 H -4.27000 -1.31900 0.90600 H -3.12900 -2.12600 -0.20200 1023 H 5.20100 0.90000 1.08400 H 3.67200 0.42800 1.86400 H 3.67900 1.76900 0.69100 H 5.38400 -1.51900 0.29200 H 4.03700 -2.16300 -0.69700 H 3.80500 -1.87500 1.04500 C 5.68300 0.53000 -1.70900 H 3.66300 1.30200 -1.63100 H 3.78200 -0.35800 -2.22300 H 6.12000 1.26100 -1.01300 H 5.85400 0.90200 -2.72800 H 6.23300 -0.41600 -1.60500 C -6.00800 0.70600 -0.95300 H -4.17700 1.84900 -0.80800 H -4.62100 1.01200 0.67900 H -6.02400 0.63600 -2.05100 H -6.63700 1.56000 -0.66700 H -6.47400 -0.20200 -0.54400 1024 Table C.2.112. Atomic coordinates and single point energies for B4. G = –2150.484428 GSP = –2152.20457 N 0.36900 1.98100 -0.07900 N -0.31400 -1.66400 0.67200 Na 1.34800 -0.12200 -0.00900 Na -1.40800 0.39600 0.32400 Si 0.35800 2.87200 1.38200 Si -0.20700 -2.90600 -0.50500 C 0.27700 2.58500 -1.40300 C -0.48900 -1.96900 2.09500 C -1.39800 3.01100 2.13700 C 0.98200 4.66900 1.39400 C 1.46400 2.00700 2.67100 C 0.53100 -2.16000 -2.09200 C 0.93100 -4.38700 -0.11200 H -0.08500 -1.34500 -2.50300 H 0.60300 -2.93700 -2.86800 H 1.55200 -1.77000 -1.93900 H 1.95800 -4.05800 0.10900 H 0.97600 -5.05800 -0.98500 H 0.58400 -4.98500 0.74300 C -1.84500 -3.70200 -1.07400 H -2.49500 -2.96400 -1.57100 H -2.40800 -4.13400 -0.23300 H -1.65200 -4.51000 -1.79900 H 1.47200 0.90900 2.58200 H 1.15300 2.24600 3.70000 1025 H 2.50200 2.35500 2.54900 H -2.03900 3.60400 1.46300 H -1.38400 3.52000 3.11400 H -1.89600 2.03800 2.29700 H 0.40700 5.33500 0.73300 H 2.04100 4.73100 1.10000 H 0.89600 5.06500 2.41900 C 1.50100 3.46000 -1.73900 C -0.99100 3.44700 -1.57000 C 0.22600 1.47300 -2.46100 H 2.42100 2.86800 -1.60800 H 1.46900 3.83000 -2.77600 H 1.56200 4.32900 -1.07000 H -1.88900 2.83600 -1.37800 H -1.07700 3.87400 -2.58200 H -0.99400 4.27900 -0.84900 H 1.14500 0.86400 -2.42400 H 0.13500 1.87200 -3.48300 H -0.63400 0.80500 -2.28300 C -1.08100 -0.75100 2.82500 C 0.86500 -2.29200 2.75800 C -1.44900 -3.14500 2.36100 H -0.46300 0.14500 2.66600 H -1.14700 -0.91300 3.91200 H -2.10600 -0.54800 2.47000 H 1.55000 -1.43400 2.65300 H 1.33000 -3.16000 2.26800 H 0.76500 -2.51300 3.83300 H -2.42900 -2.94000 1.90300 H -1.59800 -3.30900 3.43900 H -1.06300 -4.08300 1.93200 C -4.23200 -0.98200 0.43700 N -3.74400 0.17700 -0.30800 C -3.37100 -0.07200 -1.70000 C -4.40700 1.44900 -0.03000 C 3.87900 -1.77300 -0.12600 N 3.68600 -0.38500 -0.53900 C 4.02200 -0.06700 -1.92300 C 4.00500 0.64100 0.45400 H -2.44900 -0.68600 -1.70400 H -3.09600 0.90100 -2.14100 C -4.38300 -0.78000 -2.60200 C -5.73100 -1.28600 0.38400 H -3.96000 -0.84400 1.49800 H -3.65100 -1.85300 0.09200 C 5.43200 1.18900 0.48900 1026 H 3.74700 0.22300 1.44300 H 3.31600 1.49300 0.29800 C 5.23300 -2.15600 0.47300 H 3.66700 -2.40400 -1.00500 H 3.09800 -2.03000 0.61600 C 5.41500 -0.45800 -2.42000 H 3.86800 1.01700 -2.05000 H 3.27900 -0.55400 -2.58000 H 6.21600 -0.01100 -1.81700 H 5.54300 -0.12400 -3.46000 H 5.54500 -1.55000 -2.40900 C -5.62300 1.81700 -0.88100 H -3.66300 2.25900 -0.13500 H -4.68400 1.43800 1.03700 H -5.34200 1.94600 -1.93700 H -6.04000 2.77400 -0.53500 H -6.41600 1.05900 -0.82800 H -3.97400 -0.85600 -3.62000 H -5.34100 -0.24600 -2.65500 H -4.57500 -1.80400 -2.25000 H -6.09700 -1.43300 -0.64000 H -6.31600 -0.47700 0.84500 H -5.93600 -2.20400 0.95400 H 6.06600 -1.94300 -0.21000 H 5.24200 -3.23200 0.70100 H 5.41400 -1.61900 1.41500 H 5.67200 1.72100 -0.44300 H 6.18100 0.40100 0.63900 H 5.52500 1.91300 1.31100 1027 Table C.2.113. Atomic coordinates and single point energies for B14. G = –3205.636372 GSP = –3208.07967 N 0.25500 1.70500 0.61300 N -0.35500 -1.86800 -0.25500 Na -1.46900 0.10400 0.49000 Na 1.34100 -0.26000 -0.02600 Si -0.14000 2.72700 -0.69400 Si -0.55000 -2.88600 1.10300 C 1.02200 2.14000 1.77400 C -0.14800 -2.35500 -1.61500 C 1.20500 2.84200 -2.04400 C -0.64300 4.52600 -0.31700 C -1.67700 2.02300 -1.58200 C -1.47000 -1.91100 2.46100 C -1.58900 -4.47800 0.91500 H -0.95300 -0.98700 2.76800 H -1.56000 -2.53200 3.36600 H -2.49000 -1.64000 2.14300 H -2.61100 -4.26100 0.57000 H -1.66900 -4.97700 1.89500 H -1.14900 -5.20200 0.21300 C 1.08500 -3.46000 1.90100 H 1.73000 -2.59200 2.12000 H 1.64100 -4.12300 1.21800 H 0.92200 -4.00600 2.84400 H -1.55500 0.98800 -1.94400 1028 H -1.90400 2.64300 -2.46500 H -2.55700 2.04400 -0.91700 H 2.14000 3.25400 -1.63400 H 0.89600 3.47400 -2.89300 H 1.42800 1.83600 -2.43800 H 0.15600 5.10800 0.16700 H -1.52200 4.55000 0.34700 H -0.91000 5.04400 -1.25200 C 0.14900 2.96200 2.74100 C 2.26400 2.97300 1.39100 C 1.54600 0.91600 2.55200 H -0.72000 2.35900 3.05000 H 0.70100 3.27200 3.64300 H -0.22900 3.86400 2.24000 H 2.91000 2.37300 0.72600 H 2.84700 3.27300 2.27900 H 1.97900 3.89200 0.85600 H 0.72600 0.21500 2.76800 H 2.00100 1.20800 3.51200 H 2.32700 0.38600 1.98000 C 0.52700 -1.26800 -2.47800 C -1.49500 -2.70500 -2.27600 C 0.76800 -3.59300 -1.69100 H -0.00800 -0.31000 -2.38400 H 0.53900 -1.54500 -3.54300 H 1.58100 -1.11700 -2.18200 H -2.15000 -1.81800 -2.27300 H -1.99600 -3.49800 -1.70000 H -1.37600 -3.05300 -3.31600 H 1.73700 -3.36700 -1.21900 H 0.95400 -3.90100 -2.73300 H 0.32600 -4.45000 -1.16200 O 3.48400 -0.20100 -0.32100 P 4.97700 -0.08400 -0.20900 N 5.63800 -1.52100 0.31500 N 5.60500 0.34400 -1.69300 N 5.58800 1.01700 0.88900 C 5.30900 0.83400 2.30500 C 5.93700 2.37800 0.52400 C 6.92000 -1.66800 0.97300 C 4.98700 -2.77100 -0.04000 C 4.81000 1.06300 -2.67300 C 7.01700 0.24000 -1.98100 H 7.35300 -0.68400 1.18900 H 7.62900 -2.23700 0.34500 H 6.80300 -2.21500 1.92400 1029 H 4.00400 -2.56500 -0.48000 H 4.83600 -3.38900 0.86000 H 5.59200 -3.34700 -0.76100 H 7.51200 -0.42100 -1.25800 H 7.52400 1.22300 -1.95500 H 7.16700 -0.18900 -2.98500 H 3.76200 1.09000 -2.35200 H 4.86600 0.56000 -3.65200 H 5.16700 2.10100 -2.80000 H 4.97900 -0.19500 2.49700 H 4.51400 1.51900 2.64400 H 6.21700 1.02800 2.90000 H 6.09000 2.45800 -0.55900 H 6.87200 2.67300 1.02800 H 5.14800 3.09000 0.81700 H -8.19200 0.15700 1.14700 H -7.63400 1.16800 -0.21800 C -7.51800 0.98300 0.85700 H -7.23200 -2.03900 -0.25700 H -7.10700 -0.74200 -1.48300 C -6.60300 -1.62500 -1.06700 H -6.53700 -2.38100 -1.86500 H -7.84600 1.88800 1.39600 H -6.42900 -0.32500 3.01600 N -6.13600 0.69200 1.17500 C -5.86100 0.52100 2.59100 N -5.27200 -1.27800 -0.61300 P -4.98900 0.23600 0.04300 N -5.31500 1.26500 -1.22900 H -4.83000 -0.14800 -2.70900 C -4.45300 -2.40400 -0.18900 H -6.14600 1.43300 3.14200 H -4.45300 -3.16600 -0.98400 H -4.82800 -2.87300 0.74000 H -4.79000 0.34500 2.74000 C -4.98200 0.93200 -2.60600 H -5.62500 2.89000 0.07200 H -5.80200 1.24300 -3.27300 C -5.45000 2.69400 -0.99300 H -6.30100 3.09400 -1.56900 O -3.63500 0.25200 0.69000 H -3.41500 -2.08400 -0.03300 H -4.05900 1.44600 -2.92300 H -4.53900 3.23300 -1.30100 1030 Table C.2.114. Atomic coordinates and single point energies for B5. G = –2111.77108 GSP = –2113.45482 N -0.22000 -1.84500 -0.30800 N 0.09200 1.90200 0.31400 Na 1.32800 -0.09300 0.03700 Na -1.43700 0.15700 -0.06400 Si 0.21500 -2.85100 1.01200 Si 0.71200 2.84000 -0.98000 C -0.68500 -2.40800 -1.57800 C -0.38600 2.51700 1.55400 C 1.35900 -1.86400 2.17600 C 1.23600 -4.41800 0.63900 C -1.22100 -3.42400 2.12300 C 0.83000 1.73700 -2.52900 C -0.32100 4.33600 -1.55000 H 1.29800 0.75000 -2.36400 H 1.43300 2.24600 -3.29700 H -0.16600 1.55600 -2.96300 H -1.35200 4.03800 -1.80000 H 0.12800 4.78400 -2.45100 H -0.38000 5.12500 -0.78500 C 2.48800 3.49900 -0.76300 H 3.18300 2.65200 -0.64500 H 2.60000 4.15500 0.11300 H 2.80200 4.06900 -1.65300 H -1.72500 -2.55300 2.57400 H -0.86300 -4.06400 2.94500 1031 H -1.97500 -3.99200 1.55700 H 2.34100 -1.65700 1.71600 H 1.55200 -2.45500 3.08400 H 0.92000 -0.91000 2.50400 H 2.18500 -4.16400 0.14000 H 0.71400 -5.14900 0.00400 H 1.48500 -4.92300 1.58700 C -1.65700 -3.59200 -1.40300 C 0.50100 -2.87400 -2.44400 C -1.44300 -1.33900 -2.38600 H -2.52200 -3.28400 -0.79400 H -2.03100 -3.95800 -2.37200 H -1.17300 -4.43800 -0.89200 H 1.16100 -2.01800 -2.65600 H 0.17200 -3.30100 -3.40600 H 1.08900 -3.63500 -1.91200 H -2.38500 -1.05600 -1.88600 H -1.70900 -1.70100 -3.39100 H -0.81700 -0.44200 -2.51300 C -0.36500 1.48000 2.68800 C -1.83700 3.02500 1.40700 C 0.47500 3.70500 2.02800 H -0.93600 0.57200 2.42000 H -0.79800 1.87900 3.61900 H 0.67000 1.17100 2.89800 H -2.51700 2.19400 1.15600 H -1.89900 3.76400 0.59500 H -2.20600 3.49500 2.33300 H 1.52400 3.39300 2.14900 H 0.12000 4.10100 2.99200 H 0.44900 4.52900 1.29900 C -4.67800 -0.14600 0.21000 C -3.94900 -1.02500 1.22200 H -3.19800 -1.65400 0.71800 H -3.44100 -0.40000 1.97300 H -4.65000 -1.68800 1.74500 C -5.39700 -1.01000 -0.82400 H -4.68200 -1.67600 -1.32800 H -6.16000 -1.62800 -0.33000 H -5.90600 -0.39900 -1.58300 C -5.64600 0.80000 0.91600 H -6.35500 0.22000 1.52200 H -5.09700 1.48300 1.58100 H -6.22900 1.39700 0.20000 O -3.62100 0.59500 -0.42200 C -3.95600 1.64600 -1.29500 1032 H -3.01800 1.98800 -1.75500 H -4.40600 2.49600 -0.75800 H -4.63900 1.31500 -2.09500 H 4.97000 1.08400 -1.68600 H 6.04700 1.13700 -0.26300 C 5.53100 0.46900 -0.96700 H 6.30000 -0.09600 -1.51300 H 4.65000 1.72400 1.30900 H 3.33000 -0.78000 -1.98900 C 4.58500 -0.49200 -0.24900 C 3.80200 1.04500 1.48900 O 3.51700 0.24700 0.36400 C 3.87600 -1.39200 -1.25500 H 2.90500 1.65700 1.66700 H 4.59700 -2.01700 -1.80000 C 5.33000 -1.33000 0.78800 H 5.87300 -0.70000 1.50700 H 4.00500 0.43100 2.38200 H 6.06500 -1.97400 0.28600 H 3.15800 -2.05500 -0.74600 H 4.62900 -1.97400 1.34100 1033 Table C.2.115. Atomic coordinates and single point energies for B23. G = –2606.923723 GSP = –2609.16356 N 0.41000 -1.38600 -1.48900 N -0.14700 1.05300 1.45000 Na 1.26600 0.76100 -0.43500 Na -0.85500 -1.00300 0.49300 Si -0.49000 -1.53500 -2.94600 Si 0.44200 0.88000 3.04700 C 1.58000 -2.23800 -1.24800 C -1.14300 2.06700 1.09000 C -1.97500 -0.34900 -2.93200 C -1.36700 -3.19400 -3.32700 C 0.48000 -1.20900 -4.56200 C 2.01900 -0.18500 3.05200 C 0.92200 2.46800 3.99300 H 1.79200 -1.25500 2.92300 H 2.53600 -0.07400 4.01900 H 2.72600 0.10100 2.25600 H 1.70000 3.04800 3.47300 H 1.31800 2.19800 4.98500 H 0.06800 3.14300 4.15600 C -0.73000 -0.06100 4.22600 H -1.02700 -1.01400 3.75500 H -1.64900 0.50500 4.44700 H -0.24100 -0.29700 5.18500 H 1.07700 -0.28400 -4.53100 H -0.21100 -1.13800 -5.41700 H 1.17300 -2.04000 -4.77300 H -2.59600 -0.54400 -2.04100 H -2.59600 -0.55800 -3.81700 H -1.72600 0.72100 -2.94100 H -2.06000 -3.48900 -2.52400 1034 H -0.68400 -4.03600 -3.50800 H -1.96900 -3.05800 -4.24000 C 2.84600 -1.67500 -1.92400 C 1.43100 -3.69300 -1.73500 C 1.84100 -2.29600 0.26300 H 3.09000 -0.68400 -1.51200 H 3.72700 -2.31900 -1.76200 H 2.68300 -1.57000 -3.00700 H 0.50900 -4.14800 -1.34200 H 2.28600 -4.30700 -1.40900 H 1.38900 -3.74100 -2.83300 H 1.97400 -1.28800 0.68300 H 2.74300 -2.87700 0.51900 H 0.98700 -2.76200 0.78100 C -1.88100 1.60300 -0.17400 C -0.47800 3.41700 0.75800 C -2.20100 2.33400 2.17900 H -1.15900 1.39100 -0.97900 H -2.61200 2.34100 -0.54200 H -2.45100 0.67700 0.01600 H 0.18300 3.30000 -0.11500 H 0.13000 3.76300 1.60800 H -1.22300 4.19500 0.52000 H -2.65500 1.39100 2.51600 H -3.00400 2.98900 1.80400 H -1.75300 2.81600 3.06000 N 3.67700 1.64300 -0.08200 N 1.72700 2.70700 -2.13700 C 4.06600 2.09600 -1.42200 C 2.96700 2.02500 -2.48200 C 3.12800 2.74300 0.71100 H 4.88000 1.45200 -1.78800 H 4.49400 3.11800 -1.36400 H 2.72100 0.96800 -2.66500 H 3.38400 2.41700 -3.43600 C 0.65500 2.32700 -3.04400 C 1.88600 4.15200 -2.13100 H 0.48600 1.24200 -2.99500 H 0.88300 2.59500 -4.09700 H -0.27500 2.83600 -2.75000 H 2.69100 4.45600 -1.44900 H 0.95600 4.62900 -1.79100 H 2.12800 4.53700 -3.14300 H 2.24900 3.17500 0.22600 H 3.88100 3.54300 0.86900 H 2.80700 2.36300 1.69000 1035 H -2.78900 -4.41700 0.24100 H -2.84000 -2.71400 -0.33000 H -3.85900 -3.56000 2.23900 C -2.23900 -3.45300 0.21800 H -4.91600 -3.13200 0.35500 H -1.30100 -3.59800 -0.33500 C -3.15100 -2.71100 2.34500 H -1.65700 -4.86500 2.48200 H -4.65200 -1.29200 2.86500 C -5.35600 -2.12700 0.37400 N -4.37500 -1.13200 0.76800 N -1.94200 -2.96300 1.56100 C -3.84400 -1.37600 2.10200 C -1.10400 -3.92900 2.26200 H -5.72400 -1.91200 -0.63800 H -2.85700 -2.69300 3.40500 H -0.23500 -4.19300 1.64400 H -6.22800 -2.14500 1.06300 H -0.74200 -3.50300 3.20800 H -3.11500 -0.58000 2.32600 C 4.82700 1.08300 0.63900 C 5.16300 -0.34400 0.23600 N 6.38500 -0.82600 0.84800 C 6.79500 -2.08000 0.25500 H 4.57900 1.10700 1.70900 H 5.72700 1.71900 0.50700 H 5.29100 -0.39800 -0.85600 H 4.29600 -0.99600 0.48200 H 6.93500 -1.95800 -0.82900 H 6.05200 -2.89300 0.41400 H 7.75200 -2.40700 0.68800 C 6.27500 -0.94800 2.28800 H 6.10400 0.03100 2.75600 H 7.21300 -1.34800 2.69600 H 5.44700 -1.62600 2.59400 C -4.95800 0.20500 0.71700 C -5.23000 0.69000 -0.70500 N -5.28400 2.13700 -0.79300 C -6.39000 2.70400 -0.05500 C -5.28100 2.57400 -2.17100 H -6.30900 2.46300 1.01400 H -7.37700 2.33900 -0.41800 H -6.37700 3.79900 -0.15000 H -6.17700 2.23000 -2.73300 H -4.38800 2.18400 -2.68300 H -5.25300 3.67200 -2.21600 1036 H -4.40000 0.34300 -1.33900 H -6.16300 0.23600 -1.11100 H -5.88300 0.23800 1.33400 H -4.24900 0.91300 1.16600 1037 Table C.2.116. Atomic coordinates and single point energies for B6. G = –2030.932848 GSP = –2032.52148 N 0.67300 1.77600 -0.03100 N -0.74700 -1.60600 0.66100 Na -1.33000 0.65400 0.43200 Na 1.28800 -0.45400 0.41400 Si 1.45100 2.55200 1.28200 Si -0.67400 -2.61000 -0.71900 C 0.43300 2.43100 -1.31500 C -1.22800 -2.02800 1.97400 C 0.35000 3.71100 2.31400 C 3.03900 3.54100 0.91300 C 2.02900 1.20000 2.49900 C 0.72900 -1.97400 -1.85500 C -0.20600 -4.44300 -0.49300 H 0.72500 -0.88400 -2.01700 H 0.65800 -2.44600 -2.84700 H 1.71200 -2.25300 -1.43900 H 0.75500 -4.53800 0.03800 H -0.08700 -4.91300 -1.48300 H -0.95200 -5.03200 0.06100 C -2.24500 -2.59800 -1.79700 H -2.47500 -1.56800 -2.12100 H -3.11400 -2.97700 -1.23400 H -2.13300 -3.21700 -2.70100 H 1.21900 0.52400 2.82100 H 2.41800 1.67300 3.41300 H 2.84900 0.58700 2.08600 1038 H 0.04200 4.59700 1.73800 H 0.86800 4.06300 3.22000 H -0.56700 3.18700 2.63300 H 2.86700 4.40300 0.25100 H 3.80600 2.90600 0.44100 H 3.46200 3.92800 1.85400 C 1.67200 2.32400 -2.22500 C 0.05400 3.91900 -1.18300 C -0.74200 1.75200 -2.04900 H 1.91300 1.26200 -2.40000 H 1.52100 2.80900 -3.20300 H 2.53800 2.79500 -1.73600 H -0.82700 4.02400 -0.53000 H -0.18100 4.36900 -2.16100 H 0.87400 4.50200 -0.73700 H -0.59700 0.66200 -2.10900 H -0.85900 2.13200 -3.07500 H -1.69300 1.95000 -1.52600 C -1.67200 -0.79500 2.78600 C -0.10800 -2.73200 2.76400 C -2.44100 -2.97700 1.91400 H -0.85700 -0.05500 2.85300 H -1.95600 -1.06100 3.81500 H -2.55300 -0.31500 2.32300 H 0.75500 -2.05500 2.87900 H 0.23100 -3.62400 2.21700 H -0.43300 -3.04400 3.77000 H -3.27100 -2.50400 1.36700 H -2.80300 -3.23900 2.92100 H -2.18500 -3.91300 1.39800 C 4.40300 -0.80100 -1.90800 C 4.15700 -0.08200 -0.58400 O 3.44900 -1.03600 0.19600 C 4.06600 -2.29600 -0.02100 C 4.57000 -2.27500 -1.48000 H 5.27400 -0.40600 -2.44600 H 3.52200 -0.68800 -2.55600 H 3.53300 0.82000 -0.66600 H 5.10500 0.18000 -0.07900 H 3.31900 -3.07500 0.18400 H 4.90100 -2.41800 0.68900 H 3.98300 -2.94500 -2.12100 H 5.61700 -2.60000 -1.53300 C -4.71400 1.53800 -1.75200 C -4.21000 2.17400 -0.46200 O -3.52200 1.11600 0.18600 1039 C -4.27600 -0.08200 -0.00200 C -5.11100 0.12700 -1.28300 H -3.89100 1.48900 -2.48000 H -5.54500 2.09100 -2.20700 H -5.04600 2.52300 0.17000 H -3.50600 3.00500 -0.60600 H -4.91800 -0.25100 0.87900 H -3.55900 -0.91200 -0.07700 H -6.18400 0.07600 -1.05600 H -4.89300 -0.63800 -2.04000 1040 Table C.2.117. Atomic coordinates and single point energies for B7. G = –2262.996185 GSP = –2264.84874 N 0.96500 1.67100 -0.12300 N -0.29200 -1.87400 0.07700 Na 1.58300 -0.56600 -0.16500 Na -1.17200 0.38700 -0.05400 Si 0.83600 2.28400 -1.71400 Si -0.64200 -2.25500 1.70100 C 1.95500 2.16400 0.83400 C -0.06700 -2.85800 -0.97800 C 2.12000 1.60600 -2.95800 C 0.88000 4.17500 -1.94500 C -0.85200 1.75900 -2.42500 C -1.52900 -0.74600 2.46800 C -1.78900 -3.73300 2.07600 H -0.93400 0.18100 2.39600 H -1.73000 -0.91300 3.53800 H -2.50100 -0.57100 1.97500 H -2.78500 -3.62800 1.61900 H -1.93400 -3.81300 3.16600 H -1.36600 -4.68900 1.73100 C 0.88500 -2.55400 2.80700 H 1.52900 -1.65900 2.82300 H 1.48200 -3.39800 2.42700 H 0.60800 -2.77900 3.85000 H -0.98700 0.66500 -2.48500 H -0.95600 2.14200 -3.45200 H -1.67400 2.18200 -1.82500 1041 H 3.14300 1.92300 -2.70000 H 1.91200 1.95500 -3.98300 H 2.10000 0.50300 -2.97900 H 1.84100 4.61600 -1.64000 H 0.08600 4.66600 -1.36000 H 0.72100 4.42700 -3.00500 C 1.54900 3.51700 1.45300 C 3.35900 2.33500 0.21600 C 2.10200 1.17200 2.00500 H 0.62800 3.40100 2.04100 H 2.33100 3.91100 2.12200 H 1.36300 4.26100 0.66500 H 3.68000 1.38900 -0.25200 H 4.11000 2.61800 0.97300 H 3.35800 3.11400 -0.56200 H 1.11100 0.90200 2.40100 H 2.70000 1.59700 2.82600 H 2.61900 0.24500 1.69900 C 0.63400 -2.19500 -2.18400 C -1.39900 -3.42800 -1.50300 C 0.83100 -4.02900 -0.53200 H 0.11500 -1.26400 -2.46200 H 0.64100 -2.85600 -3.06400 H 1.69300 -1.96900 -1.96800 H -2.01400 -2.59900 -1.88900 H -1.95100 -3.92100 -0.68800 H -1.24800 -4.16200 -2.31100 H 1.79900 -3.64200 -0.17200 H 1.02700 -4.73400 -1.35600 H 0.36400 -4.59400 0.28900 C -2.14500 3.26700 2.46700 C -2.00500 3.34200 0.94500 O -2.60600 2.14300 0.48400 C -3.79300 1.98700 1.23800 C -3.43800 2.44400 2.66600 H -2.18600 4.26000 2.93300 H -1.28300 2.73100 2.89200 H -0.96800 3.35100 0.58400 H -2.55400 4.21100 0.53600 H -4.10600 0.93800 1.16300 H -4.58600 2.62500 0.80700 H -3.25800 1.58100 3.32000 H -4.25000 3.03700 3.10600 C 5.87400 -0.42500 -0.39200 C 4.68300 -0.93800 -1.22900 O 3.69300 -1.34000 -0.29000 1042 C 4.38200 -1.83700 0.84700 C 5.50900 -0.82800 1.05200 H 5.99600 0.66100 -0.48500 H 6.81000 -0.89500 -0.72200 H 4.97100 -1.80800 -1.84400 H 4.23700 -0.17800 -1.88500 H 4.77600 -2.84600 0.63000 H 3.66900 -1.91100 1.67900 H 6.35500 -1.24800 1.61100 H 5.12700 0.04000 1.60800 H -4.57600 -1.19600 0.56700 H -3.14800 -2.16400 0.08000 H -5.80700 -2.19000 -1.14500 C -3.92500 -1.48100 -0.28100 C -4.76400 -2.03800 -1.45100 H -4.37500 -3.00200 -1.80200 O -3.26700 -0.32800 -0.78000 C -4.64300 -0.94700 -2.53400 H -5.58900 -0.74100 -3.05000 C -4.12500 0.25200 -1.74300 H -4.95400 0.78600 -1.23800 H -3.89700 -1.23300 -3.28900 H -3.54700 0.97400 -2.33200 1043 Table C.2.118. Atomic coordinates and single point energies for B8. G = –2495.065233 GSP = –2497.18165 N -0.21700 1.46100 -1.27600 N 0.18500 -1.70700 0.81600 Na -1.45600 -0.12400 -0.00100 Na 1.42800 0.09800 -0.11300 Si 0.07200 3.07100 -0.79600 Si 0.33100 -3.20400 -0.00300 C -0.31700 1.05300 -2.67600 C 0.04300 -1.65200 2.27100 C -1.20700 4.42400 -1.24300 C 1.71000 3.83800 -1.42200 C 0.16200 3.09900 1.10000 C 1.04400 -2.95000 -1.74900 C 1.48000 -4.52400 0.77500 H 0.31000 -2.54600 -2.46100 H 1.37900 -3.92200 -2.14500 H 1.91000 -2.27100 -1.74100 H 2.50800 -4.15800 0.92200 H 1.52900 -5.39900 0.10600 H 1.11700 -4.88000 1.75100 C -1.30600 -4.14200 -0.29400 H -2.05300 -3.43800 -0.69100 H -1.70700 -4.56900 0.63900 H -1.18000 -4.96400 -1.01800 H -0.75200 2.65900 1.52800 H 0.26700 4.12700 1.48200 H 1.01900 2.51200 1.46500 H -1.13400 4.72500 -2.29800 1044 H -1.01900 5.32100 -0.63100 H -2.24500 4.10800 -1.06200 H 1.68600 3.98800 -2.51300 H 2.56900 3.18300 -1.20500 H 1.90200 4.82000 -0.96000 C 1.05500 0.60100 -3.21900 C -0.84900 2.15400 -3.61300 C -1.29300 -0.13300 -2.79300 H 1.42700 -0.26600 -2.65000 H 1.01200 0.30600 -4.28100 H 1.78000 1.42400 -3.11400 H -1.82400 2.52200 -3.25700 H -0.97400 1.78100 -4.64200 H -0.15700 3.01000 -3.65000 H -0.97200 -0.96600 -2.14600 H -1.35500 -0.52400 -3.82100 H -2.30400 0.18200 -2.48600 C -0.49600 -0.26800 2.68100 C 1.40100 -1.84900 2.97700 C -0.94600 -2.69300 2.83200 H 0.09100 0.53600 2.20700 H -0.46500 -0.11700 3.77200 H -1.54800 -0.14800 2.37200 H 2.12300 -1.10900 2.60200 H 1.80200 -2.84900 2.75700 H 1.32400 -1.74400 4.07200 H -1.91400 -2.60700 2.31100 H -1.11500 -2.55800 3.91300 H -0.57400 -3.71700 2.67900 C 4.70400 -2.04700 -2.25800 C 4.36500 -0.58000 -1.97600 O 3.45600 -0.62700 -0.89300 C 3.93500 -1.61700 0.00700 C 4.53500 -2.72400 -0.87900 H 5.71300 -2.16400 -2.67400 H 3.98900 -2.46300 -2.98100 H 3.87800 -0.05900 -2.81000 H 5.26700 -0.01400 -1.67600 H 3.08600 -1.94500 0.62500 H 4.69900 -1.16800 0.66700 H 3.85400 -3.58300 -0.94500 H 5.48800 -3.08300 -0.47100 C -4.82800 -3.10500 -0.91000 C -4.05100 -1.90900 -1.50200 O -3.42300 -1.26200 -0.40600 C -4.25100 -1.45000 0.72800 1045 C -4.71500 -2.89800 0.61300 H -4.38600 -4.06200 -1.21500 H -5.87300 -3.09500 -1.24700 H -4.73300 -1.19900 -2.00400 H -3.26800 -2.19900 -2.21500 H -5.10400 -0.74300 0.69100 H -3.66100 -1.22900 1.62700 H -5.65700 -3.08300 1.14600 H -3.94400 -3.56000 1.03200 H 3.65300 0.69600 3.37500 H 1.93900 1.17400 3.24700 H 4.16000 2.96000 3.72500 C 2.94500 1.36400 2.85200 C 3.39000 2.83700 2.95200 H 2.54900 3.49200 3.21100 O 2.94200 1.04500 1.46700 C 3.92800 3.15100 1.54100 H 4.89400 3.67100 1.55100 C 4.01500 1.77200 0.89100 H 4.97400 1.27300 1.13200 H 3.21100 3.77100 0.98400 H 3.88700 1.77000 -0.19900 H -2.48600 2.04200 2.73000 C -3.35800 2.06700 2.06000 H -4.22500 1.64000 2.59800 H -4.25400 4.07000 2.21200 C -3.67800 3.45000 1.51200 H -2.74300 3.97400 1.26000 O -3.06500 1.28600 0.91200 C -4.44600 3.09000 0.23800 C -3.71600 1.83100 -0.24200 H -5.49400 2.86000 0.48100 H -4.39700 1.07300 -0.66100 H -4.43900 3.88900 -0.51500 H -2.93400 2.05000 -0.98600 1046 Table C.2.119. Atomic coordinates and single point energies for B20. G = –2572.536062 GSP = –2574.72058 N 0.51800 1.82400 -0.58900 N -0.31700 -1.81100 0.36300 Na 1.54800 -0.35300 0.00600 Na -1.35200 0.31400 -0.10700 Si 0.38700 3.19600 0.43500 Si -0.87500 -3.01600 -0.72000 C 1.02700 1.97900 -1.95700 C -0.32500 -2.05800 1.80700 C -0.32800 2.66800 2.11200 C -0.82000 4.59400 -0.07500 C 2.00000 4.15500 0.79700 C -0.42500 -2.57400 -2.51000 C -0.21000 -4.78900 -0.48500 H -0.87800 -1.62600 -2.83400 H -0.79700 -3.36700 -3.17800 H 0.66200 -2.49500 -2.66400 H 0.89000 -4.83100 -0.54400 H -0.61200 -5.44100 -1.27700 H -0.50500 -5.22700 0.48100 C -2.77700 -3.21000 -0.76900 H -3.22600 -2.20400 -0.74500 H -3.17200 -3.77200 0.09100 H -3.11400 -3.71700 -1.68800 H 2.83100 3.49900 1.10500 H 1.83500 4.89100 1.60100 H 2.33300 4.71300 -0.09200 1047 H -1.30100 2.17000 1.96300 H -0.51200 3.56600 2.72200 H 0.31100 1.99100 2.69600 H -1.79800 4.20400 -0.39600 H -0.43600 5.22600 -0.88800 H -0.99400 5.25000 0.79400 C 2.56800 2.04600 -2.00000 C 0.51600 3.23600 -2.69200 C 0.60200 0.76100 -2.78800 H 2.99200 1.10200 -1.63300 H 2.94500 2.20700 -3.02400 H 2.93700 2.86200 -1.36200 H -0.57900 3.31900 -2.62800 H 0.80300 3.21600 -3.75500 H 0.94600 4.14800 -2.25100 H 0.91600 -0.17900 -2.30800 H 1.02600 0.77300 -3.80500 H -0.49400 0.72800 -2.88000 C -0.27000 -0.71000 2.53400 C 0.90800 -2.86400 2.26000 C -1.58600 -2.79200 2.30500 H 0.59300 -0.12100 2.19400 H -0.19000 -0.81700 3.62900 H -1.17100 -0.11700 2.32800 H 1.82100 -2.28500 2.04600 H 0.97200 -3.81800 1.71700 H 0.88700 -3.07800 3.34200 H -2.49000 -2.28100 1.93500 H -1.62700 -2.83000 3.40600 H -1.61700 -3.82800 1.93500 N 3.58900 -1.31900 -1.11500 N 3.66200 -0.31600 1.69700 C 4.82600 -0.82200 -0.46800 C 4.50900 0.22600 0.62500 C 3.22800 -2.64000 -0.61200 C 3.59800 -1.35200 -2.57200 C 3.06600 0.74500 2.49700 C 4.33600 -1.27300 2.55900 H 3.81500 -0.36400 -2.99400 H 2.59900 -1.64800 -2.92200 H 4.32400 -2.08200 -2.98100 H 2.46000 1.40700 1.85800 H 3.81500 1.37000 3.02200 H 2.41000 0.30300 3.26000 H 4.75800 -2.10200 1.97500 H 3.61000 -1.70000 3.26600 1048 H 5.15400 -0.81500 3.15100 H 3.17200 -2.63000 0.48200 H 3.96000 -3.41400 -0.92400 H 2.23400 -2.92700 -0.98700 H -3.79300 2.53400 -2.13500 H -2.95200 2.36400 -0.56300 C -3.07200 1.91900 -1.55700 H -4.65400 2.82100 0.51400 H -2.09400 1.97700 -2.05400 C -4.82100 0.42300 -0.79400 C -4.27900 2.48700 1.49000 N -3.80900 1.10700 1.43400 N -3.49800 0.52700 -1.45400 C -4.71700 0.18500 0.73200 C -3.40300 -0.09100 -2.77200 H -3.44400 3.14600 1.77400 C -3.53200 0.65900 2.79300 H -2.70400 1.24600 3.21700 H -5.08900 2.62800 2.23100 H -3.24300 -0.39900 2.79500 H -4.40100 0.78400 3.47000 C 5.80300 0.93500 1.11500 C 5.87300 -0.20400 -1.40300 C 7.06300 0.12500 0.82900 C 7.23000 -0.07700 -0.68300 H 6.99200 -0.85100 1.33600 H 7.94800 0.62300 1.25000 H 7.83700 -0.97500 -0.87300 H 7.78500 0.76900 -1.11400 H 6.00200 -0.81100 -2.30700 H 5.51600 0.78600 -1.73400 H 5.32300 -1.69200 0.00300 H 5.88900 1.91200 0.61400 H 5.72300 1.15800 2.19000 H 3.88700 0.98700 0.13200 C -6.12500 0.14300 1.35400 C -5.71500 -0.67200 -1.40300 C -6.99900 -0.94100 0.73500 C -7.10100 -0.72100 -0.76700 H -7.62800 0.22900 -0.96100 H -7.69400 -1.51600 -1.24300 H -6.55100 -1.93000 0.93100 H -7.99500 -0.94300 1.20200 H -6.04500 -0.01200 2.44000 H -6.61200 1.12300 1.20700 H -4.26000 -0.81600 0.84500 1049 H -5.36300 1.38100 -0.95400 H -5.82200 -0.50400 -2.48200 H -5.22600 -1.65200 -1.27500 H -3.59200 -1.17000 -2.72500 H -2.38100 0.04700 -3.14900 H -4.09000 0.36400 -3.51300 1050 Table C.2.120. Atomic coordinates and single point energies for B17. G = –2261.004779 GSP = –2262.85322 N -0.12200 1.89800 0.44700 N -0.01400 -1.86600 -0.43800 Na -1.52100 -0.05800 0.00100 Na 1.39700 0.04700 0.01800 Si 0.21500 3.17500 -0.65100 Si 0.32500 -3.12900 0.66900 C -0.45700 2.20000 1.84500 C -0.18800 -2.14800 -1.86500 C 0.59200 2.48400 -2.37700 C 1.78600 4.22600 -0.33700 C -1.15600 4.48500 -0.87800 C 0.09500 -2.52000 2.45000 C -0.72700 -4.71900 0.54700 H 0.74400 -1.66000 2.67000 H 0.35900 -3.32700 3.15300 H -0.94100 -2.21600 2.66500 H -1.80700 -4.51600 0.61400 H -0.46000 -5.39800 1.37300 H -0.55100 -5.26400 -0.39300 C 2.12400 -3.78100 0.66400 H 2.82500 -2.94600 0.82000 H 2.39800 -4.27600 -0.27900 H 2.28000 -4.50500 1.48100 H -2.14000 4.03200 -1.08100 H -0.91100 5.15400 -1.71800 H -1.26300 5.11400 0.02000 1051 H 1.46700 1.81600 -2.32600 H 0.85800 3.32400 -3.03900 H -0.22900 1.92900 -2.85200 H 2.67400 3.58600 -0.20500 H 1.71800 4.88400 0.54100 H 1.97200 4.86500 -1.21600 C -1.93400 2.61300 2.01600 C 0.38500 3.33400 2.46600 C -0.24500 0.93800 2.69300 H -2.59100 1.78200 1.72500 H -2.16600 2.87700 3.06100 H -2.17000 3.47900 1.38100 H 1.45600 3.17400 2.28500 H 0.21500 3.40800 3.55100 H 0.11600 4.30500 2.02300 H -0.86500 0.10600 2.32400 H -0.50500 1.09400 3.75300 H 0.80500 0.60900 2.64300 C -0.08000 -0.83200 -2.64500 C -1.58100 -2.73200 -2.17900 C 0.86500 -3.12000 -2.43300 H -0.84200 -0.11700 -2.29900 H -0.22500 -0.96800 -3.72900 H 0.90000 -0.36100 -2.49300 H -2.35300 -1.99700 -1.90300 H -1.76000 -3.65300 -1.60800 H -1.69800 -2.95900 -3.25200 H 1.87900 -2.77800 -2.17400 H 0.79200 -3.20800 -3.52900 H 0.74000 -4.12800 -2.00800 N -3.55400 -0.55700 1.40500 N -3.67000 0.32500 -1.49300 C -4.64500 0.24000 0.83600 C -4.26300 1.06800 -0.38900 C -3.57000 -1.93500 0.92500 C -3.59200 -0.54600 2.86200 H -4.98300 0.96300 1.59400 H -5.52200 -0.40500 0.62300 H -3.53200 1.83000 -0.08000 H -5.16900 1.61800 -0.72900 C -3.11900 1.25500 -2.46800 C -4.63700 -0.55000 -2.13500 H -3.47800 0.47900 3.23800 H -2.76200 -1.14600 3.25800 H -4.54000 -0.96800 3.25400 H -2.33000 1.86500 -2.00300 1052 H -3.89600 1.93900 -2.86900 H -2.67900 0.70100 -3.30900 H -5.04700 -1.27700 -1.42200 H -4.15300 -1.10900 -2.94700 H -5.48300 0.02700 -2.56400 H -3.46200 -1.96900 -0.16500 H -4.50800 -2.45700 1.20700 H -2.72000 -2.48400 1.35200 H 4.42500 1.56400 2.11100 H 3.15000 1.75200 0.86200 H 5.39000 -0.02800 0.87200 C 3.42600 1.21100 1.77800 H 4.77400 1.75200 -0.40100 H 2.69500 1.48500 2.54700 C 4.51200 -0.69100 0.73500 H 4.36600 -0.72000 3.41800 H 5.13600 -1.23400 -1.23200 C 4.56900 1.42500 -1.42600 N 3.66900 0.28100 -1.45800 N 3.39900 -0.23400 1.57600 C 4.20100 -0.87600 -0.74500 C 3.42200 -0.91000 2.86900 H 4.10800 2.26500 -1.96400 H 4.82700 -1.68300 1.09000 H 2.58800 -0.55200 3.48900 C 3.45500 -0.09300 -2.85100 H 2.95000 0.71900 -3.39300 H 5.53900 1.18900 -1.91300 H 3.30100 -1.99300 2.73300 H 2.83300 -0.99400 -2.91400 H 3.46100 -1.68700 -0.84300 H 4.41800 -0.30500 -3.35900 1053 Table C.2.121. Atomic coordinates and single point energies for B2. G = –2109.040898 GSP = –2110.69767 N -0.68300 -1.80100 0.19800 N 0.66600 1.64300 -0.35000 Na 1.30000 -0.57400 0.17900 Na -1.36300 0.48300 -0.09300 Si -0.98700 -2.55900 -1.30800 Si 1.32700 2.61500 0.89700 C -1.21300 -2.30000 1.46400 C 0.77700 2.02200 -1.76100 C -2.50800 -1.82300 -2.20700 C -1.29300 -4.43700 -1.37000 C 0.52100 -2.34200 -2.45400 C 1.29900 1.62000 2.51500 C 3.14500 3.14500 0.66200 H 0.27400 1.34100 2.80200 H 1.71200 2.23500 3.33100 H 1.90300 0.69800 2.47600 H 3.77400 2.26500 0.45200 H 3.52900 3.62800 1.57400 H 3.27700 3.85400 -0.17000 C 0.41400 4.22500 1.36200 H -0.56800 4.00500 1.81000 H 0.25500 4.89400 0.50400 H 0.99500 4.78100 2.11500 H 1.02800 -1.36800 -2.37000 H 0.23900 -2.46600 -3.51200 H 1.26100 -3.12400 -2.21800 H -3.41200 -2.03000 -1.61000 H -2.65800 -2.26600 -3.20400 1054 H -2.44300 -0.73000 -2.34400 H -2.17700 -4.75800 -0.79800 H -0.42500 -5.00100 -0.99500 H -1.45400 -4.73200 -2.42000 C -0.58600 -3.64800 1.87100 C -2.74400 -2.47300 1.43300 C -0.88400 -1.29800 2.58000 H 0.51000 -3.55300 1.87900 H -0.91900 -3.97100 2.87000 H -0.85200 -4.43600 1.15400 H -3.21800 -1.52000 1.15300 H -3.14900 -2.78900 2.40900 H -3.03900 -3.22600 0.68600 H 0.20700 -1.15600 2.66300 H -1.25300 -1.63500 3.56100 H -1.34000 -0.31300 2.37800 C -0.32400 1.32300 -2.57700 C 2.13700 1.58600 -2.34300 C 0.61400 3.53300 -2.01100 H -0.29000 0.23300 -2.43100 H -0.22300 1.51000 -3.65700 H -1.31800 1.69200 -2.27600 H 2.25600 0.49300 -2.24800 H 2.95600 2.06300 -1.78600 H 2.24200 1.84500 -3.41000 H -0.35200 3.87700 -1.61000 H 0.64700 3.77100 -3.08600 H 1.41100 4.11000 -1.51700 H -3.32500 3.07600 -1.86700 C -3.47100 2.54400 -0.92600 C -4.33400 1.45000 -0.87300 H -4.85800 1.12800 -1.77700 C -4.55200 0.75700 0.32700 C -3.85900 1.18100 1.46900 H -4.00800 0.65000 2.41200 C -2.98300 2.27000 1.41900 H -2.44900 2.58000 2.32000 C -2.78900 2.96000 0.22100 H -2.09800 3.80200 0.17900 H 3.62000 -2.21900 -1.72800 C 3.68300 -1.93900 -0.67400 C 3.04600 -2.72500 0.28900 H 2.47700 -3.60600 -0.01400 C 3.11800 -2.37300 1.63900 H 2.62500 -2.98500 2.39500 C 3.82200 -1.22600 2.01300 1055 H 3.87700 -0.93800 3.06400 C 4.45300 -0.44200 1.04700 H 5.00000 0.45300 1.35000 C 4.40400 -0.79000 -0.31100 C 5.14700 0.02100 -1.33800 H 4.70700 -0.09700 -2.33700 H 5.14300 1.08900 -1.08100 H 6.19600 -0.30700 -1.39100 C -5.52200 -0.39300 0.37500 H -6.53100 -0.05800 0.09400 H -5.22700 -1.18500 -0.32900 H -5.57300 -0.83300 1.37900 1056 Table C.2.122. Atomic coordinates and single point energies for B9. G = –783.358287 GSP = –783.895448 N 0.34300 0.43800 0.01500 Na 0.05100 2.55700 -0.00400 Si -1.20500 -0.25400 -0.00100 C 1.61600 -0.24700 0.01000 C -2.40800 1.23300 -0.18100 C -1.62100 -1.43500 -1.43200 H -2.35700 1.91800 0.68800 H -3.45400 0.89200 -0.22500 H -2.23300 1.80300 -1.11200 H -1.36700 -0.98300 -2.40300 H -2.69100 -1.69800 -1.43900 H -1.05200 -2.37400 -1.34200 C -1.79000 -1.14200 1.57600 H -1.62400 -0.50900 2.46200 H -1.24500 -2.08400 1.73700 H -2.86400 -1.38300 1.52300 C 2.71200 0.73500 0.45900 C 1.97800 -0.74700 -1.40200 C 1.64200 -1.45100 0.97100 H 2.74800 1.59800 -0.23100 H 3.71400 0.27900 0.46500 H 2.49100 1.10100 1.47500 H 1.99100 0.10100 -2.10400 H 1.21900 -1.46100 -1.75600 H 2.96200 -1.24400 -1.43100 H 1.34600 -1.13100 1.98100 H 2.63800 -1.91900 1.02200 H 0.92800 -2.22100 0.63600 1057 1058 Table C.2.123. Atomic coordinates and single point energies for B31. G = –1397.763752 GSP = –1398.99983 Na 0.53800 0.29800 -0.39100 N -1.68200 0.46200 -0.09100 Si -2.72500 -0.83200 0.24200 C -2.47300 -1.54700 2.00200 C -4.61400 -0.53900 0.24100 C -2.48100 -2.30800 -0.95000 H -4.91700 0.10000 1.08500 H -5.12500 -1.50800 0.35900 H -4.99200 -0.07600 -0.68300 H -2.84400 -2.02700 -1.95200 H -3.02300 -3.21400 -0.63300 H -1.41400 -2.56500 -1.06700 H -3.26300 -2.28500 2.21500 H -2.56800 -0.73200 2.73900 H -1.51100 -2.04900 2.18600 C -2.05700 1.70300 -0.74200 C -0.81000 2.59000 -0.95800 C -2.68500 1.47700 -2.13400 H -1.07800 3.57600 -1.36700 H -0.11700 2.13400 -1.69100 H -0.28600 2.74000 -0.00100 H -1.99000 0.89400 -2.75900 H -2.91700 2.42300 -2.65100 H -3.61800 0.90000 -2.04800 O 2.85000 0.67600 -0.95900 O 1.40400 -1.65800 -1.40900 O 1.65000 -1.08000 1.27000 O 1.53500 1.66500 1.29600 C 2.66600 2.30300 0.76200 C 3.58000 1.31900 0.05800 1059 C 3.49800 -0.45400 -1.49000 C 2.47900 -1.29200 -2.23900 C 1.02100 -2.27000 0.85100 C 1.64900 -2.67900 -0.46300 C 1.70800 0.92800 2.49000 C 1.00500 -0.40100 2.33100 H 1.27500 1.48400 3.33800 H 2.77900 0.75800 2.69400 H -0.06000 -0.22400 2.08300 H 1.06200 -0.98400 3.26800 H -0.05900 -2.10100 0.69800 H 1.14000 -3.07300 1.60100 H 1.20700 -3.62800 -0.81000 H 2.73200 -2.83100 -0.32100 H 2.04700 -0.70400 -3.06100 H 2.97200 -2.17700 -2.67700 H 4.31800 -0.15900 -2.17100 H 3.94200 -1.04200 -0.66500 H 3.94800 0.56300 0.77600 H 4.45600 1.85000 -0.35900 H 2.28800 3.03900 0.03700 H 3.23100 2.84700 1.54000 C -3.03500 2.53400 0.11500 H -3.97600 1.98600 0.25900 H -2.58800 2.70800 1.10500 H -3.27300 3.50800 -0.34600 1060 Table C.2.124. Atomic coordinates and single point energies for B32. G = –1551.370243 GSP = –1552.78082 Na -0.57300 -0.03400 -0.02200 N 1.75300 -0.04600 -0.00000 Si 2.05400 -1.71400 0.12100 C 2.88100 -2.55900 -1.38100 C 3.03300 -2.33900 1.63800 C 0.37200 -2.60500 0.28100 H 4.10300 -2.08700 1.58400 H 2.95200 -3.43400 1.72900 H 2.62900 -1.89000 2.56000 H -0.19500 -2.22800 1.14900 H 0.53500 -3.68300 0.43500 H -0.23300 -2.49000 -0.63300 H 2.94300 -3.65200 -1.24500 H 3.90400 -2.19000 -1.55600 H 2.29800 -2.36200 -2.29600 C 2.80600 0.92300 -0.25000 C 4.18400 0.51500 0.31500 C 2.46300 2.27500 0.40600 H 4.10200 0.31800 1.39500 H 4.93600 1.30500 0.16000 H 4.55700 -0.40000 -0.17200 H 3.18000 3.06400 0.12600 H 2.48200 2.17500 1.50400 H 1.45200 2.59100 0.11500 O -1.84300 -1.13100 -1.85900 O -2.73300 -1.01400 0.69800 O -1.45900 1.53800 -1.81100 O -0.86500 2.11600 0.72900 1061 O -0.85200 -0.00600 2.36700 C -0.81600 2.75500 -1.53100 C -1.19000 3.18000 -0.12500 H -2.26800 3.41400 -0.05800 H -0.61700 4.08700 0.13900 C -0.65000 2.40800 2.08200 C -0.11300 1.13600 2.73000 H -1.58700 2.76200 2.55400 H 0.10600 3.20700 2.19900 H -0.08100 1.25900 3.82900 H 0.89500 0.93600 2.33900 C -2.19000 -0.06400 2.77500 C -2.80200 -1.25700 2.08100 H -2.23400 -2.17000 2.33900 H -3.85100 -1.39400 2.40300 H -2.27100 -0.17400 3.87300 H -2.74300 0.84300 2.47100 C -3.11600 -1.63200 -1.54000 C -3.10800 -2.10300 -0.10500 C -1.76300 -0.41400 -3.07000 C -0.87300 0.78600 -2.85000 H -2.76700 -0.06400 -3.36600 H -1.36100 -1.05100 -3.87600 H -0.80200 1.37500 -3.78300 H 0.14600 0.46400 -2.55700 H -1.11200 3.53700 -2.25600 H 0.27800 2.62300 -1.58600 H -3.39700 -2.47000 -2.20400 H -3.86900 -0.83100 -1.65000 H -2.39700 -2.93800 0.03000 H -4.12100 -2.45900 0.16000 C 2.99000 1.16500 -1.76400 H 2.06000 1.56100 -2.20100 H 3.80200 1.87800 -1.98600 H 3.21300 0.21100 -2.26600 1062 Table C.2.125. Atomic coordinates and single point energies for B33. G = –1704.958517 GSP = –1706.54423 Na -0.44400 -0.11600 0.10500 N 1.78000 -0.25900 -0.55900 Si 2.92300 0.60100 0.36200 C 2.44600 0.60300 2.20300 C 4.73300 -0.01400 0.36200 C 3.06200 2.48000 -0.01600 H 4.78800 -1.06700 0.68000 H 5.32800 0.58500 1.07100 H 5.21900 0.06200 -0.62400 H 3.18700 2.69000 -1.09000 H 3.91100 2.93500 0.51900 H 2.14800 2.99300 0.32800 H 3.03500 1.36200 2.74300 H 2.63200 -0.37000 2.68400 H 1.38200 0.85800 2.30600 C 2.08500 -0.74000 -1.90100 C 2.97000 -2.00400 -1.86600 C 0.78900 -1.11700 -2.64100 H 3.15600 -2.41100 -2.87500 H 2.47900 -2.78300 -1.26200 H 3.94100 -1.78500 -1.40100 H 0.26700 -1.92400 -2.10500 H 0.99400 -1.46700 -3.66600 H 0.11400 -0.24800 -2.69100 O -3.35400 0.39500 -0.26400 O -1.18200 1.45800 -1.66400 O -1.72700 -1.86300 -0.71200 O -0.70300 -2.71700 1.65400 O -0.65700 2.08200 0.99900 1063 O -0.85500 -0.09400 2.47400 C -1.58500 2.11200 2.05600 C -1.11100 1.13000 3.10600 C -0.32500 -1.08900 3.31900 C 0.30300 -2.16000 2.46000 C -0.26400 -3.29100 0.45200 C -1.41500 -3.22400 -0.52300 C -3.84500 -0.78400 -0.85600 C -2.77400 -1.56800 -1.59700 C -3.51700 1.58400 -0.98900 C -2.48000 1.76700 -2.09500 C -0.33800 2.53100 -1.29500 C -0.72300 3.11900 0.05100 H -2.58400 1.81300 1.68800 H -1.64900 3.11900 2.50600 H -1.88500 1.02300 3.88900 H -0.18700 1.50800 3.58100 H -1.12600 -1.51600 3.94900 H 0.45100 -0.65600 3.97600 H 0.77300 -2.92400 3.10900 H 1.08800 -1.70500 1.82700 H 0.04700 -4.34400 0.59000 H 0.59300 -2.71900 0.04400 H -2.29100 -3.76100 -0.11400 H -1.12300 -3.69500 -1.48000 H -3.22600 -2.49200 -2.00000 H -2.36400 -0.99800 -2.44800 H -4.22500 -1.41200 -0.03600 H -4.68700 -0.55700 -1.53700 H -3.43700 2.39700 -0.25300 H -4.53000 1.64200 -1.43000 H -2.53900 2.80200 -2.48100 H -2.70900 1.09800 -2.94000 H -0.34000 3.31500 -2.07200 H 0.66800 2.08900 -1.22000 H -1.73800 3.55500 0.01800 H -0.02200 3.93200 0.31300 C 2.79800 0.31100 -2.78100 H 2.17800 1.21900 -2.85900 H 3.76800 0.60000 -2.34600 H 2.98700 -0.06600 -3.79900 1064 Table C.2.126. Atomic coordinates and single point energies for B29. G = –1245.337655 GSP = –1246.40374 N 1.21000 0.52700 0.08200 Na -0.67900 -0.10000 -0.87100 Si 2.44600 -0.36200 -0.65900 C 1.34200 1.51800 1.12200 C 1.70000 -1.10500 -2.25600 C 4.01600 0.57300 -1.20300 H 0.89400 -1.82000 -2.01400 H 2.45500 -1.66300 -2.83100 H 1.30500 -0.31400 -2.91700 H 3.76200 1.42700 -1.84900 H 4.69600 -0.09100 -1.76000 H 4.57300 0.96400 -0.33600 C 3.07500 -1.88200 0.30900 H 2.22900 -2.55700 0.52100 H 3.52500 -1.59400 1.27200 H 3.82800 -2.45200 -0.25900 C -0.05000 1.80600 1.71600 C 1.89300 2.85100 0.57300 C 2.25900 1.05700 2.27200 H -0.72900 2.14500 0.91600 H -0.02200 2.57800 2.50300 H -0.46700 0.88300 2.15400 H 1.24100 3.20700 -0.24000 H 2.89900 2.70100 0.15500 H 1.95300 3.63300 1.34900 H 1.89400 0.10300 2.68600 H 2.31300 1.79600 3.08900 H 3.28300 0.89000 1.90100 1065 O -2.44100 -0.58100 0.53100 O -0.66500 -2.42700 -0.09500 C -1.46600 -3.52300 -0.45000 H -1.26200 -4.38900 0.20300 H -1.21500 -3.79500 -1.48200 H -2.54200 -3.28100 -0.39700 C -0.74000 -2.04700 1.26100 C -2.09900 -1.43900 1.59700 H -2.88800 -2.20400 1.72400 H -2.01600 -0.87800 2.54400 H -0.53300 -2.90700 1.92300 H 0.05200 -1.28900 1.38200 C -3.32700 0.46400 0.83000 C -3.62400 1.19000 -0.46500 H -4.27100 0.08100 1.25900 H -2.86300 1.15300 1.55800 C -2.51800 2.44300 -2.13300 O -2.40400 1.50200 -1.09300 H -4.19400 2.11000 -0.24400 H -4.23900 0.55600 -1.13100 H -3.18300 2.07700 -2.93400 H -1.51300 2.60800 -2.54100 H -2.91000 3.40200 -1.75400 1066 Table C.2.127. Atomic coordinates and single point energies for B30. G = –1707.29832 GSP = –1708.89543 N 1.79500 0.57300 0.28300 Na -0.49100 0.00200 -0.02800 Si 3.13000 0.06600 -0.63300 C 1.90700 1.34200 1.51300 C 2.56900 -0.58700 -2.34600 C 4.45800 1.33800 -1.17200 H 1.51600 -0.89500 -2.37400 H 3.19100 -1.44000 -2.66600 H 2.70200 0.20700 -3.09800 H 3.98600 2.23800 -1.60000 H 5.08000 0.88200 -1.96000 H 5.12900 1.66300 -0.36500 C 4.18400 -1.33300 0.15100 H 4.66100 -0.97300 1.07800 H 4.98900 -1.66800 -0.52500 H 3.58000 -2.21500 0.42100 C 0.65900 2.23000 1.66900 C 3.12400 2.28800 1.56600 C 1.98800 0.44000 2.76400 H 0.58500 2.89500 0.79500 H 0.69000 2.84300 2.58600 H -0.25700 1.61600 1.71800 H 3.14600 2.93500 0.67600 H 4.06300 1.71400 1.59300 H 3.09700 2.92600 2.46500 H 1.05900 -0.14000 2.85800 H 2.12300 1.02200 3.69100 H 2.83100 -0.26200 2.66700 1067 O -2.84000 1.93300 0.48600 O -2.97800 -0.71600 -0.23300 C -3.79000 1.48500 -0.44000 C -4.13300 0.05900 -0.09700 C -2.27900 3.18500 0.19700 C -1.50300 3.19900 -1.12000 H -3.05700 3.97100 0.16300 H -1.60400 3.40600 1.03200 C 0.18300 2.03200 -2.25700 O -0.84800 1.97400 -1.29700 H -0.77600 4.03100 -1.08200 H -2.16900 3.39500 -1.98400 H 1.06300 -3.53900 1.98900 H -0.01800 -1.96000 3.52300 H 1.28300 -1.85200 1.38700 C 0.54500 -2.65700 1.56900 H 1.50700 -2.32800 -0.71600 C -0.49500 -2.16300 2.54600 H -1.51100 -0.03500 3.80900 H 0.42400 -2.86900 -2.89700 H -2.81600 -1.07400 3.14600 H -1.27800 -2.93200 2.69500 C -1.99900 -0.37700 2.87800 C 0.68800 -3.06400 -0.77100 C -0.17600 -2.76600 -1.97400 O -0.12000 -2.97700 0.37200 H -1.01900 -3.48200 -2.02500 O -1.07200 -0.99300 2.02400 H 1.13200 -4.07200 -0.87500 H -2.41500 0.48800 2.34500 H -0.96900 -1.09900 -3.87300 O -0.67300 -1.45500 -1.85400 C -1.50700 -1.06100 -2.90900 H -2.40200 -1.70700 -2.97100 H -1.82500 -0.03000 -2.70700 H -3.38300 1.51200 -1.46700 H -4.70100 2.11300 -0.40900 C -3.18700 -2.07000 0.07200 H -3.90400 -2.52700 -0.63600 H -3.59300 -2.18400 1.09500 H -2.21800 -2.57900 0.01900 H -4.93400 -0.30300 -0.77100 H -4.51600 0.00400 0.94100 H 0.57900 1.01900 -2.38400 H 1.00700 2.67300 -1.90400 H -0.20600 2.40900 -3.22100 1068 1069 Table C.2.128. Atomic coordinates and single point energies for B26. G = –1091.741915 GSP = –1092.6332 N 1.21000 0.43100 0.19200 Na -0.95000 0.55400 0.52600 Si 1.66100 -1.17500 0.46700 C 2.05700 1.52900 -0.21200 C 0.03900 -2.10400 0.89600 C 2.43400 -2.12200 -0.99800 H -0.39000 -1.74300 1.84800 H 0.22100 -3.18200 1.02500 H -0.72700 -2.00100 0.10700 H 1.80400 -2.05700 -1.89900 H 2.58400 -3.18800 -0.76100 H 3.41900 -1.70100 -1.25600 C 2.80800 -1.55100 1.94100 H 2.43700 -1.05800 2.85300 H 3.83300 -1.19100 1.76400 H 2.86300 -2.63500 2.13400 C 1.38300 2.85400 0.18900 C 2.25200 1.54700 -1.74200 C 3.44800 1.49300 0.44700 H 0.39100 2.92900 -0.29100 H 1.96700 3.73700 -0.11700 H 1.24800 2.88500 1.28200 H 1.27600 1.65800 -2.24100 H 2.69800 0.59700 -2.07400 H 2.90400 2.37300 -2.07600 H 3.34200 1.43900 1.54200 H 4.05200 2.38000 0.19300 H 4.00600 0.60200 0.11600 O -3.22200 0.31000 0.94400 O -1.94500 -0.10100 -1.39700 1070 C -3.98300 0.10100 -0.22700 C -3.17700 -0.73600 -1.19500 H -4.23800 1.07400 -0.68400 H -4.92300 -0.42500 0.01800 H -3.02000 -1.75000 -0.78100 H -3.73800 -0.83400 -2.14200 C -1.11000 -0.72000 -2.35600 C -3.95900 0.90800 1.98400 H -4.79900 0.26300 2.29100 H -4.35700 1.89000 1.67600 H -3.28600 1.04400 2.84000 H -0.11300 -0.27600 -2.24100 H -1.50100 -0.55400 -3.37400 H -1.03800 -1.80500 -2.16700 1071 Table C.2.129. Atomic coordinates and single point energies for B27. G = –1400.11138 GSP = –1401.35793 N -1.57100 -0.13600 -0.25900 Na 0.65500 0.05200 0.03100 Si -2.52600 0.71100 0.85200 C -2.02100 -1.15500 -1.17900 C -1.59400 2.29600 1.34700 C -4.24500 1.30700 0.27600 H -0.54600 2.09100 1.62400 H -2.07300 2.79600 2.20300 H -1.59000 3.01000 0.50600 H -4.16400 1.91800 -0.63700 H -4.72200 1.92200 1.05700 H -4.92400 0.46800 0.05600 C -2.86200 -0.18400 2.51200 H -1.92100 -0.32700 3.06900 H -3.31100 -1.17800 2.35200 H -3.54200 0.39200 3.16000 C -0.78800 -1.86600 -1.77300 C -2.81800 -0.55800 -2.35900 C -2.90800 -2.23000 -0.51600 H -0.15100 -1.12700 -2.29100 H -1.05400 -2.65200 -2.49900 H -0.19700 -2.32800 -0.96400 H -2.20900 0.20300 -2.87100 H -3.72800 -0.06600 -1.98900 H -3.11400 -1.32500 -3.09600 H -2.37900 -2.68700 0.33400 H -3.19900 -3.02700 -1.21900 H -3.83100 -1.77100 -0.12600 O 1.19400 -1.88600 1.23100 1072 O 2.86300 -0.71300 -0.60800 C 2.20900 -2.66900 0.66200 C 3.32600 -1.73500 0.24300 H 1.81000 -3.23400 -0.20400 H 2.60000 -3.40600 1.38900 H 3.72700 -1.24400 1.14100 H 4.14400 -2.30500 -0.23200 C 2.88800 -1.02800 -1.98200 C 0.12500 -2.63300 1.77100 H 0.42700 -3.11700 2.71600 H -0.20500 -3.41000 1.06000 H -0.71000 -1.94100 1.93800 H 2.28000 -1.92000 -2.21000 H 3.92300 -1.20000 -2.32400 H 2.46800 -0.16200 -2.50900 H 0.64600 3.27600 -0.26400 H 2.92700 3.37700 0.77200 O 1.97900 1.58000 1.16100 C 2.56700 2.47300 0.24800 C 1.53600 2.86900 -0.77900 H -0.83800 2.08900 -1.84600 C 2.82300 1.23100 2.22400 H 3.79700 0.86800 1.85200 H 1.95200 3.65700 -1.43300 C 0.10100 1.97800 -2.41100 H 0.29800 2.86900 -3.03200 O 1.18500 1.73800 -1.53500 H 3.42600 1.98300 -0.24900 H 2.33200 0.43100 2.79300 H 0.00300 1.10000 -3.06200 H 3.00200 2.09400 2.88800 1073 Table C.2.130. Atomic coordinates and single point energies for B15. G = –2422.2183 GSP = –2424.13598 N -0.05400 2.56400 -0.40900 Na -0.12900 0.35600 -0.83700 Si -0.33200 2.99100 1.20200 C -0.30900 3.37800 -1.57500 C 0.71000 1.82100 2.29000 C 0.13800 4.75000 1.77200 H 0.78200 0.82100 1.83400 H 0.31100 1.71600 3.31200 H 1.73800 2.21200 2.36900 H 1.19700 4.96100 1.55600 H -0.01600 4.85800 2.85800 H -0.46700 5.52400 1.27300 C -2.14700 2.77900 1.78700 H -2.52300 1.80000 1.44700 H -2.79300 3.55000 1.33600 H -2.25800 2.84100 2.88200 C -0.24400 2.48900 -2.83300 C 0.75200 4.48600 -1.73500 C -1.70000 4.04500 -1.55300 H 0.73600 1.98300 -2.87900 H -0.36900 3.06500 -3.76400 H -1.04100 1.72500 -2.80600 H 1.75400 4.03200 -1.77100 H 0.72300 5.16400 -0.87000 H 0.60200 5.08500 -2.65000 H -2.47500 3.27300 -1.42200 H -1.91300 4.60800 -2.47700 H -1.77400 4.74600 -0.70600 O 1.48700 -0.87700 0.02700 1074 P 2.97600 -1.07900 -0.01900 N 3.76200 0.22200 -0.71000 N 3.54100 -1.43200 1.51500 N 3.54100 -2.35800 -0.94900 C 3.33000 -2.28800 -2.38800 C 3.47700 -3.71400 -0.43200 C 5.14000 0.17700 -1.16200 C 3.28200 1.57400 -0.43400 C 2.69600 -1.27900 2.68600 C 4.96600 -1.40700 1.77300 H 5.45300 -0.85600 -1.35600 H 5.82900 0.62300 -0.42200 H 5.23900 0.75200 -2.09700 H 2.19800 1.61200 -0.24300 H 3.47200 2.20300 -1.31700 H 3.81300 2.02300 0.42400 H 5.52400 -1.69100 0.87000 H 5.21400 -2.13700 2.56100 H 5.31700 -0.41300 2.10700 H 1.64300 -1.35600 2.39300 H 2.84200 -0.30300 3.18100 H 2.92300 -2.07700 3.41100 H 3.34000 -1.24300 -2.72300 H 2.36400 -2.73600 -2.67900 H 4.13400 -2.83100 -2.91000 H 3.66000 -3.71700 0.64900 H 4.24700 -4.32900 -0.92300 H 2.49400 -4.18200 -0.62300 H -5.76200 -3.30800 -0.89800 H -5.19900 -2.58300 0.62500 C -4.89900 -3.21800 -0.21800 H -5.65000 -0.34300 1.45000 H -4.20400 -1.05000 2.23300 C -4.56200 -0.22500 1.60600 H -4.39500 0.72500 2.14200 H -4.67200 -4.22600 0.17700 H -4.17600 -3.37200 -2.84100 N -3.77000 -2.64100 -0.91300 C -3.34700 -3.32800 -2.11600 N -3.84800 -0.20600 0.34400 P -2.86400 -1.41600 -0.23300 N -2.20800 -2.05600 1.17500 H -1.81700 -0.13900 1.98500 C -4.27600 0.83100 -0.58400 H -3.02800 -4.36500 -1.90200 H -4.20900 1.81400 -0.09200 1075 H -5.31700 0.67000 -0.91600 H -2.51300 -2.78200 -2.57000 C -1.39800 -1.15400 1.99000 H -2.28000 -4.05000 0.49700 H -1.37900 -1.51200 3.03100 C -1.64800 -3.39700 1.11300 H -1.60500 -3.82000 2.12800 O -1.89000 -0.90500 -1.25800 H -3.61300 0.84200 -1.45800 H -0.36000 -1.10300 1.61400 H -0.62400 -3.39600 0.69600 1076 Table C.2.131. Atomic coordinates and single point energies for B16. G = –3241.636769 GSP = –3244.24285 N -0.42400 -2.46800 1.12100 Na 0.05800 -0.44800 0.14300 Si -1.16000 -3.57100 0.07700 C -0.01200 -2.71200 2.48400 C -1.05900 -2.81700 -1.67100 C -0.41800 -5.33100 -0.06200 H -1.56800 -1.84000 -1.68000 H -1.52800 -3.46100 -2.43300 H -0.01200 -2.64500 -1.96700 H 0.64600 -5.31500 -0.34300 H -0.95900 -5.91900 -0.82200 H -0.50000 -5.87400 0.89400 C -3.01900 -3.93300 0.37600 H -3.58900 -2.99400 0.44000 H -3.16400 -4.47700 1.32300 H -3.45200 -4.54600 -0.43300 C 0.19200 -1.36200 3.19800 C 1.32800 -3.47500 2.53500 C -1.04600 -3.51700 3.29800 H 0.93200 -0.75100 2.65700 H 0.53900 -1.48600 4.23800 H -0.75700 -0.80200 3.21600 H 2.08600 -2.91300 1.96600 H 1.21700 -4.46100 2.05700 H 1.69300 -3.62700 3.56600 1077 H -2.02300 -3.00800 3.26900 H -0.74600 -3.63900 4.35200 H -1.17700 -4.52200 2.86600 O 1.87100 -0.56300 -1.20100 P 3.32200 -0.77400 -0.88100 N 3.58500 -2.35300 -0.40500 N 4.22500 -0.32300 -2.23000 N 4.07500 0.08900 0.33600 C 3.80600 -0.24200 1.73000 C 4.45100 1.47900 0.15700 C 4.91100 -2.84500 -0.09600 C 2.59300 -3.37200 -0.72200 C 3.60300 -0.34700 -3.54100 C 5.67100 -0.39500 -2.25600 H 5.55900 -2.02100 0.22900 H 5.38800 -3.34900 -0.95800 H 4.85100 -3.57300 0.72900 H 1.58600 -2.99300 -0.50300 H 2.76500 -4.23600 -0.06400 H 2.65400 -3.71600 -1.77100 H 6.07800 -0.29900 -1.24100 H 6.07600 0.43100 -2.86500 H 6.03600 -1.34300 -2.69200 H 2.51400 -0.30700 -3.42800 H 3.86900 -1.25900 -4.10600 H 3.93500 0.52500 -4.13000 H 3.51900 -1.29500 1.82600 H 2.98300 0.37800 2.12300 H 4.71400 -0.06600 2.32900 H 4.60200 1.70300 -0.90600 H 5.39300 1.67800 0.69500 H 3.67300 2.15300 0.55300 H -6.18800 2.18800 -1.26800 H -5.46100 1.06500 -2.45300 C -5.28600 1.98100 -1.87400 H -5.91200 0.62800 1.39700 H -6.08200 -0.02300 -0.25800 C -5.62400 -0.20200 0.72500 H -6.05900 -1.13100 1.12700 H -5.16200 2.81800 -2.58200 H -4.64100 3.14400 0.54600 N -4.10400 1.84300 -1.05200 C -3.83800 2.98300 -0.20000 N -4.18800 -0.34300 0.60800 P -3.37600 0.37000 -0.65800 N -3.70700 -0.53800 -2.01400 1078 H -4.81500 -2.04800 -1.06400 C -3.48300 -0.75200 1.81600 H -3.75600 3.90000 -0.80900 H -4.00700 -1.61500 2.25700 H -3.45500 0.05700 2.56800 H -2.88200 2.83100 0.31600 C -4.41100 -1.80300 -2.05100 H -2.60200 0.83400 -3.15900 H -5.24100 -1.75300 -2.77800 C -3.10800 -0.13400 -3.27200 H -3.87900 -0.03200 -4.05600 O -1.93100 0.59000 -0.31800 H -2.45800 -1.08200 1.57700 H -3.73300 -2.62100 -2.34600 H -2.36500 -0.87800 -3.60600 H 2.09700 4.25300 3.30500 H -0.93500 2.80000 3.33000 H 2.28500 2.53900 2.81400 H -1.17300 1.44600 2.17600 C -1.35400 2.51300 2.34800 C 2.49700 3.57600 2.52700 H -2.44200 2.68100 2.38000 H 1.76300 5.95900 1.44200 N 1.91600 3.85200 1.22600 C 2.14600 5.19600 0.74000 H 3.59200 3.70900 2.49200 O 1.01300 1.41200 1.08700 N -0.78600 3.29000 1.25500 H -2.18000 4.85300 1.32700 H 1.65900 5.33900 -0.23100 P 0.71300 2.81700 0.66000 C -1.08800 4.70700 1.28900 H -0.71500 5.19700 0.37900 H 3.22900 5.37100 0.61500 H -0.64800 5.21600 2.16800 H 2.77000 3.41400 -1.15400 N 0.67700 3.19300 -0.96900 C 1.92100 2.99700 -1.70900 C -0.49900 2.88600 -1.77600 H -0.44400 1.86700 -2.19300 H -1.40700 2.94200 -1.16900 H 1.84500 3.52700 -2.67000 H -0.56000 3.61100 -2.60300 H 2.11300 1.92600 -1.90100 1079 Table C.2.132. Atomic coordinates and single point energies for B24. G = –1303.467832 GSP = –1304.58691 N 1.78600 -0.19600 0.12600 Na -0.43600 -0.05900 -0.04100 Si 2.33300 0.89800 -1.04200 C 2.60400 -1.10500 0.89500 C 0.76100 1.63900 -1.85200 C 3.31200 2.42400 -0.44600 H 0.17100 0.86500 -2.37700 H 1.02300 2.40200 -2.60100 H 0.11100 2.13100 -1.10700 H 2.78000 2.93100 0.37500 H 3.45400 3.15000 -1.26300 H 4.30800 2.14500 -0.07100 C 3.35400 0.20100 -2.49500 H 2.82000 -0.63000 -2.98200 H 4.32500 -0.18700 -2.15000 H 3.55800 0.97200 -3.25500 C 1.88000 -1.45100 2.20800 C 3.97900 -0.51800 1.27300 C 2.84600 -2.42000 0.12600 H 1.76600 -0.54000 2.81700 H 2.42200 -2.20200 2.80500 H 0.87400 -1.84500 1.98700 H 3.84300 0.43800 1.80300 H 4.57800 -0.32300 0.36800 H 4.55700 -1.19900 1.91700 H 1.87800 -2.89500 -0.10600 H 3.45800 -3.14000 0.69600 H 3.35100 -2.20900 -0.82800 N -2.79000 0.61300 -0.79000 1080 N -1.68900 -2.10200 -0.32200 C -2.81700 1.60600 -1.85400 H -2.27300 2.51000 -1.55400 H -3.85500 1.89400 -2.12300 H -2.31900 1.21100 -2.75100 C -1.40400 -3.20500 0.58000 C -1.08500 -2.33200 -1.62700 H -1.78100 -2.97400 1.58700 H -0.31800 -3.35700 0.64700 H -1.87100 -4.15300 0.24100 H -1.53300 -3.20200 -2.15100 H -0.00600 -2.50300 -1.50200 H -1.20000 -1.44800 -2.27200 C -3.11700 -1.84100 -0.39300 C -3.48000 -0.60400 -1.20900 H -3.23400 -0.78200 -2.26600 H -4.58300 -0.47400 -1.17500 H -3.66400 -2.70600 -0.83100 H -3.48800 -1.73800 0.64000 C -3.35800 1.15500 0.44500 C -2.42100 2.10000 1.19400 H -4.30800 1.68800 0.23200 H -3.62200 0.31600 1.10500 C -0.12800 2.39200 1.93800 C -1.40300 0.52300 2.72500 N -1.19600 1.45300 1.62900 H -2.97900 2.54100 2.04800 H -2.14500 2.93900 0.53800 H -1.80000 1.02600 3.63200 H -0.44700 0.04600 2.98000 H -2.10500 -0.27400 2.43900 H 0.02000 3.07800 1.09200 H 0.81000 1.83400 2.07400 H -0.34600 2.99200 2.84500 1081 Table C.2.133. Atomic coordinates and single point energies for B35. G = –1823.515158 GSP = –1825.22436 N 2.42800 1.05500 0.59900 Na 0.74800 0.40200 -0.74100 Si 3.80600 1.09500 -0.40100 C 2.46000 1.49100 1.98600 C 3.22300 0.83400 -2.20300 C 4.80900 2.71600 -0.47300 H 2.69800 -0.12200 -2.34600 H 4.09100 0.82300 -2.88000 H 2.56000 1.64900 -2.53700 H 4.16000 3.57100 -0.72400 H 5.59700 2.64700 -1.24000 H 5.30100 2.94200 0.48600 C 5.12200 -0.26300 -0.12900 H 5.66600 -0.11200 0.81500 H 5.86300 -0.26300 -0.94500 H 4.66400 -1.26400 -0.08500 C 1.25000 0.92100 2.74000 C 2.39900 3.02900 2.09600 C 3.71900 1.01500 2.74200 H 0.31400 1.19600 2.22800 H 1.19600 1.29100 3.77700 H 1.30800 -0.17800 2.76900 H 1.49000 3.40700 1.60300 H 3.26300 3.48300 1.59000 H 2.39400 3.37200 3.14400 H 3.81600 -0.07800 2.65700 1082 H 3.68100 1.28300 3.81000 H 4.62700 1.47100 2.31700 N -3.67400 2.23000 0.55400 N -4.19200 -0.48900 -0.43800 C -4.02700 3.61300 0.80000 H -3.41700 4.29700 0.19700 H -3.91100 3.89700 1.86900 H -5.07600 3.77700 0.51900 C -5.14100 0.09200 -1.36800 C -4.64300 1.36100 1.19700 C -4.47200 -0.13400 0.94200 C -2.30100 1.91400 0.92300 C -1.22000 2.66700 0.15200 H -2.13500 2.10400 2.00800 H -2.14000 0.83900 0.75500 C 0.09000 2.99500 -1.80200 C -2.09900 2.03000 -2.02300 N -0.91600 2.14200 -1.18000 H -0.28800 2.61300 0.73600 H -1.47500 3.74500 0.08300 H -2.78100 1.27300 -1.61700 H -1.79300 1.74300 -3.04000 H -2.64600 2.99300 -2.09200 H -0.28300 4.02900 -1.95300 H 0.37100 2.58700 -2.78400 H 0.98900 3.03600 -1.16500 H 2.49900 -3.44600 1.51500 H 0.77600 -2.70200 3.22900 H 1.87100 -1.80600 1.28200 C 1.58600 -2.87200 1.23600 H 2.47300 -1.70800 -0.77500 C 0.50000 -3.19300 2.26900 H -0.09400 -1.03300 1.05400 H 2.10700 -2.02800 -3.17500 H -1.08300 -0.81500 2.51400 H 0.48900 -4.27600 2.47100 C -0.98000 -1.41100 1.58100 C 2.03300 -2.65000 -1.14100 C 1.33300 -2.36500 -2.46900 N 1.14900 -3.15700 -0.11500 H 0.90400 -3.29000 -2.90600 N -0.83300 -2.82500 1.82700 H 1.61200 -5.23900 -0.11700 C 0.77200 -4.53700 -0.31400 H 2.88700 -3.33800 -1.33700 H -1.85800 -1.22400 0.94500 1083 H -1.79700 -2.88700 3.73400 H 1.08000 -0.19100 -3.99600 C -1.86100 -3.32100 2.71200 H -0.07300 -4.79300 0.33900 N 0.30800 -1.31900 -2.39100 C 0.14100 -0.67000 -3.68400 H -0.17000 -1.38700 -4.47100 H 0.44100 -4.69400 -1.35100 H -1.79000 -4.41500 2.80100 H -2.85500 -3.07700 2.30600 C -0.98200 -1.82500 -1.92200 H -0.84900 -2.37000 -0.97900 H -0.63700 0.10200 -3.60800 H -1.44200 -2.50600 -2.67100 H -1.67500 -0.98200 -1.75300 H -5.64000 1.67300 0.84500 H -4.65100 1.50500 2.30200 C -4.12800 -1.92900 -0.59100 H -4.88900 -0.22500 -2.39000 H -5.08300 1.18800 -1.32700 H -6.18700 -0.22500 -1.16100 H -5.08900 -2.42400 -0.33000 H -3.34100 -2.35300 0.05000 H -3.88600 -2.18500 -1.63200 H -5.40500 -0.62600 1.30100 H -3.66100 -0.53500 1.57000 1084 Table C.2.134. Atomic coordinates and single point energies for B10. G = –1015.439329 GSP = –1016.23891 N 0.98300 0.32400 -0.38500 Na -0.50600 -0.48600 -1.74700 Si 1.99900 -0.93200 0.12000 C 1.02900 1.72100 -0.02500 C 1.45600 -2.45400 -0.91100 C 3.86900 -0.73400 -0.16400 H 0.40400 -2.72900 -0.70800 H 2.05500 -3.34400 -0.66700 H 1.58100 -2.27700 -1.99400 H 4.08000 -0.42000 -1.19800 H 4.40700 -1.67500 0.03100 H 4.29000 0.03100 0.50900 C 1.83300 -1.51100 1.93000 H 0.78400 -1.74500 2.17400 H 2.17300 -0.74100 2.63900 H 2.43100 -2.41900 2.11300 C -0.27600 2.39400 -0.49400 C 2.20400 2.45000 -0.70600 C 1.14500 1.93500 1.49700 H -0.36800 2.31100 -1.59200 H -0.31800 3.46500 -0.23900 H -1.14300 1.89200 -0.03200 H 2.13500 2.32200 -1.79700 H 3.15900 2.01300 -0.37900 H 2.21900 3.52800 -0.47500 1085 H 0.33000 1.40600 2.01600 H 1.10600 3.00100 1.77300 H 2.09900 1.52600 1.86600 C -3.17400 0.03100 1.43200 C -2.15900 -0.83400 0.69900 O -2.46700 -0.66000 -0.69900 C -3.76100 -0.07600 -0.86100 C -4.39900 -0.09500 0.52500 H -2.82700 1.07500 1.47000 H -3.35200 -0.31000 2.45900 H -2.27900 -1.90000 0.95700 H -1.11100 -0.53000 0.85000 H -4.32500 -0.65400 -1.60700 H -3.64400 0.95700 -1.23100 H -4.90500 -1.05600 0.70000 H -5.13400 0.70900 0.66000 1086 Table C.2.135. Atomic coordinates and single point energies for B11. G = –1247.5127 GSP = –1248.57507 N 1.56800 -0.72700 0.12700 Na -0.46400 -0.55600 0.96100 Si 2.48000 0.57200 0.71300 C 2.03100 -1.80600 -0.71600 C 1.38500 1.42500 2.03200 C 4.13100 0.19700 1.58200 H 0.41700 1.74800 1.61000 H 1.86600 2.32600 2.44300 H 1.19200 0.74500 2.88000 H 3.99500 -0.55000 2.37900 H 4.56200 1.10600 2.02900 H 4.87200 -0.20500 0.87100 C 2.90500 1.95400 -0.53900 H 2.01800 2.25000 -1.12300 H 3.66600 1.61600 -1.26000 H 3.29900 2.85300 -0.03700 C 0.81000 -2.53100 -1.31200 C 2.84400 -2.84200 0.08600 C 2.90300 -1.31500 -1.88800 H 0.17700 -2.92600 -0.49800 H 1.09400 -3.37800 -1.95600 H 0.21100 -1.82600 -1.91200 H 2.23500 -3.22500 0.91900 H 3.73900 -2.36900 0.51700 H 3.16800 -3.69400 -0.53500 H 2.36000 -0.55200 -2.46800 H 3.19200 -2.13400 -2.56600 H 3.82800 -0.85200 -1.50700 C -0.80000 3.35300 -0.60200 1087 C -1.77200 2.48000 0.17700 O -1.46600 1.15000 -0.22300 C -0.86500 1.15400 -1.53400 C -0.76000 2.62600 -1.94700 H 0.19000 3.32600 -0.12200 H -1.12700 4.39800 -0.67700 H -2.82100 2.71900 -0.07800 H -1.65400 2.55400 1.26900 H -1.50100 0.57000 -2.21800 H 0.11800 0.66200 -1.44100 H -1.62200 2.92200 -2.56300 H 0.15300 2.82900 -2.52000 H -2.74500 -3.09300 -0.02200 H -2.22500 -1.64400 -0.92900 C -2.90100 -2.01200 -0.13700 H -4.57800 -1.64500 -1.50200 C -4.34800 -1.62700 -0.42900 H -5.03800 -2.31300 0.08300 O -2.57300 -1.36400 1.09600 C -4.42100 -0.23200 0.19200 H -3.92900 0.49900 -0.46500 C -3.58500 -0.42200 1.45100 H -4.18600 -0.83200 2.28100 H -5.44400 0.10400 0.40500 H -3.10300 0.50600 1.79300 1088 Table C.2.136. Atomic coordinates and single point energies for B12. G = –1479.587384 GSP = –1480.91188 N -1.47100 0.38900 0.55700 Na 0.41500 -0.40500 -0.36100 Si -2.29100 1.37400 -0.54400 C -1.89700 0.00700 1.88200 C -1.36200 1.20100 -2.20500 C -4.11100 0.95200 -0.92900 H -0.29100 1.43500 -2.08500 H -1.75900 1.88500 -2.97200 H -1.44200 0.17600 -2.60100 H -4.21600 -0.09600 -1.25300 H -4.51200 1.59700 -1.72800 H -4.75000 1.09000 -0.04100 C -2.31200 3.25200 -0.18000 H -1.30000 3.62200 0.05200 H -2.94800 3.48400 0.68800 H -2.69500 3.82700 -1.03900 C -0.67300 -0.49400 2.67200 C -2.92200 -1.14500 1.83600 C -2.52100 1.17200 2.67500 H -0.20900 -1.34500 2.14100 H -0.93200 -0.83300 3.68800 H 0.07400 0.31200 2.75400 H -2.47300 -2.01600 1.33100 H -3.80700 -0.83900 1.25700 H -3.25300 -1.46000 2.84000 H -1.81900 2.02000 2.71000 H -2.77900 0.88600 3.70800 H -3.44400 1.51800 2.18100 1089 C 1.48600 3.61300 -1.32100 C 2.18300 2.27500 -1.52200 O 1.79100 1.48700 -0.40500 C 1.41600 2.33900 0.69500 C 1.58900 3.77600 0.19600 H 0.43100 3.53300 -1.62600 H 1.95500 4.43000 -1.88500 H 3.28300 2.39600 -1.53100 H 1.88300 1.75200 -2.44200 H 2.06700 2.11500 1.55600 H 0.37300 2.09200 0.95600 H 2.58000 4.16800 0.46800 H 0.82900 4.45100 0.61100 H 2.59700 -1.91300 2.27300 H 2.39500 -0.17100 1.94300 C 2.87600 -1.09900 1.59000 H 4.81000 -0.25900 2.19800 C 4.38100 -0.91600 1.43100 H 4.89400 -1.88800 1.48500 O 2.38800 -1.40700 0.28300 C 4.46700 -0.34500 0.01500 H 4.18100 0.71700 0.02100 C 3.38900 -1.15200 -0.70000 H 3.78100 -2.11300 -1.07500 H 5.45600 -0.45100 -0.44700 H 2.93300 -0.61000 -1.54300 H -1.87200 -2.38200 -2.61400 H -2.04100 -1.61500 -0.99600 H -2.87800 -3.75500 -0.32100 C -1.59900 -2.45800 -1.55000 C -1.98100 -3.82100 -0.95000 H -2.17600 -4.55600 -1.74400 O -0.17200 -2.34400 -1.41700 C -0.72700 -4.21600 -0.16500 H -0.72700 -3.74300 0.82900 C 0.36700 -3.59700 -1.02200 H -0.61600 -5.30100 -0.03500 H 0.57200 -4.22100 -1.91200 H 1.30700 -3.40500 -0.49000 1090 Table C.2.137. Atomic coordinates and single point energies for B13. G = –1711.654317 GSP = –1713.24246 N -2.12800 0.14600 0.37600 Na 0.12300 -0.03000 0.07800 Si -3.04500 -0.29000 -0.97000 C -2.58000 0.70900 1.62400 C -1.78500 -0.74300 -2.33200 C -4.18800 -1.81500 -0.80200 H -1.18100 0.14000 -2.60100 H -2.26800 -1.11400 -3.24900 H -1.09900 -1.52300 -1.96200 H -3.65700 -2.66100 -0.33600 H -4.56500 -2.14600 -1.78300 H -5.06000 -1.59200 -0.16800 C -4.18500 1.04000 -1.73600 H -3.63200 1.96900 -1.95100 H -5.00900 1.29800 -1.05000 H -4.63600 0.68800 -2.67800 C -1.45200 0.57600 2.66700 C -3.83400 0.00800 2.18200 C -2.89000 2.21600 1.49200 H -1.18000 -0.48300 2.80100 H -1.73200 0.99400 3.64900 H -0.56200 1.12000 2.30600 H -3.65300 -1.07600 2.26100 H -4.68700 0.15700 1.50000 H -4.12400 0.39200 3.17400 H -1.97300 2.74000 1.17800 H -3.23900 2.66200 2.43900 1091 H -3.66000 2.38100 0.72300 C -0.49200 4.22300 -0.84000 C -0.29700 2.72200 -1.02600 O 0.48600 2.29600 0.09400 C 0.99800 3.40700 0.80900 C 0.78700 4.61700 -0.10000 H -1.37300 4.41400 -0.20800 H -0.63000 4.75200 -1.79100 H 0.26300 2.49400 -1.95200 H -1.23300 2.14200 -1.01500 H 2.06000 3.22600 1.04200 H 0.44800 3.51800 1.76000 H 1.62400 4.71000 -0.81000 H 0.70500 5.55800 0.45800 H 2.97200 1.10500 -0.12000 H 2.53700 2.17100 -1.48100 C 2.81600 1.13700 -1.20900 H 4.73900 1.43700 -2.22900 C 4.00100 0.64800 -2.03500 H 4.51100 -0.18300 -1.52100 O 1.74400 0.25800 -1.53400 C 3.29600 0.13700 -3.29200 H 3.01300 0.98200 -3.93800 C 2.05200 -0.51200 -2.69100 H 2.26100 -1.55300 -2.38800 H 3.89700 -0.56300 -3.88600 H 1.17900 -0.51700 -3.35900 H -1.40600 -2.11200 0.92800 H -0.13000 -3.03100 1.81400 H -1.50900 -4.87800 0.97700 C -0.61700 -2.87700 0.83300 C -1.07700 -4.19800 0.23300 H -1.83000 -4.01100 -0.54800 O 0.35500 -2.37600 -0.09500 C 0.22000 -4.71100 -0.39300 H 0.87000 -5.14400 0.38300 C 0.82700 -3.41800 -0.93600 H 0.06900 -5.46700 -1.17400 H 0.49400 -3.22400 -1.97100 H 1.93000 -3.42600 -0.92500 H 2.39200 1.32100 2.52600 H 1.41600 0.19300 3.50300 H 4.19000 0.24900 3.75100 C 2.22500 0.25600 2.76200 C 3.51500 -0.43000 3.21500 H 3.28500 -1.27700 3.87900 1092 H 4.57200 -0.12600 1.33900 O 1.82500 -0.41800 1.57200 C 4.07900 -0.94400 1.89000 C 2.80300 -1.36900 1.17300 H 4.80000 -1.76400 2.00500 H 2.86800 -1.35200 0.07500 H 2.48600 -2.38200 1.47900 1093 Table C.2.138. Atomic coordinates and single point energies for B21. G = –1286.267493 GSP = –1287.36217 N 2.40600 0.14200 -0.34600 Na 0.29900 0.72100 -0.15100 Si 3.02000 0.07200 1.22900 C 3.11900 -0.10600 -1.57800 C 1.54800 0.50100 2.38200 C 3.68600 -1.61100 1.83100 H 1.23400 1.55200 2.24300 H 1.83200 0.39900 3.44000 H 0.67700 -0.15700 2.22000 H 2.96000 -2.41900 1.65000 H 3.92100 -1.59300 2.90800 H 4.61200 -1.87500 1.29600 C 4.36300 1.32700 1.73400 H 4.07300 2.34600 1.43100 H 5.33400 1.10600 1.26700 H 4.51100 1.32300 2.82700 C 2.32900 0.51400 -2.74600 C 3.26300 -1.61700 -1.85000 C 4.53000 0.51300 -1.59200 H 1.31800 0.07400 -2.79400 H 2.81300 0.34400 -3.72200 H 2.23000 1.60000 -2.58900 H 2.26800 -2.09000 -1.88900 H 3.82400 -2.09500 -1.03300 H 3.78400 -1.82600 -2.79900 H 4.47000 1.58500 -1.34900 H 5.02400 0.39600 -2.57000 H 5.16800 0.02900 -0.83500 N -1.95300 1.62900 -0.17300 N -1.19700 -1.13700 0.01500 C -2.97500 0.58200 -0.33500 C -2.57400 -0.75400 0.32400 C -0.65600 -2.16500 0.89100 1094 C -0.95000 -1.47800 -1.37900 C -1.83300 2.13700 1.18800 C -2.10900 2.71900 -1.12500 H -1.67200 1.31100 1.89600 H -2.71600 2.71700 1.51700 H -0.96200 2.80800 1.25400 H -2.15400 2.31900 -2.14700 H -1.24000 3.39100 -1.06100 H -3.01500 3.33000 -0.94700 H -0.85800 -1.90800 1.94100 H 0.43500 -2.21300 0.75100 H -1.07800 -3.17000 0.69100 H -1.29600 -0.67500 -2.04700 H -1.43800 -2.42200 -1.69000 H 0.13500 -1.59400 -1.52400 C -4.37900 0.99200 0.14200 C -3.62300 -1.82700 -0.01300 C -5.41800 -0.07900 -0.18300 C -5.02400 -1.41700 0.43800 H -5.75200 -2.19700 0.17400 H -5.04200 -1.32600 1.53700 H -3.63200 -1.99400 -1.10400 H -3.33400 -2.78100 0.45400 H -2.60500 -0.60400 1.41900 H -6.41000 0.23700 0.17100 H -5.49500 -0.19400 -1.27800 H -4.36000 1.14900 1.23400 H -4.66300 1.95200 -0.31500 H -3.04400 0.40300 -1.42300 1095 Table C.2.139. Atomic coordinates and single point energies for B22. G = –1789.134444 GSP = –1790.79097 N -0.93100 -2.36000 0.37800 Na -0.11500 -0.21100 0.02000 Si -0.79100 -3.28100 -1.04000 C -1.69800 -2.78900 1.53300 C 0.23700 -4.89300 -0.97200 C -2.40200 -3.87000 -1.89300 H 1.20100 -4.73700 -0.46300 H 0.44800 -5.25700 -1.99100 H -0.29400 -5.69600 -0.43800 H -2.90900 -4.62700 -1.27300 H -2.17500 -4.34500 -2.86200 H -3.12700 -3.06200 -2.07300 C 0.16800 -2.23700 -2.32500 H 1.24500 -2.26700 -2.10000 H -0.13900 -1.17900 -2.36400 H 0.03700 -2.65100 -3.33800 C -1.10500 -2.16400 2.80600 C -1.70000 -4.31600 1.75300 C -3.16600 -2.32700 1.42600 H -0.08200 -2.53700 2.96500 H -1.70300 -2.38800 3.70400 H -1.06000 -1.07100 2.68400 H -0.66600 -4.68500 1.82400 H -2.19100 -4.83500 0.91500 H -2.23500 -4.59500 2.67600 H -3.19800 -1.22900 1.33300 1096 H -3.77200 -2.61900 2.30100 H -3.63100 -2.75600 0.52400 N -1.98100 0.83900 -1.46000 N -1.12000 1.81900 1.37500 C -2.72600 1.71600 -0.54000 C -1.78500 2.59600 0.31000 C -1.98000 1.50400 2.50800 C 0.07700 2.49800 1.84800 C -1.55200 1.51100 -2.67800 C -2.77800 -0.33600 -1.80500 H -0.96800 2.41400 -2.44700 H -2.39600 1.80500 -3.33100 H -0.91400 0.83000 -3.26000 H -2.93700 -0.95400 -0.91300 H -2.23200 -0.95000 -2.53200 H -3.75300 -0.06500 -2.25800 H -2.31000 2.40600 3.06000 H -1.42700 0.87000 3.21400 H -2.86700 0.94000 2.18900 H -0.11800 3.53100 2.20000 H 0.83000 2.52800 1.04800 H 0.49600 1.94100 2.69600 H 2.12300 0.70700 2.13700 H 2.10400 3.65000 -0.29900 H 2.77100 -0.83600 2.76500 C 2.08500 -0.38400 2.02000 H 1.07100 -0.73300 2.26500 C 1.94600 3.05200 -1.21000 H 2.61000 3.45500 -2.00000 H 0.90900 3.20700 -1.54400 C 3.39300 1.40400 -0.16600 N 2.41200 -0.75600 0.65400 N 2.16400 1.64500 -0.93200 C 3.61300 -0.09000 0.14400 C 2.48100 -2.20800 0.54400 H 3.23100 -2.65300 1.23000 H 1.48600 -2.62400 0.76900 C 2.06100 0.86500 -2.15200 H 2.86400 1.08500 -2.88600 H 1.10300 1.09200 -2.63800 H 2.74500 -2.49300 -0.48600 H 2.07100 -0.20900 -1.92900 C 4.85400 -0.25900 1.03800 C 4.66400 1.97800 -0.82300 C 6.10800 0.30600 0.37800 C 5.90600 1.77900 0.04300 1097 H 6.98100 0.17100 1.03400 H 6.31900 -0.25500 -0.54900 H 6.79000 2.19200 -0.46600 H 5.78800 2.34900 0.98100 H 4.68900 0.26300 1.99500 H 4.99000 -1.32500 1.27500 H 3.84500 -0.58500 -0.81500 H 4.82100 1.48500 -1.79800 H 4.52700 3.04900 -1.02600 H 3.26000 1.93600 0.79700 C -3.77900 2.59500 -1.23200 C -2.51800 3.86700 0.80900 C -4.74100 3.22700 -0.22100 C -4.00900 3.63900 1.06900 H -4.13100 2.85400 1.82900 H -4.45900 4.54600 1.49600 H -5.22700 4.10000 -0.68300 H -5.54700 2.51700 0.02000 H -3.26100 3.38800 -1.79600 H -4.34100 2.00600 -1.97100 H -3.25800 1.03600 0.14700 H -2.02400 4.25000 1.71500 H -2.40900 4.66200 0.05400 H -0.96600 2.91800 -0.35400 1098 Table C.2.140. Atomic coordinates and single point energies for B18. G = –1130.490703 GSP = –1131.41767 N 1.57100 0.28700 -0.13200 Na -0.59700 -0.03100 -0.20400 Si 2.31200 -1.16600 0.32300 C 2.23400 1.52800 -0.45800 C 0.91600 -2.47600 0.31300 C 3.67100 -1.85800 -0.81900 H 0.11900 -2.23400 1.03900 H 1.29100 -3.47500 0.58000 H 0.46800 -2.55300 -0.69400 H 3.32000 -1.91200 -1.86200 H 3.98200 -2.86700 -0.50600 H 4.56700 -1.21700 -0.80400 C 3.05000 -1.26500 2.07800 H 2.31200 -0.93100 2.82500 H 3.93800 -0.62300 2.18100 H 3.35100 -2.29500 2.32900 C 1.20800 2.67300 -0.38300 C 2.80400 1.50200 -1.89000 C 3.38200 1.86800 0.51200 H 0.37800 2.47500 -1.08500 H 1.64200 3.65200 -0.64200 H 0.79900 2.73000 0.64000 H 1.99400 1.28800 -2.60500 H 3.55200 0.70100 -1.98300 H 3.28100 2.45600 -2.17000 H 3.01100 1.86000 1.54800 H 3.82800 2.85400 0.30100 H 4.18400 1.11500 0.43300 N -2.45800 1.42500 0.43800 1099 N -2.64100 -1.38500 -0.41900 C -3.73100 0.81000 0.08900 C -3.74900 -0.70600 0.24300 H -3.96100 1.08400 -0.95200 H -4.55700 1.22400 0.70600 H -4.72500 -1.07700 -0.13800 H -3.71600 -0.97500 1.31000 C -2.64200 -2.80100 -0.07700 C -2.67700 -1.20800 -1.86400 C -2.12400 1.24000 1.84500 C -2.46600 2.84000 0.09700 H -2.02000 0.17100 2.08700 H -2.89500 1.67100 2.51700 H -1.16100 1.72500 2.06000 H -2.64700 2.96400 -0.98000 H -1.49200 3.28700 0.33300 H -3.25400 3.39200 0.64900 H -2.55500 -2.92100 1.01200 H -1.78200 -3.30100 -0.54100 H -3.57200 -3.30300 -0.41300 H -2.57900 -0.14500 -2.13100 H -3.61800 -1.58900 -2.31000 H -1.83600 -1.74900 -2.32200 1100 Table C.2.141. Atomic coordinates and single point energies for B19. G = –1477.597601 GSP = –1478.91841 N 1.96000 -0.03700 -0.35000 Na -0.33600 0.03600 -0.06200 Si 2.62500 -0.81600 1.00000 C 2.74300 0.66100 -1.35100 C 3.64100 -2.41300 0.71900 C 3.78100 0.19000 2.14900 H 3.12700 -3.11100 0.03900 H 3.81100 -2.93500 1.67500 H 4.62700 -2.19300 0.28300 H 4.73100 0.41300 1.63700 H 4.03000 -0.39100 3.05300 H 3.35200 1.15100 2.47000 C 1.16300 -1.41800 2.07600 H 0.63500 -2.23100 1.55100 H 0.42900 -0.62700 2.30100 H 1.51600 -1.82400 3.03700 C 1.99500 0.63500 -2.69400 C 4.13200 0.04100 -1.60300 C 2.95400 2.13700 -0.95600 H 1.92400 -0.40200 -3.06000 H 2.49500 1.24100 -3.46800 H 0.97500 1.02200 -2.55200 H 4.02400 -1.02200 -1.87200 H 4.75900 0.10100 -0.69900 H 4.66900 0.55400 -2.41700 H 1.97300 2.62700 -0.82900 H 3.53000 2.70400 -1.70600 H 3.48400 2.19500 0.00800 N -0.59500 1.86300 1.69200 1101 N -1.75100 1.90300 -1.30300 C -1.03900 2.97000 0.85100 C -2.17600 2.60900 -0.09600 H -0.17300 3.31900 0.27000 H -1.35300 3.82800 1.48300 H -2.72200 3.53500 -0.37700 H -2.89700 1.96300 0.43000 C -1.00900 2.78200 -2.19700 C -2.92900 1.39900 -1.99200 C -1.51400 1.64700 2.79600 C 0.74200 2.13900 2.20700 H -2.52400 1.42000 2.42700 H -1.57900 2.53800 3.45500 H -1.17300 0.79700 3.40300 H 1.46200 2.15000 1.37800 H 1.04600 1.34100 2.89800 H 0.77300 3.10400 2.75400 H -1.59800 3.68700 -2.45600 H -0.77100 2.24700 -3.12600 H -0.05700 3.09500 -1.75200 H -3.66500 2.20500 -2.19300 H -3.41100 0.62400 -1.38200 H -2.64200 0.95900 -2.95700 H -1.92300 -0.91900 -2.26300 H -4.79000 -0.15900 -0.03700 H -1.21000 -2.30800 -3.13700 C -1.04800 -1.57600 -2.31700 H -0.16900 -0.96600 -2.56600 H -3.62700 -1.77600 -1.27200 C -4.36200 -0.55200 0.89600 H -5.09600 -1.26600 1.32800 H -4.24900 0.28300 1.60300 C -3.23700 -2.23400 -0.34800 N -0.83000 -2.23400 -1.04000 N -3.07700 -1.17900 0.64600 H -2.23100 -3.78000 -1.43000 H -4.01100 -2.96300 -0.01600 C -1.97400 -3.03400 -0.64500 C 0.38100 -3.04000 -1.11000 H 0.31400 -3.80500 -1.91200 H 1.23900 -2.37400 -1.28700 C -2.53500 -1.70100 1.89100 H -1.69000 -3.61500 0.24600 H -3.14800 -2.53900 2.28900 H -2.51800 -0.90500 2.64600 H 0.54500 -3.55900 -0.15500 1102 H -1.50500 -2.05300 1.75500 1103 Table C.2.142. Atomic coordinates and single point energies for C47. G = –1550.014741 GSP = –1551.409497 Na 0.42200 -0.30700 0.31800 N -1.68100 0.12600 -0.30000 Si -3.12600 -0.57400 0.26100 C -2.86400 -2.40100 0.71400 C -3.80500 0.25300 1.84100 C -4.56300 -0.52200 -0.98800 H -3.13600 0.06100 2.69500 H -4.80800 -0.11800 2.10800 H -3.87700 1.34600 1.71700 H -4.80500 0.51800 -1.26000 H -5.48000 -0.98300 -0.58700 H -4.28900 -1.05100 -1.91400 H -3.73300 -2.77400 1.27900 H -1.97100 -2.52100 1.34900 H -2.75500 -3.04100 -0.17700 C -1.73900 1.52300 -0.67500 C -1.64500 1.72200 -2.19500 H -2.70300 2.00500 -0.37700 H -0.63600 1.45600 -2.55000 H -1.86200 2.75500 -2.51400 H -2.37100 1.05300 -2.67500 O 2.67200 -0.54900 0.94400 O 1.70300 0.71600 -1.35200 O 1.18000 -1.97400 -1.36900 O 0.64200 -2.44300 1.30400 C 1.81000 -2.43700 2.09100 C 2.99200 -1.86200 1.33400 C 3.57100 0.01900 0.02000 1104 C 2.87200 1.15600 -0.70300 C 0.86000 -1.17900 -2.49100 C 1.85700 -0.04300 -2.53100 C 0.53300 -3.47300 0.33700 C 0.15900 -2.87400 -1.00000 H -0.24300 -4.19000 0.65100 H 1.49100 -4.01300 0.24400 H -0.80000 -2.33100 -0.91900 H 0.04900 -3.68100 -1.74900 H -0.16300 -0.77400 -2.37600 H 0.91700 -1.77000 -3.42400 H 1.67400 0.59200 -3.41600 H 2.87900 -0.45300 -2.60700 H 2.54400 1.91800 0.02200 H 3.57200 1.63600 -1.41000 H 4.47500 0.39800 0.53100 H 3.89100 -0.75600 -0.70100 H 3.19800 -2.47100 0.43400 H 3.89200 -1.87700 1.97700 H 1.59200 -1.80700 2.96500 H 2.05400 -3.45000 2.45300 C -0.68700 2.37000 0.06800 C -0.45200 2.11800 1.42900 C 0.05100 3.39800 -0.53500 C 0.48200 2.85600 2.15800 H -1.03500 1.32900 1.91000 C 0.98200 4.14400 0.19100 H -0.09600 3.62400 -1.59100 C 1.20700 3.87600 1.54100 H 0.63400 2.64100 3.21800 H 1.54000 4.94000 -0.30700 H 1.93500 4.45900 2.10800 1105 Table C.2.143. Atomic coordinates and single point energies for C46. G = –1550.006419 GSP = –1551.402819 Na 1.38200 0.10300 -0.67700 N -0.81600 0.30400 -0.24500 Si -1.59600 1.81800 -0.37500 C -0.34800 3.18000 0.09800 C -2.21500 2.27000 -2.12400 C -3.08200 2.14800 0.76700 H -1.40100 2.19700 -2.86400 H -2.61800 3.29500 -2.15800 H -3.01900 1.58700 -2.44100 H -3.96700 1.55600 0.48800 H -3.35900 3.21500 0.72800 H -2.83200 1.89800 1.81100 H -0.75300 4.16500 -0.18500 H 0.63100 3.06500 -0.39400 H -0.18400 3.20400 1.18800 C -1.45500 -0.94700 -0.60200 C -1.28500 -1.30500 -2.08700 H -0.96000 -1.77900 -0.05000 H -1.68100 -0.50400 -2.72900 H -1.77700 -2.25500 -2.35300 H -0.21100 -1.41000 -2.31400 O 3.66800 -0.56000 -1.03400 O 1.57000 -2.21300 -0.26900 O 2.13200 -0.30400 1.64000 O 2.76400 1.84800 0.03200 C 4.02100 1.74400 -0.58900 C 4.58400 0.34300 -0.46000 C 3.92300 -1.90500 -0.70600 C 2.67100 -2.71600 -0.98400 C 1.13500 -1.27900 1.88600 C 1.51800 -2.52200 1.11200 C 2.76000 1.96800 1.44500 1106 C 1.75800 0.99900 2.03600 H 2.48500 2.99900 1.72300 H 3.76400 1.75300 1.84700 H 0.74200 1.21800 1.66000 H 1.75900 1.09700 3.13700 H 0.15900 -0.89100 1.53800 H 1.07700 -1.51900 2.96400 H 0.77300 -3.31600 1.28700 H 2.50000 -2.88400 1.46100 H 2.40900 -2.64400 -2.04900 H 2.85400 -3.78000 -0.75100 H 4.77100 -2.30200 -1.29300 H 4.18600 -1.97500 0.36500 H 4.72100 0.09000 0.60800 H 5.56800 0.28100 -0.95900 H 3.86600 1.98500 -1.65100 H 4.73700 2.47600 -0.17600 C -2.91500 -1.02500 -0.15900 C -3.18900 -1.15800 1.20900 C -3.99700 -0.89400 -1.03400 C -4.49200 -1.14700 1.69300 H -2.34800 -1.25100 1.90200 C -5.31000 -0.87200 -0.55500 H -3.82000 -0.79800 -2.10700 C -5.56300 -0.99600 0.80800 H -4.67900 -1.24800 2.76400 H -6.13900 -0.75900 -1.25600 H -6.58800 -0.97800 1.18200 1107 Table C.2.144. Atomic coordinates and single point energies for C48. G = –1703.612192 GSP = –1705.182516 Na 1.31600 0.00600 0.03200 N -0.82800 -0.77900 -0.08500 Si -1.14100 -0.79900 -1.75300 C -1.87500 -2.39500 -2.49900 C -2.18500 0.63600 -2.44900 C 0.55100 -0.59200 -2.61800 H -3.20500 0.65700 -2.03700 H -2.26200 0.57800 -3.54800 H -1.69900 1.59400 -2.19600 H 0.96500 0.41000 -2.41000 H 0.44300 -0.67700 -3.71100 H 1.27300 -1.35800 -2.28800 H -1.87800 -2.35600 -3.60000 H -2.91400 -2.55700 -2.17300 H -1.28400 -3.27200 -2.18800 C -1.80200 -0.98600 0.95300 C -1.96300 -2.46900 1.32800 H -2.24000 -3.05800 0.44000 H -2.71800 -2.63200 2.11500 H -0.99900 -2.86700 1.67900 H -1.46400 -0.46400 1.88000 O 3.10500 -1.53300 -0.43900 O 3.26800 1.10400 -0.96700 O 2.16500 -1.11100 2.08300 O 0.73000 1.16000 1.93700 O 0.87400 2.29300 -0.52200 C 1.17700 -0.84800 3.05000 C 1.04900 0.65300 3.20300 H 1.99600 1.09200 3.57200 H 0.25000 0.87800 3.93300 C 0.33200 2.49700 1.84400 1108 C -0.10200 2.71900 0.40000 H 1.15700 3.17200 2.14600 H -0.52700 2.70700 2.51000 H -0.36400 3.78100 0.23800 H -0.97400 2.08300 0.19300 C 2.03000 3.07600 -0.63600 C 2.96500 2.33800 -1.56700 H 2.46500 2.17900 -2.54100 H 3.88400 2.92900 -1.73700 H 1.79600 4.07600 -1.04600 H 2.52800 3.20600 0.34200 C 4.29800 -1.01400 -0.96500 C 3.96100 0.20300 -1.79500 C 3.25800 -2.51800 0.55700 C 2.09500 -2.40000 1.51500 H 4.19800 -2.34800 1.11100 H 3.28900 -3.52700 0.11100 H 2.17100 -3.18300 2.29100 H 1.13600 -2.51700 0.97200 H 1.44300 -1.30700 4.02000 H 0.20800 -1.25500 2.71700 H 4.82000 -1.75900 -1.59200 H 4.97200 -0.71800 -0.14000 H 3.33100 -0.07900 -2.65800 H 4.89600 0.65500 -2.17400 C -3.16200 -0.34800 0.65800 C -3.37900 0.99800 0.97800 C -4.19100 -1.03200 -0.00000 C -4.55400 1.65500 0.62000 H -2.60000 1.53200 1.53000 C -5.37200 -0.38300 -0.36400 H -4.06900 -2.08900 -0.24100 C -5.55500 0.96600 -0.06500 H -4.69300 2.70600 0.87900 H -6.15500 -0.93800 -0.88400 H -6.47700 1.47500 -0.35300 1109 Table C.2.145. Atomic coordinates and single point energies for C49. G = –1857.195357 GSP = –1858.941593 Na -1.18700 -0.00900 0.13300 N 1.11300 0.23900 0.50900 Si 1.84900 1.73600 0.19700 C 0.78300 3.14500 0.91100 C 3.59500 2.08100 0.87300 C 1.95700 2.21600 -1.65900 H 3.68400 1.78100 1.92900 H 3.80600 3.16100 0.80400 H 4.37300 1.54500 0.30800 H 2.50600 1.46500 -2.25000 H 2.46600 3.18400 -1.79600 H 0.93800 2.30900 -2.07100 H 1.13800 4.12800 0.56100 H 0.81500 3.14300 2.01300 H -0.26400 3.02400 0.59600 C 1.77200 -1.02900 0.73700 C 1.58300 -1.52500 2.17800 H 1.30500 -1.81300 0.09200 H 1.95600 -0.77000 2.88700 H 2.09500 -2.48300 2.36700 H 0.51100 -1.66700 2.35800 O -3.28200 -1.47000 -0.73700 O -0.69600 -1.64100 -1.74500 O -1.66400 -1.89000 1.51000 O -2.57500 0.56700 2.28500 O -1.28000 1.05100 -2.00700 O -2.48100 2.04800 0.05500 C -2.26100 2.00600 -2.29700 C -2.42300 2.88300 -1.07100 C -2.85300 2.68100 1.25600 1110 C -2.23100 1.92300 2.40700 C -1.90100 -0.26600 3.19300 C -2.20000 -1.69100 2.79500 C -3.45200 -2.61100 0.07100 C -2.16400 -2.98900 0.79300 C -3.08200 -1.70100 -2.10700 C -1.72500 -2.32700 -2.40700 C 0.09700 -0.77000 -2.52900 C -0.70700 0.38200 -3.10000 H -3.21800 1.50600 -2.54500 H -1.96800 2.63400 -3.15800 H -3.34300 3.48700 -1.17100 H -1.56100 3.57000 -0.98200 H -3.95500 2.69600 1.34400 H -2.48200 3.72100 1.28300 H -2.59200 2.34200 3.36500 H -1.13300 2.03200 2.36700 H -2.24000 -0.08400 4.23000 H -0.81100 -0.08600 3.13700 H -3.29500 -1.84200 2.79400 H -1.74700 -2.39400 3.51700 H -2.34700 -3.85100 1.46100 H -1.37600 -3.26800 0.08100 H -4.23100 -2.36400 0.80800 H -3.81900 -3.46900 -0.52300 H -3.16100 -0.71600 -2.58600 H -3.88400 -2.34500 -2.51900 H -1.56100 -2.35300 -3.50000 H -1.70900 -3.37500 -2.06200 H 0.60100 -1.32400 -3.34100 H 0.83600 -0.35400 -1.82500 H -1.49400 0.03300 -3.79800 H -0.03200 1.05300 -3.66300 C 3.25700 -1.06300 0.34500 C 4.29700 -1.10400 1.27900 C 3.60800 -1.00100 -1.01100 C 5.63400 -1.05500 0.87800 H 4.06800 -1.15800 2.34400 C 4.93700 -0.94900 -1.42000 H 2.81300 -0.98800 -1.75900 C 5.96200 -0.96900 -0.47200 H 6.42500 -1.07700 1.63100 H 5.17800 -0.89600 -2.48400 H 7.00600 -0.92500 -0.78600 1111 Table C.2.146. Atomic coordinates and single point energies for C13. G = –935.596762 GSP = –936.2939343 Na -2.66800 1.84500 -0.84000 N -1.09400 0.75100 0.09900 Si -1.56200 -0.88900 0.09800 C -3.29600 -0.91200 -0.72300 C -1.74400 -1.65500 1.82400 C -0.50200 -2.09700 -0.90800 H -0.37300 -1.74100 -1.94200 H -0.95600 -3.10000 -0.93900 H 0.50400 -2.19000 -0.46800 H -2.41200 -1.05300 2.45800 H -0.76100 -1.69700 2.32000 H -2.13600 -2.68300 1.77900 H -4.03900 -0.33000 -0.14700 H -3.69300 -1.93600 -0.78300 H -3.26400 -0.54200 -1.76500 C 0.07900 1.19400 0.80700 C 0.21500 2.72100 0.72700 H 0.30900 3.02700 -0.32900 H 1.09800 3.09300 1.26800 H -0.68200 3.19700 1.15800 C 1.37400 0.55000 0.30900 C 2.27900 -0.04100 1.19300 C 1.66400 0.52100 -1.06100 C 3.44700 -0.64900 0.72500 C 2.83000 -0.07500 -1.53200 C 3.72700 -0.66600 -0.63900 H 2.05900 -0.03500 2.26400 1112 H 4.13800 -1.11500 1.43100 H 0.93800 0.94900 -1.75500 H 3.04000 -0.09000 -2.60300 H 4.63700 -1.14300 -1.00800 H 0.02700 0.94900 1.89300 1113 Table C.2.147. Atomic coordinates and single point energies for C12. G = –935.602447 GSP = –936.2994237 Na -0.67600 -1.47100 1.01100 N 0.70400 -0.04100 0.16500 Si 2.38700 -0.22800 -0.00600 C 3.47700 0.95400 1.01100 C 2.98400 -0.07600 -1.80300 C 2.80600 -1.97500 0.61500 H 2.47900 -2.10000 1.66200 H 3.88700 -2.17900 0.58900 H 2.30700 -2.74100 -0.00100 H 2.80800 0.94000 -2.19100 H 2.44600 -0.78000 -2.45700 H 4.06200 -0.28000 -1.89200 H 3.37700 1.99500 0.66800 H 4.54200 0.68000 0.94000 H 3.18600 0.92600 2.07300 C -0.05700 0.98900 -0.50100 C 0.21000 2.40500 0.02400 H -0.47400 3.15400 -0.40700 H 1.24000 2.69500 -0.22800 H 0.13300 2.42600 1.12200 C -1.52700 0.59200 -0.37500 C -2.30000 0.94600 0.74000 C -3.56600 0.38700 0.94800 C -4.08300 -0.54000 0.04200 C -3.33100 -0.89100 -1.08300 C -2.06800 -0.33200 -1.28300 H -1.90200 1.66500 1.45900 H -5.07100 -0.97400 0.20200 H -4.15100 0.68200 1.82100 H -1.46900 -0.62000 -2.15100 1114 H -3.73300 -1.60300 -1.80700 H 0.14400 1.02000 -1.59800 1115 Table C.2.148. Atomic coordinates and single point energies for C1. G = –1871.258409 GSP = –1872.643134 Na 0.07700 1.31000 1.29400 Na 0.79300 -0.46200 -0.81600 N 2.22200 0.83500 0.59100 N -1.32300 -0.00200 0.03500 Si -1.73500 -1.25200 1.14500 Si 2.72400 2.34100 -0.04900 C -0.44600 -1.13900 2.54900 C -1.61000 -2.98800 0.38100 C -3.41700 -1.16600 2.01000 C 3.98700 3.37000 0.92700 C 1.15700 3.43100 -0.10300 C 3.37900 2.31300 -1.83900 H -3.55200 -0.19000 2.50200 H -3.48700 -1.95200 2.77900 H -4.25400 -1.29600 1.30800 H -0.60700 -3.18100 -0.03700 H -2.34100 -3.09800 -0.43600 H -1.82200 -3.77600 1.12000 H 0.59000 -1.03900 2.18100 H -0.47800 -2.04300 3.17500 H -0.65900 -0.29400 3.22900 H 4.35000 1.79500 -1.90300 H 3.52900 3.33400 -2.22500 H 2.67900 1.79900 -2.51900 H 0.82400 3.72500 0.90900 H 0.31700 2.95400 -0.63500 H 1.36700 4.37200 -0.63300 H 3.74200 3.38600 2.00100 H 3.97800 4.40900 0.56200 H 5.01300 2.99000 0.82000 1116 C -2.15100 0.18800 -1.14600 C 3.09100 -0.23300 1.05700 C 4.57000 0.13000 1.24500 C -1.62300 1.33300 -2.02200 H -1.67100 2.28300 -1.46800 H -2.21500 1.44600 -2.94200 H -0.57100 1.17100 -2.31700 C -3.62400 0.45400 -0.84000 C -3.99000 1.48000 0.04000 C -4.63300 -0.32700 -1.40600 C -5.32600 1.71500 0.34900 C -5.97600 -0.10300 -1.09400 C -6.32600 0.91800 -0.21400 H -3.20500 2.08500 0.50100 H -5.59400 2.51700 1.03900 H -4.36100 -1.13600 -2.09000 H -6.75000 -0.73200 -1.53800 H -7.37400 1.09400 0.03500 H -2.15600 -0.71800 -1.79700 H 4.67200 0.93500 1.98500 H 5.01300 0.47800 0.29600 H 5.15000 -0.73900 1.59000 C 2.99000 -1.46100 0.14400 C 2.47100 -2.67600 0.60100 C 3.33800 -1.35900 -1.21500 C 2.29200 -3.75800 -0.26900 C 2.63100 -3.63900 -1.61400 H 2.74700 -0.59300 2.05000 H 2.19100 -2.77500 1.65300 H 1.87400 -4.69300 0.10900 C 3.16200 -2.43300 -2.08500 H 3.73400 -0.41200 -1.58900 H 3.44300 -2.33400 -3.13500 H 2.48600 -4.47900 -2.29500 1117 Table C.2.149. Atomic coordinates and single point energies for C3. G = –1871.274394 GSP = –1872.657317 Na 0.00300 0.02000 0.60300 Na -0.00800 -0.08200 -2.25300 N 1.79200 -0.44900 -0.89500 N -1.79800 0.38300 -0.91200 Si -2.87200 -0.92000 -1.20300 Si 2.86100 0.83300 -1.27900 C -3.58600 -1.70800 0.37100 C -1.87500 -2.26300 -2.11200 C -4.35900 -0.47900 -2.29300 C 3.58300 1.72500 0.23500 C 1.85300 2.11100 -2.26700 C 4.34300 0.32700 -2.34700 H -4.95200 0.33100 -1.83800 H -5.03100 -1.34000 -2.43600 H -4.03000 -0.13200 -3.28500 H -0.94100 -2.50400 -1.57700 H -1.62600 -1.96700 -3.14700 H -2.44900 -3.19800 -2.19200 H -4.21700 -2.58300 0.14800 H -4.21300 -0.98300 0.91500 H -2.77800 -2.02800 1.04800 H 4.94400 -0.44700 -1.84200 H 5.00800 1.17900 -2.55400 H 4.00900 -0.08900 -3.31000 H 1.60100 1.74700 -3.28000 H 2.42000 3.04300 -2.40900 H 0.92000 2.37900 -1.74400 H 2.77800 2.08300 0.89700 H 4.20600 2.58800 -0.04900 1118 H 4.21900 1.04100 0.81900 C -2.38100 1.62700 -0.42000 C 2.37800 -1.65700 -0.32200 C -2.41600 2.71500 -1.49500 H -1.40900 2.87900 -1.91200 H -2.80000 3.67500 -1.11500 H -3.05900 2.37800 -2.31900 C -1.62200 2.05800 0.83600 C -1.88200 1.38100 2.04000 C -0.56400 2.97400 0.81300 C -1.09700 1.59100 3.17200 C 0.22900 3.18600 1.94700 C -0.02700 2.49000 3.12600 H -2.70000 0.65700 2.06800 H -1.31700 1.04700 4.09300 H -0.34700 3.53000 -0.10000 H 1.05400 3.90000 1.90300 H 0.59500 2.65300 4.00800 H -3.43300 1.49400 -0.08100 C 2.40200 -2.81800 -1.31800 H 2.78800 -3.75000 -0.87500 H 3.04000 -2.54100 -2.16900 H 1.39200 -3.00800 -1.71500 C 1.63000 -1.99700 0.96700 C 0.57200 -2.91100 1.01900 C -0.21100 -3.04100 2.17300 C 0.05500 -2.26200 3.29700 C 1.12500 -1.36200 3.26900 C 1.90000 -1.23500 2.11800 H 0.34700 -3.53100 0.15000 H -0.56000 -2.36100 4.19300 H -1.03500 -3.75600 2.18700 H 2.71900 -0.51100 2.08700 H 1.35300 -0.75400 4.14600 H 3.43300 -1.50200 -0.00300 1119 Table C.2.150. Atomic coordinates and single point energies for C4. G = –1871.265765 GSP = –1872.649141 Na 1.05700 -0.40400 1.01800 Na -0.79300 0.27300 -1.10500 N 1.06200 1.44700 -0.39300 N -0.94900 -1.44300 0.52100 Si -0.50100 -2.94000 -0.17200 Si 0.32300 2.80100 0.34700 C 1.31500 -2.72000 -0.70500 C -1.42500 -3.42900 -1.76900 C -0.53400 -4.49400 0.91900 C 1.44400 4.31500 0.52300 C -0.27500 2.28500 2.07800 C -1.23600 3.37000 -0.58800 H -0.09700 -4.29200 1.90900 H 0.05400 -5.29600 0.44600 H -1.55500 -4.87500 1.07200 H -1.34000 -2.64700 -2.54300 H -2.49800 -3.59800 -1.58300 H -1.01600 -4.35800 -2.19600 H 1.46500 -1.81800 -1.32300 H 1.65300 -3.57700 -1.30800 H 2.01200 -2.65700 0.15100 H -0.96700 3.70600 -1.60300 H -1.74600 4.20500 -0.08000 H -1.99200 2.56900 -0.68500 H 0.58000 2.09100 2.74800 H -0.87700 1.36100 2.01000 H -0.90900 3.04500 2.56000 H 2.36800 4.07700 1.07300 1120 H 0.92300 5.11400 1.07100 H 1.73500 4.71700 -0.45900 C -2.17100 -1.14800 1.24400 C 2.33200 1.53400 -1.08400 C -3.01400 -2.36600 1.65500 H -3.33100 -2.93400 0.76400 H -3.92000 -2.06000 2.19900 H -2.42600 -3.03300 2.30000 C -3.08300 -0.17300 0.49000 C -3.63700 0.94500 1.12300 C -3.40200 -0.39100 -0.86000 C -4.47300 1.82400 0.43400 C -4.23200 0.48900 -1.55600 C -4.76900 1.60500 -0.91000 H -3.40100 1.13100 2.17400 H -4.88500 2.69500 0.94700 H -3.00000 -1.27800 -1.35900 H -4.47200 0.29700 -2.60400 H -5.41400 2.29700 -1.45300 H -1.93300 -0.62400 2.19400 C 2.18700 1.30200 -2.59100 H 3.13800 1.39600 -3.13900 H 1.48100 2.04200 -2.99500 H 1.77700 0.29600 -2.79000 C 3.34700 0.57300 -0.44600 C 4.00300 -0.45200 -1.13400 C 4.85100 -1.34300 -0.46800 C 5.06800 -1.22300 0.90100 C 4.44000 -0.18900 1.60300 C 3.59400 0.69300 0.93400 H 3.84600 -0.57700 -2.20600 H 5.72700 -1.92000 1.41900 H 5.33700 -2.14300 -1.02900 H 3.10600 1.50600 1.48100 H 4.62100 -0.06500 2.67300 H 2.79400 2.53900 -0.97400 1121 Table C.2.151. Atomic coordinates and single point energies for C2. G = –1871.26324 GSP = –1872.646265 Na -0.96400 -0.00800 -1.35400 Na 0.52400 -0.02100 1.07900 N 0.39900 1.64200 -0.53100 N -0.61100 -1.81300 0.09100 Si 0.63300 -2.98700 0.27300 Si -0.40300 3.00800 0.11100 C 2.01500 -2.26100 1.36900 C 1.50400 -3.49500 -1.33500 C 0.04700 -4.56400 1.14600 C 0.55600 4.63000 -0.06800 C -0.72600 2.72900 1.97100 C -2.11000 3.26000 -0.67600 H -0.40200 -4.32500 2.12300 H 0.89400 -5.24500 1.32200 H -0.70500 -5.11500 0.56000 H 1.95100 -2.60600 -1.81000 H 0.80000 -3.94100 -2.05500 H 2.31200 -4.22200 -1.15500 H 2.52600 -1.39100 0.92000 H 2.80400 -3.01300 1.52000 H 1.64500 -1.99100 2.37400 H -2.00100 3.50800 -1.74400 H -2.69200 4.06400 -0.19700 H -2.71000 2.33700 -0.60100 H 0.22000 2.65400 2.53500 H -1.30300 1.80100 2.12900 H -1.31300 3.54300 2.42400 H 1.55800 4.57200 0.38600 H 0.01200 5.45100 0.42300 H 0.68600 4.90300 -1.12700 1122 C -1.97700 -2.30400 -0.02500 C 1.62300 1.73700 -1.30000 C -2.24100 -3.09200 -1.31700 H -2.01600 -2.48500 -2.21200 H -3.28000 -3.44900 -1.39200 H -1.57900 -3.96700 -1.35600 C -2.97400 -1.15300 0.14900 C -2.99300 -0.46600 1.37300 C -3.85900 -0.72900 -0.85100 C -3.87600 0.58500 1.60200 C -4.74200 0.33600 -0.63000 C -4.75800 0.99100 0.59600 H -2.30900 -0.79500 2.16000 H -3.88000 1.09200 2.56800 H -3.89300 -1.24900 -1.81000 H -5.42500 0.64400 -1.42300 H -5.44800 1.81800 0.77000 H -2.22700 -3.00600 0.80300 C 1.46100 1.14800 -2.70800 H 2.34700 1.29100 -3.34400 H 0.60900 1.64000 -3.20000 H 1.26800 0.06000 -2.66000 C 2.80700 1.10100 -0.55400 C 3.66500 0.14600 -1.11100 C 4.72100 -0.39600 -0.37000 C 4.94400 0.00900 0.94200 C 4.10000 0.96500 1.51300 C 3.04700 1.49700 0.77300 H 3.52100 -0.19000 -2.13800 H 5.76700 -0.41500 1.51900 H 5.36900 -1.14600 -0.82700 H 2.39300 2.25200 1.21900 H 4.26900 1.30100 2.53800 H 1.93100 2.79400 -1.45400 1123 Table C.2.152. Atomic coordinates and single point energies for C44. G = –1397.59153 GSP = –1398.816821 Na 0.25200 0.88400 -0.45700 N -1.58900 -0.21000 0.12500 Si -2.92300 0.41200 -0.71000 C -2.28400 1.94200 -1.65300 C -4.39400 1.02000 0.33900 C -3.68700 -0.76400 -1.99700 H -2.93700 -1.07000 -2.74300 H -4.52900 -0.29400 -2.53000 H -4.07000 -1.67800 -1.51700 H -4.06100 1.73100 1.11200 H -4.88400 0.17800 0.85400 H -5.15800 1.52000 -0.27800 H -1.83100 2.67100 -0.95800 H -3.09000 2.46500 -2.18900 H -1.52900 1.65700 -2.40700 C -1.59700 -1.47000 0.81500 C -2.13300 -1.36400 2.25700 H -1.50900 -0.66100 2.83200 H -2.13400 -2.33500 2.77900 H -3.15900 -0.96800 2.24100 C -0.19100 -2.06800 0.86200 C 0.89500 -1.28600 1.28400 C 0.06700 -3.38900 0.48500 C 2.19200 -1.79300 1.29900 C 1.36300 -3.91000 0.50600 C 2.43400 -3.11200 0.90500 H 0.70700 -0.26000 1.61800 H 3.01800 -1.15600 1.62500 H -0.76600 -4.01700 0.15800 H 1.53700 -4.94400 0.20300 1124 H 3.44800 -3.51500 0.91800 H -2.22300 -2.24200 0.31000 O 0.43000 2.45400 1.19900 O 2.53900 1.54200 -0.16100 O 1.53900 -0.11500 -2.04400 C -0.52700 2.38600 2.23600 C 1.70900 2.85900 1.60300 C 2.60500 2.83500 0.38500 H -0.12300 1.82300 3.09600 H -1.39000 1.83800 1.83400 H -0.81400 3.39700 2.57100 H 2.10200 2.16600 2.37000 H 1.69200 3.87700 2.03400 H 3.64000 3.09500 0.67100 H 2.25400 3.57800 -0.35600 C 3.25000 1.35400 -1.36100 C 2.92800 -0.03400 -1.86700 H 4.33800 1.45600 -1.19700 H 2.94000 2.11000 -2.10700 H 3.25700 -0.78700 -1.12800 H 3.46300 -0.21800 -2.81700 C 1.07300 -1.41300 -2.35800 H -0.02300 -1.39300 -2.27900 H 1.46300 -2.14700 -1.63400 H 1.37600 -1.69900 -3.37900 1125 Table C.2.153. Atomic coordinates and single point energies for C45. G = –1859.536636 GSP = –1861.294224 Na 0.86700 0.19800 -0.08200 N -1.00900 1.29100 0.68300 Si -1.41900 2.91700 0.43900 C 0.14600 3.91200 0.02400 C -2.22100 3.74200 1.95800 C -2.61000 3.30800 -1.00600 H -2.20500 2.93300 -1.96200 H -2.76700 4.39400 -1.11300 H -3.59400 2.83600 -0.85600 H -1.59500 3.61600 2.85600 H -3.20900 3.30600 2.17700 H -2.36600 4.82200 1.79300 H 0.84300 3.92500 0.87700 H -0.09500 4.95500 -0.23500 H 0.66900 3.45400 -0.83100 C -1.83300 0.41600 1.46700 C -0.96700 -0.60500 2.23800 H -0.34600 -1.19400 1.54300 H -1.56300 -1.30900 2.84000 H -0.28700 -0.06900 2.91400 C -2.93200 -0.33500 0.68600 C -3.78800 -1.24800 1.32000 C -3.12700 -0.10600 -0.67800 C -4.78000 -1.92700 0.61300 C -4.12200 -0.77500 -1.39300 C -4.94900 -1.69900 -0.75400 H -3.68600 -1.42500 2.39400 H -5.43100 -2.63200 1.13300 H -2.47300 0.62400 -1.15400 1126 H -4.26000 -0.56700 -2.45700 H -5.72900 -2.22300 -1.30900 H -2.40300 0.96200 2.25700 O 2.12800 0.66400 1.85000 O 2.86800 -1.12500 0.03700 O 1.24100 -3.11400 0.97400 C 1.79200 1.69700 2.74400 C 3.45800 0.23400 1.88700 C 3.51400 -1.15400 1.28600 H 1.86700 1.35100 3.79000 H 0.75600 1.97700 2.50500 H 2.45500 2.57300 2.61800 H 3.83200 0.18100 2.92700 H 4.10900 0.93200 1.33000 H 2.99200 -1.84700 1.96500 H 4.56800 -1.47600 1.18300 C 2.79300 -2.35000 -0.65400 C 2.34400 -3.51100 0.21800 H 3.77200 -2.60700 -1.10200 H 2.07100 -2.17600 -1.46200 H 3.16400 -3.84300 0.88800 H 2.10100 -4.37300 -0.43600 C 0.78900 -4.08800 1.86800 H -0.04100 -3.65400 2.44200 H 1.58800 -4.39000 2.57100 H 0.43000 -4.99100 1.34000 H -2.30200 -2.84700 -0.84800 H -0.85900 0.43500 -2.54100 H -1.74400 -1.82900 -2.74700 H 1.00900 1.80600 -3.16300 H 3.42700 2.20100 -2.87300 C -1.24400 -2.87600 -0.53200 H 3.33400 3.66000 -0.99300 C -0.21100 -0.36300 -2.94600 C -0.68200 -1.70800 -2.45900 O -0.54000 -1.78300 -1.07000 C 1.71500 0.95600 -3.13800 O 1.11600 -0.15200 -2.51700 H -1.20500 -2.80300 0.55800 O 2.50400 1.76300 -1.07200 C 2.93000 1.36600 -2.34700 C 3.34800 2.69600 -0.45500 H -0.78800 -3.83300 -0.85100 H -0.26800 -0.34100 -4.05000 H -0.10200 -2.51600 -2.95100 H 1.99900 0.70900 -4.17900 1127 H 3.64500 0.52600 -2.26600 H 4.38900 2.32900 -0.41100 H 2.97300 2.85700 0.56100 1128 Table C.2.154. Atomic coordinates and single point energies for C43. G = –2796.077203 GSP = –2798.032141 O 2.91300 -1.02700 -2.09400 C 4.25000 -1.42700 -1.87800 C 2.67500 -0.10500 -3.13200 C 4.87300 -0.70600 -0.68200 H 4.23500 -2.50900 -1.67900 H 4.86000 -1.26200 -2.78300 C 3.26500 1.25900 -2.81900 H 1.58000 -0.03400 -3.21500 H 3.07600 -0.47500 -4.09200 O 6.14400 -1.21800 -0.39900 H 4.98700 0.36700 -0.88900 H 4.19400 -0.80400 0.18800 O 2.84700 1.61700 -1.52700 H 4.37200 1.22700 -2.85900 H 2.92400 1.99500 -3.57000 C 6.13500 -2.35500 0.42200 C 3.45800 2.78100 -1.02600 H 7.17800 -2.64900 0.59200 H 5.65600 -2.14400 1.39400 H 5.60600 -3.20700 -0.04300 H 3.16100 2.89100 0.02400 H 3.13300 3.67300 -1.58800 H 4.55800 2.69800 -1.08900 C -0.77000 1.97100 -2.53500 Si -1.38100 0.17800 -2.69200 H -1.28700 2.40800 -1.66400 H -1.05800 2.56600 -3.41700 1129 H 0.31800 2.07100 -2.38400 C -1.02500 -0.40100 -4.48300 C -3.27400 0.43500 -2.69800 N -0.62900 -0.71700 -1.44500 H -1.63400 -1.28200 -4.74400 H -1.30200 0.39900 -5.19000 H 0.02600 -0.67000 -4.66500 H -3.54100 1.16900 -1.92100 H -3.56400 0.87300 -3.66700 H -3.87000 -0.47800 -2.55300 C -0.54100 -2.16100 -1.32500 C 0.08500 -2.90100 -2.51800 C -1.87200 -2.81200 -0.94400 H 0.12500 -2.39300 -0.46800 H 0.21300 -3.97200 -2.29400 H 1.07100 -2.46600 -2.73700 H -0.54000 -2.81400 -3.41800 C -2.92900 -2.89500 -1.86200 C -2.09400 -3.28300 0.35400 C -4.17100 -3.39700 -1.48600 H -2.77300 -2.54900 -2.88700 C -3.33700 -3.79300 0.74000 H -1.27400 -3.25100 1.08100 C -4.38400 -3.84200 -0.17700 H -4.98100 -3.44700 -2.21700 H -3.48200 -4.16100 1.75800 H -5.35700 -4.24100 0.11600 O -2.86900 1.06400 0.54400 C -3.86100 0.05800 0.50700 C -3.21100 2.28100 1.17100 C -4.07700 -0.57800 1.86800 H -3.49100 -0.70200 -0.19900 H -4.81600 0.43100 0.10400 C -4.20200 3.11300 0.37000 H -3.60700 2.10900 2.18900 H -2.26300 2.83100 1.27900 O -2.82300 -0.98700 2.35100 H -4.54400 0.12200 2.58800 H -4.75400 -1.44500 1.75200 O -3.70600 3.48200 -0.88400 H -5.13100 2.54900 0.19600 H -4.47700 4.00300 0.96900 C -2.86700 -1.58200 3.62000 C -2.95300 4.66200 -0.88000 H -3.22200 -0.86400 4.38100 H -3.53600 -2.46100 3.62100 1130 H -1.85000 -1.90100 3.87900 H -2.50900 4.77600 -1.87700 H -3.59000 5.54100 -0.66700 H -2.13700 4.63600 -0.13600 C 2.26800 -2.81400 0.96000 Si 1.88300 -1.56900 2.35300 H 1.46600 -3.56300 0.86800 H 3.19100 -3.36200 1.20700 H 2.40100 -2.36300 -0.03700 C 3.53000 -1.11600 3.19900 C 0.96500 -2.62100 3.65200 N 1.04200 -0.20400 1.74700 H 4.11000 -2.02500 3.42400 H 3.36700 -0.59600 4.15600 H 4.14900 -0.45700 2.56800 H 0.02100 -3.00800 3.23200 H 1.56500 -3.49000 3.96400 H 0.72500 -2.03900 4.55600 C 0.98400 0.94800 2.63300 C -0.31300 1.00800 3.47000 C 1.11800 2.29000 1.91400 H 1.81200 0.94900 3.37300 H -0.31900 1.86300 4.16500 H -1.19600 1.10200 2.81500 H -0.42000 0.07900 4.04800 C 0.44200 2.56700 0.71800 C 1.88000 3.31700 2.48700 C 0.52400 3.82700 0.12200 H -0.17000 1.79700 0.23200 C 1.95600 4.58200 1.90300 H 2.42100 3.11700 3.41600 C 1.27300 4.84400 0.71600 H 0.00900 4.00600 -0.82300 H 2.55600 5.36300 2.37400 H 1.33400 5.82800 0.24800 Na -1.11300 -0.47400 0.86000 Na 1.43300 0.03500 -0.54900 1131 Table C.2.155. Atomic coordinates and single point energies for C37. G = –2488.010374 GSP = –2490.102736 Na -0.94500 -1.05500 0.49900 Na 1.17400 0.77400 -0.19500 N -1.09000 1.27800 0.08400 N 1.26200 -1.58900 -0.06900 Si 1.53400 -2.32700 -1.58800 Si -1.30700 2.34200 1.40200 C 0.07600 -1.92100 -2.73300 C 1.67800 -4.22200 -1.49000 C 3.07200 -1.75100 -2.55600 C -1.27600 4.21300 1.01600 C 0.13700 2.01800 2.59700 C -2.84300 2.13400 2.51600 H 3.00100 -0.66600 -2.73500 H 3.15000 -2.25500 -3.53300 H 4.00400 -1.93700 -2.00100 H 0.85100 -4.65600 -0.90600 H 2.61900 -4.53900 -1.01400 H 1.65700 -4.66500 -2.49800 H 0.16400 -2.44600 -3.69700 H 0.03700 -0.84200 -2.94800 H -0.88800 -2.20300 -2.28000 H -3.79500 2.15400 1.96500 H -2.86900 2.94500 3.26100 H -2.78100 1.17800 3.05800 H 1.12400 2.19700 2.13700 H 0.10100 0.96800 2.93600 H 0.06400 2.65200 3.49400 H -0.47300 4.48200 0.31300 H -1.12200 4.77900 1.95000 1132 H -2.22700 4.56200 0.58100 C 1.97700 -2.11000 1.08700 C -1.63800 1.37900 -1.25100 C -1.42400 2.73200 -1.94900 C 1.06800 -2.15600 2.32000 H 0.64300 -1.16000 2.53500 H 1.59600 -2.49800 3.22300 H 0.23100 -2.84500 2.12300 C 3.25800 -1.32200 1.36300 C 4.47500 -1.75200 0.81800 C 3.25300 -0.12800 2.09500 C 5.64400 -1.01100 0.98400 C 4.42000 0.61700 2.26800 C 5.62100 0.18100 1.71100 H 4.49900 -2.69100 0.25800 H 6.58100 -1.37000 0.55200 H 2.32400 0.23300 2.54200 H 4.38500 1.54600 2.84000 H 6.53600 0.76000 1.84900 H 2.31500 -3.15700 0.92900 H -0.35600 3.00000 -1.90300 H -1.98900 3.53400 -1.45500 H -1.74100 2.69400 -3.00400 C -3.11200 0.97700 -1.32200 C -3.50100 -0.23900 -1.89300 C -4.10600 1.79000 -0.75900 C -4.83800 -0.64400 -1.88900 C -5.81200 0.16300 -1.30300 H -1.12400 0.63300 -1.89700 H -2.73900 -0.87600 -2.35100 H -5.12200 -1.59100 -2.35400 C -5.43900 1.38700 -0.74100 H -3.82600 2.75000 -0.31800 H -6.19600 2.03400 -0.29200 H -6.85700 -0.14900 -1.29700 H 3.93700 1.41400 -2.88700 H 1.94900 0.83400 -4.25400 C 3.27100 2.00200 -2.22800 C 1.42000 1.55300 -3.60500 H 0.36100 1.27600 -3.54300 H 3.86400 0.79100 -0.53900 C 3.74500 1.85700 -0.79200 H 3.31100 3.05500 -2.56700 H 4.72900 2.34500 -0.67100 H 1.49700 2.56400 -4.04200 H 1.97800 3.98400 -0.89900 1133 C 2.54800 3.75100 0.01700 H 3.48600 4.33300 0.02200 H 1.94200 4.03800 0.88600 H -3.07100 -1.72000 4.25700 C -2.24600 -1.96900 3.56700 H -2.31700 -3.03500 3.29200 H -1.29000 -1.80300 4.07900 H -4.33700 -0.89900 2.44500 C -3.50100 -1.09100 1.74900 H -3.94000 -3.23000 1.63900 C -3.75300 -2.36800 0.96900 H -3.43400 -0.23800 1.05500 H -4.64600 -2.22900 0.33500 H -3.01500 -4.64000 -0.06900 C -2.74000 -3.74400 -0.65200 H -3.50900 -3.57400 -1.42600 H -1.77000 -3.91700 -1.13300 O -2.61300 -2.62300 0.18300 O -2.27100 -1.13000 2.44000 O 2.81200 2.37400 0.13000 O 1.94800 1.53200 -2.30100 1134 Table C.2.156. Atomic coordinates and single point energies for C38. G = –2488.006788 GSP = –2490.099309 Na -1.16800 -0.02800 -0.00200 Na 1.85900 0.18100 -0.04300 N 0.30700 1.95300 -0.36800 N 0.52900 -1.76300 0.28300 Si 1.25000 -2.39000 1.70700 Si 0.79600 2.45700 -1.92900 C 0.26200 -3.72000 2.64800 C 1.54100 -1.01500 2.98900 C 2.93200 -3.25000 1.39800 C -0.56500 2.58100 -3.25700 C 2.05100 1.21200 -2.63900 C 1.66800 4.14800 -2.01100 H 2.77500 -4.21200 0.88300 H 3.45900 -3.46600 2.34200 H 3.58700 -2.64100 0.75500 H 0.59800 -0.77500 3.50400 H 1.94700 -0.06900 2.59600 H 2.24100 -1.37800 3.75800 H 0.90200 -4.20100 3.40500 H -0.10200 -4.51400 1.97600 H -0.60600 -3.29000 3.16800 H 1.04300 4.94600 -1.57900 H 1.87700 4.42100 -3.05700 H 2.62600 4.14200 -1.46700 H 2.99600 1.21100 -2.07000 H 2.29900 1.48400 -3.67700 1135 H 1.66700 0.17900 -2.66700 H -1.16300 1.65600 -3.30300 H -0.12000 2.75000 -4.25000 H -1.25500 3.41700 -3.06000 C 0.33600 -2.76400 -0.76400 C -0.19400 2.99200 0.52200 C 1.50900 -2.83400 -1.75500 H 1.61300 -1.86700 -2.27200 H 1.36100 -3.61300 -2.52000 H 2.44600 -3.03100 -1.21600 C -0.95500 -2.54600 -1.55000 C -1.98100 -3.49400 -1.52900 C -1.14900 -1.38400 -2.31200 C -3.17700 -3.28300 -2.21600 C -2.34100 -1.16500 -3.00000 C -3.36300 -2.11500 -2.95300 H -1.84200 -4.41200 -0.95100 H -3.96500 -4.03800 -2.18100 H -0.35400 -0.63400 -2.36800 H -2.46800 -0.25300 -3.58900 H -4.29400 -1.95000 -3.49800 H 0.23400 -3.79300 -0.34700 C 0.91800 3.66100 1.35100 H 0.51500 4.39800 2.06400 H 1.62400 4.17600 0.68400 H 1.46400 2.88700 1.91600 C -1.25000 2.49100 1.50400 C -1.02200 1.33200 2.25500 C -1.97300 0.85700 3.15700 C -3.17100 1.55000 3.33900 C -3.40000 2.72100 2.61700 C -2.44400 3.18600 1.71400 H -0.08100 0.79500 2.12400 H -3.91700 1.18500 4.04800 H -1.77200 -0.05300 3.72900 H -2.63100 4.10300 1.14900 H -4.32900 3.27700 2.75900 H -0.69800 3.82100 -0.02900 H 3.71200 -1.23000 -2.64200 C 4.55800 -1.21100 -1.94700 H 4.93400 -2.23900 -1.80400 H 3.98800 -0.71300 1.99100 C 5.15100 -0.47900 0.19400 H 5.66300 -1.43400 0.41700 H 5.36400 -0.59100 -2.37700 C 4.55300 0.07500 1.47500 1136 H 5.90700 0.20800 -0.23300 H 5.36300 0.41800 2.14500 C 4.20100 2.26800 0.65400 H 3.40700 3.02100 0.60300 H 5.02900 2.64800 1.27700 H 4.57500 2.07700 -0.36700 H -2.33900 2.68900 -1.19300 C -3.31100 2.18500 -1.23100 H -4.09800 2.86900 -0.86400 H -4.31900 -0.28300 1.68700 C -4.39100 0.27800 -0.39600 H -5.27200 0.91300 -0.18100 H -3.53500 1.91000 -2.27800 C -4.25100 -0.76200 0.69200 H -4.54100 -0.20900 -1.37700 H -5.07000 -1.50100 0.60000 C -2.81600 -2.47200 1.40900 H -1.79000 -2.82700 1.26000 H -2.94700 -2.16700 2.46400 H -3.53100 -3.28300 1.18000 O 4.11000 -0.66800 -0.72900 O 3.63600 1.11100 1.22400 O -3.00400 -1.38200 0.54700 O -3.22100 1.04800 -0.41800 1137 Table C.2.157. Atomic coordinates and single point energies for C39. G = –1243.983526 GSP = –1245.034898 Na 0.70800 -0.33600 -0.73400 N -1.24500 0.57800 -0.26100 Si -2.58900 -0.40000 0.05000 C -4.11200 -0.18900 -1.07300 C -3.27500 -0.27100 1.82400 C -2.00500 -2.19500 -0.22400 H -1.77300 -2.35200 -1.29100 H -2.76500 -2.93800 0.06200 H -1.09100 -2.40000 0.36000 H -3.61300 0.75800 2.03100 H -2.51600 -0.52600 2.58000 H -4.14000 -0.93700 1.97300 H -4.61800 0.77100 -0.88600 H -4.85000 -0.99100 -0.91000 H -3.81400 -0.20600 -2.13300 C -1.14700 1.98500 0.01800 C -1.95600 2.87100 -0.94200 H -1.79000 3.94600 -0.76400 H -3.02700 2.65700 -0.81600 H -1.70200 2.63400 -1.98600 C 0.33900 2.34500 -0.00300 C 1.04300 2.41900 -1.21600 C 2.43000 2.57900 -1.23700 C 3.14500 2.67500 -0.04100 C 2.45700 2.62100 1.17100 C 1.07000 2.45800 1.18500 H 0.49000 2.34400 -2.15600 H 4.22800 2.80300 -0.05500 H 2.95600 2.64000 -2.19300 1138 H 0.53500 2.40800 2.13700 H 3.00300 2.70600 2.11200 H -1.49500 2.24600 1.04600 C 1.11200 -3.43100 -1.81400 H 0.43400 -3.88700 -1.07500 H 1.81700 -4.19300 -2.18600 H 0.51100 -3.06100 -2.65300 C 2.63900 -2.64800 -0.17200 C 1.86300 -2.60800 1.13100 H 3.42900 -1.88300 -0.14000 H 3.11500 -3.63300 -0.31400 H 2.54900 -2.80100 1.97700 H 1.07500 -3.38700 1.15300 C 0.49500 -1.10900 2.36500 H -0.24000 -1.92200 2.49700 H -0.04800 -0.17200 2.19300 H 1.12700 -1.03800 3.26700 O 1.28500 -1.33600 1.21900 O 1.81400 -2.33100 -1.27600 1139 Table C.2.158. Atomic coordinates and single point energies for C40. G = –1243.979263 GSP = –1245.031332 Na -1.75200 -0.09600 -1.14600 N 0.31300 0.50500 -0.77200 Si 0.38900 1.55800 0.56300 C -1.42200 1.85600 1.10500 C 1.13700 3.26400 0.18800 C 1.31000 0.93900 2.10900 H 0.90900 -0.02200 2.46800 H 1.24100 1.66700 2.93400 H 2.37700 0.77900 1.88500 H 0.63900 3.73200 -0.67400 H 2.20700 3.16600 -0.05600 H 1.05600 3.94500 1.05000 H -1.97000 2.41800 0.32900 H -1.48000 2.44200 2.03500 H -1.95300 0.90400 1.28800 C 1.47000 0.27300 -1.59900 C 1.11700 -0.63500 -2.78300 H 0.73100 -1.60000 -2.41400 H 1.98200 -0.83700 -3.43200 H 0.33200 -0.15500 -3.39200 C 2.63900 -0.32100 -0.81300 C 3.84700 0.36600 -0.67600 C 2.49200 -1.54100 -0.13900 C 4.87800 -0.13700 0.12200 C 3.51800 -2.05400 0.64900 C 4.71600 -1.34900 0.78900 H 3.97500 1.32200 -1.19200 H 5.81000 0.42300 0.22400 H 1.54800 -2.08300 -0.23300 H 3.38500 -3.00700 1.16600 H 5.51800 -1.74400 1.41500 H 1.86700 1.21400 -2.04400 1140 C -1.32000 -1.80900 1.51500 H -1.37900 -2.85500 1.86000 H -1.47300 -1.13300 2.37400 H -0.33700 -1.59700 1.07400 C -3.61100 -1.53600 0.95300 C -4.47100 -1.22100 -0.25600 H -3.73500 -0.76900 1.74200 H -3.91100 -2.51100 1.38000 H -5.53800 -1.18100 0.02300 H -4.34100 -2.01500 -1.00500 C -4.70000 1.14200 -0.35000 H -4.47700 1.28200 0.72000 H -5.79200 1.08300 -0.49300 H -4.31400 2.00700 -0.90200 O -2.28200 -1.56000 0.51000 O -4.07200 -0.01100 -0.87100 1141 Table C.2.159. Atomic coordinates and single point energies for C41. G = –1552.35116 GSP = –1553.756869 Na 0.49400 0.38000 -0.03000 N -1.55900 -0.61100 -0.14000 Si -3.17900 -0.11100 0.02200 C -3.83800 -0.07900 1.81500 C -4.40200 -1.16900 -0.98600 C -3.48100 1.66800 -0.59300 H -2.96900 2.43300 0.01100 H -4.55900 1.88700 -0.53200 H -3.17600 1.79300 -1.64400 H -4.41700 -2.22100 -0.66400 H -4.12900 -1.15500 -2.05400 H -5.42800 -0.77900 -0.89500 H -3.76200 -1.06900 2.28900 H -4.89100 0.24200 1.86600 H -3.24600 0.62500 2.42500 C -1.31200 -2.02900 -0.33600 C -1.76600 -2.93100 0.82300 H -1.50200 -3.98900 0.65700 H -2.85800 -2.86900 0.93500 H -1.32400 -2.60100 1.77400 C 0.16600 -2.25900 -0.66300 C 1.10300 -2.73300 0.26200 C 2.45100 -2.87100 -0.08100 C 2.89400 -2.52600 -1.35500 C 1.97200 -2.05200 -2.29100 C 0.62800 -1.92700 -1.94500 H 0.77400 -3.02000 1.26300 H 3.94600 -2.63600 -1.62200 1142 H 3.16000 -3.25700 0.65500 H -0.10400 -1.58100 -2.67800 H 2.30200 -1.79800 -3.30200 H -1.84900 -2.41700 -1.23400 C 0.16900 -0.61200 3.07800 H 0.21100 -0.16100 4.08600 H 0.43800 -1.68000 3.16000 H -0.84400 -0.53300 2.66000 C 2.39600 -0.13200 2.44200 C 3.17700 0.73100 1.47700 H 2.66100 -1.19600 2.30000 H 2.65300 0.15600 3.47900 H 4.25900 0.55300 1.62300 H 2.95800 1.79800 1.66600 C 3.54700 1.03600 -0.82400 H 3.52200 2.13300 -0.69500 H 3.10400 0.78200 -1.79400 H 4.59900 0.69900 -0.79800 H 1.73000 3.70900 -0.63800 H 0.47300 0.51300 -3.45800 C 0.69500 3.55800 -0.29500 C -0.19600 1.24300 -2.98700 C -0.12100 3.00600 -1.44300 H -0.19100 3.76900 -2.24200 H 0.28500 4.53700 0.01300 C -0.38700 2.68000 1.63100 H -1.09000 0.72300 -2.59800 H -0.48700 1.99700 -3.73900 H -0.75500 3.70800 1.78900 H -1.14900 2.76600 -1.11700 H -1.20000 2.06400 1.20900 H -0.09100 2.24500 2.59200 O 0.75800 2.68100 0.80200 O 0.51700 1.84900 -1.92900 O 2.79200 0.39600 0.16900 O 1.03100 0.05700 2.19200 1143 Table C.2.160. Atomic coordinates and single point energies for C42. G = –1552.350548 GSP = –1553.756404 Na -1.32200 -0.10700 -0.04000 N 0.80900 0.62700 -0.12700 Si 1.12300 1.89100 0.96100 C -0.52100 2.30500 1.83600 C 1.76300 3.49100 0.14600 C 2.38300 1.57000 2.35800 H 2.13100 0.68000 2.95900 H 2.43600 2.43200 3.04300 H 3.38800 1.40300 1.94100 H 1.09000 3.85300 -0.64700 H 2.75000 3.31300 -0.31200 H 1.88400 4.29800 0.88600 H -1.23800 2.73000 1.11500 H -0.38200 3.03300 2.65000 H -0.97600 1.40000 2.27800 C 1.69400 0.32900 -1.21200 C 1.02600 -0.66400 -2.18100 H 0.80000 -1.59000 -1.62800 H 1.66300 -0.91900 -3.04200 H 0.08000 -0.23600 -2.55800 C 3.05400 -0.26400 -0.81800 C 4.18100 -0.09300 -1.62900 C 3.18600 -1.02500 0.34700 C 5.40600 -0.66800 -1.29200 C 4.40600 -1.60700 0.68900 C 5.52200 -1.43200 -0.13000 H 4.09500 0.51100 -2.53800 H 6.27500 -0.51500 -1.93400 H 2.30800 -1.11700 0.98800 H 4.49200 -2.19200 1.60700 1144 H 6.48000 -1.87900 0.14100 C -4.43100 -0.60800 -1.05200 H -4.28700 -1.69500 -1.03300 H -3.99300 -0.21400 -1.98600 H -5.51100 -0.37900 -1.03600 C -4.04000 1.28100 0.32300 C -3.50400 2.17300 -0.78800 H -3.52000 1.51800 1.26200 H -5.12200 1.46200 0.46300 H -3.50500 3.22100 -0.43400 H -4.13900 2.13100 -1.69400 C -1.42300 2.62800 -1.83600 H -0.41300 2.19900 -1.87400 H -1.83900 2.75100 -2.85100 H -1.37100 3.61500 -1.34400 H 0.38100 -2.25400 1.73500 H -0.65600 -3.60600 -1.74100 H -0.96800 -3.72000 0.66800 H -2.42100 -3.78300 -2.02000 C -1.61400 -3.06100 -1.79700 C -0.18600 -1.62500 2.44100 H -1.55200 -2.32400 -2.60600 H -0.28100 -2.14600 3.40900 H 0.36800 -0.68800 2.57000 C -1.94100 -3.21300 0.52400 H -2.70300 -4.00200 0.37600 H -2.35700 -3.02800 2.62800 C -2.32500 -2.37900 1.73300 H -3.32100 -1.94500 1.56900 H 1.94800 1.22900 -1.82700 O -3.78800 -0.08400 0.08200 O -2.20600 1.73900 -1.07500 O -1.46100 -1.29100 1.93500 O -1.87900 -2.37100 -0.60100 1145 Table C.2.161. Atomic coordinates and single point energies for C6. G = –2298.037393 GSP = –2299.903617 Na 1.14300 -0.73100 -0.29200 Na -1.42700 0.57500 0.34100 N 0.59500 1.55600 -0.26800 N -0.88100 -1.68000 0.46600 Si -0.90000 -2.32000 2.05300 Si 1.05100 2.24200 -1.76800 C 0.70300 -3.22100 2.54700 C -2.30300 -3.56200 2.36100 C -1.14100 -0.92600 3.33000 C -0.12900 3.55600 -2.47600 C 1.05400 0.84600 -3.06300 C 2.77900 3.04000 -1.88000 H -0.71800 0.04000 3.00800 H -0.67400 -1.17500 4.29600 H -2.21500 -0.77300 3.52000 H -2.15600 -4.50500 1.81300 H -3.27200 -3.13800 2.05200 H -2.36600 -3.81100 3.43200 H 0.90100 -4.05300 1.85200 H 0.65000 -3.63600 3.56600 H 1.57300 -2.54300 2.50900 H 2.82400 4.00800 -1.35700 H 3.02600 3.23400 -2.93700 H 3.56400 2.39700 -1.45600 H 0.04100 0.48300 -3.29600 H 1.65500 -0.01900 -2.73800 H 1.48900 1.20400 -4.01000 1146 H -1.13200 3.13000 -2.64400 H 0.23800 3.93900 -3.44100 H -0.24000 4.41300 -1.79300 C -1.42300 -2.48500 -0.61600 C 0.87000 2.14700 1.02900 C 0.73400 3.67300 1.10300 C -0.37100 -2.81500 -1.68900 H 0.01300 -1.89900 -2.17300 H -0.77500 -3.45500 -2.48900 H 0.47400 -3.33700 -1.21300 C -2.62900 -1.80500 -1.26300 C -3.91000 -2.35900 -1.17500 C -2.48800 -0.58200 -1.93600 C -5.01600 -1.71500 -1.73600 C -3.58600 0.06800 -2.49700 C -4.86000 -0.49800 -2.39600 H -4.04100 -3.31200 -0.65600 H -6.00500 -2.16900 -1.65500 H -1.49300 -0.13700 -2.04100 H -3.44500 1.01500 -3.02300 H -5.72200 0.00500 -2.83700 H -1.80300 -3.46700 -0.26400 H -0.28700 3.96200 0.81300 H 1.42300 4.17300 0.40600 H 0.93600 4.05500 2.11600 C 2.21600 1.66300 1.58100 C 2.28200 0.42300 2.23400 C 3.40900 2.37600 1.41200 C 3.49300 -0.09300 2.69600 C 4.67500 0.62200 2.50400 H 0.13300 1.76200 1.77700 H 1.35800 -0.13800 2.40700 H 3.51000 -1.05200 3.21900 C 4.62500 1.86000 1.86200 H 3.39300 3.35000 0.92100 H 5.54100 2.43500 1.71700 H 5.62500 0.22600 2.86500 N -3.41400 1.57900 1.22700 C -3.97800 2.52100 0.26000 C -3.01100 3.62300 -0.14200 C -4.29400 0.42800 1.38600 C -3.14800 2.21400 2.51000 H -4.91700 2.95900 0.66300 H -4.25800 1.93800 -0.63000 H -2.81900 4.33100 0.67800 H -3.42000 4.20000 -0.98300 1147 H -2.04600 3.19900 -0.46300 H -4.45900 -0.05200 0.41000 H -5.27700 0.71500 1.81000 H -3.82800 -0.31200 2.05300 H -2.39600 3.00700 2.40100 H -2.75500 1.47100 3.21700 H -4.06700 2.65900 2.94400 N 3.19200 -1.72200 -1.16100 C 3.22300 -2.39200 -2.46400 C 4.57500 -2.95700 -2.90000 C 3.47200 -2.63200 -0.05900 H 2.87100 -1.67000 -3.21800 H 2.47700 -3.20100 -2.43500 H 5.33700 -2.17000 -2.99000 H 4.47300 -3.43300 -3.88500 H 4.94800 -3.72000 -2.20200 H 2.77900 -3.48600 -0.09200 H 3.33000 -2.10800 0.89700 H 4.50900 -3.01900 -0.07000 C 4.05200 -0.54600 -1.10400 H 3.85000 0.10100 -1.97000 H 5.13000 -0.80000 -1.10000 H 3.84400 0.03300 -0.18900 1148 Table C.2.162. Atomic coordinates and single point energies for C7. G = –2454.97145 GSP = –2457.011609 Na 1.28900 -0.63700 -0.15200 Na -1.51900 0.31900 0.00900 N 0.42100 1.49700 -0.63700 N -0.68200 -1.80500 0.49300 Si -0.56100 -2.16200 2.16200 Si 0.70500 2.01400 -2.24300 C 1.24000 -2.34900 2.75200 C -1.45800 -3.74900 2.68200 C -1.30200 -0.75900 3.21900 C -0.65700 3.06800 -3.05900 C 0.80200 0.46500 -3.36000 C 2.30000 3.00100 -2.60600 H -1.19700 0.22900 2.73800 H -0.82800 -0.69200 4.21100 H -2.37800 -0.93300 3.37900 H -0.99100 -4.65000 2.25600 H -2.51200 -3.73100 2.36200 H -1.44000 -3.85200 3.77800 H 1.74700 -3.14100 2.17400 H 1.30300 -2.61700 3.81900 H 1.81000 -1.41400 2.62000 H 2.30800 3.98500 -2.11300 H 2.37200 3.18200 -3.69100 H 3.20900 2.46200 -2.29900 H -0.16000 0.27100 -3.86100 1149 H 1.07800 -0.45700 -2.82300 H 1.55000 0.61200 -4.15400 H -1.61800 2.52700 -3.06600 H -0.39100 3.28700 -4.10500 H -0.81600 4.02900 -2.54500 C -1.10700 -2.84100 -0.43200 C 0.46300 2.32300 0.55500 C 0.24800 3.83100 0.34700 C 0.03200 -3.32700 -1.34300 H 0.43800 -2.49000 -1.94000 H -0.29600 -4.10600 -2.04900 H 0.84200 -3.73500 -0.72100 C -2.28400 -2.38600 -1.29200 C -3.51700 -3.04400 -1.25100 C -2.15900 -1.27400 -2.13800 C -4.59700 -2.60000 -2.01700 C -3.23400 -0.82100 -2.90200 C -4.46400 -1.48200 -2.84000 H -3.63100 -3.91600 -0.60100 H -5.55100 -3.12800 -1.96600 H -1.19400 -0.76500 -2.21400 H -3.10800 0.04400 -3.55700 H -5.30800 -1.13300 -3.43700 H -1.47300 -3.74600 0.09400 H -0.71500 4.01700 -0.14600 H 1.03900 4.25500 -0.29000 H 0.26300 4.37300 1.30500 C 1.73900 2.11600 1.37900 C 1.70700 1.48300 2.62500 C 2.97700 2.57900 0.90600 C 2.86900 1.32700 3.38900 C 4.08500 1.81400 2.91800 H -0.35300 2.01800 1.25900 H 0.75500 1.11400 3.01400 H 2.81500 0.82800 4.35900 C 4.13400 2.44100 1.66900 H 3.02500 3.06600 -0.07000 H 5.08300 2.82800 1.29000 H 4.99100 1.70800 3.51600 N -3.70400 1.11500 0.74300 C -4.22400 1.91100 -0.36500 C -3.34700 3.11700 -0.66500 C -4.29200 -0.22600 0.81700 C -3.63500 1.83400 2.02100 H -5.26800 2.23900 -0.18900 H -4.25400 1.25300 -1.24900 1150 H -3.34200 3.84100 0.16300 H -3.70100 3.63900 -1.56500 H -2.30800 2.80200 -0.84800 H -4.21200 -0.65800 -0.19200 H -3.64600 -0.84500 1.46200 H -2.74500 2.48800 2.00900 H -3.44400 1.08300 2.80200 N 3.64100 -1.22400 -0.59100 C 3.72300 -2.56600 -1.15900 C 5.07400 -3.28400 -1.11100 C 4.11800 -1.08200 0.78500 H 3.37100 -2.49800 -2.20200 H 2.99000 -3.20100 -0.63300 H 5.87300 -2.71400 -1.60300 H 4.98900 -4.25800 -1.61400 H 5.38000 -3.47700 -0.07300 H 3.86400 -2.01500 1.31400 H 3.53200 -0.28300 1.27600 C 3.96900 -0.11700 -1.48800 H 3.15700 -0.01600 -2.22700 H 3.93200 0.80000 -0.87800 C -4.84800 2.68300 2.40800 H -5.77800 2.10100 2.42400 H -4.69300 3.10100 3.41300 H -4.99100 3.52800 1.72000 C -5.74100 -0.34100 1.28700 H -6.08200 -1.37900 1.16100 H -5.85100 -0.08300 2.35000 H -6.41200 0.30400 0.70100 C 5.28800 -0.17700 -2.26200 H 5.29400 -1.01700 -2.97200 H 5.40400 0.74600 -2.84700 H 6.16100 -0.27700 -1.60300 C 5.59500 -0.74800 0.99900 H 5.83700 0.24200 0.58500 H 5.80400 -0.70800 2.07800 H 6.26700 -1.48900 0.54500 1151 Table C.2.163. Atomic coordinates and single point energies for C31. G = –3510.122028 GSP = –3512.884786 Na -1.51300 0.10800 0.47900 Na 1.30000 0.44000 -0.26400 N -0.28200 2.06900 0.32400 N -0.04800 -1.44700 -0.56400 Si -0.40000 -1.55300 -2.23400 Si 0.34800 2.83100 1.71200 C -2.06200 -0.71300 -2.62300 C -0.44800 -3.32800 -2.89900 C 0.86800 -0.62600 -3.32200 C 2.14600 3.46900 1.57100 C 0.42400 1.49400 3.05900 C -0.61700 4.29000 2.46600 H 1.05200 0.40700 -2.97400 H 0.51000 -0.54800 -4.36100 H 1.83500 -1.15300 -3.34400 H -1.20400 -3.94400 -2.38900 H 0.52900 -3.81300 -2.74700 H -0.67200 -3.34200 -3.97700 H -2.88400 -1.21000 -2.08400 H -2.30000 -0.72400 -3.69900 H -2.05300 0.34600 -2.30900 H -0.79400 5.09000 1.73000 H -0.05200 4.72500 3.30600 H -1.59700 3.97000 2.85500 1152 H 1.14600 0.70200 2.79800 H -0.55800 1.01500 3.21000 H 0.74100 1.91600 4.02500 H 2.79300 2.68900 1.13500 H 2.53500 3.73200 2.56900 H 2.22100 4.36500 0.93600 C 0.20800 -2.61900 0.23200 C -0.54800 2.64400 -0.96800 C 0.37400 3.81800 -1.35400 C -0.12800 -2.33800 1.70900 H 0.46900 -1.48200 2.06700 H 0.07600 -3.19000 2.37400 H -1.19500 -2.08100 1.80900 C 1.63400 -3.19500 0.14300 C 2.62700 -2.61000 -0.64600 C 1.96900 -4.36100 0.85200 C 3.91500 -3.15100 -0.71100 C 3.24800 -4.90700 0.79300 C 4.23400 -4.29800 0.01000 H 2.38300 -1.71600 -1.21900 H 4.67400 -2.66600 -1.32700 H 1.20400 -4.85900 1.45400 H 3.47700 -5.81500 1.35300 H 5.23600 -4.72800 -0.04600 H -0.43600 -3.48200 -0.06300 H 1.42700 3.50300 -1.28600 H 0.22100 4.66000 -0.65800 H 0.17800 4.18100 -2.37400 C -1.99900 3.09000 -1.20200 C -2.50700 3.17100 -2.50700 C -2.82800 3.48000 -0.14700 C -3.78900 3.65700 -2.75500 C -4.59300 4.08100 -1.69500 H -0.38300 1.87600 -1.76300 H -1.87800 2.84800 -3.34200 H -4.16200 3.71000 -3.78000 C -4.10700 3.98800 -0.39200 H -2.45000 3.38900 0.87100 H -4.72700 4.31700 0.44600 H -5.59200 4.47600 -1.88500 O 3.43700 0.69300 -0.31400 P 4.87800 0.51200 0.07300 N 5.04400 -0.76500 1.12700 N 5.81600 0.28000 -1.28600 N 5.62000 1.82100 0.80800 C 6.30500 -1.44300 1.32600 1153 C 3.97900 -1.15800 2.03100 C 5.21400 -0.22400 -2.50700 C 7.22900 0.58100 -1.38400 C 5.65400 3.08200 0.08200 H 3.05100 -0.63900 1.76400 H 4.23000 -0.91700 3.08000 H 3.79600 -2.24300 1.94900 H 6.99900 -1.22000 0.50600 H 6.13400 -2.53200 1.33800 H 6.78700 -1.15900 2.28000 H 7.59700 0.99500 -0.43800 H 7.41200 1.32300 -2.18200 H 7.81200 -0.32400 -1.62900 H 4.14500 -0.41200 -2.34900 H 5.70100 -1.15800 -2.83300 H 5.31500 0.51500 -3.32000 C 5.65400 1.96900 2.25200 H 6.60400 3.60300 0.27900 H 4.82000 3.74000 0.38000 H 5.57700 2.89700 -0.99800 H 5.67400 0.98600 2.73700 H 4.78300 2.53300 2.62800 H 6.56800 2.51300 2.54200 O -3.36100 -0.75100 1.25200 P -4.73400 -1.10900 0.75600 N -5.67500 -1.57700 2.05800 N -4.61500 -2.28100 -0.43200 N -5.66000 0.07300 0.02400 C -5.05700 -1.97700 3.30900 H -4.01700 -1.63200 3.33100 H -5.07400 -3.07400 3.43900 H -5.59800 -1.52500 4.15600 C -7.06500 -1.95700 1.90900 H -7.19700 -3.05400 1.88600 H -7.47900 -1.53200 0.98600 H -7.65300 -1.56500 2.75600 C -5.78600 -2.79400 -1.11600 C -3.47300 -3.18400 -0.41900 H -5.52100 -3.05100 -2.15400 H -6.57400 -2.03100 -1.14500 H -6.19000 -3.70300 -0.63400 H -2.57400 -2.65500 -0.07500 H -3.28600 -3.53300 -1.44600 H -3.64500 -4.06900 0.22100 C -5.25800 0.54500 -1.30100 C -6.18300 1.14600 0.86200 1154 H -6.46500 0.75700 1.84700 H -7.07400 1.57800 0.38200 H -5.44000 1.95000 0.99600 H -4.40200 1.24200 -1.25200 H -6.10400 1.08100 -1.75700 H -4.98500 -0.29900 -1.94600 1155 Table C.2.164. Atomic coordinates and single point energies for C32. G = –1755.040992 GSP = –1756.42638 Na -0.70900 0.55800 1.11100 N -1.89500 -0.80900 -0.17200 Si -1.90500 -2.45900 0.23100 C -1.75200 -3.69600 -1.21200 C -3.45100 -3.01800 1.18900 C -0.39600 -2.74500 1.35300 H 0.51100 -2.32300 0.88700 H -0.21100 -3.81300 1.54800 H -0.53200 -2.25000 2.32900 H -4.36200 -2.89600 0.58200 H -3.58000 -2.42300 2.10700 H -3.38700 -4.08000 1.47600 H -2.63200 -3.63600 -1.87200 H -1.68200 -4.73300 -0.84700 H -0.86200 -3.49200 -1.82800 C -3.01300 -0.13500 -0.78600 C -2.99200 -0.20800 -2.31800 H -3.81300 0.35900 -2.78500 H -3.07400 -1.26000 -2.62500 H -2.03100 0.16500 -2.70600 C -3.02000 1.30700 -0.27200 C -2.55300 2.39800 -1.01100 C -2.43000 3.66500 -0.42800 C -2.78000 3.86600 0.90400 C -3.26800 2.78900 1.65300 C -3.38300 1.52900 1.06800 1156 H -2.28200 2.26300 -2.05900 H -2.68600 4.85400 1.35700 H -2.06000 4.50100 -1.02600 H -3.75200 0.68000 1.65100 H -3.56700 2.93700 2.69200 H -3.99600 -0.55500 -0.46800 H 4.45300 2.62000 -1.53700 H 3.96600 0.97600 -2.01700 C 4.35500 1.57900 -1.18700 H 3.86300 3.42900 0.72500 N 3.44700 1.52700 -0.05900 H 1.52800 2.10100 -1.61400 H 5.36600 1.21600 -0.92700 C 3.81800 2.37900 1.05600 H 4.04900 -1.32900 -1.32000 C 1.13300 1.15600 -2.00800 H 3.06600 2.29300 1.84800 H 4.80800 2.10900 1.46700 H 1.35600 1.10400 -3.08600 C 4.15100 -1.72700 -0.30200 P 2.37300 0.26400 0.19600 N 1.74200 0.02300 -1.32300 H 5.16700 -1.49600 0.06700 H 0.03600 1.14200 -1.88100 N 3.12300 -1.18100 0.56100 H 4.05100 -2.82300 -0.35700 O 1.44700 0.65000 1.32300 C 1.19300 -1.25900 -1.76500 H 1.43400 -1.40300 -2.83000 C 3.09600 -1.72300 1.90800 H 1.63100 -2.08300 -1.19100 H 0.09800 -1.27000 -1.62400 H 4.06200 -1.57100 2.42200 H 2.30400 -1.23400 2.48400 H 2.88700 -2.80400 1.87300 1157 Table C.2.165. Atomic coordinates and single point energies for C33. G = –1755.035557 GSP = –1756.422346 Na -0.04800 2.06500 -1.41500 N 1.82300 1.08800 -0.86900 Si 2.74100 1.86300 0.33600 C 1.81100 3.47600 0.74400 C 4.50400 2.33100 -0.19300 C 2.94100 0.93000 1.98500 H 1.96500 0.68800 2.43300 H 3.51100 1.52600 2.71600 H 3.47300 -0.02300 1.83200 H 4.49300 2.92000 -1.12400 H 5.10300 1.42500 -0.37900 H 5.02300 2.91700 0.58200 H 1.77900 4.14400 -0.13400 H 2.29200 4.03700 1.56000 H 0.77400 3.27100 1.06600 C 2.31800 -0.05800 -1.58500 C 1.34200 -0.44800 -2.70400 H 0.34800 -0.64300 -2.26600 H 1.66200 -1.34600 -3.25500 H 1.25100 0.38300 -3.42200 C 2.55500 -1.25800 -0.66900 C 3.82700 -1.80200 -0.48300 C 1.49200 -1.79000 0.07300 C 4.04100 -2.84000 0.42900 C 1.69600 -2.82600 0.97800 C 2.97700 -3.35400 1.16600 H 4.66800 -1.39400 -1.05100 H 5.04600 -3.24300 0.56800 H 0.49800 -1.35500 -0.06400 H 0.85600 -3.22600 1.55300 1158 H 3.14200 -4.15900 1.88300 H 3.29800 0.13500 -2.08000 H -4.55500 -1.76800 -0.04000 H -4.02800 0.12100 2.29700 C -5.12700 -0.83300 0.01400 H -5.66200 -0.81100 0.98100 H -5.88400 -0.84900 -0.78800 H -2.76400 -0.83500 3.12500 H -2.83400 -3.13500 0.20500 H -1.79000 -2.12500 1.25200 C -2.97700 0.12000 2.61000 C -1.96500 -2.45100 0.21800 N -2.16000 -1.30400 -0.64600 H -3.22200 -2.20600 -2.25300 N -2.10400 0.32400 1.47400 C -2.30800 -1.61500 -2.05800 H -2.83800 0.93200 3.34100 N -4.25200 0.30600 -0.14800 P -2.58600 0.21900 -0.11300 H -2.35400 -0.68500 -2.63800 H -1.08100 -3.01900 -0.11300 H -0.31400 -0.44700 2.31600 C -0.69000 0.45400 1.79800 C -4.90200 1.60300 -0.13900 H -5.37400 1.81900 0.83700 H -1.43900 -2.19400 -2.40500 H -5.68600 1.63700 -0.91300 H -0.07400 0.59100 0.89400 O -2.00200 1.30100 -0.98000 H -0.53000 1.32000 2.46100 H -4.16600 2.38400 -0.36300 1159 Table C.2.166. Atomic coordinates and single point energies for C34. G = –2574.460756 GSP = –2576.5365 Na 0.09700 0.39200 -0.90900 N 1.33300 2.19900 -0.37200 Si 1.81700 2.86300 -1.85800 C 3.69300 3.00800 -2.19100 C 1.13800 4.61000 -2.18400 C 1.13700 1.75000 -3.25300 H 1.44300 0.69400 -3.15300 H 1.49300 2.08800 -4.23800 H 0.03400 1.78400 -3.27600 H 1.58800 5.35100 -1.50400 H 0.04700 4.64100 -2.03600 H 1.35300 4.93400 -3.21400 H 4.17000 3.66800 -1.44800 H 3.89000 3.43300 -3.18800 H 4.19900 2.03100 -2.13500 C 1.23100 3.02700 0.80200 C 2.54100 3.13100 1.59600 H 2.47800 3.84000 2.43800 H 3.33800 3.47300 0.92000 H 2.84000 2.14600 1.98800 C 0.05600 2.59400 1.69100 C 0.16100 2.35400 3.06600 C -0.96000 2.01800 3.83100 C -2.21500 1.92300 3.23500 C -2.33600 2.14200 1.86000 C -1.21300 2.46500 1.10300 H 1.13000 2.44000 3.56100 1160 H -3.09500 1.68800 3.83900 H -0.85000 1.84400 4.90300 H -1.29700 2.64700 0.02800 H -3.31400 2.05900 1.37900 H 0.96800 4.08200 0.54100 H -5.96900 -1.22000 -0.62100 H -4.94900 -0.55600 1.56700 C -5.91900 -0.14400 -0.82200 H -6.49700 0.39200 -0.04800 H -6.40400 0.05000 -1.79500 H -4.26200 -2.04500 2.28000 H -3.88400 -4.22400 -0.93700 H -3.11700 -3.33500 0.40000 C -4.03600 -1.00600 1.97600 C -3.20300 -3.39500 -0.69200 N -3.74400 -2.15800 -1.22400 H -4.76100 -2.97000 -2.87400 N -2.95900 -0.94000 1.01400 C -4.00400 -2.20100 -2.65400 H -3.75600 -0.43800 2.87800 N -4.54100 0.29900 -0.84300 P -3.21400 -0.68400 -0.60800 H -4.38800 -1.23000 -2.99500 H -2.20700 -3.63400 -1.11000 H -1.65700 -2.16100 2.13500 C -1.63400 -1.23100 1.53800 C -4.35300 1.70300 -1.16200 H -4.85000 2.35000 -0.41900 H -3.09100 -2.42900 -3.23200 H -4.77900 1.93300 -2.15300 H -0.90500 -1.37800 0.73000 O -1.99600 -0.10700 -1.26600 H -1.28600 -0.40800 2.18700 H -3.28300 1.94000 -1.18500 H 4.81600 -3.31400 -0.20900 H 3.52800 -3.43700 2.17300 C 4.06100 -4.10000 -0.32300 H 4.21400 -4.86000 0.46500 H 4.21400 -4.59500 -1.29800 H 4.14700 -1.93300 2.91700 H 5.20300 0.33400 -0.15600 H 4.27000 -0.09700 1.29300 C 3.23200 -2.49000 2.64100 C 4.19600 0.08800 0.21300 N 3.73500 -1.11800 -0.47400 H 4.94000 -0.97100 -2.18900 1161 N 2.37300 -1.73500 1.75700 C 3.87500 -1.05400 -1.92200 H 2.69000 -2.72800 3.57000 N 2.73400 -3.52600 -0.25200 P 2.39300 -1.93100 0.10000 H 3.47100 -1.96700 -2.38100 H 3.52000 0.94500 0.03600 H 2.51800 0.04100 2.89500 C 1.76700 -0.54900 2.34100 C 1.64200 -4.47300 -0.35300 H 1.63500 -5.17800 0.49800 H 3.34200 -0.18400 -2.34500 H 1.73300 -5.06000 -1.28200 H 1.35000 0.10600 1.56100 O 1.06600 -1.53800 -0.49000 H 0.96100 -0.81800 3.04500 H 0.68900 -3.93200 -0.38100 1162 Table C.2.167. Atomic coordinates and single point energies for C35. G = –2574.464998 GSP = –2576.541491 Na 0.47900 0.35200 -0.26100 N 0.11400 -1.86800 -0.18300 Si 0.33900 -2.59600 1.33500 C 1.19800 -1.29900 2.43300 C 1.43800 -4.15700 1.33000 C -1.22400 -3.17800 2.25900 H -2.01000 -2.40800 2.27100 H -0.99600 -3.45900 3.30000 H -1.65500 -4.06000 1.75900 H 2.45900 -3.95900 0.96700 H 0.99800 -4.92500 0.67300 H 1.51400 -4.59300 2.33800 H 2.11900 -0.93700 1.94700 H 1.47000 -1.70600 3.42000 H 0.54400 -0.42600 2.60700 C -0.48900 -2.59300 -1.27000 C -0.25000 -1.86800 -2.60300 H -0.69300 -0.85700 -2.56200 H -0.69500 -2.39900 -3.45900 H 0.83300 -1.76200 -2.77100 C -1.99300 -2.80100 -1.08000 C -2.57700 -4.06900 -1.05800 C -2.82000 -1.68900 -0.87600 C -3.94600 -4.22800 -0.82500 C -4.18500 -1.83800 -0.64700 C -4.75600 -3.11500 -0.61600 H -1.94400 -4.94800 -1.21000 H -4.38000 -5.23000 -0.80100 H -2.36600 -0.69500 -0.88100 1163 H -4.80100 -0.95100 -0.48100 H -5.82400 -3.23700 -0.42800 H -0.06300 -3.61600 -1.39900 H 5.98900 -0.87400 0.62300 H 6.44500 0.53800 -1.24700 C 5.69500 -0.31200 1.51800 H 6.51600 0.37500 1.79200 H 5.56400 -1.03000 2.34500 H 6.56300 2.02800 -2.21100 H 4.71900 -1.46500 -2.91800 H 4.36000 0.28500 -2.92400 C 6.22800 1.61500 -1.24600 C 4.04800 -0.68600 -2.52400 N 4.11600 -0.68300 -1.06900 H 4.25500 -2.76900 -0.89900 N 4.80700 1.83900 -1.08200 C 3.65600 -1.94400 -0.48200 H 6.82400 2.09500 -0.44700 N 4.45300 0.39700 1.28400 P 3.85700 0.74000 -0.24100 H 3.79400 -1.93200 0.60600 H 3.02600 -0.90500 -2.88000 H 4.63300 3.59800 -2.21300 C 4.38600 3.22200 -1.20600 C 3.94100 1.11800 2.43600 H 4.65500 1.88800 2.78100 H 2.58200 -2.12000 -0.68200 H 3.75800 0.41700 3.26600 H 3.30300 3.28800 -1.05800 O 2.46500 1.29900 -0.13000 H 4.88900 3.87300 -0.46800 H 2.99100 1.59900 2.17600 H -4.25400 3.08100 2.19300 H -5.40800 1.85100 0.40800 C -3.93100 2.09700 2.55500 H -4.82200 1.46000 2.70000 H -3.45000 2.22400 3.54000 H -5.65000 2.77200 -1.10500 H -3.52000 5.51300 -0.53700 H -3.80200 4.06000 -1.52300 C -5.25000 1.83200 -0.67800 C -3.08300 4.55600 -0.85900 N -2.81500 3.73200 0.30700 H -2.38000 5.28100 1.65900 N -3.85000 1.63600 -0.98700 C -1.91500 4.36700 1.25900 1164 H -5.84100 0.99800 -1.08900 N -3.00300 1.49300 1.62000 P -2.65800 2.06900 0.10000 H -1.70900 3.68700 2.09500 H -2.16600 4.77300 -1.43700 H -3.89800 2.14500 -3.04800 C -3.54700 1.34000 -2.37500 C -2.55400 0.15800 1.99500 H -3.40100 -0.54800 2.04500 H -0.95200 4.63900 0.79200 H -2.07000 0.19000 2.98500 H -2.46400 1.22200 -2.49500 O -1.32700 1.59200 -0.40400 H -4.03300 0.39600 -2.67200 H -1.83200 -0.23900 1.26700 1165 Table C.2.168. Atomic coordinates and single point energies for C36. G = –3394.563871 GSP = –3396.64362 Na -0.07500 0.27800 -0.90900 N 1.88800 0.86100 -2.01000 Si 1.72200 2.04100 -3.21300 C -0.06100 2.69000 -3.11500 C 2.01500 1.40900 -4.98600 C 2.82500 3.59400 -3.06100 H 2.65200 4.10500 -2.09900 H 2.62000 4.31800 -3.86800 H 3.89300 3.32800 -3.10700 H 1.38600 0.53000 -5.19400 H 3.06600 1.11200 -5.13400 H 1.78300 2.18600 -5.73200 H -0.77100 1.88800 -3.37800 H -0.24400 3.54500 -3.78400 H -0.28200 3.01100 -2.08400 C 2.92100 -0.12700 -2.05400 C 2.42100 -1.43400 -1.40700 H 2.15700 -1.23000 -0.35700 H 3.16500 -2.24800 -1.43200 H 1.50800 -1.76600 -1.92600 C 4.23800 0.26600 -1.35900 C 5.33300 -0.61100 -1.31800 C 4.37100 1.50300 -0.72300 C 6.50000 -0.28400 -0.63000 C 5.54200 1.84400 -0.04100 C 6.60700 0.94600 0.02300 H 5.26900 -1.57200 -1.83700 1166 H 7.33500 -0.98700 -0.61000 H 3.52900 2.19000 -0.79100 H 5.62700 2.82400 0.43600 H 7.52200 1.20800 0.55800 H 3.22500 -0.40000 -3.09400 H -1.74700 -5.77100 -1.25100 H -2.64600 -4.97700 0.62100 C -2.47700 -5.31400 -1.93100 H -3.49400 -5.57600 -1.58400 H -2.33900 -5.76200 -2.93000 H -1.96500 -4.31600 2.12900 H 0.85200 -4.74800 1.13900 H 0.04000 -3.16900 1.39800 C -2.65200 -4.10600 1.28700 C 0.61800 -3.77000 0.68400 N -0.12900 -3.95500 -0.54800 H 0.83300 -5.64300 -1.36300 N -2.28200 -2.90200 0.57800 C 0.63400 -4.58700 -1.61200 H -3.66900 -4.00400 1.70000 N -2.28100 -3.88200 -2.00100 P -1.44200 -2.97300 -0.87100 H 0.07600 -4.54700 -2.55600 H 1.56000 -3.22900 0.49500 H -1.71000 -1.77300 2.27200 C -2.35500 -1.69500 1.37700 C -3.16700 -3.19900 -2.92400 H -4.22500 -3.26600 -2.60800 H 1.59900 -4.07700 -1.76100 H -3.08100 -3.65200 -3.92500 H -2.01600 -0.82600 0.79900 O -1.22800 -1.58600 -1.40200 H -3.39600 -1.52900 1.70500 H -2.87800 -2.14400 -2.99700 H 3.66800 1.13500 3.54500 H 4.11600 -0.14400 1.30900 C 3.23400 1.94100 2.93900 H 4.06300 2.44600 2.41800 H 2.75400 2.66900 3.62000 H 4.83900 -1.16400 2.59300 H 1.47100 1.09000 5.43100 H 2.41900 -0.34300 4.94800 C 4.00900 -1.08100 1.87000 C 1.40200 0.05700 5.04200 N 0.71200 -0.00000 3.77000 H -0.63900 1.56500 4.23800 1167 N 2.73300 -1.12400 2.57100 C -0.63100 0.54300 3.81100 H 4.09100 -1.91300 1.15000 N 2.30700 1.39800 1.96600 P 1.50800 -0.03100 2.27800 H -1.05100 0.57900 2.79600 H 0.86400 -0.54700 5.79200 H 3.19100 -2.48100 4.12000 C 2.48900 -2.36800 3.27500 C 1.68300 2.37000 1.07200 H 2.38900 3.20200 0.93200 H -1.28400 -0.08600 4.44200 H 0.74300 2.78500 1.48200 H 1.46500 -2.39600 3.66800 O 0.48800 -0.30800 1.21300 H 2.63300 -3.23200 2.60600 H 1.51000 1.92400 0.08000 H -2.93400 4.56700 -2.14200 H -4.39200 5.30100 -0.24300 C -3.32800 3.54800 -1.99900 H -4.19000 3.41400 -2.67800 H -2.53600 2.84200 -2.27200 C -4.73900 4.25800 -0.14500 H -5.67200 4.16000 -0.73100 N -3.71000 3.35300 -0.61000 H -4.97200 4.07300 0.91100 H -4.80500 -0.24400 -1.93200 H -2.27000 4.00600 1.43100 P -3.32200 1.90200 0.13700 C -4.29100 -0.38700 -0.96400 O -2.00500 1.39500 -0.36300 H -3.39700 4.13500 2.81100 C -2.72600 3.45100 2.26100 H -3.21700 -0.51600 -1.14800 N -4.51600 0.74500 -0.08000 H -4.67700 -1.31300 -0.50300 N -3.46100 2.30600 1.75400 H -3.30400 1.14500 3.51200 H -1.92400 3.13100 2.94700 C -4.05700 1.47200 2.77600 C -5.90700 1.11200 0.09200 H -4.50500 0.58000 2.32500 H -4.84100 2.02700 3.32200 H -6.01000 1.91500 0.83500 H -6.48200 0.24400 0.45400 H -6.36700 1.45400 -0.85400 1168 1169 Table C.2.169. Atomic coordinates and single point energies for C8. G = –2416.255832 GSP = –2418.259911 Na 1.34400 -0.33400 -0.05100 Na -1.54000 0.02700 -0.02600 N 0.14200 1.66200 -0.29300 N -0.30500 -1.87100 0.63000 Si -0.12600 -2.25700 2.29000 Si -0.39200 2.34000 -1.76300 C 0.67700 -0.78600 3.17100 C 0.96000 -3.78300 2.62500 C -1.76300 -2.65400 3.18100 C -1.80300 3.61600 -1.64500 C -1.09600 0.88400 -2.77100 C 0.89000 3.17400 -2.90300 H -2.47100 -1.81100 3.14800 H -1.59600 -2.90900 4.24000 H -2.25600 -3.52000 2.71000 H 1.99600 -3.63300 2.28200 H 0.56300 -4.67000 2.10500 H 0.99400 -4.01900 3.70000 H 1.70000 -0.60700 2.80000 H 0.75300 -0.96700 4.25500 H 0.09900 0.14100 3.02700 H 1.35800 4.04300 -2.41300 H 0.40100 3.53700 -3.82100 H 1.69700 2.48700 -3.20500 H -2.04500 0.48400 -2.37100 1170 H -0.38700 0.04100 -2.81800 H -1.31100 1.19100 -3.80700 H -2.52700 3.29200 -0.88200 H -2.33100 3.71000 -2.60800 H -1.43700 4.61600 -1.36500 C -0.70300 -2.98300 -0.22600 C 0.67000 2.36500 0.85200 C 0.30400 3.85700 0.94000 C 0.46600 -3.49800 -1.06700 H 0.87400 -2.69100 -1.70000 H 0.19500 -4.34900 -1.71200 H 1.26200 -3.82300 -0.38100 C -1.92300 -2.62100 -1.07700 C -3.11300 -2.28000 -0.41200 C -1.92500 -2.59500 -2.47500 C -4.26200 -1.93200 -1.11500 C -3.07400 -2.23600 -3.18700 C -4.24600 -1.90500 -2.51300 H -3.11800 -2.29800 0.68200 H -5.17500 -1.68000 -0.57200 H -1.02100 -2.85600 -3.02600 H -3.04800 -2.21500 -4.27800 H -5.14400 -1.63100 -3.07000 H -1.05200 -3.86100 0.36600 H -0.79000 3.97900 0.93600 H 0.71200 4.40200 0.07300 H 0.70900 4.32000 1.85200 C 2.19100 2.24500 1.00800 C 2.77100 2.06200 2.27000 C 3.03900 2.36600 -0.09900 C 4.15700 2.01100 2.42700 C 4.99100 2.15900 1.31900 H 0.27200 1.91400 1.78800 H 2.12000 1.95600 3.14300 H 4.58700 1.86100 3.41900 C 4.42500 2.34100 0.05600 H 2.59400 2.48700 -1.08800 H 5.07000 2.46600 -0.81700 H 6.07500 2.13100 1.43800 O -3.57300 1.09500 0.15500 C -3.93100 1.43800 1.50500 C -4.97900 0.45400 2.02300 H -4.60800 -0.57700 1.92300 H -5.92900 0.54200 1.47700 H -5.18800 0.64700 3.08500 C -4.43000 2.87900 1.58700 1171 C -2.63100 1.29200 2.28900 H -5.39500 3.00900 1.07600 H -3.69600 3.56600 1.13900 H -4.57100 3.16100 2.64000 H -2.77200 1.57900 3.33900 H -1.85200 1.93200 1.84500 H -2.28500 0.24500 2.28200 C -4.51600 1.36200 -0.85500 H -4.13900 0.90300 -1.77800 H -4.63500 2.44400 -1.02400 H -5.50000 0.91800 -0.62800 O 3.15700 -0.78700 -1.34100 C 3.91500 -1.72700 0.65000 C 4.20800 -2.96200 -1.52400 C 5.58500 -0.91800 -1.03300 C 3.29400 -0.20700 -2.61300 H 3.56000 -0.95200 -3.38100 H 4.04600 0.60000 -2.61500 H 2.31900 0.23000 -2.87200 C 4.23200 -1.59800 -0.83600 H 4.65600 -2.35800 1.16000 H 2.92500 -2.19300 0.78800 H 3.92100 -0.73000 1.12200 H 4.98700 -3.61200 -1.10100 H 4.40300 -2.86900 -2.60200 H 3.23200 -3.44200 -1.38300 H 6.36400 -1.50900 -0.53200 H 5.57400 0.08800 -0.59400 H 5.85400 -0.84600 -2.09700 1172 Table C.2.170. Atomic coordinates and single point energies for C27. G = –2911.403226 GSP = –2913.961724 Na -0.62600 0.88500 -0.48800 Na 1.17000 -1.38600 0.19300 N 1.17900 0.88200 1.11900 N -0.27000 -1.05900 -1.75200 Si 0.85800 -1.01100 -3.04700 Si 0.17500 1.07600 2.49200 C 2.11800 0.37000 -2.73900 C 0.14400 -0.67500 -4.77800 C 1.78300 -2.66400 -3.21400 C 0.96200 1.08700 4.22700 C -1.10800 -0.33000 2.39800 C -0.99200 2.59000 2.51100 H 2.19000 -2.95800 -2.23400 H 2.60600 -2.63400 -3.94800 H 1.08400 -3.45600 -3.52800 H -0.32000 0.32200 -4.84500 H -0.61300 -1.42100 -5.06500 H 0.95100 -0.71800 -5.52700 H 1.71000 1.32700 -3.10000 H 3.06800 0.19400 -3.26700 H 2.33300 0.48800 -1.66600 H -0.48800 3.56300 2.59000 H -1.70000 2.50100 3.35300 H -1.58400 2.60000 1.58000 H -0.71400 -1.27700 2.00200 H -1.94000 -0.03300 1.74100 H -1.55700 -0.53900 3.38300 H 1.74600 0.32800 4.35300 H 0.18200 0.90900 4.98500 1173 H 1.41100 2.06800 4.45100 C -1.46400 -1.82200 -2.11200 C 2.42500 1.60500 0.91200 C 3.46500 1.42100 2.02800 C -2.57600 -0.89900 -2.63400 H -2.79100 -0.12200 -1.88200 H -3.51100 -1.44000 -2.85600 H -2.23600 -0.39600 -3.55100 C -1.99900 -2.68700 -0.97700 C -1.82500 -4.07600 -0.99100 C -2.71700 -2.12500 0.08600 C -2.36200 -4.88200 0.01300 C -3.24800 -2.92300 1.10000 C -3.07900 -4.30900 1.06400 H -1.27100 -4.53000 -1.81700 H -2.22600 -5.96500 -0.02700 H -2.87600 -1.04400 0.11000 H -3.80200 -2.46000 1.92000 H -3.50400 -4.93600 1.84800 H -1.26400 -2.55000 -2.93100 H 3.55900 0.34800 2.26300 H 3.16800 1.93200 2.95500 H 4.45400 1.79000 1.71700 C 2.25700 3.09200 0.59200 C 2.42300 3.55300 -0.72000 C 1.94000 4.03300 1.58000 C 2.26200 4.90300 -1.04300 C 1.92800 5.82200 -0.05000 H 2.91200 1.20800 0.00300 H 2.69000 2.83600 -1.50100 H 2.40100 5.23600 -2.07300 C 1.76900 5.38000 1.26500 H 1.82900 3.70600 2.61700 H 1.52000 6.09300 2.05400 H 1.80100 6.87800 -0.29500 H 5.40600 -3.85900 -0.66200 C 4.34400 -3.65500 -0.90500 H 3.78300 -4.59100 -0.77500 H 4.27700 -3.37400 -1.96500 H 4.84000 -3.43000 1.57400 N 3.77800 -2.60400 -0.07600 C 3.87700 -2.93300 1.34000 C 4.28900 -1.28300 -0.41700 H 4.02500 -1.09400 -1.47000 H 2.53000 -4.56700 0.99900 C 2.72700 -3.82700 1.79000 1174 H 3.85900 -1.99700 1.92000 H 3.01600 -4.39700 2.69700 H 3.75700 -0.53800 0.19500 H 0.27400 -4.44100 0.99500 N 1.49500 -3.08100 2.03600 C 0.33900 -3.96700 1.98400 H 0.39300 -4.76300 2.75600 H 2.38900 -1.69000 3.35100 C 1.56300 -2.41300 3.33000 H 1.71100 -3.14400 4.15200 H -0.58800 -3.39800 2.14100 H 0.63700 -1.85800 3.52200 C -5.05400 0.51600 -0.78800 H -4.89000 0.80400 -1.83600 H -4.79800 -0.55400 -0.73500 H -5.01500 3.10800 -0.50800 H -5.28800 1.56200 1.80400 N -4.10300 1.26100 0.03800 C -4.01100 2.66600 -0.33800 C -4.34400 1.09500 1.46400 H -4.41500 0.02400 1.70400 H -3.36000 2.14000 -2.32400 C -3.15100 2.91900 -1.57400 H -3.58600 3.21700 0.51400 H -3.44500 3.88700 -2.03400 H -3.51100 1.53400 2.02900 H -1.17800 1.78800 -3.01400 N -1.71400 2.91400 -1.31000 C -0.96500 2.76500 -2.55200 H -1.20900 3.56500 -3.28200 H -0.24300 4.03500 -0.29800 C -1.28500 4.13500 -0.63400 H -1.35900 5.01300 -1.30800 H 0.11200 2.82700 -2.33700 H -1.90100 4.32900 0.25300 C 5.78800 -1.05300 -0.19300 H 6.38200 -1.57300 -0.98100 H 6.07800 -1.50400 0.77100 N 6.11200 0.35800 -0.13100 C 7.49000 0.57200 0.24500 H 7.68300 1.64800 0.36500 H 7.69900 0.07900 1.20500 H 8.20800 0.17600 -0.50800 C 5.77400 1.07200 -1.34400 H 6.02600 2.13600 -1.22500 H 6.31800 0.68400 -2.23400 1175 H 4.69600 1.01300 -1.54800 C -6.54000 0.69700 -0.46200 H -7.13800 0.47700 -1.37600 H -6.73100 1.75600 -0.22300 N -6.99900 -0.10700 0.65800 C -8.24100 0.39300 1.20200 H -8.53800 -0.20600 2.07400 H -8.11600 1.43500 1.53300 H -9.07600 0.36400 0.46800 C -7.09900 -1.51400 0.33300 H -7.40000 -2.08000 1.22500 H -7.84700 -1.71000 -0.46800 H -6.13100 -1.91500 0.00100 1176 Table C.2.171. Atomic coordinates and single point energies for C28. G = –1455.704153 GSP = –1456.98378 Na -0.54300 -0.14800 -0.20100 N 1.47100 -1.11800 -0.15900 Si 1.34500 -2.80200 -0.31200 C 1.75500 -3.83900 1.23400 C 2.35300 -3.55900 -1.73700 C -0.48100 -3.20100 -0.69500 H -1.15600 -2.79500 0.07900 H -0.66600 -4.28500 -0.74800 H -0.76900 -2.76000 -1.66400 H 3.43600 -3.43000 -1.58100 H 2.09700 -3.06900 -2.69000 H 2.15900 -4.63800 -1.84300 H 2.81000 -3.72500 1.52600 H 1.56400 -4.91200 1.07000 H 1.14200 -3.51300 2.09100 C 2.72300 -0.44000 -0.35600 C 3.86800 -0.95800 0.54200 H 4.79600 -0.37900 0.41100 H 4.08500 -2.01200 0.30900 H 3.55900 -0.90100 1.59800 C 2.60600 1.06000 -0.10600 C 1.98100 1.52700 1.05800 C 1.94500 2.88600 1.36400 C 2.52100 3.81600 0.49500 C 3.13400 3.36800 -0.67500 C 3.17600 2.00300 -0.96800 H 1.54500 0.78100 1.72800 1177 H 2.49600 4.88100 0.73100 H 1.47000 3.22900 2.28600 H 3.66900 1.65500 -1.88000 H 3.58600 4.08600 -1.36200 N -1.62000 0.21100 1.99300 N -3.07700 -0.54500 -0.57100 N -1.33800 1.79300 -1.33800 C -1.28700 1.46600 -2.75200 C -0.53800 2.97200 -1.04500 H -1.80300 2.22400 -3.38000 H -1.74300 0.48500 -2.94500 H -0.23700 1.41000 -3.06900 H -0.90900 3.86800 -1.58500 H 0.51100 2.79700 -1.32100 H -0.56400 3.18000 0.03400 C -2.68900 1.95300 -0.82700 C -3.59500 0.74400 -1.04100 H -3.19300 2.82600 -1.30000 H -2.60000 2.18800 0.24400 C -3.49200 -1.61100 -1.47900 H -3.79100 0.65400 -2.11900 H -4.58100 0.96400 -0.58100 H -4.59600 -1.68300 -1.55300 H -3.10300 -2.57500 -1.12800 H -3.08700 -1.43200 -2.48400 C -3.51900 -0.88500 0.78100 C -3.06600 0.06600 1.88000 H -3.15900 -1.90200 0.99900 H -4.63000 -0.93500 0.82300 H -3.50400 -0.28900 2.83800 H -3.50100 1.06100 1.70400 C -0.99400 -0.97200 2.57600 C -1.28300 1.39000 2.77500 H -1.28000 -1.87500 2.02100 H -1.29000 -1.10900 3.63700 H 0.10000 -0.89400 2.50300 H -1.66500 2.29800 2.28600 H -0.19200 1.48100 2.85800 H -1.70600 1.34200 3.80000 H 3.09700 -0.53300 -1.40300 1178 Table C.2.172. Atomic coordinates and single point energies for C29. G = –1455.709216 GSP = –1456.98804 Na -0.77200 -0.01500 -0.15500 N 1.04900 -1.29700 -0.03200 Si 0.67600 -2.65600 -0.97300 C -1.10300 -2.40300 -1.62300 C 0.69700 -4.33600 -0.07600 C 1.77800 -2.89800 -2.50600 H 1.68400 -2.03800 -3.18900 H 1.52500 -3.81200 -3.06600 H 2.83800 -2.97300 -2.21200 H 0.01900 -4.33300 0.79300 H 1.71100 -4.55500 0.29700 H 0.40300 -5.16500 -0.73900 H -1.82000 -2.27300 -0.79300 H -1.44400 -3.26500 -2.21500 H -1.16400 -1.51800 -2.28200 C 2.33200 -1.20000 0.61700 C 2.27600 -1.62300 2.09000 H 1.58700 -0.97000 2.65000 H 3.26100 -1.59800 2.58500 H 1.88500 -2.64800 2.14800 C 2.93000 0.19900 0.44000 C 3.29800 1.03900 1.49500 C 3.12600 0.66700 -0.86900 C 3.84300 2.30600 1.25200 C 3.68000 1.91800 -1.11700 C 4.04000 2.75100 -0.05100 1179 H 3.16800 0.70900 2.52600 H 4.12000 2.94400 2.09400 H 2.82500 0.01400 -1.69300 H 3.83600 2.25200 -2.14600 H 4.47300 3.73400 -0.24000 H 3.09700 -1.86800 0.15000 N -3.15100 0.81900 -0.62200 N -2.05500 -0.64400 1.74500 N -0.63100 2.35600 -0.55900 C 0.35200 3.07700 0.23500 C -0.14600 2.14700 -1.91500 H 1.29900 2.52000 0.24800 H -0.00500 3.17500 1.27100 H 0.54600 4.09300 -0.16400 H 0.84800 1.68200 -1.87100 H -0.06900 3.09800 -2.48300 H -0.81200 1.46900 -2.47200 C -1.93200 3.00100 -0.51900 C -3.04400 2.17300 -1.15800 H -1.90900 3.99100 -1.02700 H -2.17100 3.20700 0.53700 H -2.86100 2.09200 -2.24000 H -4.00100 2.72700 -1.05400 C -3.87600 -0.04500 -1.54200 H -3.35600 -0.08800 -2.50800 H -4.91300 0.31100 -1.71400 H -3.92300 -1.07000 -1.15100 C -3.77400 0.81400 0.70100 C -3.47400 -0.43700 1.52400 H -4.87600 0.92300 0.61200 H -3.42800 1.69800 1.25400 H -3.86400 -1.32500 1.00300 H -4.03600 -0.36500 2.48200 C -1.73900 -1.98700 2.20300 C -1.45300 0.35400 2.61200 H -2.17400 -2.72700 1.51500 H -2.12800 -2.18500 3.22300 H -0.64800 -2.12000 2.18900 H -1.58500 1.36500 2.19900 H -0.37200 0.16500 2.68100 H -1.88100 0.33800 3.63700 1180 Table C.2.173. Atomic coordinates and single point energies for C30. G = –1975.760506 GSP = –1977.629145 Na -0.83900 0.54600 0.20300 N -2.78800 -0.61800 0.01600 Si -4.02100 -0.02500 -0.99800 C -5.72100 0.14600 -0.15000 C -4.36200 -1.12800 -2.51800 C -3.60700 1.71600 -1.66400 H -2.53500 1.94600 -1.57100 H -4.16400 2.48800 -1.10800 H -3.88800 1.80700 -2.72500 H -4.55400 -2.16900 -2.20900 H -3.50000 -1.14400 -3.20500 H -5.23900 -0.78400 -3.08900 H -6.07200 -0.82100 0.24600 H -6.48800 0.51700 -0.84900 H -5.66300 0.85100 0.69600 C -3.12200 -1.85200 0.69600 C -3.47200 -1.62600 2.17600 H -2.60500 -1.23400 2.73200 H -3.83400 -2.53500 2.68300 H -4.26800 -0.87100 2.22500 C -2.06000 -2.94400 0.49700 C -1.62600 -3.81300 1.50600 C -1.51700 -3.11400 -0.78500 C -0.68300 -4.81100 1.24700 C -0.58900 -4.11800 -1.05500 C -0.16100 -4.97200 -0.03500 H -2.01900 -3.71000 2.51900 H -0.35600 -5.46800 2.05500 1181 H -1.85300 -2.43100 -1.56700 H -0.19500 -4.23600 -2.06700 H 0.56900 -5.75700 -0.24000 H -4.03700 -2.33400 0.26900 N -0.44800 3.21400 -0.86900 N -1.08300 2.36900 2.04400 N 0.32300 0.51400 -1.94200 C 1.20600 -0.63000 -1.81000 C -0.66900 0.25800 -2.97400 H 0.62700 -1.52300 -1.52900 H 1.94600 -0.43000 -1.02400 H 1.73200 -0.84200 -2.76700 C 1.09700 1.71900 -2.19000 C 0.28300 3.00400 -2.11400 H 1.56900 1.68700 -3.19900 H 1.92300 1.73700 -1.46000 H -0.45200 3.02800 -2.93200 H 0.98000 3.85300 -2.30100 C -1.27000 4.40400 -1.00600 H -1.95000 4.28100 -1.86100 H -0.65500 5.31400 -1.17200 H -1.88900 4.56600 -0.11600 C 0.45100 3.29200 0.27000 C -0.20600 3.46300 1.63700 H 1.17000 4.13500 0.14000 H 1.05400 2.36800 0.30300 H -0.72800 4.44000 1.71400 H 0.62600 3.51400 2.35800 C -2.45400 2.52800 1.56500 C -1.10300 2.24200 3.49400 H -0.09300 2.03900 3.87900 H -1.75500 1.40500 3.78100 H -1.48600 3.16000 3.98400 N 4.80800 -1.36900 -0.82200 C 6.06400 -1.67000 -0.16900 C 4.49000 -2.36700 -1.82200 N 3.65000 1.27200 0.48000 N 1.31900 -0.65800 1.55900 C 0.16600 -0.85700 2.42300 C 1.79900 -1.96400 1.12500 H 5.23000 -2.38800 -2.65200 H 3.49900 -2.16800 -2.25100 H 4.46700 -3.36400 -1.36000 H 6.92800 -1.61000 -0.86700 H 6.03000 -2.68700 0.24700 H 6.25000 -0.97600 0.66300 1182 C 4.77800 -0.03000 -1.38500 C 4.81200 1.12600 -0.39100 H 3.86100 0.06600 -1.98400 H 5.63400 0.11500 -2.08600 H 4.87900 2.04000 -1.00100 H 5.74900 1.10300 0.20900 C 3.62400 2.62700 0.99900 H 2.79800 2.75600 1.71000 H 3.48100 3.34900 0.18200 H 4.56600 2.88400 1.53100 C 3.66200 0.30900 1.57900 C 2.33100 0.09400 2.29000 H 4.40100 0.62900 2.34800 H 4.01100 -0.65200 1.18600 H 2.62000 -1.87300 0.40100 H 0.97200 -2.51400 0.65300 H 2.15700 -2.56700 1.98800 H 0.41700 -1.46900 3.31600 H -0.62500 -1.38100 1.87200 H -0.22300 0.10900 2.76300 H 1.88400 1.06200 2.57600 H 2.56600 -0.43100 3.24400 H -2.93200 3.43200 1.99900 H -3.04100 1.63700 1.83000 H -2.47500 2.60500 0.47400 H -1.26600 -0.61900 -2.68900 H -0.18900 0.06800 -3.95800 H -1.36200 1.10100 -3.07800 1183 Table C.2.174. Atomic coordinates and single point energies for C10. G = –2335.414234 GSP = –2337.323678 Na -1.87100 -0.05300 -0.09900 Na 1.04900 0.01900 -0.00700 N -0.52900 1.83800 -0.23700 N -0.41100 -1.81300 0.39100 Si -0.17500 -2.22100 2.03200 Si 0.09700 2.50300 -1.68200 C 0.71300 -0.74900 2.84300 C 0.88800 -3.76900 2.32800 C -1.78000 -2.53400 3.00400 C 1.23000 4.00600 -1.41400 C -1.23500 3.05400 -2.92100 C 1.15700 1.18500 -2.55200 H -2.46200 -1.67300 2.91700 H -1.59200 -2.72100 4.07300 H -2.30400 -3.41800 2.60300 H 1.91400 -3.62700 1.95500 H 0.46100 -4.64100 1.80600 H 0.94700 -4.02100 3.39900 H 1.75800 -0.67800 2.49300 H 0.74000 -0.83100 3.94000 H 0.19800 0.19400 2.58800 H 2.11600 1.02900 -2.03000 H 1.39100 1.50000 -3.58000 H 0.63500 0.21400 -2.61700 H -1.88300 3.83100 -2.48300 1184 H -1.87500 2.20100 -3.19700 H -0.80000 3.47200 -3.84300 H 0.68500 4.83600 -0.93700 H 1.65600 4.38400 -2.35700 H 2.06000 3.72300 -0.74600 C -0.86100 -2.86100 -0.51300 C -1.25400 2.77700 0.61400 C 0.25300 -3.32200 -1.45400 H 0.66000 -2.45800 -2.00100 H -0.08500 -4.08200 -2.17800 H 1.07400 -3.73900 -0.85200 C -2.08900 -2.35700 -1.27300 C -3.34100 -2.38600 -0.63500 C -1.99700 -1.69300 -2.50300 C -4.45500 -1.76500 -1.19700 C -3.11000 -1.06100 -3.06800 C -4.34100 -1.09000 -2.41600 H -3.42300 -2.88400 0.33500 H -5.41300 -1.79700 -0.67600 H -1.04100 -1.65700 -3.02900 H -3.01000 -0.54200 -4.02200 H -5.20800 -0.59400 -2.85400 H -1.21500 -3.77000 0.02500 C -0.42500 3.26400 1.80300 H -0.99100 3.94100 2.46400 H 0.45900 3.79600 1.42500 H -0.06600 2.41000 2.39600 C -2.58000 2.15100 1.05300 C -2.74600 1.48700 2.27400 C -3.92900 0.79600 2.56200 C -4.96700 0.75900 1.63400 C -4.81900 1.42500 0.41400 C -3.63900 2.10800 0.13000 H -1.94400 1.50100 3.01400 H -5.88800 0.21900 1.86000 H -4.03500 0.28400 3.52000 H -3.51200 2.60800 -0.83400 H -5.62600 1.40700 -0.32100 H -1.56000 3.69500 0.06100 C 5.17400 1.54000 1.14100 C 4.13000 1.50400 0.01100 O 2.89100 1.26500 0.65500 C 2.92200 2.04800 1.83700 C 4.32700 1.82100 2.40400 H 5.93100 2.31400 0.96000 H 5.69900 0.57800 1.22700 1185 H 4.28300 0.71100 -0.73000 H 4.08400 2.47500 -0.51400 H 2.10900 1.71900 2.49300 H 2.76200 3.11000 1.57700 H 4.32600 0.95000 3.07400 H 4.68400 2.68400 2.97800 C 5.04000 -2.00200 -0.63100 C 3.63900 -1.83500 -0.00300 O 2.84800 -1.19300 -0.98900 C 3.27400 -1.70600 -2.23700 C 4.80100 -1.73200 -2.13300 H 5.43200 -3.01100 -0.45000 H 5.76100 -1.29000 -0.20900 H 3.62600 -1.20500 0.89800 H 3.19300 -2.81400 0.24200 H 2.87900 -1.05500 -3.02800 H 2.87400 -2.72600 -2.37900 H 5.21600 -0.75700 -2.42700 H 5.24900 -2.49400 -2.78300 1186 Table C.2.175. Atomic coordinates and single point energies for C9. G = –2335.41935 GSP = –2337.32694 Na -0.83500 0.06700 0.00700 Na 2.01000 -0.43200 -0.49400 N 0.91900 1.61800 -0.53000 N 0.41400 -1.95000 0.16900 Si 0.93100 -2.35000 1.75100 Si 1.05700 2.00500 -2.19400 C -0.44800 -2.24800 3.05400 C 2.31500 -1.13600 2.25600 C 1.68800 -4.08300 1.92600 C -0.61600 2.34400 -3.03000 C 1.88100 0.55600 -3.11600 C 2.15100 3.51500 -2.56000 H 0.98300 -4.86900 1.61300 H 1.96900 -4.28800 2.97100 H 2.59300 -4.18200 1.30500 H 2.09400 -0.08800 1.99000 H 3.25800 -1.41500 1.75700 H 2.50000 -1.16400 3.34100 H -0.10900 -2.51600 4.06700 H -1.26700 -2.93200 2.77700 H -0.86800 -1.23000 3.08700 H 1.78900 4.41900 -2.04500 H 2.17000 3.73500 -3.63900 H 3.18900 3.33900 -2.23500 H 2.93500 0.43900 -2.81400 H 1.87700 0.75300 -4.19800 1187 H 1.38200 -0.41800 -2.97700 H -1.26700 1.45800 -2.94800 H -0.52700 2.60900 -4.09600 H -1.12800 3.17500 -2.51600 C -0.22400 -3.01100 -0.59400 C 0.74000 2.76000 0.35800 C 0.73200 -3.62700 -1.62700 H 1.09400 -2.84700 -2.31800 H 0.25600 -4.42200 -2.22300 H 1.60600 -4.04500 -1.10600 C -1.49900 -2.53700 -1.28700 C -2.74800 -3.05800 -0.93500 C -1.45600 -1.56800 -2.30100 C -3.91600 -2.63700 -1.57400 C -2.61600 -1.14700 -2.94800 C -3.85400 -1.68300 -2.58800 H -2.80100 -3.81500 -0.14800 H -4.87800 -3.06500 -1.28400 H -0.49300 -1.14600 -2.60100 H -2.55300 -0.40600 -3.74800 H -4.76400 -1.36200 -3.10000 H -0.55900 -3.85500 0.05000 C 2.01500 3.08000 1.15200 H 1.86600 3.89900 1.87400 H 2.81300 3.37200 0.45300 H 2.35300 2.18600 1.70000 C -0.44100 2.59000 1.31200 C -0.40600 1.66800 2.37000 C -1.48300 1.53600 3.24600 C -2.62500 2.32100 3.08100 C -2.68000 3.23200 2.02800 C -1.59800 3.36100 1.15600 H 0.48500 1.05500 2.52400 H -3.46300 2.22700 3.77500 H -1.42400 0.82500 4.07300 H -1.64200 4.08600 0.33800 H -3.56700 3.85500 1.89000 H 0.49700 3.69200 -0.20000 C -5.32700 0.69900 -0.17900 C -3.90700 1.13200 -0.52700 O -3.05600 0.31500 0.27700 C -3.80800 -0.38000 1.27300 C -5.17300 0.29800 1.28800 H -5.61300 -0.17600 -0.78300 H -6.06500 1.49500 -0.34500 H -3.73300 2.18900 -0.26900 1188 H -3.65000 0.97700 -1.58400 H -3.27200 -0.30800 2.23000 H -3.88800 -1.44100 0.98700 H -5.14100 1.19600 1.92500 H -5.97000 -0.36200 1.65300 C 5.93200 -0.59200 0.98400 C 5.24800 -1.29000 -0.21200 O 4.24700 -0.39300 -0.66800 C 4.72800 0.92500 -0.43800 C 5.36600 0.84300 0.94600 H 7.02300 -0.60400 0.86700 H 5.69600 -1.08900 1.93400 H 4.75700 -2.23900 0.04400 H 5.96700 -1.47900 -1.02700 H 3.87000 1.61100 -0.50200 H 5.46800 1.19200 -1.21400 H 4.58900 0.97100 1.71400 H 6.13100 1.61300 1.10400 1189 Table C.2.176. Atomic coordinates and single point energies for C11. G = –2335.4162 GSP = –2337.324007 Na 1.29000 0.85400 0.11100 Na -1.07400 -0.87600 0.34300 N 1.12100 -1.44600 -0.24800 N -0.92100 1.44600 0.48000 Si -1.48400 1.96300 2.00800 Si 1.48400 -1.79200 -1.88400 C -1.39000 0.46900 3.18400 C -3.27500 2.60400 2.12600 C -0.41700 3.31100 2.82300 C 3.21500 -2.53600 -2.14700 C 1.41100 -0.19500 -2.91400 C 0.26900 -3.01300 -2.69200 H 0.63600 2.98800 2.87100 H -0.74800 3.54000 3.84900 H -0.44900 4.24600 2.24200 H -3.99400 1.91500 1.65800 H -3.39600 3.58700 1.64500 H -3.55500 2.72400 3.18500 H -1.98600 -0.38900 2.82900 H -1.77100 0.73800 4.18200 H -0.35200 0.12500 3.32300 H 0.27400 -3.96600 -2.13800 H 0.51200 -3.23100 -3.74400 H -0.76000 -2.61800 -2.65700 H 2.05700 0.58800 -2.48200 1190 H 0.39400 0.21700 -2.99800 H 1.76500 -0.38600 -3.93900 H 3.99700 -1.91200 -1.68500 H 3.44200 -2.63300 -3.22100 H 3.29200 -3.54200 -1.70500 C -1.21600 2.10000 -0.78200 C 1.65200 -2.33600 0.77400 C -1.18600 3.63200 -0.74500 H -1.92100 4.03200 -0.02900 H -1.39300 4.07500 -1.73100 H -0.19400 3.96600 -0.40700 C -2.51400 1.55200 -1.38300 C -2.48700 0.29600 -2.00800 C -3.74800 2.20100 -1.27500 C -3.64700 -0.30200 -2.49600 C -4.91600 1.60800 -1.76100 C -4.87300 0.35600 -2.37200 H -1.52600 -0.21500 -2.13200 H -3.59200 -1.27600 -2.98700 H -3.80500 3.18300 -0.80300 H -5.86700 2.13500 -1.66700 H -5.78500 -0.09900 -2.76100 H -0.44100 1.81500 -1.53200 C 0.57800 -2.77900 1.77900 H 0.98200 -3.45300 2.54900 H -0.22700 -3.30800 1.24400 H 0.14100 -1.91300 2.30400 C 2.82200 -1.67400 1.50000 C 2.62300 -0.51700 2.26900 C 3.69400 0.16100 2.84700 C 4.99700 -0.31600 2.67900 C 5.20900 -1.47500 1.93600 C 4.13000 -2.14600 1.35400 H 1.60600 -0.14500 2.43000 H 5.83800 0.21100 3.13200 H 3.51100 1.06000 3.44000 H 4.30500 -3.04800 0.76300 H 6.22100 -1.86200 1.80500 H 2.06600 -3.27700 0.35100 C -5.39900 -1.76800 0.55900 C -4.16200 -0.96400 0.94100 O -3.05300 -1.84600 0.71900 C -3.50500 -3.17300 0.45500 C -4.96300 -3.19400 0.89700 H -5.59000 -1.67200 -0.52000 H -6.29600 -1.44000 1.10000 1191 H -4.17700 -0.67700 2.00600 H -4.02000 -0.05800 0.33300 H -2.86700 -3.88000 1.00300 H -3.41300 -3.38100 -0.62500 H -5.02900 -3.36900 1.98200 H -5.54900 -3.96900 0.38600 C 4.24100 2.43900 -2.58700 C 3.46000 2.99800 -1.38800 O 3.16300 1.87200 -0.58100 C 4.31500 1.03600 -0.61000 C 4.81600 1.10300 -2.05900 H 5.02200 3.13600 -2.91600 H 3.57000 2.26300 -3.43700 H 2.51400 3.48700 -1.65700 H 4.07400 3.71000 -0.80900 H 4.01600 0.03100 -0.27700 H 5.06500 1.42900 0.09800 H 4.42600 0.25600 -2.63900 H 5.91100 1.06500 -2.10600 1192 Table C.2.177. Atomic coordinates and single point energies for C15. G = –1167.678031 GSP = –1168.637285 Na 1.65000 0.77400 -0.01400 N -0.45500 0.59200 0.44000 Si -1.23400 2.04400 0.01400 C 0.14400 3.18400 -0.66800 C -2.05300 2.95300 1.46600 C -2.55300 1.95400 -1.34900 H -2.14800 1.48300 -2.25800 H -2.92900 2.95500 -1.61400 H -3.40900 1.34200 -1.02100 H -1.33500 3.12300 2.28300 H -2.88200 2.35100 1.87100 H -2.47000 3.92500 1.16000 H 0.91300 3.40200 0.09600 H -0.26000 4.15600 -0.98900 H 0.63000 2.74500 -1.55800 C -1.14500 -0.44500 1.15500 C -0.16600 -1.55200 1.57700 H 0.29400 -1.99200 0.67400 H -0.65900 -2.36200 2.13500 H 0.62700 -1.12100 2.21100 C -2.29500 -1.08900 0.37500 C -3.51700 -1.37900 0.98700 C -2.14000 -1.40400 -0.98000 C -4.56000 -1.96800 0.26900 C -3.17200 -1.99900 -1.70000 C -4.39000 -2.28200 -1.07700 H -3.65600 -1.12700 2.04300 H -5.51200 -2.17600 0.76300 H -1.19700 -1.13900 -1.46400 H -3.03500 -2.23400 -2.75700 H -5.20400 -2.73800 -1.64300 H -1.60600 -0.07400 2.10000 1193 C 5.97100 -0.63600 -0.50400 C 4.80900 0.22000 -0.99900 O 3.73200 -0.03300 -0.08900 C 4.05400 -1.12600 0.78300 C 5.23700 -1.82100 0.12500 H 6.54700 -0.09500 0.26100 H 6.65600 -0.92100 -1.31200 H 4.49600 -0.07600 -2.01300 H 5.03100 1.29600 -1.00000 H 3.16600 -1.76400 0.89000 H 4.32400 -0.72800 1.77500 H 4.88700 -2.51500 -0.65400 H 5.84600 -2.38600 0.84100 1194 Table C.2.178. Atomic coordinates and single point energies for C17. G = –1399.754029 GSP = –1400.976329 Na -0.03800 -0.55900 -1.44900 N -1.67800 0.58200 -0.51400 Si -3.05400 -0.27300 -0.00100 C -2.86900 -2.09200 -0.51700 C -4.70300 0.35200 -0.71500 C -3.28600 -0.28000 1.89200 H -2.43300 -0.77900 2.38400 H -4.20800 -0.79300 2.20700 H -3.32800 0.75100 2.27900 H -4.70700 0.26800 -1.81300 H -4.86000 1.41300 -0.46200 H -5.56300 -0.21400 -0.32300 H -2.75500 -2.19000 -1.60900 H -3.74900 -2.68300 -0.21900 H -1.98500 -2.54100 -0.03900 C -1.68200 2.02100 -0.39700 C -1.94000 2.70700 -1.74400 H -1.11500 2.49100 -2.44500 H -2.05600 3.80000 -1.66400 H -2.86200 2.29200 -2.17400 C -0.40100 2.53500 0.27400 C 0.32900 3.64200 -0.17200 C 0.06600 1.86000 1.41400 C 1.49200 4.05500 0.48900 C 1.21300 2.27400 2.08300 C 1.94100 3.37400 1.61700 H -0.00200 4.19600 -1.05100 1195 H 2.04700 4.91900 0.11600 H -0.51000 1.00000 1.76100 H 1.54500 1.74200 2.97800 H 2.84500 3.69900 2.13500 H -2.49300 2.38800 0.28000 C 3.68200 0.49800 0.19100 C 2.76800 0.95700 -0.93700 O 2.19500 -0.25500 -1.41700 C 3.21900 -1.24200 -1.43700 C 4.23600 -0.83400 -0.34700 H 3.07800 0.34200 1.09700 H 4.46300 1.23000 0.42900 H 3.34100 1.44500 -1.74700 H 1.95800 1.62300 -0.61500 H 3.69200 -1.26100 -2.43300 H 2.74000 -2.21300 -1.25400 H 5.23500 -0.70100 -0.78400 H 4.32200 -1.59300 0.44200 H -0.83600 -3.24800 1.92700 H 0.71600 -3.17300 2.80000 H 1.70600 -1.75100 1.08000 C 0.25700 -3.22000 1.80400 H 0.01200 -1.15700 1.04400 C 0.65300 -2.04500 0.91900 C 0.73200 -4.40800 0.96500 O 0.50600 -2.52200 -0.42400 H 0.24500 -5.35500 1.22700 H 1.82000 -4.53800 1.07400 C 0.39000 -3.94400 -0.44900 H -0.64300 -4.21400 -0.72300 H 1.07100 -4.34400 -1.21500 1196 Table C.2.179. Atomic coordinates and single point energies for C19. G = –1631.824525 GSP = –1633.309602 Na -0.93400 0.31500 -0.42100 N 1.20500 0.90200 -0.49200 Si 1.59100 1.80300 0.89700 C -0.04100 2.03200 1.86700 C 2.27300 3.54300 0.55200 C 2.84300 1.01500 2.10000 H 2.55900 -0.01400 2.37400 H 2.94800 1.60100 3.02800 H 3.83400 0.95300 1.62200 H 1.60000 4.10400 -0.11500 H 3.25600 3.48000 0.06000 H 2.40400 4.12100 1.48000 H -0.73100 2.66900 1.28700 H 0.12100 2.51300 2.84400 H -0.54200 1.06700 2.05400 C 2.13900 0.84400 -1.58800 C 1.50700 0.17500 -2.81400 H 1.21500 -0.85900 -2.56800 H 2.19500 0.14000 -3.67300 H 0.60100 0.72700 -3.10700 C 3.43500 0.12200 -1.21500 C 4.67600 0.75900 -1.29000 C 3.39500 -1.18800 -0.72000 C 5.84500 0.11500 -0.87400 C 4.55500 -1.84000 -0.31200 C 5.78900 -1.18600 -0.38300 H 4.72400 1.78400 -1.66900 H 6.80300 0.63700 -0.93200 1197 H 2.42600 -1.68900 -0.64500 H 4.50300 -2.86200 0.06900 H 6.69900 -1.69100 -0.05400 H 2.45900 1.85800 -1.92600 C -1.99800 -3.49800 -0.95800 C -1.23100 -2.40100 -1.69000 O -2.07100 -1.24400 -1.65000 C -3.35500 -1.57600 -1.13600 C -3.44900 -3.09500 -1.22500 H -1.78500 -3.44100 0.12000 H -1.74600 -4.50300 -1.31800 H -1.03900 -2.66300 -2.74300 H -0.26600 -2.16000 -1.21500 H -4.12000 -1.05300 -1.73000 H -3.43100 -1.23100 -0.09100 H -3.75200 -3.40000 -2.23800 H -4.16400 -3.51900 -0.50800 H 0.48400 -0.60800 3.38500 H 1.03500 -2.29600 3.52600 H 0.31700 -2.79600 1.24100 C 0.26600 -1.64500 3.09000 H 0.92000 -1.11000 1.03500 C 0.20000 -1.74700 1.57300 C -1.16100 -2.03300 3.48000 O -1.12000 -1.29400 1.23500 H -1.45700 -1.68600 4.47800 H -1.27900 -3.12600 3.44800 C -1.98200 -1.37700 2.36800 H -2.29800 -0.35700 2.64800 H -2.88100 -1.95700 2.10100 H -3.20800 2.11300 1.58300 H -4.32600 0.80800 1.08300 C -3.80100 1.71900 0.74500 H -5.75000 2.73100 0.66700 C -4.77900 2.73300 0.15700 O -2.92100 1.37800 -0.32100 H -4.35800 3.74800 0.21900 H -5.50200 1.39900 -1.39800 C -4.84800 2.28000 -1.30300 C -3.39700 1.89300 -1.56500 H -5.21200 3.05500 -1.98900 H -2.79300 2.77100 -1.85000 H -3.26900 1.11700 -2.33300 1198 Table C.2.180. Atomic coordinates and single point energies for C20. G = –1863.890307 GSP = –1865.638841 Na 0.86600 0.28800 -0.03100 N -0.94900 -1.12300 -0.08000 Si -1.07000 -2.25300 1.18200 C 0.29800 -1.89300 2.45800 C -0.86600 -4.07100 0.63300 C -2.68100 -2.26300 2.20200 H -2.85700 -1.28300 2.67700 H -2.64400 -3.02300 3.00000 H -3.55500 -2.47800 1.56600 H 0.09000 -4.24700 0.11500 H -1.67200 -4.36400 -0.05900 H -0.91300 -4.75200 1.49800 H 1.24500 -1.62700 1.96300 H 0.47700 -2.76400 3.10900 H 0.01400 -1.05000 3.10600 C -1.71700 -1.31000 -1.27900 C -1.01800 -0.64300 -2.48100 H -0.85400 0.42500 -2.26600 H -1.59400 -0.72100 -3.41500 H -0.03700 -1.11600 -2.64200 C -3.17200 -0.80700 -1.22700 C -4.06900 -1.11400 -2.26000 C -3.64400 -0.04000 -0.16000 C -5.38300 -0.65600 -2.23800 C -4.96000 0.42700 -0.13100 C -5.83500 0.12400 -1.17100 H -3.72800 -1.73500 -3.09400 H -6.06300 -0.91200 -3.05300 1199 H -2.95100 0.16700 0.65700 H -5.30600 1.02200 0.71700 H -6.86600 0.48200 -1.14800 H -1.81800 -2.38600 -1.56500 C 3.80000 1.08700 -3.03800 C 2.44300 1.23800 -2.35700 O 2.72700 1.43000 -0.97400 C 4.08800 1.13200 -0.69400 C 4.61900 0.41900 -1.93300 H 4.21900 2.07500 -3.28100 H 3.74500 0.50000 -3.96400 H 1.83600 0.32300 -2.48200 H 1.84700 2.08900 -2.71700 H 4.13700 0.51900 0.21600 H 4.63500 2.07400 -0.51100 H 4.37000 -0.65100 -1.87500 H 5.70400 0.52700 -2.05900 H -1.89600 4.00700 0.58400 H -2.42000 4.56100 -1.02200 H -1.44200 2.63700 -2.12100 C -1.61300 4.05300 -0.47900 H -1.96300 1.86400 -0.60200 C -1.33000 2.65700 -1.02200 C -0.24700 4.72100 -0.64000 O 0.02900 2.38300 -0.67900 H -0.10300 5.59900 0.00300 H -0.10400 5.03600 -1.68500 C 0.70600 3.57700 -0.29600 H 0.91900 3.52800 0.78600 H 1.66800 3.62500 -0.82300 H 3.33300 -1.51900 1.51700 H 4.47700 -1.89400 0.19200 C 3.43800 -2.03400 0.55000 H 3.88500 -4.14300 0.97400 C 3.07300 -3.51000 0.59500 O 2.52600 -1.45600 -0.37300 H 2.18400 -3.65300 1.22800 H 3.64500 -3.91200 -1.45900 C 2.72600 -3.76600 -0.87200 C 2.02800 -2.46300 -1.26700 H 2.08300 -4.64300 -1.02100 H 0.93500 -2.50600 -1.13300 H 2.25200 -2.16200 -2.30400 H -1.13200 0.76000 1.86600 C -0.52800 1.55900 2.32500 H -0.76700 0.62300 4.27200 1200 C -0.60900 1.62600 3.84700 H -1.42300 2.27500 4.19600 O 0.84800 1.31100 2.02200 C 1.65100 1.41600 3.18900 C 0.78400 2.14400 4.21100 H 1.07800 1.93100 5.24700 H 0.84100 3.23200 4.05200 H 2.57600 1.95400 2.93400 H -0.81900 2.52100 1.86700 H 1.91700 0.40400 3.54400 1201 Table C.2.181. Atomic coordinates and single point energies for C14. G = –1167.682086 GSP = –1168.642051 Na -0.09600 -0.46800 -1.78200 N -1.13400 0.61500 -0.20100 Si -2.74500 0.12800 -0.00800 C -4.09400 1.47000 -0.02700 C -3.07900 -0.88800 1.56800 C -3.13800 -0.98500 -1.50900 H -3.03000 -0.41200 -2.44600 H -4.17500 -1.35300 -1.47900 H -2.49300 -1.88000 -1.57200 H -2.86200 -0.28300 2.46400 H -2.44300 -1.78600 1.61900 H -4.13000 -1.21100 1.63600 H -4.09600 2.05600 0.90500 H -5.09500 1.02400 -0.13700 H -3.93400 2.17000 -0.86100 C -0.39200 1.41500 0.73200 C -0.89600 2.86600 0.85000 H -0.27000 3.47000 1.52600 H -1.92800 2.87300 1.23000 H -0.90300 3.33700 -0.14500 C 1.08600 1.44500 0.34500 C 1.46600 1.79600 -0.96100 C 2.80600 1.82000 -1.34500 C 3.80500 1.49800 -0.42200 C 3.44600 1.16700 0.88300 C 2.10000 1.14100 1.25900 H 0.68200 2.08600 -1.66900 H 4.85600 1.51800 -0.71700 H 3.07800 2.10900 -2.36200 H 1.82500 0.87700 2.28400 1202 H 4.21800 0.92300 1.61600 H -0.41000 1.00000 1.76900 C 0.69600 -2.26400 1.34900 C 0.11500 -2.82700 0.06500 O 0.93300 -2.26400 -0.96400 C 2.25300 -2.02400 -0.45100 C 2.19500 -2.33600 1.04900 H 0.39900 -2.82800 2.24300 H 0.35900 -1.22000 1.45100 H -0.92500 -2.51900 -0.11200 H 0.17800 -3.92900 0.02800 H 2.51100 -0.96800 -0.63500 H 2.97200 -2.66000 -0.99000 H 2.79100 -1.62600 1.63500 H 2.57300 -3.35000 1.24800 1203 Table C.2.182. Atomic coordinates and single point energies for C16. G = –1399.757176 GSP = –1400.978377 Na 0.33200 -0.09200 0.45600 N -1.64200 0.88100 0.22800 Si -3.01800 0.26500 1.00000 C -4.40900 -0.37400 -0.14100 C -3.86500 1.46700 2.20400 C -2.43200 -1.25100 1.99200 H -1.82800 -1.90900 1.34400 H -3.26000 -1.85100 2.39900 H -1.79700 -0.93400 2.83600 H -4.26200 2.34400 1.66800 H -3.14900 1.83400 2.95600 H -4.70600 0.99200 2.73300 H -4.87400 0.45200 -0.70200 H -5.20500 -0.87900 0.42900 H -4.01500 -1.08900 -0.88200 C -1.51700 2.20300 -0.32300 C -2.41700 2.46500 -1.54000 H -2.22900 3.44800 -2.00100 H -3.47100 2.42700 -1.22700 H -2.27600 1.67900 -2.29900 C -0.04200 2.41700 -0.66700 C 0.53800 1.77800 -1.77400 C 1.90900 1.86300 -2.01900 C 2.73400 2.58800 -1.15600 C 2.17300 3.22500 -0.05000 C 0.80000 3.13500 0.19100 H -0.10100 1.20400 -2.44900 H 3.80500 2.66400 -1.35200 H 2.33600 1.36600 -2.89300 H 0.36200 3.62900 1.06200 1204 H 2.80600 3.80000 0.62900 H -1.76200 3.00300 0.41500 C 4.36000 -1.71300 0.53200 C 3.28700 -0.95000 -0.24900 O 2.53700 -0.28400 0.75600 C 3.49000 0.25000 1.66100 C 4.58500 -0.82600 1.78000 H 5.27300 -1.86100 -0.05900 H 3.98400 -2.70300 0.82400 H 2.59600 -1.57600 -0.82800 H 3.73900 -0.19700 -0.91900 H 2.97800 0.47900 2.60500 H 3.89400 1.18700 1.24200 H 4.47200 -1.41000 2.70200 H 5.58400 -0.37200 1.79500 H -1.44400 -1.01600 -1.41800 H -0.46400 -1.93800 -2.62300 C -0.91200 -1.96100 -1.61400 H -2.46400 -3.06100 -0.58500 C -1.75800 -3.21100 -1.41600 O 0.14000 -2.07300 -0.64100 H -2.33200 -3.47900 -2.31200 C 0.25400 -3.41700 -0.17300 C -0.69400 -4.24400 -1.04100 H 1.30300 -3.74000 -0.25000 H -1.09400 -5.11700 -0.50900 H -0.04300 -3.45200 0.88900 H -0.17500 -4.60000 -1.94300 1205 Table C.2.183. Atomic coordinates and single point energies for C18. G = –1631.82335 GSP = –1633.308281 Na 0.23600 -0.07900 -0.22200 N -1.86700 -0.74400 -0.54900 Si -3.21900 0.23500 -0.84200 C -4.39400 0.51600 0.63900 C -4.33300 -0.35200 -2.26900 C -2.61000 1.97800 -1.31400 H -1.74900 2.26500 -0.68600 H -3.39100 2.74600 -1.19600 H -2.27600 1.99000 -2.36400 H -4.80600 -1.32100 -2.04300 H -3.74200 -0.47900 -3.19000 H -5.13900 0.37000 -2.47600 H -4.79100 -0.43700 1.02200 H -5.25100 1.15100 0.36000 H -3.87000 1.01200 1.47200 C -1.92000 -2.18200 -0.64200 C -2.96100 -2.83900 0.28400 H -2.91300 -3.93900 0.25200 H -3.97400 -2.53100 -0.01600 H -2.81100 -2.50400 1.32300 C -0.53500 -2.76000 -0.35100 C 0.00700 -2.67800 0.94100 C 1.28400 -3.15900 1.22100 C 2.05600 -3.73000 0.20700 C 1.53700 -3.80800 -1.08300 C 0.25500 -3.32500 -1.35600 H -0.60000 -2.22900 1.73200 1206 H 3.05500 -4.11300 0.42400 H 1.67900 -3.10000 2.23900 H -0.15100 -3.39000 -2.36900 H 2.13200 -4.25200 -1.88500 H -2.17000 -2.53400 -1.67100 C 4.55000 0.17100 -0.47200 C 3.30400 -0.23100 0.31400 O 2.36300 -0.67300 -0.65600 C 2.81600 -0.39000 -1.97200 C 3.93800 0.62800 -1.79700 H 5.19900 -0.70300 -0.63500 H 5.13900 0.94700 0.03300 H 2.87600 0.63000 0.85900 H 3.48000 -1.04900 1.02900 H 1.96900 -0.01300 -2.56600 H 3.17900 -1.32100 -2.44100 H 3.50700 1.63500 -1.68400 H 4.64700 0.63700 -2.63500 H 1.30300 2.63700 1.13200 H 2.43900 3.35000 -0.06500 C 1.39000 3.04400 0.11600 H -0.53000 4.01400 0.31700 C 0.42300 4.17900 -0.20700 O 1.02900 2.01400 -0.78900 H 0.80900 5.16200 0.09300 C 0.75100 2.62600 -2.04300 C 0.22900 4.04400 -1.73000 H 1.67800 2.66600 -2.64300 H -0.82600 4.15200 -2.01000 H 0.01800 1.99500 -2.56500 H 0.80600 4.80000 -2.27900 H -1.23200 1.70100 1.46400 H -1.61600 0.14600 2.22200 H -1.75400 1.44100 4.24000 H -0.72300 2.72700 3.59400 C -0.92900 1.00800 2.26200 C -0.84400 1.63800 3.66000 O 0.39600 0.56200 1.98000 C 0.41300 0.98200 4.28000 H 0.20300 0.46300 5.22300 H 1.18800 1.73500 4.47900 C 0.87900 0.00800 3.18900 H 0.43600 -0.99300 3.34200 H 1.96800 -0.10000 3.11100 1207 Table C.2.184. Atomic coordinates and single point energies for C22. G = –2565.480392 GSP = –2567.649345 Na 1.32200 -0.19300 0.09100 Na -1.70900 0.29000 -0.05700 N -0.05600 1.78500 0.83000 N -0.45000 -1.58600 -0.83100 Si -1.02900 -1.84800 -2.43200 Si -0.63500 1.81700 2.44700 C -0.51200 -3.50400 -3.21400 C -0.49700 -0.53100 -3.68600 C -2.94100 -1.84300 -2.56000 C 0.51200 1.13400 3.80600 C -2.19900 0.73700 2.59800 C -1.16100 3.50400 3.16000 H -3.36800 -2.81500 -2.26500 H -3.28700 -1.62700 -3.58400 H -3.37200 -1.09000 -1.87800 H -0.75500 0.50000 -3.40500 H -1.01700 -0.74900 -4.63300 H 0.58100 -0.57500 -3.89100 H -0.87400 -3.54400 -4.25400 H -0.94200 -4.36900 -2.68800 H 0.58100 -3.63200 -3.23600 H -0.33300 4.23000 3.15600 H -1.47100 3.36600 4.20800 H -2.00600 3.95300 2.61600 H -2.98600 1.02600 1.88300 H -2.61900 0.86200 3.60800 1208 H -2.00600 -0.33900 2.47400 H 0.86400 0.12000 3.56600 H -0.03500 1.08200 4.76200 H 1.39000 1.77600 3.97200 C -0.65100 -2.76100 0.02100 C 0.77000 2.91500 0.43300 C -2.03700 -2.81300 0.68500 H -2.21500 -1.93400 1.32300 H -2.16300 -3.71200 1.31100 H -2.82000 -2.80200 -0.08500 C 0.44400 -2.94500 1.07200 C 1.55300 -3.75000 0.77700 C 0.36200 -2.40000 2.36000 C 2.52100 -4.03700 1.73800 C 1.32800 -2.68200 3.32900 C 2.40600 -3.51000 3.02600 H 1.62600 -4.18600 -0.22400 H 3.36100 -4.68800 1.48800 H -0.48900 -1.77100 2.63100 H 1.22800 -2.25700 4.33000 H 3.15200 -3.74600 3.78600 H -0.58300 -3.69800 -0.57200 C -0.04000 4.19400 0.10100 H 0.62200 5.04100 -0.13900 H -0.68600 4.48400 0.93800 H -0.67200 4.00300 -0.78000 C 1.62200 2.70100 -0.81700 C 1.15700 1.94800 -1.90000 C 1.83700 1.94500 -3.12200 C 3.01800 2.66700 -3.27300 C 3.51000 3.40300 -2.19200 C 2.81100 3.42600 -0.98800 H 0.23200 1.37800 -1.78200 H 3.55000 2.66100 -4.22500 H 1.43700 1.37500 -3.96100 H 3.17300 4.04900 -0.16600 H 4.43300 3.97700 -2.29600 H 1.49600 3.21000 1.22500 H -5.11800 -2.75600 -0.37100 C -5.60900 -1.77400 -0.42500 H -5.56500 -1.44200 -1.47000 H -6.67700 -1.90200 -0.14500 H -4.59400 -2.31000 1.90400 N -4.93700 -0.83700 0.45600 H -2.97300 1.08000 -2.69800 C -5.03500 -1.30600 1.82500 1209 H -6.09000 -1.36700 2.17200 H -4.98300 0.54500 -1.78700 C -2.99000 1.99600 -2.08900 C -5.47300 0.50700 0.30900 H -6.58400 0.49000 0.27600 H -1.95600 2.35200 -1.95600 H -4.48500 -0.63700 2.50000 C -4.95300 1.23200 -0.92800 H -3.54800 2.77600 -2.64600 N -3.58400 1.72200 -0.78700 H -5.20500 1.08500 1.20600 H -5.63500 2.07400 -1.17500 C -3.52800 2.92400 0.03600 H -2.48000 3.17400 0.24800 H -4.01300 3.78400 -0.47100 H -4.03600 2.76500 0.99600 H 3.00500 1.93700 2.69800 C 3.85000 1.81700 2.00800 H 3.92000 2.72000 1.38900 H 4.78100 1.73000 2.60800 H 2.71600 -0.34600 2.76200 N 3.63000 0.65300 1.16800 H 2.16400 -0.81000 -2.58000 C 3.48500 -0.52900 2.00200 H 4.42900 -0.78700 2.53000 H 3.51400 0.68600 -1.58100 C 2.84600 -1.62900 -2.31800 C 4.69400 0.50800 0.17800 H 5.10500 1.50500 -0.04100 H 2.24300 -2.54000 -2.20300 H 3.18000 -1.40100 1.40800 C 4.21000 -0.04800 -1.15300 H 3.56500 -1.76800 -3.15400 N 3.51700 -1.32400 -1.06700 H 5.53300 -0.09100 0.59100 H 5.07700 -0.11400 -1.85000 C 4.42500 -2.40000 -0.71400 H 3.88300 -3.35400 -0.70600 H 5.26100 -2.48000 -1.44200 H 4.85300 -2.24800 0.28700 1210 Table C.2.185. Atomic coordinates and single point energies for C21. G = –2565.499966 GSP = –2567.668225 Na -1.00100 1.11700 -0.40600 Na 0.93100 -1.14100 -0.12200 N -1.40000 -1.28700 -0.50400 N 1.37300 1.17200 0.16300 Si 1.31500 1.72300 1.78600 Si -1.91900 -1.49500 -2.11500 C -0.02500 0.69000 2.64900 C 0.81700 3.55800 1.94900 C 2.90200 1.62400 2.83600 C -2.33400 -3.25300 -2.72800 C -0.54900 -0.80700 -3.24400 C -3.41200 -0.44500 -2.68800 H 3.53800 0.76400 2.57900 H 2.65300 1.56900 3.90800 H 3.51500 2.52600 2.68300 H -0.16800 3.75800 1.50200 H 1.55200 4.20000 1.43600 H 0.78300 3.87400 3.00400 H -0.98700 0.72900 2.11100 H -0.21000 1.03500 3.67900 H 0.26800 -0.37200 2.69900 H -4.34400 -0.64800 -2.14100 H -3.60200 -0.60700 -3.76200 H -3.17700 0.62500 -2.55700 H 0.46400 -1.12200 -2.95100 H -0.56400 0.29400 -3.21300 H -0.71200 -1.09900 -4.29300 H -1.57000 -3.99400 -2.45100 H -2.41900 -3.24200 -3.82600 1211 H -3.29800 -3.60900 -2.33200 C 2.33400 1.80200 -0.72300 C -1.83200 -2.00400 0.67800 C -1.84700 -3.53900 0.54600 C 2.15900 1.30600 -2.16100 H 2.34300 0.22000 -2.20900 H 2.85000 1.80100 -2.86100 H 1.12500 1.47400 -2.49600 C 3.79100 1.58300 -0.31000 C 4.29700 0.28200 -0.20700 C 4.64500 2.64500 -0.01000 C 5.60800 0.04300 0.19300 C 5.96100 2.41700 0.39900 C 6.44800 1.11700 0.50400 H 3.62600 -0.55100 -0.43400 H 5.98300 -0.98100 0.26800 H 4.26600 3.66800 -0.08200 H 6.60900 3.26200 0.64000 H 7.47500 0.93700 0.82500 H 2.21400 2.91000 -0.75400 H -0.86500 -3.90300 0.20800 H -2.59600 -3.86800 -0.18700 H -2.08800 -4.01700 1.50900 C -3.19000 -1.58800 1.24200 C -3.30700 -1.05100 2.52800 C -4.36200 -1.77800 0.49700 C -4.55300 -0.68900 3.04900 C -5.70700 -0.86500 2.28800 H -1.11800 -1.78700 1.50100 H -2.40500 -0.91400 3.13000 H -4.62000 -0.26700 4.05400 C -5.60600 -1.41900 1.00900 H -4.29400 -2.22000 -0.50000 H -6.50600 -1.57500 0.41000 H -6.68100 -0.58200 2.69000 H 3.47300 -2.53400 2.93000 C 2.81100 -1.93700 2.26600 H 3.43400 -1.41400 1.52900 H 2.31500 -1.17000 2.87300 H 3.13200 -4.42800 1.51300 H 1.50100 -3.96700 3.36100 N 1.80900 -2.77700 1.62100 C 2.43100 -3.85900 0.86400 C 0.93400 -3.33900 2.64200 H 0.44500 -2.53200 3.20500 H 4.01900 -2.73600 -0.08600 1212 C 3.20800 -3.42300 -0.37200 H 1.64100 -4.56800 0.57300 H 3.70100 -4.33100 -0.78500 H 0.15400 -3.95600 2.18000 H 4.06100 -1.70200 -2.16700 N 2.40900 -2.77500 -1.41000 C 3.27300 -2.38400 -2.51600 H 3.75700 -3.26600 -2.98400 H 0.58700 -3.82300 -1.14400 C 1.36100 -3.66100 -1.90400 H 1.77100 -4.64500 -2.21400 H 2.68500 -1.86500 -3.28500 H 0.86800 -3.20300 -2.77100 H -0.42100 4.94900 -1.99300 C -0.27100 3.89500 -1.67800 H -0.08300 3.86900 -0.59700 H 0.62900 3.51300 -2.17300 H -2.76400 4.69400 -2.01900 H -1.60200 3.86200 -4.00700 N -1.41600 3.06500 -2.03900 C -2.66300 3.67400 -1.58700 C -1.46000 2.89300 -3.48500 H -0.52000 2.44900 -3.84000 H -1.97900 4.40600 0.32800 C -2.80500 3.80100 -0.07700 H -3.49900 3.08400 -1.99300 H -3.73700 4.37500 0.12100 H -2.28500 2.22200 -3.76500 H -1.97100 3.30400 2.40200 N -2.83900 2.53100 0.63800 C -2.87700 2.77700 2.07500 H -3.76200 3.38600 2.35500 H -4.08000 0.86200 0.89800 C -4.01200 1.74900 0.26000 H -4.94500 2.33900 0.37800 H -2.93800 1.82000 2.61000 H -3.94600 1.40000 -0.77800 1213 Table C.2.186. Atomic coordinates and single point energies for C23. G = –1282.734583 GSP = –1283.821188 Na -0.28900 -0.72800 0.59800 N 1.69800 0.17100 0.40600 Si 2.85300 -1.02500 0.09300 C 4.40100 -1.06000 1.19800 C 3.51900 -1.04200 -1.69200 C 1.96600 -2.69300 0.37400 H 1.59900 -2.76500 1.41300 H 2.63700 -3.54900 0.20900 H 1.10900 -2.82300 -0.31100 H 4.03300 -0.09500 -1.92100 H 2.70000 -1.15500 -2.42000 H 4.24100 -1.85700 -1.85700 H 5.04200 -0.18500 1.00300 H 5.01000 -1.96000 1.01900 H 4.12100 -1.03600 2.26300 C 1.92700 1.58400 0.27000 C 2.62500 2.20500 1.49300 H 2.76000 3.29400 1.39100 H 3.61100 1.73700 1.62900 H 2.03800 2.00200 2.40200 C 0.59600 2.29100 0.01800 C -0.43400 2.22900 0.97100 C -1.67800 2.81200 0.73000 C -1.92500 3.46800 -0.47900 C -0.90900 3.54800 -1.43000 C 0.33700 2.96900 -1.17700 H -0.23900 1.72900 1.92600 H -2.89700 3.92700 -0.66900 1214 H -2.45600 2.78000 1.49700 H 1.12800 3.03000 -1.92900 H -1.08500 4.06500 -2.37500 H 2.56100 1.83900 -0.61100 N -1.40800 -1.33900 -1.46000 N -2.56700 -1.17400 1.25200 C -2.51800 -2.59900 1.54200 H -1.96200 -3.13800 0.76200 H -3.53100 -3.04600 1.62400 H -1.99700 -2.76100 2.49600 C -3.33800 -0.87500 0.04500 C -2.82100 -1.57900 -1.20600 H -3.31700 0.21800 -0.09700 H -4.40400 -1.15900 0.18300 H -3.44700 -1.26100 -2.06600 H -2.97200 -2.66400 -1.10400 C -1.16200 0.00400 -1.97600 C -0.84000 -2.33600 -2.35100 H -1.58100 0.76800 -1.30300 H -1.61200 0.14500 -2.98000 H -0.07800 0.18200 -2.03100 H -0.95200 -3.34200 -1.91900 H 0.23300 -2.13800 -2.48600 H -1.32400 -2.32700 -3.34900 C -3.09600 -0.43000 2.38500 H -2.46800 -0.59600 3.27100 H -3.09200 0.64400 2.15400 H -4.13400 -0.73000 2.63200 1215 Table C.2.187. Atomic coordinates and single point energies for C24. G = –1282.730358 GSP = –1283.817328 Na -1.47600 0.30100 -0.61500 N 0.66100 0.79600 -0.54600 Si 0.83900 2.23600 0.33500 C -0.92600 2.74800 0.87100 C 1.57500 3.68400 -0.65000 C 1.84500 2.15700 1.94800 H 1.41700 1.42900 2.65600 H 1.87800 3.13700 2.45200 H 2.88100 1.84400 1.74400 H 1.01800 3.84700 -1.58500 H 2.62400 3.47800 -0.91700 H 1.56000 4.61900 -0.06800 H -1.56100 2.98500 -0.00200 H -0.91600 3.64400 1.51100 H -1.40900 1.94600 1.45800 C 1.68400 0.27300 -1.40100 C 1.06100 -0.62600 -2.48700 H 0.53600 -1.46800 -2.00400 H 1.80500 -1.04800 -3.17900 H 0.33400 -0.03900 -3.07200 C 2.78200 -0.53600 -0.69200 C 3.95500 -0.89000 -1.37300 C 2.64100 -0.95200 0.63300 C 4.94700 -1.64900 -0.75600 C 3.63100 -1.71500 1.25800 C 4.78600 -2.07000 0.56600 H 4.09400 -0.55600 -2.40600 H 5.85400 -1.91000 -1.30600 H 1.74500 -0.63600 1.16900 H 3.50200 -2.02500 2.29700 1216 H 5.56300 -2.66100 1.05300 H 2.23300 1.07200 -1.95200 N -3.82400 -0.35300 -0.83700 N -1.91500 -1.17000 1.22000 C -1.34000 -0.76200 2.49200 C -1.11800 -2.23200 0.61900 H -1.29900 -1.59700 3.22100 H -1.93400 0.05300 2.93000 H -0.31900 -0.38800 2.32100 H -1.12600 -3.15300 1.23600 H -0.08100 -1.88600 0.50100 H -1.50000 -2.48900 -0.38000 C -3.32200 -1.51500 1.32500 C -4.02500 -1.55600 -0.03000 H -3.80800 -0.76900 1.97200 H -3.47100 -2.49800 1.82000 H -5.10800 -1.73200 0.14600 H -3.66400 -2.41400 -0.61700 C -4.37600 0.83000 -0.18900 H -3.84800 1.04400 0.75200 H -5.45700 0.71700 0.03400 H -4.25300 1.70300 -0.84600 C -4.40000 -0.53000 -2.16200 H -4.20500 0.35800 -2.77900 H -3.94500 -1.40000 -2.65500 H -5.49700 -0.68900 -2.12100 1217 Table C.2.188. Atomic coordinates and single point energies for C25. G = –1629.835018 GSP = –1631.315717 Na 0.45900 -0.15800 -0.25500 N -1.44800 0.93500 0.47700 Si -2.22100 2.38800 0.04000 C -1.19300 3.96600 0.36400 C -3.86000 2.68800 0.95700 C -2.69000 2.48400 -1.81100 H -1.83000 2.57300 -2.49300 H -3.32200 3.37000 -1.98700 H -3.26700 1.59500 -2.11100 H -3.71400 2.77300 2.04600 H -4.58100 1.87400 0.77900 H -4.32000 3.62600 0.60900 H -0.99600 4.06900 1.44400 H -1.72200 4.87300 0.03000 H -0.21700 3.94200 -0.14600 C -1.92300 0.22700 1.65000 C -1.04400 0.46400 2.88800 H -1.38300 -0.11300 3.76400 H -1.07800 1.53700 3.14000 H 0.00800 0.21000 2.67700 C -2.06100 -1.26700 1.36200 C -0.94800 -2.11700 1.34500 C -1.06900 -3.46700 1.00800 C -2.31900 -4.00200 0.69800 C -3.44100 -3.17100 0.72800 C -3.30800 -1.82100 1.05100 1218 H 0.02800 -1.72000 1.63800 H -2.42100 -5.05900 0.44700 H -0.18800 -4.11500 1.00900 H -4.18700 -1.17200 1.06100 H -4.42700 -3.58000 0.49600 H -2.94600 0.54100 1.94500 N 2.55500 -1.40000 0.60300 N 2.37200 0.99000 2.24400 C 1.96900 1.97300 1.26200 H 2.10900 1.56700 0.25000 H 2.56700 2.91000 1.32600 H 0.90000 2.21400 1.37600 C 3.65700 0.39400 1.95800 C 3.66500 -0.45800 0.69200 H 3.93600 -0.23300 2.81900 H 4.46300 1.15600 1.85900 H 4.63700 -0.99900 0.65900 H 3.63400 0.17700 -0.20500 C 2.48700 -2.24600 1.78400 C 2.67200 -2.19700 -0.60500 H 2.18000 -1.65100 2.65500 H 3.46100 -2.73300 1.99800 H 1.74100 -3.03700 1.63100 H 2.67400 -1.53500 -1.48400 H 1.80800 -2.87200 -0.68800 H 3.60000 -2.80700 -0.62200 C 2.30400 1.52700 3.58500 H 1.29500 1.91700 3.77400 H 2.50700 0.73400 4.32100 H 3.03100 2.35100 3.75000 H 3.73900 0.31200 -2.59200 H 1.16400 -2.52300 -3.07500 H -0.05900 -3.35600 -2.08500 C 3.18500 1.25800 -2.49900 C 0.09300 -2.56600 -2.83500 H 3.35700 1.85000 -3.42200 H 1.89700 -0.61500 -3.59600 N -0.38800 -1.30000 -2.30800 N 1.77100 0.99800 -2.27900 H -1.96400 -2.29100 -1.33800 H -0.45500 -2.85600 -3.75600 C 1.23900 0.25200 -3.42000 C -1.81000 -1.41700 -1.98300 C -0.20000 -0.21600 -3.26600 H -0.57400 -0.52000 -4.26800 H 1.30100 0.87900 -4.33600 1219 C 1.06000 2.26100 -2.10100 H -2.13600 -0.52300 -1.43100 H -2.41700 -1.54700 -2.90300 H 0.97600 2.82200 -3.05500 H -0.83500 0.62500 -2.94800 H 0.05200 2.09700 -1.69900 H 3.60200 1.82300 -1.65300 H 1.60000 2.89200 -1.38300 1220 Table C.2.189. Atomic coordinates and single point energies for C26. G = –1629.836764 GSP = –1631.317047 Na -0.48100 -0.17500 -0.19700 N 1.53600 0.81700 -0.16000 Si 2.04800 2.24100 0.62500 C 1.06200 2.50000 2.23200 C 1.80100 3.81600 -0.43100 C 3.87700 2.30600 1.13600 H 4.12500 1.50400 1.84800 H 4.11500 3.27400 1.60500 H 4.53900 2.17900 0.26500 H 0.74200 4.00000 -0.67200 H 2.34000 3.71200 -1.38700 H 2.19200 4.71500 0.07200 H -0.02600 2.54800 2.07300 H 1.36400 3.44100 2.71900 H 1.26800 1.68100 2.94000 C 2.39400 0.26900 -1.17900 C 1.64400 -0.78000 -2.02300 H 1.32300 -1.60000 -1.35900 H 2.27500 -1.21700 -2.81300 H 0.75600 -0.33400 -2.50200 C 3.66000 -0.43100 -0.65900 C 4.81500 -0.50500 -1.44400 C 3.66700 -1.05200 0.59300 C 5.94900 -1.18100 -0.99400 C 4.79500 -1.73500 1.04600 C 5.94200 -1.80200 0.25500 H 4.82700 -0.01400 -2.42200 H 6.84500 -1.21700 -1.61700 H 2.77200 -0.95400 1.21100 H 4.78500 -2.20900 2.03000 H 6.82900 -2.32700 0.61300 1221 N -2.07300 1.48000 -1.25500 N -4.62900 0.22000 0.08100 C -5.29600 0.44400 1.35000 C -5.30800 -0.83000 -0.65400 H -5.27900 -0.47800 1.95000 H -6.35600 0.75000 1.22300 H -4.78000 1.23000 1.91900 H -5.21800 -1.79000 -0.12200 H -4.86500 -0.95600 -1.65100 H -6.38800 -0.60700 -0.78800 C -4.54700 1.44600 -0.70100 C -3.44600 1.48300 -1.75300 H -4.40600 2.28900 -0.00900 H -5.51000 1.64400 -1.22100 H -3.62000 2.40600 -2.35000 H -3.55700 0.64000 -2.45600 C -1.86200 2.43500 -0.17800 H -2.38900 2.11800 0.73300 H -2.19600 3.46000 -0.44900 H -0.78800 2.47900 0.04500 C -1.16200 1.77100 -2.35800 H -0.12200 1.75200 -1.99300 H -1.28200 1.01800 -3.15200 H -1.36400 2.76900 -2.80200 H -2.08500 -0.51800 3.77700 H 0.38700 -3.92900 -0.86500 H -0.84400 -3.71400 1.05800 H -1.12900 -4.43300 -1.67800 C -0.48600 -3.56500 -1.42400 C -1.87000 -0.07700 2.78100 H -0.12600 -3.11500 -2.35900 H -2.81300 0.28900 2.35200 H -1.18700 0.77300 2.91800 C -1.67800 -3.15400 0.60900 H -2.48300 -3.89700 0.41900 N -1.20200 -2.57300 -0.63900 N -1.27700 -1.04300 1.87300 H -2.45900 -2.67700 2.54500 C -2.20500 -2.13200 1.60900 C -2.28400 -1.98300 -1.40700 H -1.88100 -1.54200 -2.33200 H -3.05300 -2.73500 -1.69000 C 0.01800 -1.49700 2.35700 H 0.52800 -2.10200 1.59300 H -0.07100 -2.09400 3.28900 H -3.13900 -1.67900 1.23700 1222 H -2.77100 -1.18000 -0.83200 H 0.65600 -0.62300 2.54700 H 2.76500 1.03300 -1.90600 1223 Table C.2.190. Atomic coordinates and single point energies for C5. G = –2413.516696 GSP = –2415.493639 Na 0.87600 1.72300 -0.01600 Na -0.36100 -0.99800 -0.01900 N 1.88600 -0.32400 -0.37700 N -1.38600 1.08500 0.20000 Si -1.76500 1.36400 1.84100 Si 2.19100 -0.28000 -2.05500 C -2.09800 3.16600 2.37400 C -0.22600 0.78200 2.81100 C -3.17100 0.37600 2.65500 C 3.98700 -0.18900 -2.67700 C 1.39500 1.31300 -2.74500 C 1.32500 -1.66700 -3.03500 H -4.16600 0.60900 2.24900 H -3.18800 0.58800 3.73700 H -3.00300 -0.70300 2.52700 H 0.71400 1.28800 2.52900 H -0.06300 -0.30200 2.67300 H -0.36400 0.94300 3.89100 H -1.32200 3.85800 2.01500 H -2.13300 3.23600 3.47300 H -3.06500 3.53600 1.99700 H 1.58300 -2.66800 -2.65400 H 1.57200 -1.63100 -4.10800 H 0.23000 -1.54900 -2.95000 H 1.93500 2.21100 -2.40000 H 0.33200 1.41200 -2.46500 H 1.42900 1.32100 -3.84500 H 4.49800 0.68400 -2.24000 H 3.98600 -0.06400 -3.77100 1224 H 4.59400 -1.07800 -2.44700 C -2.10600 1.49700 -0.98900 C 2.69400 -0.85700 0.69800 C 4.11000 -0.26300 0.77200 C -2.04700 3.01400 -1.24500 H -2.48100 3.56700 -0.39800 H -2.58800 3.29700 -2.16100 H -0.99800 3.33500 -1.35500 C -3.55400 1.02300 -1.08900 C -3.92400 0.07300 -2.04600 C -4.55400 1.54500 -0.26000 C -5.24700 -0.35600 -2.16900 C -5.87600 1.11800 -0.37000 C -6.22900 0.16300 -1.32700 H -3.15800 -0.32800 -2.71600 H -5.51300 -1.09500 -2.92700 H -4.29400 2.30400 0.48300 H -6.63900 1.53700 0.28800 H -7.26400 -0.16800 -1.41700 H -1.61800 1.03100 -1.87200 H 4.03600 0.83400 0.80400 H 4.69800 -0.54400 -0.11400 H 4.65100 -0.61200 1.66600 C 2.80700 -2.38200 0.74900 C 2.48600 -3.08400 1.91500 C 3.27200 -3.11700 -0.35000 C 2.60300 -4.47400 1.98200 C 3.05300 -5.19100 0.87600 H 2.21500 -0.58600 1.66300 H 2.13300 -2.52600 2.78800 H 2.34100 -4.99900 2.90300 C 3.39400 -4.50300 -0.29200 H 3.54900 -2.59400 -1.26700 H 3.75900 -5.05300 -1.16200 H 3.14400 -6.27700 0.92200 C 3.64100 3.64300 0.34100 C 3.00300 4.20100 -0.77600 C 2.90500 3.50900 1.52600 C 1.67800 4.62900 -0.70900 C 1.57800 3.94500 1.60200 C 0.96100 4.51000 0.48400 H 3.55800 4.30300 -1.71100 H 1.20000 5.06000 -1.59200 H 3.38100 3.06800 2.40400 H 1.02400 3.84100 2.53700 H -0.07400 4.85000 0.53800 1225 C 5.08600 3.22800 0.25700 H 5.71900 4.09100 0.00300 H 5.23200 2.46700 -0.52400 H 5.44000 2.81000 1.20700 H -5.05200 -2.64200 -0.12200 C -1.18000 -3.52000 -1.08800 H -0.81800 -3.69800 -2.10100 C -2.46600 -3.01000 -0.88800 C -0.35600 -3.80300 0.00600 H -3.10500 -2.79400 -1.74700 H 0.65400 -4.19300 -0.14000 C -2.96500 -2.78200 0.40300 C -0.84200 -3.58300 1.29700 C -4.34700 -2.22800 0.61100 C -2.13100 -3.08100 1.49000 H -0.21100 -3.81400 2.15600 H -4.71400 -2.44900 1.62200 H -2.50400 -2.93200 2.50600 H -4.34600 -1.13400 0.48400 1226 Table C.2.191. Atomic coordinates and single point energies for methyl benzoate. G = –459.468251 GSP = –459.9874395 C 1.09400 1.22000 -0.00000 C 2.47100 1.02100 -0.00000 C 0.23200 0.11900 0.00000 C 2.98700 -0.27600 -0.00000 C 0.74700 -1.18000 0.00000 C 2.12700 -1.37400 0.00000 H 0.65900 2.22000 -0.00000 H 3.14600 1.87800 -0.00000 H 4.06700 -0.43100 -0.00000 H 2.53300 -2.38600 0.00000 H 0.06200 -2.02700 0.00000 C -1.23700 0.38900 0.00000 O -1.72600 1.48700 0.00000 O -1.96800 -0.73300 -0.00000 C -3.37400 -0.54700 -0.00000 H -3.81700 -1.54700 0.00000 H -3.68800 0.01300 -0.89100 H -3.68800 0.01400 0.89000 1227 Table C.2.192. Atomic coordinates and single point energies for TMSOMe. G = –523.890036 GSP = –524.2725978 O -1.05500 -0.00000 -0.85500 C -2.31600 -0.00000 -0.25100 H -3.08800 -0.00500 -1.03300 H -2.47300 -0.89100 0.38400 H -2.47600 0.89500 0.37600 Si 0.38200 0.00000 0.00700 C 0.46800 -1.53600 1.08500 H 1.43500 -1.59000 1.60800 H -0.32200 -1.54100 1.85100 H 0.36000 -2.44600 0.47700 C 1.73500 -0.00200 -1.28000 H 1.65700 0.88600 -1.92300 H 2.73000 -0.00200 -0.81100 H 1.65600 -0.89300 -1.92000 C 0.46900 1.53900 1.08100 H 1.43600 1.59300 1.60500 H 0.36200 2.44700 0.47000 H -0.32200 1.54700 1.84600 1228 Table C.2.193. Atomic coordinates and single point energies for 38. G = –926.416471 GSP = –927.2379638 H 4.21000 2.06600 1.16800 C 3.63700 1.31700 0.62000 C 4.29100 0.23400 0.02700 H 5.37400 0.13700 0.11100 C 3.55700 -0.71900 -0.67600 H 4.06500 -1.56000 -1.15100 C 2.17100 -0.59700 -0.78000 H 1.59100 -1.33000 -1.34100 C 1.51300 0.48200 -0.18200 C 2.25600 1.44400 0.51400 H 1.72200 2.28300 0.96100 C 0.03200 0.62400 -0.28500 O -0.62000 -0.47600 -0.74500 N -0.54100 1.70800 0.02400 C -1.98500 1.82400 -0.09100 C -2.35400 2.15900 -1.53600 C -2.46900 2.89300 0.88100 H -1.84900 3.08500 -1.84500 H -3.44000 2.30000 -1.63600 H -2.04100 1.34700 -2.20800 H -3.56200 3.00300 0.83300 H -2.00500 3.85900 0.63400 H -2.18700 2.63600 1.91200 H -2.47400 0.86600 0.16500 Si -1.19500 -1.76500 0.20800 H -0.02000 -3.49100 -1.14100 C -0.09900 -3.25700 -0.06800 C -2.92800 -2.11700 -0.39600 C -1.13700 -1.20900 1.99400 1229 H 0.91400 -3.08900 0.32500 H -0.52100 -4.13800 0.43900 H -2.91500 -2.34500 -1.47200 H -3.59200 -1.25400 -0.24000 H -3.35800 -2.98200 0.13000 H -1.51000 -2.00000 2.66200 H -1.74500 -0.30700 2.15600 H -0.10100 -0.97600 2.28900 1230 Table C.2.194. Atomic coordinates and single point energies for 39. G = –926.407965 GSP = –927.230799 H -2.01600 2.92200 2.08800 C -1.53000 2.62500 1.15700 C -1.15800 3.59100 0.22300 H -1.35900 4.64500 0.41900 C -0.52300 3.20700 -0.95900 H -0.22600 3.96100 -1.68900 C -0.25400 1.86300 -1.20100 H 0.26900 1.55400 -2.10800 C -0.64200 0.88600 -0.27700 C -1.27800 1.27700 0.90700 H -1.55900 0.52200 1.64300 C -0.28100 -0.54900 -0.53500 O 1.00800 -0.69000 -0.93600 N -1.00400 -1.57600 -0.43100 C -2.42000 -1.52600 -0.12200 C -2.64700 -2.18200 1.23900 C -3.17100 -2.27700 -1.21900 H -2.27200 -3.21600 1.21800 H -3.71700 -2.19800 1.49100 H -2.10900 -1.64800 2.03600 H -4.25100 -2.29200 -1.01200 H -2.80300 -3.31200 -1.28100 H -3.00700 -1.79900 -2.19500 H -2.80600 -0.49100 -0.08900 Si 2.33500 -0.59100 0.12100 H 3.00500 1.69800 -0.58200 1231 C 2.79500 1.20700 0.38100 C 3.70600 -1.52400 -0.73300 C 1.80600 -1.39000 1.73000 H 1.98000 1.76100 0.87200 H 3.69600 1.29000 1.00900 H 3.92200 -1.07600 -1.71400 H 3.41500 -2.57200 -0.89300 H 4.63000 -1.50400 -0.13600 H 2.65100 -1.49400 2.42700 H 1.38300 -2.38700 1.53400 H 1.03000 -0.78600 2.22500 1232 Table C.2.195. Atomic coordinates and single point energies for E23. G = xx GSP = xx C -3.90800 -0.29400 -1.29700 C -5.26100 -0.60800 -1.17400 C -3.02700 -0.52200 -0.23500 C -5.75000 -1.14500 0.01700 C -3.52000 -1.09000 0.94400 C -4.87500 -1.38600 1.07700 H -3.52500 0.11800 -2.23300 H -5.93700 -0.43500 -2.01300 H -6.81000 -1.38300 0.11600 H -5.25000 -1.81700 2.00700 H -2.82300 -1.30400 1.75600 C -1.53900 -0.25600 -0.34800 N -1.04300 0.93200 -0.61700 C -1.86100 2.12900 -0.66700 C -2.19000 2.62800 0.74400 C -1.11400 3.20000 -1.45800 H -2.79800 3.54500 0.71700 H -1.26100 2.84700 1.29500 H -2.74700 1.86100 1.30300 H -1.69600 4.13100 -1.53000 H -0.89400 2.84100 -2.47400 H -0.15400 3.42900 -0.96700 H -2.82400 1.95400 -1.17800 O -0.79200 -1.26100 -0.15200 Na 1.02300 -0.08900 -0.79900 O 2.03900 0.86700 2.16400 O 2.92700 1.21000 -0.54900 O 1.99700 -1.44800 0.86400 O 2.75400 -1.41900 -1.70300 C 1.86500 2.05800 1.44400 C 3.00400 2.20700 0.45700 H 1.85700 2.93400 2.12000 H 0.90800 2.05000 0.89200 1233 H 3.96100 2.12300 0.99700 H 2.96000 3.19900 -0.02100 C 4.04900 0.36100 -0.64700 C 3.85700 -0.54900 -1.84600 H 4.15200 -0.22800 0.28100 H 4.97000 0.95300 -0.80200 H 4.78200 -1.12100 -2.03100 H 3.65600 0.06800 -2.73400 C 1.95100 -2.67500 0.18300 C 2.98300 -2.58200 -0.92300 H 3.98900 -2.53600 -0.47300 H 2.93300 -3.47200 -1.57000 H 2.21400 -3.51800 0.85000 H 0.93400 -2.84100 -0.21600 C 0.90500 0.04900 2.33500 C 1.28900 -1.39600 2.08300 H 0.11100 0.33400 1.62400 H 0.49700 0.14700 3.35700 H 0.36500 -1.99300 2.01600 H 1.93000 -1.78700 2.89400 1234 Table C.2.196. Atomic coordinates and single point energies for E22. G = –1818.012775 GSP = –1819.709952 Na 0.99800 -0.05100 -0.02100 N -1.30200 -0.83400 0.48100 Si -1.26200 -2.57600 0.07300 C -0.25500 -3.49900 1.40000 C -2.91600 -3.48900 -0.00500 C -0.36600 -2.88700 -1.54900 H -3.33600 -3.71400 0.98500 H -2.76200 -4.44600 -0.52900 H -3.64100 -2.89400 -0.57500 H -0.26700 -3.97700 -1.68800 H 0.62900 -2.42400 -1.59000 H -0.94500 -2.46500 -2.38000 H -0.08300 -4.52500 1.03700 H -0.77900 -3.57700 2.36400 H 0.73200 -3.04300 1.58600 C -1.81900 -0.40400 1.79500 C -3.13400 -1.07200 2.21000 C -0.77700 -0.53700 2.91000 H -3.58600 -0.54400 3.06300 H -2.96700 -2.11700 2.51600 H -3.85000 -1.07300 1.37600 H -2.02200 0.67200 1.71900 H -0.46100 -1.57900 3.05700 H -1.20000 -0.18200 3.86300 H 0.10400 0.08000 2.68700 O 2.13100 1.80100 -0.88700 O 2.37400 -0.83700 -1.75900 O 3.51900 -0.51400 0.65800 O 1.88000 1.30600 1.82600 1235 C 2.02800 2.61600 1.31900 C 2.81600 2.61700 0.02200 C 2.80400 1.52500 -2.09100 C 2.24500 0.23600 -2.67200 C 3.71400 -1.71500 -0.04700 C 3.65300 -1.36100 -1.51800 C 2.97700 0.77300 2.53400 C 3.25200 -0.62800 2.02900 H 2.75500 0.75000 3.61400 H 3.87800 1.39000 2.37700 H 2.36700 -1.27200 2.20400 H 4.10500 -1.06900 2.57800 H 2.90800 -2.43700 0.19000 H 4.68200 -2.18100 0.20900 H 3.83400 -2.25700 -2.13700 H 4.44300 -0.62300 -1.73900 H 1.16000 0.33900 -2.82600 H 2.74700 0.00700 -3.62800 H 2.66500 2.34700 -2.81700 H 3.88800 1.43600 -1.89200 H 3.83500 2.21700 0.19000 H 2.91100 3.65300 -0.35400 H 1.01000 2.98800 1.13400 H 2.50900 3.27500 2.06100 H -3.70400 -1.09100 -3.11200 C -4.06000 2.82400 0.21100 C -3.56200 1.56100 -0.11000 C -3.21000 3.93100 0.23000 C -2.20700 1.38500 -0.41000 C -1.86500 3.76800 -0.10000 C -1.60200 0.00300 -0.77600 C -1.37200 2.50400 -0.43100 C -2.91300 -0.42600 -2.73700 O -0.54700 0.10900 -1.52900 O -2.68400 -0.76000 -1.39800 H -5.12000 2.94700 0.44400 H -4.22200 0.69300 -0.13800 H -3.60000 4.91800 0.48200 H -1.20100 4.63500 -0.11900 H -0.33600 2.36100 -0.74700 H -2.00200 -0.55200 -3.34200 H -3.25200 0.62100 -2.84300 1236 Table C.2.197. Atomic coordinates and single point energies for E21. G = –1818.006832 GSP = –1819.711972 Na 0.81900 0.03500 -0.14200 N -1.00800 -0.92000 0.79500 Si -1.49400 -2.50100 0.41100 C -1.45100 -3.77800 1.83400 C -3.25300 -2.72000 -0.32100 C -0.30800 -3.23000 -0.90800 H -4.01800 -2.72000 0.47100 H -3.34000 -3.67600 -0.86400 H -3.50300 -1.90100 -1.01400 H -0.86700 -3.85500 -1.62300 H 0.44000 -3.89200 -0.44200 H 0.22700 -2.45400 -1.47900 H -1.68800 -4.79300 1.47400 H -2.17800 -3.52600 2.62300 H -0.45200 -3.80600 2.30100 C -1.66600 -0.10700 1.79900 C -3.18900 -0.29600 1.88800 C -1.08400 -0.29500 3.21000 H -3.65500 0.46500 2.53500 H -3.42900 -1.28800 2.30700 H -3.64700 -0.23800 0.89100 H -1.50800 0.96900 1.55600 H -1.14700 -1.35500 3.50500 H -1.62100 0.30900 3.96100 H -0.03000 0.01000 3.23000 O 2.54400 1.59700 -0.83900 O 2.22100 -1.05400 -1.70300 O 2.98400 -0.90500 0.92200 O 1.63400 1.33300 1.78500 1237 C 2.18400 2.53700 1.31200 C 3.18600 2.28900 0.20200 C 3.43200 1.03700 -1.77700 C 2.71600 -0.04900 -2.55700 C 2.86600 -2.16000 0.29700 C 3.15500 -1.96900 -1.17600 C 2.45200 0.58400 2.66100 C 2.44800 -0.86300 2.22500 H 2.06900 0.66700 3.69200 H 3.48800 0.96400 2.64700 H 1.41100 -1.24900 2.21800 H 3.05500 -1.46800 2.92500 H 1.84000 -2.54800 0.42700 H 3.57300 -2.89200 0.73100 H 3.07200 -2.93600 -1.70000 H 4.18600 -1.59500 -1.30000 H 1.83800 0.37000 -3.06300 H 3.40000 -0.47000 -3.31500 H 3.81100 1.81000 -2.47200 H 4.30000 0.61000 -1.24200 H 4.02500 1.67700 0.58400 H 3.60100 3.25100 -0.15500 H 1.34200 3.13300 0.93400 H 2.66400 3.10800 2.12600 H -3.06800 -1.54900 -3.57400 C -3.56300 3.00400 0.21600 C -3.21200 1.95300 -0.62700 C -2.59900 3.92600 0.62400 C -1.88700 1.81500 -1.04500 C -1.28100 3.80200 0.18400 C -1.45500 0.68900 -1.91700 C -0.92100 2.74600 -0.64900 C -2.12100 -1.10700 -3.24900 O -0.29300 0.45500 -2.18200 O -2.46400 0.00500 -2.43100 H -4.59300 3.10100 0.56100 H -3.95200 1.22300 -0.95400 H -2.87800 4.74900 1.28400 H -0.53500 4.53800 0.49100 H 0.10400 2.62800 -1.01100 H -1.53800 -1.83300 -2.66900 H -1.53100 -0.77200 -4.11300 1238 Table C.2.198. Atomic coordinates and single point energies for T9. G = –1817.993518 GSP = –1819.694107 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.34600 Si 1.63100 0.00000 2.95000 C 2.39800 1.73200 3.17600 C 1.90900 -0.83300 4.64100 C 2.77900 -0.83600 1.68400 H 1.69300 -0.13200 5.46200 H 2.95900 -1.15200 4.74700 H 1.26000 -1.70900 4.77100 H 3.64000 -1.29300 2.19900 H 3.19000 -0.08600 0.98900 H 2.26900 -1.60000 1.08300 H 3.46500 1.61100 3.42600 H 1.93000 2.30400 3.99100 H 2.33600 2.33700 2.25600 C -1.00700 0.82500 3.01300 C -1.02100 0.70600 4.54400 C -0.94300 2.30800 2.61600 H -1.92600 1.16500 4.97100 H -0.14800 1.21700 4.98500 H -0.98200 -0.34800 4.85200 H -2.00200 0.49100 2.66900 H 0.03100 2.75300 2.86800 H -1.72300 2.88500 3.13800 H -1.11700 2.41200 1.53700 O -0.97900 -0.54600 -2.09500 O 1.70300 -0.83700 -1.38000 O 1.02900 1.77500 -1.64900 O -1.53300 1.79300 -0.70500 C -2.45800 1.23500 -1.60900 1239 C -1.75400 0.45400 -2.70200 C -0.09100 -1.21000 -2.96200 C 1.03200 -1.81800 -2.14000 C 2.37800 1.42300 -1.46900 C 2.56300 0.04100 -2.06000 C -0.90400 2.99000 -1.10800 C 0.58700 2.86800 -0.88400 H -1.30200 3.83800 -0.52600 H -1.09100 3.18700 -2.17800 H 0.79100 2.69500 0.19100 H 1.09300 3.80400 -1.18400 H 2.62400 1.40200 -0.39100 H 3.05200 2.14900 -1.96100 H 3.61300 -0.28000 -1.94800 H 2.32700 0.07900 -3.13800 H 0.61800 -2.51800 -1.40200 H 1.73100 -2.35700 -2.80400 H -0.61100 -2.00300 -3.52900 H 0.31200 -0.48500 -3.69400 H -1.09500 1.12700 -3.28400 H -2.50000 0.01900 -3.39300 H -3.09800 0.56500 -1.01900 H -3.09900 2.01400 -2.05600 H 0.94900 -4.34100 3.46700 C -4.07500 -1.76100 3.30100 C -2.69800 -1.95600 3.21900 C -4.80500 -1.40500 2.16600 C -2.03400 -1.78000 2.00300 C -4.14900 -1.26700 0.94200 C -0.54100 -1.96400 1.86400 C -2.77100 -1.46100 0.86100 C 1.03400 -3.53400 2.72900 O -0.04200 -2.12700 0.73600 O -0.06800 -2.68000 2.93600 H -4.58500 -1.89100 4.25700 H -2.12100 -2.24400 4.09800 H -5.88300 -1.25300 2.23200 H -4.72200 -1.02300 0.04500 H -2.25000 -1.39600 -0.09800 H 1.98700 -3.00800 2.88700 H 1.02000 -3.94700 1.71200 1240 Table C.2.199. Atomic coordinates and single point energies for E26. G = –xx GSP = –xx C 4.20100 0.21800 0.47300 C 5.55100 -0.09400 0.30500 C 3.22700 -0.37400 -0.33700 C 5.94300 -0.99500 -0.68300 C 3.62900 -1.30100 -1.30500 C 4.97700 -1.59900 -1.49000 H 3.90000 0.91700 1.25400 H 6.29900 0.36800 0.95200 H 6.99900 -1.23300 -0.81900 H 5.27700 -2.31400 -2.25800 H 2.85700 -1.79000 -1.90100 C 1.73900 -0.13000 -0.15900 N 1.20500 1.04900 0.04000 C 1.91800 2.30000 -0.07200 C 1.17200 3.20000 -1.06100 C 2.00700 3.00700 1.28400 H 1.66700 4.17600 -1.18100 H 0.14800 3.36200 -0.68700 H 1.10700 2.71300 -2.04500 H 2.57800 3.94600 1.21400 H 2.48100 2.36500 2.04000 H 0.99300 3.25200 1.64100 H 2.94500 2.16400 -0.45900 O 1.01800 -1.17600 -0.22800 Na -0.91000 0.02500 -0.27500 O -1.98800 1.96200 0.48500 O -1.52700 -0.22200 2.08300 O -2.38900 0.93800 -2.00300 O -2.11100 -2.83500 1.32400 1241 O -2.25700 -1.65600 -1.16700 C -1.15400 1.06700 2.50400 C -2.12900 2.04100 1.88200 H -1.92400 3.06800 2.23700 H -3.15900 1.76500 2.17300 H -1.20600 1.15100 3.60600 H -0.12700 1.29800 2.16700 C -0.68400 -1.26200 2.54000 C -1.48400 -2.55600 2.54300 H -0.35400 -1.06200 3.57700 H 0.21100 -1.33000 1.89500 H -2.29300 -2.47000 3.28300 H -0.81900 -3.38400 2.85600 C -1.26300 -3.25500 0.28400 C -1.99700 -3.03500 -1.01700 H -1.02700 -4.33200 0.38100 H -0.31500 -2.69100 0.26300 H -2.95600 -3.58500 -1.00200 H -1.38700 -3.40800 -1.85900 C -3.51200 0.09800 -2.11000 C -3.02200 -1.32000 -2.29000 H -4.13700 0.39500 -2.97200 H -4.12900 0.14400 -1.19400 H -2.42000 -1.40100 -3.21400 H -3.89500 -1.99200 -2.38500 C -3.01500 2.53100 -0.27400 C -2.67000 2.29200 -1.73600 H -3.09700 3.62100 -0.09600 H -3.98800 2.07800 -0.00300 H -1.75200 2.84300 -1.98300 H -3.48600 2.66000 -2.38300 1242 Table C.2.200. Atomic coordinates and single point energies for E25. G = –1971.62198 GSP = –1973.495108 Na -1.19700 -0.03400 0.04800 N 1.29400 0.74000 0.60300 Si 1.53400 2.48200 0.39600 C 1.14900 3.38200 2.02500 C 3.28100 3.02500 -0.07600 C 0.34500 3.30600 -0.81800 H 3.46700 2.84700 -1.14400 H 4.05100 2.49500 0.50500 H 3.39000 4.10500 0.11300 H 0.58000 3.01400 -1.85000 H 0.43600 4.40000 -0.72500 H -0.69700 3.03200 -0.59500 H 0.09700 3.26000 2.32400 H 1.31600 4.45500 1.83700 H 1.78500 3.09400 2.87400 C 1.40900 0.04900 1.89700 C 0.31200 0.40300 2.90900 C 2.78400 0.19500 2.56300 H 0.50000 1.36400 3.40500 H 0.28000 -0.36900 3.69400 H -0.68700 0.44700 2.44800 H 1.25300 -1.01500 1.65900 H 2.83500 -0.40400 3.48500 H 2.97200 1.24500 2.83800 H 3.59100 -0.13400 1.89500 H 0.50100 -0.29900 -3.06800 C 4.09000 -0.19600 -0.85500 C 5.33800 -0.80400 -0.71200 C 1.51800 -0.20100 -0.57000 1243 C 2.92000 -0.86400 -0.48300 C 5.43400 -2.09600 -0.19500 C 3.02500 -2.17300 -0.00600 C 4.27000 -2.78200 0.15100 C 1.47400 0.19600 -2.92700 O 1.57300 0.76300 -1.65500 O 0.57200 -1.09000 -0.69800 H 4.01500 0.81000 -1.26400 H 6.24000 -0.26500 -1.00800 H 6.41000 -2.57000 -0.07500 H 2.10500 -2.70400 0.24000 H 4.33300 -3.80000 0.54000 H 1.57800 1.01200 -3.65800 H 2.27500 -0.54300 -3.10900 H -0.87400 -3.97300 1.39600 C -1.05200 -3.08500 0.76100 H -2.56000 -3.03400 2.76600 H -0.15200 -2.84500 0.17800 H -1.98500 -4.22400 -0.81000 C -2.22400 -3.35700 -0.16900 C -2.29800 -1.99300 2.50400 H -3.12500 -3.62700 0.40700 O -1.26200 -1.94100 1.56300 H -1.93600 -1.49500 3.41700 C -3.53300 -1.25900 2.01400 O -2.55700 -2.23300 -0.95000 H -4.28400 -1.22100 2.82600 H -3.98800 -1.76200 1.14200 H -0.78200 -2.09600 -2.02400 C -1.87300 -2.16500 -2.18800 H -2.11700 -3.05300 -2.80100 O -3.13800 0.04100 1.64900 C -2.34300 -0.92700 -2.90800 C -4.20400 0.87500 1.28200 O -1.86400 0.19700 -2.21200 H -4.81700 0.38700 0.50000 H -4.86300 1.07700 2.14700 H -3.44900 -0.92100 -2.94700 H -1.95500 -0.93100 -3.94300 O -2.77600 1.94400 -0.33500 C -3.61100 2.17200 0.77200 C -2.38900 1.44200 -2.59700 H -1.55900 2.16300 -2.60700 H -2.97900 2.61000 1.55800 C -3.42400 1.88300 -1.58300 H -4.41100 2.89100 0.52500 1244 H -2.83300 1.40100 -3.60600 H -4.25600 1.15300 -1.55800 H -3.83900 2.87200 -1.85300 1245 Table C.2.201. Atomic coordinates and single point energies for E24. G = –1971.599402 GSP = –1973.479406 Na -0.89800 -0.23700 0.04100 N 0.99100 0.99400 0.64400 Si 1.57700 2.57200 0.43100 C 1.54600 3.69100 1.98900 C 3.34800 2.76800 -0.25800 C 0.53200 3.53200 -0.84600 H 3.42200 2.24700 -1.22500 H 4.11900 2.35200 0.40800 H 3.58400 3.83200 -0.42900 H 0.79200 3.24700 -1.87700 H 0.73300 4.61100 -0.74800 H -0.54400 3.36000 -0.69900 H 0.52600 3.77200 2.40000 H 1.89600 4.71000 1.75500 H 2.19000 3.29500 2.78900 C 1.48400 0.11500 1.68600 C 0.71700 0.28000 3.01300 C 2.98800 0.21200 1.99300 H 0.88800 1.29100 3.42000 H 1.03800 -0.45500 3.77300 H -0.36300 0.16300 2.84700 H 1.30800 -0.94200 1.37700 H 3.30600 -0.57000 2.70300 H 3.22500 1.19000 2.44600 H 3.58800 0.11200 1.07700 H -0.10100 1.14300 -1.90400 C 4.08600 -0.62500 -1.53600 C 5.33300 -1.00600 -1.04900 C 1.58200 -0.89000 -1.55900 C 2.93800 -1.29500 -1.10300 C 5.43500 -2.05700 -0.13600 1246 C 3.04200 -2.35700 -0.20100 C 4.29100 -2.73600 0.28400 C 0.33200 0.64100 -2.78400 O 1.59700 0.11000 -2.42700 O 0.56400 -1.47100 -1.23500 H 3.98800 0.20100 -2.23900 H 6.22900 -0.47600 -1.37500 H 6.41300 -2.34700 0.25200 H 2.13200 -2.86000 0.12600 H 4.37200 -3.55600 0.99900 H 0.51900 1.37600 -3.57400 H -0.34700 -0.14800 -3.13500 H -1.13200 -4.34800 1.04200 C -1.16100 -3.37100 0.52500 H -2.37000 -3.26400 2.72500 H -0.29000 -3.28200 -0.13600 H -2.35100 -3.98100 -1.15700 C -2.42900 -3.27900 -0.30700 C -1.95300 -2.26400 2.50700 H -3.32300 -3.57300 0.28200 O -1.03900 -2.31200 1.44000 H -1.38600 -1.92700 3.38700 C -3.07800 -1.26700 2.25300 O -2.57300 -1.95600 -0.75000 H -3.62300 -1.09800 3.20000 H -3.80000 -1.63500 1.49900 H -3.27400 -2.17100 -2.68400 C -3.59300 -1.78600 -1.69800 H -4.50300 -2.33400 -1.38900 O -2.47300 -0.08800 1.80100 C -3.92100 -0.31800 -1.79000 C -3.18000 1.11400 1.94600 O -2.81000 0.36200 -2.29800 H -4.18800 1.03200 1.48800 H -3.31100 1.37000 3.01300 H -4.17300 0.03300 -0.77200 H -4.80700 -0.17100 -2.43800 O -2.21900 1.82900 -0.12300 C -2.34600 2.16800 1.24100 C -2.94900 1.75800 -2.35500 H -2.00900 2.14100 -2.77500 H -1.32300 2.15500 1.65100 C -3.17000 2.38100 -0.98500 H -2.78200 3.17400 1.36500 H -3.77600 2.05000 -3.03100 H -4.19700 2.19300 -0.61800 1247 H -3.04800 3.47800 -1.06500 1248 Table C.2.202. Atomic coordinates and single point energies for T10. G = –1971.592111 GSP = –1973.470026 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.40900 Si 1.35900 0.00000 3.46300 C 2.04400 1.74000 3.87600 C 1.15900 -0.82500 5.17100 C 2.85000 -0.90100 2.70600 H 1.17900 -1.92200 5.07800 H 0.22200 -0.54600 5.67500 H 2.00000 -0.53600 5.82300 H 2.68500 -1.98700 2.66000 H 3.73200 -0.72400 3.34100 H 3.06800 -0.52600 1.69400 H 2.31100 2.30800 2.97100 H 2.95700 1.63900 4.48600 H 1.32900 2.34800 4.45100 C -1.10700 0.92200 2.61200 C -0.84300 2.33900 2.06900 C -1.60200 1.05800 4.06300 H -0.03800 2.83000 2.63800 H -1.74600 2.96800 2.15200 H -0.54700 2.31400 1.01200 H -1.96300 0.54200 2.01400 H -2.52800 1.65300 4.11200 H -0.84500 1.57000 4.68000 H -1.80100 0.07900 4.51700 H 1.43300 -1.92800 0.66700 C -1.53800 -2.62100 4.22600 C -2.44800 -2.66900 5.27800 C -0.95900 -1.95800 1.85200 C -1.90600 -2.04500 3.00700 1249 C -3.73700 -2.15500 5.11600 C -3.20900 -1.57200 2.83300 C -4.11900 -1.61700 3.88800 C 0.95300 -2.88900 0.90600 O 0.12600 -2.75100 2.03400 O -1.34900 -1.66500 0.71900 H -0.53200 -3.02000 4.33800 H -2.15100 -3.10700 6.23200 H -4.44600 -2.18600 5.94500 H -3.49100 -1.16400 1.86200 H -5.13100 -1.23200 3.75100 H 1.72900 -3.61900 1.16700 H 0.38400 -3.23000 0.03000 H -3.86900 0.28700 -1.61300 C -2.84200 -0.01400 -1.33800 H -2.88800 2.37300 -2.14500 H -2.87500 -0.80800 -0.58200 H -2.55000 -1.50300 -2.86000 C -2.12000 -0.52600 -2.57300 C -2.06900 2.26400 -1.41200 H -2.25100 0.15900 -3.43700 O -2.15600 1.04700 -0.71800 H -2.17100 3.06100 -0.66100 C -0.72000 2.43400 -2.10400 O -0.75400 -0.64100 -2.27400 H -0.61200 3.48800 -2.41800 H -0.62500 1.79300 -3.00000 H -0.18500 -2.36800 -3.25800 C -0.00200 -1.27900 -3.27000 H -0.27500 -0.89100 -4.27100 O 0.26300 2.08900 -1.16400 C 1.45700 -0.99100 -3.02000 C 1.54100 2.63700 -1.32300 O 1.82400 -1.57200 -1.80300 H 1.95300 2.39000 -2.32300 H 1.51600 3.73900 -1.23200 H 1.58500 0.10800 -2.99300 H 2.06900 -1.39100 -3.85200 O 2.42100 0.63400 -0.33800 C 2.39000 2.03700 -0.21700 C 3.15000 -1.34300 -1.40500 H 3.28800 -1.90300 -0.47000 H 1.91800 2.25600 0.75300 C 3.44000 0.12700 -1.15700 H 3.40800 2.46300 -0.22100 H 3.86500 -1.73500 -2.15400 1250 H 3.49200 0.68800 -2.10900 H 4.42600 0.22500 -0.66600 1251 Table C.2.202. Atomic coordinates and single point energies for T19. G = –1971.568611 GSP = –1973.448083 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.35500 Si 1.49400 0.00000 3.22000 C 2.19000 1.77400 3.35300 C 1.50400 -0.63400 5.03500 C 2.86800 -1.00100 2.38100 H 2.09500 -1.55800 5.12600 H 0.49400 -0.84200 5.41300 H 1.95800 0.11900 5.69900 H 2.60200 -2.06100 2.25300 H 3.76300 -0.95900 3.02300 H 3.12900 -0.56600 1.40500 H 2.22900 2.26500 2.36700 H 3.20900 1.76000 3.77100 H 1.56900 2.40300 4.01000 C -0.91700 1.06400 2.77900 C -1.35800 0.97300 4.25100 C -2.17700 1.15400 1.90900 H -1.78100 -0.02300 4.44800 H -2.11900 1.73500 4.48500 H -0.51000 1.13300 4.93400 H -0.41900 2.05400 2.66700 H -2.75600 2.05300 2.17200 H -2.81600 0.27600 2.07200 H -1.92800 1.24700 0.84200 H -3.50200 -1.12000 0.73300 C 0.52000 -3.48600 1.21600 C 1.51300 -4.44000 1.45300 C -1.26000 -1.90600 2.09000 C -0.11100 -2.85300 2.28900 1252 C 1.87700 -4.76500 2.75800 C 0.22800 -3.21000 3.59700 C 1.22600 -4.14900 3.83100 C -2.81500 -1.87100 0.31600 O -1.48400 -1.65500 0.72500 O -2.17900 -1.83200 2.87100 H 0.22800 -3.22700 0.19800 H 2.00300 -4.93400 0.61100 H 2.65700 -5.50600 2.94200 H -0.31000 -2.73400 4.41700 H 1.49700 -4.40900 4.85600 H -2.81600 -1.81000 -0.78100 H -3.16700 -2.86500 0.63000 H -3.89800 1.66500 -2.11700 C -3.01200 1.16500 -1.68000 H -2.29500 3.18100 -3.00800 H -3.33200 0.63300 -0.77300 H -3.21500 -0.63800 -2.82700 C -2.46900 0.16700 -2.68500 C -1.57600 3.01600 -2.18400 H -2.31100 0.64200 -3.67500 O -2.06200 2.09500 -1.25000 H -1.44600 3.97000 -1.65000 C -0.22700 2.60800 -2.75200 O -1.25100 -0.34900 -2.21200 H 0.16000 3.44500 -3.36300 H -0.30800 1.71900 -3.40700 H -1.21900 -2.36100 -2.69200 C -0.75000 -1.40600 -2.99300 H -0.96800 -1.23300 -4.06300 O 0.63100 2.33400 -1.67900 C 0.74500 -1.47600 -2.80900 C 1.99100 2.33400 -2.00700 O 1.01100 -1.75600 -1.46400 H 2.17500 1.71600 -2.91000 H 2.34800 3.35800 -2.22800 H 1.17700 -0.50000 -3.10500 H 1.16900 -2.25900 -3.46600 O 2.33800 0.42300 -0.61100 C 2.73400 1.75800 -0.82100 C 2.37600 -1.86800 -1.13100 H 2.40100 -2.18300 -0.07900 H 2.46300 2.32000 0.08400 C 3.10500 -0.54500 -1.27700 H 3.82500 1.83100 -0.96500 H 2.86900 -2.64200 -1.74800 1253 H 3.24100 -0.27200 -2.34100 H 4.11000 -0.63400 -0.82500 1254 Table C.2.203. Atomic coordinates and single point energies for T20. G = –1971.572716 GSP = –1973.451643 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.35800 Si 1.66900 0.00000 2.80100 C 2.63900 0.90700 1.44700 C 2.15700 0.85100 4.42900 C 2.45200 -1.73900 2.89900 H 1.86200 0.26800 5.31300 H 1.69200 1.84500 4.48600 H 3.25200 0.98000 4.46400 H 2.06200 -2.32000 3.75000 H 3.54400 -1.65800 3.02600 H 2.25700 -2.31400 1.97900 H 2.59500 0.40800 0.46600 H 3.70300 0.95300 1.73000 H 2.27100 1.94000 1.36100 C -0.97100 -0.74400 3.14200 C -0.79500 -0.65300 4.66700 C -1.04400 -2.23600 2.76900 H 0.09000 -1.23000 4.98700 H -1.67000 -1.06400 5.19600 H -0.64900 0.38600 4.98700 H -1.98200 -0.33100 2.93200 H -1.85800 -2.74800 3.31000 H -0.09900 -2.74000 3.02500 H -1.19900 -2.35700 1.69000 H 1.16100 3.61100 0.39900 C -2.89800 1.88800 1.78900 C -4.18900 1.80000 2.31200 1255 C -0.41700 2.28800 2.12500 C -1.81800 2.15100 2.63400 C -4.40800 1.98300 3.67700 C -2.04400 2.37100 3.99600 C -3.33100 2.27500 4.51700 C 0.11400 3.40000 0.13500 O -0.34200 2.20000 0.72100 O 0.43800 2.89900 2.72300 H -2.71200 1.74900 0.72400 H -5.03100 1.59300 1.64900 H -5.41700 1.91000 4.08600 H -1.19000 2.61500 4.62800 H -3.49900 2.43500 5.58400 H 0.01500 3.27800 -0.95100 H -0.50200 4.25500 0.45700 H 3.05900 2.03500 -2.73000 C 2.23100 1.58800 -2.14700 H 3.20400 -0.08700 -3.73200 H 2.15500 2.12700 -1.19100 H 0.70500 2.82100 -3.02300 C 0.93900 1.74400 -2.92700 C 2.83400 -0.62500 -2.84000 H 1.03700 1.34000 -3.95500 O 2.50900 0.26100 -1.80300 H 3.64500 -1.27000 -2.47000 C 1.66100 -1.51000 -3.21900 O -0.08500 1.06200 -2.24700 H 1.99800 -2.24800 -3.97300 H 0.83600 -0.92000 -3.66300 H -1.73500 2.30200 -2.36500 C -1.37600 1.32600 -2.73900 H -1.37200 1.35400 -3.84400 O 1.21900 -2.14200 -2.05300 C -2.29000 0.21600 -2.27800 C 0.25100 -3.13200 -2.24900 O -2.27400 0.20800 -0.87900 H -0.49800 -2.80600 -2.99900 H 0.70700 -4.07200 -2.61300 H -1.90500 -0.73900 -2.68300 H -3.31300 0.37900 -2.66700 O -1.10800 -2.16000 -0.55700 C -0.43600 -3.34500 -0.92000 C -3.00700 -0.81700 -0.24700 H -2.85300 -0.66100 0.83200 H 0.31600 -3.55800 -0.14500 C -2.50700 -2.19600 -0.63900 1256 H -1.13400 -4.19700 -0.97100 H -4.08700 -0.72800 -0.46800 H -2.82800 -2.47400 -1.66200 H -2.93100 -2.94300 0.05700 1257 Table C.2.204. Atomic coordinates and single point energies for E29. G = –xx GSP = –xx C 3.76300 -0.66000 0.38800 C 4.71800 -1.67300 0.47700 C 2.80900 -0.66200 -0.63600 C 4.74100 -2.69800 -0.46800 C 2.82900 -1.70700 -1.56800 C 3.79500 -2.70800 -1.49500 H 3.75300 0.14700 1.12500 H 5.45000 -1.66100 1.28700 H 5.49200 -3.48700 -0.40500 H 3.80800 -3.50700 -2.23900 H 2.06800 -1.72000 -2.35000 C 1.66500 0.34800 -0.67100 N 1.84900 1.63500 -0.62200 C 3.15300 2.24100 -0.76000 C 3.15200 3.14500 -1.99500 C 3.48900 3.06100 0.48800 H 4.12200 3.64700 -2.13400 H 2.37000 3.91400 -1.89400 H 2.92800 2.55500 -2.89500 H 4.47500 3.54400 0.40500 H 3.48900 2.42700 1.38800 H 2.73300 3.85000 0.63200 H 3.96100 1.49800 -0.90400 O 0.52300 -0.21300 -0.69300 Na -1.46200 -0.10200 0.19400 O -0.79300 1.99700 0.97700 O -0.55800 -0.10500 2.64500 O -2.41400 1.68400 -1.11000 O -0.90800 -2.36000 0.95800 1258 O -4.01300 -0.06100 0.21700 O -2.35900 -1.79000 -1.30900 C 0.53200 0.77900 2.51100 C 0.01400 2.14200 2.11300 H 0.88300 2.78300 1.89000 H -0.56700 2.59200 2.94000 H 1.07900 0.86000 3.47000 H 1.22900 0.42800 1.73300 C -0.18400 -1.41700 2.99100 C 0.22500 -2.23700 1.78500 H 0.63500 -1.40600 3.73200 H -1.06500 -1.88600 3.45400 H 0.56800 -3.23500 2.11900 H 1.04600 -1.75500 1.22400 C -0.64800 -3.03300 -0.25300 C -1.95300 -3.10400 -1.00400 H -0.28000 -4.05800 -0.05500 H 0.10500 -2.47100 -0.83000 H -2.70500 -3.60500 -0.36800 H -1.83100 -3.69500 -1.93000 C -3.72900 -1.63800 -1.58300 C -4.48100 -1.28300 -0.30900 H -4.15100 -2.55200 -2.04100 H -3.81900 -0.82300 -2.31700 H -4.29400 -2.04700 0.46000 H -5.57000 -1.24400 -0.49200 C -3.51000 2.17600 -0.38800 C -4.55800 1.08800 -0.39500 H -3.92100 3.09400 -0.85000 H -3.22700 2.40500 0.65500 H -4.83900 0.87700 -1.44100 H -5.46200 1.41900 0.14600 C -0.81400 3.08500 0.08900 C -1.31100 2.56100 -1.24600 H 0.20800 3.46400 -0.07100 H -1.45400 3.89500 0.49200 H -0.50300 1.96200 -1.68800 H -1.56900 3.40700 -1.91100 1259 Table C.2.205. Atomic coordinates and single point energies for E28. G = –2125.20887 GSP = –2127.255925 Na 1.14800 -0.37700 -0.11100 N -1.62900 0.92000 -0.43600 Si -1.82700 2.51400 0.29900 C -1.30100 3.77500 -1.02500 C -3.58400 3.02200 0.78100 C -0.75300 2.89900 1.80400 H -3.95000 2.39800 1.60800 H -4.29400 2.95000 -0.05700 H -3.57200 4.07100 1.12000 H -1.23900 2.51100 2.71100 H -0.63600 3.99100 1.90600 H 0.24500 2.44500 1.73900 H -0.24300 3.66800 -1.31000 H -1.42700 4.78600 -0.60700 H -1.90300 3.71800 -1.94400 C -1.60000 0.79700 -1.90300 C -2.95800 1.06000 -2.57500 C -1.04100 -0.52400 -2.44200 H -3.64500 0.21600 -2.42300 H -2.82800 1.20300 -3.66000 H -3.43800 1.96300 -2.16800 H -0.91000 1.58000 -2.26200 H -1.01700 -0.46300 -3.54100 H -1.67300 -1.37600 -2.16300 H -0.02300 -0.73400 -2.09900 H -2.23900 -0.00500 3.68200 C -4.41500 -0.35300 0.04500 C -5.60300 -1.01500 -0.25800 1260 C -1.86200 -0.30400 0.38600 C -3.18800 -1.02300 0.00300 C -5.58200 -2.36700 -0.60800 C -3.18100 -2.37800 -0.32400 C -4.36600 -3.04700 -0.63800 C -2.38000 -0.54900 2.73500 O -2.15100 0.34100 1.68600 O -0.84300 -1.11400 0.45100 H -4.43000 0.70300 0.31400 H -6.55100 -0.47500 -0.22300 H -6.51000 -2.88700 -0.85000 H -2.22100 -2.89500 -0.33300 H -4.34000 -4.10600 -0.90200 H -3.40700 -0.95900 2.71500 H -1.66900 -1.39200 2.68600 H 5.05000 -2.38300 -0.70500 H 3.83700 0.22700 1.68700 H 4.54000 0.73600 -1.64100 C 4.01200 -2.15000 -0.39800 H 4.76100 -0.88000 -2.37700 H 3.92100 -2.33900 0.67900 C 4.05400 -0.23200 -1.82800 O 3.73800 -0.78200 -0.56700 H 2.64100 -1.38800 3.40800 C 3.22900 1.07400 2.04800 O 1.86400 0.83200 1.80000 H 3.40400 1.21600 3.13100 C 3.04900 -3.03400 -1.18400 H 1.22500 0.60200 3.76100 C 1.66200 -1.33500 2.89400 H 3.21300 -4.09400 -0.91800 C 1.16000 0.09700 2.77900 H 3.08000 2.41400 -2.59300 O 3.48400 2.21100 -0.07700 H 3.25500 -2.94100 -2.26300 H 2.43700 -3.81000 1.56700 C 3.63200 2.33900 1.31400 H 4.69200 2.54800 1.52400 C 2.80100 -0.01600 -2.66300 O 1.76900 -1.85400 1.59600 H 3.07200 0.40100 -3.65000 H 0.93300 -1.90900 3.49400 C 2.15500 2.21100 -2.02700 C 1.51500 -3.21800 1.39400 C 2.30100 2.74200 -0.62200 O 1.71100 -2.65700 -0.98400 1261 O 1.88300 0.82400 -2.00300 H 2.33900 3.84900 -0.64700 H 2.27200 -0.96600 -2.82800 H 0.11500 0.09100 2.43400 H 3.03500 3.18800 1.69200 C 0.97700 -3.39200 -0.02200 H 0.74600 -3.58500 2.09600 H 1.32200 2.72500 -2.53500 H 0.96000 -4.46500 -0.28600 H 1.41600 2.44800 -0.03100 H -0.03300 -2.96300 -0.04900 1262 Table C.2.206. Atomic coordinates and single point energies for E27. G = –2125.185961 GSP = –2127.242656 Na 1.20700 -0.19600 -0.15300 N -0.67200 1.12400 -0.37900 Si -0.94300 2.64500 0.32600 C -0.46000 4.12400 -0.79500 C -2.71000 3.03400 0.94500 C 0.08900 2.89100 1.91200 H -3.01700 2.25600 1.66300 H -3.45500 3.05100 0.13600 H -2.74200 4.00900 1.46000 H -0.34100 2.33200 2.75900 H 0.06600 3.95700 2.19200 H 1.14100 2.58900 1.79900 H 0.63200 4.17200 -0.93700 H -0.77800 5.08600 -0.36000 H -0.91700 4.04300 -1.79500 C -1.14200 0.87500 -1.73200 C -2.56400 1.37900 -2.03500 C -1.10400 -0.61900 -2.07000 H -3.27600 0.93400 -1.32200 H -2.87800 1.10900 -3.05600 H -2.63600 2.47300 -1.94300 H -0.48200 1.36700 -2.49200 H -1.46000 -0.81400 -3.09400 H -1.75200 -1.16500 -1.36500 H -0.08700 -1.03400 -1.99800 H -1.70400 0.54700 3.48200 C -5.15700 0.12900 0.54700 C -6.26200 0.32200 -0.27700 C -3.08000 -1.17100 1.14100 1263 C -4.30600 -0.95700 0.32000 C -6.51600 -0.56400 -1.32500 C -4.56400 -1.84800 -0.72400 C -5.66800 -1.65000 -1.54800 C -1.66100 -0.24900 2.73100 O -2.92300 -0.25000 2.08500 O -2.31000 -2.09000 0.98200 H -4.93200 0.82700 1.35300 H -6.92300 1.17300 -0.10900 H -7.37800 -0.40500 -1.97500 H -3.87700 -2.68100 -0.88100 H -5.86600 -2.33900 -2.37000 H -1.46900 -1.22200 3.20900 H -0.89200 -0.03700 1.97200 H 4.59000 -3.07600 -0.54800 H 4.42300 -0.15800 1.32300 H 4.71100 -0.00800 -1.79100 C 3.60800 -2.61600 -0.32600 H 4.61300 -1.69300 -2.39100 H 3.44100 -2.68800 0.75900 C 4.04600 -0.87300 -1.91400 O 3.61700 -1.24500 -0.61800 H 2.85600 -1.91000 2.76800 C 3.97000 0.76500 1.72200 O 2.56300 0.65800 1.73500 H 4.34400 0.94300 2.74700 C 2.51800 -3.36800 -1.08000 H 2.53600 0.35300 3.78700 C 1.85700 -1.42600 2.77000 H 2.46200 -4.41000 -0.71500 C 1.97600 0.08300 2.87500 H 3.23900 1.96400 -2.98900 O 4.01500 1.75300 -0.49500 H 2.77500 -3.41700 -2.15100 H 1.67100 -3.71800 1.63300 C 4.36500 1.94200 0.85000 H 5.45900 2.06200 0.90500 C 2.86400 -0.48500 -2.79100 O 1.17700 -1.71600 1.58000 H 3.23100 -0.12500 -3.76900 H 1.30300 -1.80900 3.64800 C 2.41800 1.83900 -2.26100 C 0.81000 -3.06100 1.39700 C 2.83100 2.39200 -0.91600 O 1.28100 -2.71700 -0.97600 O 2.04900 0.47700 -2.17500 1264 H 2.99200 3.48300 -1.01300 H 2.21200 -1.35300 -2.97000 H 0.97000 0.51900 2.94900 H 3.90100 2.86100 1.25000 C 0.35700 -3.23200 -0.04200 H -0.02600 -3.33400 2.06400 H 1.54000 2.40400 -2.61200 H 0.15500 -4.30000 -0.23800 H 2.00700 2.23400 -0.19900 H -0.57200 -2.66900 -0.18700 1265 Table C.2.207. Atomic coordinates and single point energies for T11. G = –2125.170319 GSP = –2127.225308 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.41700 Si 1.46700 0.00000 3.31700 C 1.99600 1.75400 3.87100 C 1.54300 -1.03500 4.91700 C 2.98100 -0.65600 2.35500 H 1.52400 -2.10900 4.67600 H 0.71700 -0.82000 5.61200 H 2.49200 -0.83000 5.44000 H 3.07100 -1.75000 2.43900 H 3.88800 -0.22700 2.81400 H 2.99500 -0.39100 1.28600 H 2.39300 2.34700 3.03200 H 2.80400 1.67300 4.61500 H 1.17600 2.32600 4.33000 C -0.96200 1.05500 2.73300 C -1.51700 1.02600 4.17000 C -2.15500 1.09900 1.76700 H -2.15000 0.14200 4.33600 H -2.12600 1.92200 4.37300 H -0.70300 1.00000 4.91000 H -0.47700 2.05200 2.62900 H -2.80300 1.95800 2.00400 H -2.76100 0.18900 1.84500 H -1.84800 1.21000 0.71900 H 1.88600 -3.59200 1.49300 C -1.52000 -2.48100 4.38400 C -2.47600 -2.58600 5.39000 C -0.91300 -2.04900 1.96300 C -1.90700 -2.15700 3.08100 C -3.82700 -2.38800 5.09900 1266 C -3.26200 -2.00700 2.78300 C -4.22000 -2.11200 3.79000 C 1.05000 -2.97500 1.14100 O 0.20600 -2.76200 2.24100 O -1.24900 -1.83600 0.79900 H -0.46500 -2.62800 4.60300 H -2.16500 -2.82100 6.40900 H -4.57500 -2.46400 5.89000 H -3.54900 -1.80500 1.75100 H -5.27700 -1.98100 3.55100 H 0.51600 -3.47800 0.32000 H 1.43600 -2.01500 0.77200 H -0.50100 1.70500 -4.62400 H 2.63400 1.00000 -2.88900 H 0.99500 3.60000 -2.28100 C -0.37400 1.08400 -3.71400 H -0.56700 3.49800 -3.15300 H 0.16200 0.17100 -4.01100 C 0.06900 3.01700 -2.38500 O 0.45300 1.72100 -2.78500 H 1.87100 -1.27400 -3.43600 C 3.42200 0.77500 -2.15100 O 2.93900 -0.10900 -1.16200 H 4.28900 0.31700 -2.66600 C -1.76100 0.74200 -3.18300 H 3.86900 -1.73100 -2.04400 C 1.77700 -1.81500 -2.47300 H -2.31300 0.18000 -3.95900 C 2.92100 -1.45500 -1.54500 H 1.04300 4.20900 0.22300 O 2.80800 2.83600 -1.02100 H -2.32500 1.67000 -3.00300 H -0.41500 -1.80700 -3.67400 C 3.87400 2.07100 -1.51000 H 4.38600 2.67100 -2.27900 C -0.65600 2.99500 -1.04900 O 0.54400 -1.50600 -1.87500 H -0.92300 4.02600 -0.75300 H 1.83900 -2.89700 -2.69600 C 1.09800 3.16800 0.58500 C -0.55400 -2.01200 -2.59500 C 2.48000 2.62200 0.33100 O -1.73900 0.02700 -1.97300 O 0.11800 2.37500 -0.05500 H 3.20400 3.14000 0.99000 H -1.58900 2.41500 -1.11300 1267 H 2.85000 -2.04600 -0.62200 H 4.60400 1.85200 -0.70900 C -1.83600 -1.37700 -2.08200 H -0.62400 -3.11000 -2.47900 H 0.89700 3.16300 1.66700 H -2.66800 -1.65800 -2.75400 H 2.49500 1.55000 0.58800 H -2.05000 -1.74400 -1.07300 1268 Table C.2.208. Atomic coordinates and single point energies for T21. G = –2125.159986 GSP = –2127.21439 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.37000 Si 1.46400 0.00000 3.28800 C 2.09000 1.76700 3.67500 C 1.39100 -0.83300 5.01400 C 2.90900 -0.80400 2.36300 H 2.06800 -1.69900 5.07800 H 0.37200 -1.17600 5.24100 H 1.68500 -0.11900 5.80000 H 2.74100 -1.87200 2.16200 H 3.81500 -0.72200 2.98400 H 3.10700 -0.28500 1.41100 H 2.41000 2.31000 2.77300 H 2.96600 1.70000 4.34000 H 1.33100 2.37700 4.18900 C -0.96100 1.01700 2.81000 C -1.35000 0.94600 4.30000 C -2.26700 1.03600 2.00300 H -1.76000 -0.04700 4.53000 H -2.10800 1.70900 4.54200 H -0.48500 1.12300 4.95800 H -0.51900 2.02600 2.66300 H -2.79100 1.99300 2.15900 H -2.93500 0.23200 2.33600 H -2.09700 0.92000 0.92300 H -3.35500 -0.95900 0.10700 C 0.66200 -3.20700 0.96000 1269 C 1.73000 -4.10600 0.94700 C -1.15000 -1.94800 2.24200 C 0.06600 -2.83700 2.16800 C 2.21000 -4.64400 2.14000 C 0.52300 -3.41100 3.35700 C 1.59800 -4.29600 3.34600 C -3.04000 -1.76000 0.78900 O -1.63700 -1.67100 0.95400 O -1.89600 -1.96300 3.19400 H 0.28300 -2.79300 0.02700 H 2.18800 -4.39400 -0.00200 H 3.04800 -5.34200 2.13000 H 0.01000 -3.15400 4.28300 H 1.95500 -4.72700 4.28300 H -3.30300 -2.73800 0.35200 H -3.54900 -1.66100 1.75300 H -0.89700 1.55000 -4.48300 H 2.30300 0.96400 -2.83800 H 0.39900 3.59600 -2.27100 C -0.66500 0.91700 -3.60400 H -1.18000 3.26400 -3.04900 H 0.00700 0.11700 -3.94400 C -0.45500 2.90500 -2.29500 O 0.05200 1.63600 -2.64400 H 2.23500 -1.45500 -3.24800 C 3.12200 0.90200 -2.10200 O 2.73400 0.10500 -1.00400 H 4.01800 0.46500 -2.58700 C -1.97300 0.33800 -3.07800 H 3.96700 -1.49700 -1.45600 C 2.00400 -1.85700 -2.24200 H -2.46800 -0.23500 -3.88400 C 2.91800 -1.27300 -1.18500 H 0.55300 4.29700 0.15900 O 2.35200 2.99000 -1.13200 H -2.65400 1.15900 -2.80400 H -0.15400 -1.90600 -3.76400 C 3.46500 2.29900 -1.62900 H 3.85100 2.86800 -2.48900 C -1.10800 2.86500 -0.92400 O 0.67500 -1.55400 -1.90300 H -1.48100 3.87000 -0.65300 H 2.15500 -2.95300 -2.28100 C 0.72600 3.28700 0.57000 C -0.27800 -2.19900 -2.70400 C 2.13100 2.84500 0.25100 1270 O -1.81100 -0.46100 -1.93000 O -0.22300 2.37700 0.04800 H 2.84600 3.46700 0.82400 H -1.97100 2.18000 -0.92300 H 2.70700 -1.74400 -0.21400 H 4.26600 2.24600 -0.86900 C -1.64900 -1.84100 -2.16100 H -0.15400 -3.29800 -2.65600 H 0.60200 3.33000 1.66300 H -2.43200 -2.22000 -2.84200 H 2.25700 1.79700 0.57300 H -1.76600 -2.32300 -1.18500 1271 Table C.2.209. Atomic coordinates and single point energies for T22. G = –2125.167755 GSP = –2127.218472 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.45100 Si 1.53000 0.00000 3.29500 C 1.58200 0.74900 5.04200 C 2.25500 -1.75300 3.56000 C 2.85600 0.97300 2.35500 H 3.30300 -1.65900 3.89000 H 2.23600 -2.39100 2.66400 H 1.71300 -2.28900 4.35500 H 3.84400 0.70900 2.76600 H 2.68900 2.04500 2.52500 H 2.86800 0.78900 1.27300 H 1.05400 1.71200 5.05000 H 2.63500 0.93400 5.31400 H 1.14900 0.09200 5.81000 C -1.08300 -0.80900 3.01400 C -1.29500 -0.67600 4.53100 C -0.98000 -2.30900 2.68500 H -0.51500 -1.22700 5.08200 H -2.27000 -1.09400 4.83000 H -1.25200 0.37300 4.84800 H -2.03200 -0.46800 2.55400 H -1.87900 -2.84600 3.03100 H -0.11200 -2.76100 3.18600 H -0.87100 -2.47800 1.60600 H 0.70000 3.52300 -0.43100 C -2.80200 1.63300 1.43200 1272 C -4.17300 1.60600 1.69000 C -0.40600 2.08400 2.21800 C -1.90000 2.01400 2.42800 C -4.65700 1.97000 2.94700 C -2.39200 2.40000 3.67600 C -3.76000 2.37200 3.93700 C 0.99400 2.92500 0.44200 O -0.11500 2.13500 0.83000 O 0.30400 2.69700 2.99700 H -2.42100 1.34200 0.45500 H -4.87100 1.30300 0.90600 H -5.72800 1.95000 3.15100 H -1.67300 2.72500 4.43000 H -4.13100 2.67200 4.91900 H 1.29700 3.57700 1.27000 H 1.84400 2.28400 0.16200 H 0.30700 -0.04600 -4.93500 H -0.73000 -2.49200 -2.58200 H 2.40000 -1.67900 -2.94600 C -0.01400 0.17000 -3.89700 H 2.42500 -0.22300 -3.98700 H -1.07700 -0.09600 -3.81700 C 2.06000 -0.63600 -3.02800 O 0.65100 -0.65900 -2.98700 H -2.94600 -1.19500 -2.47800 C -0.89400 -3.03100 -1.63500 O -1.13600 -2.11400 -0.58800 H -1.75700 -3.71400 -1.74100 C 0.19600 1.65900 -3.63900 H -3.14500 -2.60000 -0.40900 C -2.92000 -0.73300 -1.47200 H -0.42600 2.24000 -4.34600 C -2.47400 -1.72200 -0.41400 H 3.69400 -1.77700 -0.84100 O 1.49800 -3.05800 -1.26800 H 1.24500 1.92100 -3.85200 H -2.61500 1.21100 -3.22600 C 0.33900 -3.84600 -1.30400 H 0.47100 -4.61000 -2.08700 C 2.62300 0.17100 -1.87100 O -2.01000 0.33600 -1.45600 H 3.72600 0.19700 -1.92800 H -3.94300 -0.38400 -1.23400 C 2.88300 -1.49600 -0.14800 C -2.42400 1.47200 -2.16700 C 1.92700 -2.65300 0.01000 1273 O -0.05600 2.03500 -2.31200 O 2.20400 -0.34800 -0.63000 H 2.44600 -3.48200 0.53000 H 2.25000 1.20600 -1.90400 H -2.53100 -1.24300 0.57700 H 0.18800 -4.36900 -0.34200 C -1.34200 2.52800 -2.03000 H -3.37000 1.87200 -1.75200 H 3.32500 -1.25300 0.83100 H -1.58800 3.38600 -2.68200 H 1.08100 -2.33900 0.64700 H -1.30900 2.86800 -0.98600 1274 Table C.2.210. Atomic coordinates and single point energies for E2. G = –1041.39379 GSP = –1042.35379 N -0.66300 0.52600 0.20900 Si -1.83900 -0.84000 0.09700 C -1.39500 -2.56700 0.79600 C -3.02200 -0.28900 1.57400 C -3.23900 -0.97800 -1.20600 H -2.49300 -0.08800 2.52300 H -3.75200 -1.09300 1.77300 H -3.60300 0.61400 1.31900 H -4.16300 -1.39500 -0.77500 H -2.91800 -1.59400 -2.05900 H -3.48200 0.02700 -1.59300 H -2.27300 -3.05800 1.24700 H -0.63600 -2.46100 1.59100 H -0.98000 -3.21800 0.01200 C -0.28600 1.63000 1.05700 C -1.42900 2.61600 1.31700 C 0.34700 1.17000 2.37800 H -1.05500 3.52100 1.82300 H -2.20100 2.16300 1.95300 H -1.89800 2.91100 0.36800 H 0.48600 2.19200 0.49900 H -0.38600 0.58900 2.95800 H 0.67700 2.02500 2.99200 H 1.21500 0.52500 2.17900 H -0.71700 2.19000 -3.31200 C 3.90600 0.55600 -0.09000 C 2.61900 0.82000 -0.56200 C 4.21600 -0.69400 0.44300 1275 C 1.62200 -0.15700 -0.49500 C 3.23000 -1.68300 0.48800 C 0.16600 0.11200 -0.90300 C 1.94600 -1.41600 0.01800 C -0.92800 1.43200 -2.54400 O -0.50200 -0.98700 -1.30600 O 0.27700 1.13500 -1.90500 H 4.67400 1.33200 -0.14300 H 2.37000 1.78700 -1.00100 H 5.22200 -0.90200 0.81300 H 3.46700 -2.67100 0.88900 H 1.16200 -2.17500 0.03200 H -1.67800 1.83600 -1.83900 H -1.35900 0.53500 -3.01700 1276 Table C.2.211. Atomic coordinates and single point energies for E1. G = –1041.363568 GSP = –1042.326452 N -0.99100 0.01400 0.57900 Si -2.07700 -0.44500 -0.60900 C -1.34300 -1.27300 -2.18100 C -3.48600 -1.65100 -0.08900 C -2.97300 1.09200 -1.28000 H -3.09000 -2.62800 0.23400 H -4.18500 -1.83100 -0.92500 H -4.06000 -1.23000 0.75300 H -3.61400 0.86000 -2.14700 H -2.21600 1.83200 -1.58300 H -3.60200 1.54400 -0.49500 H -2.12800 -1.65700 -2.85600 H -0.67100 -2.10700 -1.91900 H -0.75300 -0.52800 -2.73900 C -0.43800 -0.73800 1.64900 C -1.42800 -0.96000 2.81100 C 0.16300 -2.09700 1.23600 H -0.95400 -1.44200 3.68600 H -2.26300 -1.59600 2.47500 H -1.84900 0.00900 3.12100 H 0.40700 -0.16100 2.09800 H -0.63800 -2.76100 0.86600 H 0.67300 -2.60900 2.07200 H 0.88700 -1.95500 0.41900 H -0.43200 3.50700 2.07900 C 3.54900 -0.66900 0.72300 C 2.59200 0.34400 0.78800 1277 C 3.71800 -1.39900 -0.45200 C 1.79500 0.62400 -0.32500 C 2.93700 -1.10400 -1.57300 C 0.75500 1.70100 -0.31000 C 1.98700 -0.09000 -1.51100 C -0.50700 3.06000 1.07900 O 0.21100 2.11700 -1.30500 O 0.67000 2.30000 0.88900 H 4.16000 -0.89500 1.59900 H 2.44400 0.92100 1.70000 H 4.46000 -2.20000 -0.49700 H 3.06600 -1.67300 -2.49500 H 1.35900 0.16000 -2.36600 H -1.35800 2.36200 1.01800 H -0.59600 3.84600 0.31600 1278 Table C.2.212. Atomic coordinates and single point energies for T12. G = –1041.362248 GSP = –1042.324724 N 0.00000 0.00000 0.00000 Si 0.00000 0.00000 1.67800 C 1.72100 0.00000 2.52600 C -0.94000 1.43600 2.54600 C -0.82500 -1.58200 2.33600 H -0.51800 2.42200 2.29000 H -0.89400 1.32500 3.64300 H -2.00200 1.44100 2.24900 H -0.74800 -1.67100 3.43300 H -0.33000 -2.44900 1.87300 H -1.89300 -1.60500 2.06000 H 1.64500 0.12900 3.62000 H 2.36800 0.79700 2.12400 H 2.21000 -0.96800 2.33200 C -0.07800 1.07900 -0.92100 C -1.47200 1.73400 -0.98400 C 0.98600 2.17500 -0.71300 H -1.54900 2.48300 -1.79300 H -1.69900 2.23500 -0.02900 H -2.23400 0.95600 -1.14400 H 0.09800 0.68100 -1.94900 H 0.82200 2.67200 0.25900 H 0.96100 2.94800 -1.50300 H 1.99100 1.72500 -0.69600 H -1.58000 -2.71500 -2.25800 C 3.38400 0.43900 -2.99800 C 2.33200 -0.39700 -2.62000 C 4.44300 0.67500 -2.12400 1279 C 2.33000 -0.99100 -1.35400 C 4.45600 0.05800 -0.86900 C 1.22900 -1.89900 -0.89800 C 3.41000 -0.77800 -0.49200 C -0.90900 -2.64400 -1.39300 O 1.32400 -2.63200 0.06100 O 0.28400 -2.04900 -1.85200 H 3.37200 0.91200 -3.98200 H 1.49900 -0.59300 -3.29300 H 5.26000 1.33700 -2.41800 H 5.28500 0.23500 -0.18200 H 3.39200 -1.26700 0.48100 H -1.33400 -1.98800 -0.61700 H -0.71700 -3.64500 -0.97700 1280 Table C.2.213. Atomic coordinates and single point energies for E8. G = –2179.666164 GSP = –2181.402806 Na -0.02700 1.72600 0.08300 Na 2.25100 -0.64800 -0.67500 N -1.87200 -1.14700 -0.00300 N 2.26400 1.56900 -0.41900 Si -1.27000 -1.68100 1.55100 C -0.79500 -3.50900 1.35300 C -2.50100 -1.63500 2.97400 C 0.31800 -0.80500 2.14000 C -1.65700 -1.94500 -1.21300 C -2.69700 -1.71200 -2.31000 H -2.51300 -2.41000 -3.14000 H -2.63700 -0.68300 -2.68800 H -3.71300 -1.88400 -1.92800 C -0.23500 -1.75600 -1.76500 H -1.75300 -3.00200 -0.91900 H -0.05300 -2.35800 -2.67000 H 0.47800 -2.09500 -0.99300 H -0.09700 -0.68700 -1.99100 H -1.67000 -4.13000 1.10600 H -0.39100 -3.87500 2.31100 H -0.03300 -3.68200 0.57700 H -3.33200 -2.33600 2.80400 H -2.91400 -0.62600 3.10800 H -1.99800 -1.93200 3.90800 H 0.89700 -0.38900 1.29800 H 0.98300 -1.47700 2.70600 H 0.06100 0.04600 2.78800 C 2.40600 2.17300 -1.73800 C 1.17500 2.99000 -2.16300 C 2.68800 1.11100 -2.81100 1281 H 0.28300 2.34400 -2.25000 H 1.31900 3.48400 -3.13600 H 0.96800 3.78200 -1.42300 H 3.27100 2.86800 -1.77100 H 2.83000 1.55200 -3.80800 H 1.83500 0.41100 -2.89600 H 3.60200 0.54600 -2.56300 Si 2.85800 2.37200 0.97200 C 3.66500 1.16300 2.18800 C 1.44500 3.18600 1.98400 C 4.09800 3.75100 0.59800 H 2.97600 0.33900 2.43500 H 3.93600 1.66200 3.13100 H 4.58300 0.73300 1.75600 H 0.74300 2.43600 2.39100 H 0.87300 3.91300 1.38000 H 1.83900 3.73700 2.85200 H 4.47400 4.19400 1.53300 H 3.64100 4.55800 0.00500 H 4.96200 3.36800 0.03300 C -6.56300 0.75500 -0.66500 C -6.06400 -0.17600 0.24800 C -5.67600 1.50800 -1.43400 C -4.68800 -0.35100 0.38700 C -4.30000 1.33200 -1.28900 C -3.79500 0.40300 -0.37900 C 3.59700 -3.00000 -1.71700 C 4.61700 -2.09500 -1.40700 C 2.78700 -3.51400 -0.70000 C 2.99200 -3.11800 0.62600 C 4.82300 -1.70000 -0.08200 C 4.01000 -2.21100 0.93400 H -7.64000 0.88900 -0.77800 H -6.75200 -0.77200 0.85000 H -4.29500 -1.08900 1.08700 H -3.58000 1.89800 -1.88200 H -6.06000 2.23300 -2.15400 H 4.16600 -1.89300 1.96600 H 5.61100 -0.98500 0.15700 H 5.25000 -1.69400 -2.20000 H 1.99100 -4.22000 -0.94000 H 3.43300 -3.30500 -2.75200 C -2.26300 0.26900 -0.22500 H 2.35200 -3.51400 1.41600 O -1.92600 0.82000 1.15700 O -1.58900 0.90100 -1.13700 1282 C -2.56700 2.01300 1.52600 H -2.56700 2.74200 0.69400 H -2.01700 2.44500 2.37700 H -3.61400 1.85000 1.82800 1283 Table C.2.214. Atomic coordinates and single point energies for 37. G = –2179.682674 GSP = –2181.424485 Na 0.35600 -0.80800 -0.26800 Na -2.25000 0.47600 -0.39400 N -0.16400 1.48000 -0.18200 N -1.75500 -1.78100 -0.60500 Si 0.14400 2.14100 1.36000 C -0.53700 3.89800 1.62700 C 1.99300 2.30200 1.79800 C -0.69400 1.02400 2.64800 C 0.40500 2.18600 -1.32100 C 1.69800 1.52500 -1.82400 H 2.17900 2.09500 -2.63500 H 1.48100 0.51600 -2.21900 H 2.41800 1.41900 -0.99800 C -0.60100 2.28500 -2.47100 H 0.68200 3.23600 -1.07000 H -0.18800 2.79500 -3.35500 H -1.49800 2.83200 -2.14200 H -0.91100 1.27100 -2.78400 H -0.14200 4.58900 0.86600 H -0.25900 4.29800 2.61500 H -1.63500 3.91300 1.55100 H 2.47500 3.01200 1.10500 H 2.53900 1.35000 1.71100 H 2.14400 2.68600 2.82000 H -1.79000 1.14400 2.60800 1284 H -0.37900 1.27000 3.67400 H -0.48200 -0.04600 2.48100 C -1.83600 -2.28200 -1.96400 C -0.49100 -2.17500 -2.70300 C -2.91300 -1.55300 -2.77800 H -0.18500 -1.11500 -2.78000 H -0.53700 -2.57400 -3.72800 H 0.29100 -2.73100 -2.16000 H -2.11200 -3.35800 -1.99500 H -3.00600 -1.94400 -3.80400 H -2.67200 -0.47600 -2.85700 H -3.88700 -1.64900 -2.27400 Si -2.01900 -2.81000 0.73100 C -3.19400 -2.03400 2.00500 C -0.40600 -3.13400 1.70800 C -2.72200 -4.51200 0.28600 H -2.84300 -1.03300 2.30800 H -3.26700 -2.64600 2.91800 H -4.20600 -1.92800 1.58200 H 0.00700 -2.19300 2.11200 H 0.36200 -3.58300 1.05600 H -0.56300 -3.80700 2.56600 H -2.92800 -5.09100 1.19900 H -2.02200 -5.09700 -0.33000 H -3.66500 -4.41900 -0.27600 C 6.73800 0.40300 -1.72500 C 6.85100 0.51400 -0.33900 C 5.58500 -0.13700 -2.29700 C 5.81300 0.08400 0.48200 C 4.54200 -0.56600 -1.48200 C 4.65600 -0.45400 -0.09200 C -4.30000 2.34000 -1.41400 C -4.94900 1.10400 -1.36000 C -3.84800 2.94600 -0.23900 C -4.05800 2.32000 0.99200 C -5.14400 0.47000 -0.13000 C -4.70500 1.08200 1.04800 H 7.55400 0.74200 -2.36500 H 7.75300 0.93900 0.10300 H 5.88400 0.16600 1.56600 H 3.63000 -0.98800 -1.90600 H 5.49900 -0.22200 -3.38100 H -4.85700 0.58600 2.00700 H -5.63200 -0.50400 -0.08900 H -5.28900 0.62500 -2.27900 H -3.32200 3.90100 -0.28200 1285 H -4.13700 2.82800 -2.37700 C 3.51800 -0.91200 0.74600 H -3.70700 2.79300 1.91100 O 3.76600 -0.87100 2.04500 O 2.45400 -1.28900 0.29600 C 2.70400 -1.25400 2.91400 H 1.86200 -0.55400 2.80800 H 3.11100 -1.20400 3.92800 H 2.36300 -2.27000 2.67900 1286 Table C.2.215. Atomic coordinates and single point energies for T1. G = –2179.633266 GSP = –2181.373122 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.33100 N 2.35400 0.00000 0.22300 N -1.57400 0.12600 1.72700 Si 2.97200 -1.47800 0.89200 C 3.48200 -1.31900 2.73400 C 4.52000 -2.26100 0.12800 C 1.63700 -2.82500 0.95200 C 2.81300 1.26800 0.79400 C 2.59200 2.48400 -0.12300 H 2.59300 3.41200 0.47000 H 1.62300 2.40700 -0.64300 H 3.37100 2.58300 -0.88600 C 2.10100 1.59100 2.12500 H 3.90100 1.25000 1.02500 H 2.50400 2.50400 2.59400 H 2.22600 0.77000 2.84400 H 1.02700 1.76600 1.92900 H 4.12900 -0.44900 2.92900 H 4.04300 -2.22300 3.01700 H 2.61500 -1.25800 3.41400 H 5.40300 -1.61400 0.25400 H 4.38500 -2.47200 -0.94100 H 4.73400 -3.20900 0.64700 H 0.71300 -2.44800 1.42700 H 1.98700 -3.67600 1.55800 H 1.36400 -3.21700 -0.03700 C -2.24300 1.41000 1.55800 1287 C -1.75800 2.17300 0.31700 C -2.07400 2.30000 2.79700 H -0.68200 2.41000 0.39700 H -2.28600 3.13000 0.18700 H -1.91900 1.58200 -0.59900 H -3.33800 1.28200 1.42700 H -2.58800 3.26800 2.69600 H -1.00200 2.51400 2.97000 H -2.47300 1.78400 3.68400 Si -2.46500 -1.33700 1.69700 C -1.88400 -2.46500 3.12000 C -2.19600 -2.33100 0.09600 C -4.33200 -1.11900 1.90900 H -0.78800 -2.60500 3.14400 H -2.32100 -3.47300 3.04600 H -2.19900 -2.03600 4.08600 H -1.14600 -2.65100 -0.00500 H -2.45500 -1.72100 -0.78500 H -2.81200 -3.24300 0.06300 H -4.82300 -2.09900 2.00400 H -4.78400 -0.60300 1.04800 H -4.56500 -0.53200 2.81300 C 5.09700 2.24900 -3.56300 C 5.44200 1.21400 -2.69000 C 3.75800 2.46600 -3.88300 C 4.45200 0.40900 -2.13300 C 2.76600 1.66300 -3.32000 C 3.11000 0.64500 -2.43000 C 0.94600 1.52500 5.62700 C -0.42700 1.40700 5.85800 C 1.75200 0.38200 5.61100 C 1.18300 -0.87700 5.82600 C -0.99700 0.14800 6.06500 C -0.19100 -0.99400 6.05400 H 5.87400 2.88200 -3.99500 H 6.49000 1.03600 -2.44200 H 4.70900 -0.39000 -1.44100 H 1.71100 1.82600 -3.54000 H 3.48300 3.26700 -4.57200 H -0.63500 -1.97800 6.21400 H -2.07200 0.05600 6.23100 H -1.05600 2.29800 5.86300 H 2.82300 0.47000 5.42000 H 1.39000 2.50600 5.45300 C 1.98600 -0.18700 -1.86400 H 1.81300 -1.76800 5.81200 1288 O 2.29200 -1.53200 -1.92400 O 0.81100 0.16600 -2.01700 C 1.27100 -2.36600 -2.42900 H 0.37200 -2.36400 -1.79400 H 1.69000 -3.37900 -2.46000 H 0.97300 -2.05300 -3.44100 1289 Table C.2.216. Atomic coordinates and single point energies for E10. G = –2179.63182 GSP = –2181.370131 Na 0.76600 1.03300 -0.23200 Na -2.38000 -0.37900 -0.15400 N -1.47800 1.69500 -0.15700 N 1.56500 -1.26000 -0.32200 Si -1.72800 2.35500 1.40900 C -2.35100 4.13900 1.41500 C -0.12600 2.30700 2.42700 C -3.00200 1.33300 2.39500 C -1.71500 2.50800 -1.34400 C -0.41200 2.94100 -2.03300 H -0.59600 3.61500 -2.88500 H 0.14000 2.07100 -2.43000 H 0.24000 3.47400 -1.32100 C -2.62300 1.79000 -2.34900 H -2.24300 3.44900 -1.08700 H -2.79500 2.38300 -3.26100 H -3.60300 1.58400 -1.88900 H -2.17200 0.83000 -2.66200 H -1.64500 4.81300 0.90600 H -2.46700 4.49500 2.45000 H -3.32700 4.23400 0.91500 H 0.64000 2.95300 1.96800 H 0.28300 1.28400 2.48300 H -0.27400 2.64700 3.46400 H -3.98700 1.39400 1.90300 1290 H -3.11700 1.71400 3.42200 H -2.72600 0.26800 2.48600 C 0.99200 -1.87400 -1.54200 C 0.60900 -0.79700 -2.55600 C -0.19700 -2.81400 -1.36900 H -0.24900 -0.20100 -2.19100 H 0.31500 -1.23900 -3.52000 H 1.46200 -0.13100 -2.74200 H 1.80700 -2.45400 -2.00200 H -0.41100 -3.28400 -2.34000 H -1.11600 -2.28200 -1.07100 H -0.02300 -3.61900 -0.64100 Si 1.31300 -2.06400 1.24400 C -0.56200 -1.92100 1.66100 C 2.00500 -1.24400 2.79800 C 1.81200 -3.88700 1.25100 H -0.83500 -0.84900 1.67400 H -0.72800 -2.28800 2.68600 H -1.24400 -2.47800 1.00400 H 1.69500 -0.19700 2.92700 H 3.09900 -1.29700 2.82600 H 1.60100 -1.80500 3.65600 H 0.99600 -4.55700 1.56100 H 2.66000 -4.03200 1.93600 H 2.15500 -4.18200 0.24800 C 3.38300 3.40000 -0.29400 C 3.35700 2.62300 0.86600 C 3.40900 2.77200 -1.54100 C 3.31700 1.22800 0.77700 C 3.37900 1.37800 -1.62500 C 3.29600 0.59200 -0.47000 C -3.74400 -2.94700 -0.38100 C -4.22700 -2.41300 0.81700 C -4.01800 -2.30600 -1.59300 C -4.77700 -1.13300 -1.60800 C -4.98800 -1.24000 0.80300 C -5.26000 -0.59900 -0.40900 H 3.40700 4.48900 -0.22500 H 3.37400 3.10400 1.84600 H 3.31000 0.61700 1.68000 H 3.43900 0.85000 -2.57800 H 3.46000 3.37100 -2.45200 H -5.84500 0.32200 -0.41900 H -5.35900 -0.82000 1.73800 H -4.00500 -2.90800 1.76400 H -3.63500 -2.72100 -2.52700 1291 H -3.14400 -3.85900 -0.37000 C 3.13500 -0.94800 -0.65300 H -4.98700 -0.63100 -2.55300 O 3.73800 -1.58000 0.52000 O 3.52300 -1.37400 -1.76900 C 5.11800 -1.77600 0.38900 H 5.66400 -0.81300 0.38000 H 5.34700 -2.31100 -0.54400 H 5.45600 -2.36300 1.25500 1292 Table C.2.217. Atomic coordinates and single point energies for E6. G = –2179.671556 GSP = –2181.413918 Na 0.90200 0.81300 -0.22300 Na -1.60500 -0.63100 -0.01800 N -1.24300 1.65900 -0.16300 N 0.59500 -1.47300 -0.07000 Si -1.55800 2.53500 1.27100 C -1.26500 4.40600 1.12600 C -0.41400 1.88100 2.63400 C -3.33800 2.32000 1.90800 C -1.88100 2.13600 -1.38100 C -0.87000 2.78200 -2.33600 H -1.34100 3.16900 -3.25500 H -0.11000 2.03700 -2.63400 H -0.35400 3.61100 -1.82800 C -2.62800 1.00700 -2.10300 H -2.65100 2.91600 -1.17700 H -3.13300 1.34900 -3.02000 H -3.39600 0.57500 -1.44200 H -1.92100 0.21100 -2.40300 H -0.20800 4.61600 0.89800 H -1.52400 4.93500 2.05700 H -1.87300 4.84000 0.31600 H 0.64500 2.08400 2.40600 H -0.52500 0.79200 2.76700 H -0.63500 2.35400 3.60300 H -4.06500 2.52800 1.10600 H -3.57300 2.97900 2.75900 H -3.49100 1.27800 2.23500 C 0.80300 -2.20800 -1.30600 1293 C 1.10900 -1.25600 -2.46700 C -0.40200 -3.08300 -1.69200 H 0.28600 -0.52900 -2.58600 H 1.22500 -1.78700 -3.42500 H 2.04400 -0.70900 -2.28100 H 1.67200 -2.89800 -1.23700 H -0.21000 -3.69100 -2.59100 H -1.28100 -2.44800 -1.90900 H -0.66700 -3.76300 -0.86600 Si 0.85400 -2.21700 1.44800 C -0.78300 -2.38900 2.42600 C 1.99000 -1.20300 2.57900 C 1.60000 -3.95800 1.34800 H -1.28100 -1.41200 2.56100 H -0.62200 -2.79900 3.43500 H -1.48200 -3.06400 1.90400 H 1.64300 -0.16200 2.67400 H 3.00800 -1.18700 2.16100 H 2.03700 -1.62800 3.59400 H 1.72000 -4.38400 2.35600 H 2.59300 -3.93800 0.87300 H 0.96900 -4.64500 0.76400 C 2.53200 3.45700 -0.26000 C 2.95700 2.75600 0.87200 C 2.72800 2.91700 -1.53400 C 3.56300 1.50500 0.73700 C 3.33900 1.67200 -1.67500 C 3.74300 0.95900 -0.53900 C -3.74200 -2.47100 -0.08400 C -4.19600 -1.58400 0.89700 C -4.28700 -2.43300 -1.37000 C -5.29900 -1.52100 -1.66900 C -5.20100 -0.66200 0.59000 C -5.75500 -0.63800 -0.68900 H 2.04800 4.42800 -0.14900 H 2.81200 3.18500 1.86500 H 3.88600 0.94200 1.61200 H 3.50400 1.22500 -2.65600 H 2.39700 3.46600 -2.41600 H -6.54300 0.07900 -0.92600 H -5.55100 0.03600 1.35200 H -3.77500 -1.62300 1.90400 H -3.92600 -3.12400 -2.13400 H -2.96700 -3.20400 0.15500 C 4.34800 -0.39400 -0.75000 H -5.73000 -1.49400 -2.67100 1294 O 4.67300 -0.99500 0.39400 O 4.51400 -0.89100 -1.83200 C 5.18900 -2.31400 0.27500 H 6.16400 -2.29700 -0.23000 H 4.50000 -2.93800 -0.30900 H 5.28900 -2.69800 1.29500 1295 Table C.2.218. Atomic coordinates and single point energies for T2. G = –2179.630731 GSP = –2181.370011 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.44000 N 1.53200 0.00000 1.77100 N -2.40300 0.05500 0.24200 Si 2.27300 -1.54900 1.76400 C 4.14800 -1.51900 1.52900 C 1.53900 -2.63100 0.38900 C 1.94700 -2.49100 3.39200 C 2.34700 1.20500 1.67500 C 2.21200 1.89700 0.31100 H 2.87600 2.77100 0.21900 H 1.18100 2.25900 0.14700 H 2.46600 1.19400 -0.49900 C 2.02400 2.20000 2.79800 H 3.42600 0.97300 1.78600 H 2.61500 3.12600 2.72300 H 2.23500 1.74100 3.77700 H 0.95800 2.48900 2.76500 H 4.42500 -1.01200 0.59100 H 4.54000 -2.54600 1.48400 H 4.65900 -1.00000 2.35500 H 1.77400 -2.20700 -0.60100 H 0.44100 -2.69900 0.47700 H 1.92500 -3.66100 0.41200 H 2.40400 -1.94700 4.23600 1296 H 2.38100 -3.50300 3.37000 H 0.87000 -2.61600 3.60500 C -2.76700 1.29000 0.95600 C -1.66600 2.34200 0.82200 C -3.11200 1.16900 2.44200 H -0.75800 2.02600 1.37000 H -1.98000 3.31200 1.23600 H -1.41600 2.49700 -0.23500 H -3.65300 1.71000 0.44900 H -3.47800 2.14100 2.80500 H -2.22500 0.92300 3.05100 H -3.88300 0.41800 2.66100 Si -2.97300 -1.49700 0.83800 C -2.07800 -1.89500 2.49400 C -2.51400 -3.02800 -0.16500 C -4.84000 -1.61700 1.14300 H -0.98800 -1.91600 2.31000 H -2.35200 -2.90900 2.82700 H -2.30900 -1.20800 3.31900 H -1.43800 -3.14200 -0.35600 H -3.04900 -3.04000 -1.12300 H -2.83500 -3.90000 0.42800 H -5.06300 -2.27100 2.00000 H -5.32500 -2.04900 0.25500 H -5.30500 -0.63800 1.32500 C 1.15200 -0.15900 -3.22600 C 0.36700 -1.28500 -2.96900 C 0.62200 1.11200 -2.99500 C -0.92000 -1.14400 -2.44200 C -0.66700 1.25000 -2.47400 C -1.43400 0.12500 -2.15200 C -1.78500 0.19900 5.75000 C -1.06500 -0.97600 5.98700 C -1.12500 1.43100 5.72500 C 0.25500 1.48800 5.93800 C 0.31500 -0.91900 6.20100 C 0.97600 0.31300 6.17400 H 2.15900 -0.27100 -3.63000 H 0.75600 -2.28200 -3.18400 H -1.54200 -2.01900 -2.26300 H -1.12400 2.22900 -2.32100 H 1.21200 2.00100 -3.22900 H 2.05500 0.35600 6.33100 H 0.87700 -1.83600 6.37800 H -1.58000 -1.93800 5.99700 H -1.68700 2.34700 5.53300 1297 H -2.86100 0.15400 5.57500 C -2.79500 0.36400 -1.47500 H 0.77200 2.44900 5.91300 O -3.62300 -0.76600 -1.77100 O -3.29400 1.49500 -1.61700 C -4.96400 -0.43600 -2.03400 H -5.04400 0.27700 -2.86700 H -5.45800 0.01700 -1.16000 H -5.47400 -1.37400 -2.29400 1298 Table C.2.219. Atomic coordinates and single point energies for E7. G = –2179.631792 GSP = –2181.405502 Na 0.48900 -0.58500 0.57300 Na -2.04000 0.40300 -0.55200 N -0.07300 1.62000 0.05100 N -1.51600 -1.76400 -0.00200 Si -0.42500 2.49900 1.47200 C 0.61700 4.07400 1.71000 C -0.17200 1.38000 2.98800 C -2.23000 3.10600 1.60400 C 0.43000 2.32100 -1.11900 C 1.77300 1.74800 -1.59200 H 2.16500 2.27000 -2.47900 H 1.65900 0.68000 -1.84400 H 2.52200 1.83200 -0.78900 C -0.56500 2.29700 -2.28900 H 0.61900 3.39700 -0.91000 H -0.20100 2.85500 -3.16600 H -1.52500 2.73900 -1.97800 H -0.74400 1.25700 -2.61700 H 1.69500 3.91000 1.55700 H 0.47400 4.47400 2.72600 H 0.30600 4.85900 1.00300 H 0.86800 1.02800 3.08600 H -0.82100 0.49100 2.94000 H -0.43100 1.91000 3.91800 H -2.48200 3.73200 0.73100 1299 H -2.40500 3.70400 2.51300 H -2.94000 2.26100 1.62600 C -0.99600 -2.59900 -1.07300 C -0.52100 -1.73000 -2.24500 C -2.01600 -3.61000 -1.61500 H -1.38000 -1.18100 -2.67200 H -0.07400 -2.33100 -3.05200 H 0.23200 -0.99100 -1.92700 H -0.10600 -3.19300 -0.75400 H -1.61400 -4.18100 -2.46700 H -2.91800 -3.07100 -1.94900 H -2.32400 -4.32500 -0.84200 Si -1.93500 -2.36500 1.53600 C -3.06800 -1.09700 2.38500 C -0.39300 -2.60800 2.65200 C -2.85600 -4.02200 1.67000 H -2.79900 -0.05600 2.14100 H -3.04200 -1.19200 3.48200 H -4.10900 -1.25900 2.06300 H 0.09300 -1.65800 2.93500 H 0.35400 -3.22600 2.12500 H -0.63900 -3.12300 3.59300 H -3.16000 -4.19200 2.71500 H -2.22500 -4.87200 1.36600 H -3.76300 -4.03300 1.04600 C 7.25700 -0.41900 -1.27400 C 7.02100 -0.40500 0.10200 C 6.19200 -0.52200 -2.16900 C 5.71600 -0.47500 0.58400 C 4.88800 -0.61400 -1.69200 C 4.64900 -0.57500 -0.31500 C -4.26500 -0.35700 -2.32100 C -4.70000 -0.49000 -0.99900 C -4.05700 0.91100 -2.86600 C -4.29000 2.05200 -2.09200 C -4.93600 0.65000 -0.22800 C -4.73200 1.92200 -0.77400 H 8.27900 -0.35500 -1.64900 H 7.85500 -0.34200 0.80000 H 5.52900 -0.47500 1.65900 H 4.04100 -0.71700 -2.37200 H 6.38000 -0.53900 -3.24300 H -4.90900 2.81000 -0.16700 H -5.26900 0.55000 0.80700 H -4.82500 -1.48300 -0.56600 H -3.70700 1.01300 -3.89400 1300 H -4.07400 -1.24800 -2.92100 C 3.24100 -0.73500 0.14700 H -4.12400 3.04300 -2.51600 O 2.82600 -0.08100 1.24500 O 2.45000 -1.45600 -0.40900 C 3.36400 1.16500 1.68300 H 4.10700 1.55300 0.97600 H 3.81900 1.03100 2.67300 H 2.52100 1.86500 1.74700 1301 Table C.2.220. Atomic coordinates and single point energies for E20. G = –xx GSP = –xx Na -0.07400 1.68400 -0.31400 Na -0.65100 -1.32000 -0.25600 O 1.03400 -0.20000 0.63800 N -1.82100 0.43900 -1.24700 C -1.56600 0.97900 -2.56600 C -2.28700 2.30600 -2.85700 C -1.86900 -0.02200 -3.69100 H -3.37700 2.14700 -2.91000 H -1.96500 2.75400 -3.81200 H -2.10500 3.03200 -2.04700 H -2.93400 -0.30500 -3.65900 H -1.26400 -0.92800 -3.54300 H -1.64700 0.39000 -4.69000 H -0.47500 1.19800 -2.67000 Si -3.32400 0.44600 -0.45800 C -3.87400 2.13100 0.25700 C -4.83100 -0.17300 -1.45000 C -3.20100 -0.77600 1.00300 H -3.16700 -1.80200 0.60300 H -4.09500 -0.70100 1.64300 H -2.31900 -0.62600 1.65100 H -4.65800 -1.19600 -1.82000 H -5.03900 0.46700 -2.32300 H -5.73900 -0.18800 -0.82600 H -4.25700 2.78400 -0.54300 H -3.02800 2.65500 0.73200 H -4.67500 2.02200 1.00700 1302 C 2.13900 0.14400 0.09100 N 2.19600 1.17700 -0.69900 C 3.35400 1.62600 -1.43500 C 2.95800 1.83200 -2.89900 C 3.85400 2.94900 -0.85000 H 2.13700 2.56400 -2.95800 H 2.59800 0.89200 -3.34200 H 3.80400 2.20000 -3.49800 H 4.18100 0.89100 -1.41400 H 3.02700 3.67700 -0.87200 H 4.70000 3.35700 -1.42400 H 4.16800 2.83200 0.19800 C 3.31300 -0.74900 0.43700 C 3.08800 -2.13200 0.49000 C 4.11900 -3.00600 0.82700 C 5.38300 -2.50800 1.14700 C 4.58000 -0.25900 0.77200 C 5.60700 -1.13300 1.12900 H 2.08300 -2.51000 0.28300 H 3.93300 -4.08100 0.85500 H 6.18900 -3.19100 1.42000 H 6.58700 -0.73500 1.39800 H 4.76100 0.81600 0.77300 O 0.31900 3.97700 -0.36500 O -0.25300 2.64500 1.97300 C 0.10000 4.95900 -1.34200 H -0.18400 4.45100 -2.27200 H 1.01600 5.55000 -1.52000 H -0.71400 5.64400 -1.04400 C 0.72700 4.49200 0.88200 C 0.96000 3.34100 1.83500 H -0.05500 5.16000 1.28800 H 1.66200 5.07300 0.77100 H 1.29400 3.74100 2.81100 H 1.75100 2.67900 1.43400 C -0.24500 1.61400 2.94300 C -1.67700 1.40400 3.39100 H 0.38200 1.90500 3.80400 H 0.16500 0.68600 2.50900 O -1.73600 0.20600 4.11500 H -2.33500 1.36600 2.50400 H -2.01300 2.25700 4.01300 C -2.99500 -0.03100 4.67500 H -3.25900 0.74700 5.41600 H -2.96400 -1.00400 5.18000 H -3.78200 -0.05400 3.90100 1303 H -0.67100 -1.89500 3.16400 H -0.48600 -3.33300 -3.77500 H -2.38600 -2.61300 -2.48700 H -2.10700 -3.57800 1.88900 H -2.09800 -5.26500 0.02300 H 1.32800 -1.78900 -3.79000 C -1.82500 -3.47800 -2.10500 C -0.41300 -3.44300 -2.67600 C 1.47900 -2.02600 -2.72200 C 0.17200 -2.41400 2.67500 C -1.37300 -4.43000 0.04300 C -1.15600 -3.95000 1.46000 O -0.20300 -2.92500 1.41300 O -1.84600 -3.34000 -0.70500 O 0.25700 -2.35200 -2.10800 H 1.87700 -1.13900 -2.21200 H 0.97500 -1.69100 2.48800 H 0.53600 -3.22700 3.32800 H -0.80100 -4.79200 2.08500 H 2.20500 -2.85400 -2.63300 H -2.33500 -4.40500 -2.42300 H 0.14400 -4.37900 -2.47700 H -0.40900 -4.79300 -0.35500 1304 Table C.2.221. Atomic coordinates and single point energies for E19. G = –2409.754815 GSP = –2411.769149 Na 0.48200 -1.22600 -0.15400 Na -2.84700 0.34700 -0.19500 N 2.40500 0.86300 -0.18800 N -1.81700 -1.65200 -0.49500 Si 1.70000 1.65500 1.20300 C 1.17800 3.43400 0.78300 C 2.78400 1.83400 2.73500 C 0.06600 0.85300 1.76900 C 2.50300 1.39700 -1.55000 C 1.13900 1.41400 -2.24500 H 1.19100 1.87800 -3.24300 H 0.40300 1.96300 -1.63800 H 0.78700 0.37800 -2.36700 C 3.23000 2.73900 -1.65700 H 3.11500 0.66600 -2.09800 H 3.50300 2.93600 -2.70400 H 4.15500 2.71200 -1.06200 H 2.61400 3.58100 -1.31500 H 2.04400 4.10200 0.67100 H 0.58200 3.81000 1.63100 H 0.56400 3.50700 -0.12700 H 3.62200 2.52400 2.55300 H 3.18500 0.86200 3.05100 H 2.18200 2.25200 3.55800 H -0.63300 0.79800 0.91700 H -0.40800 1.45800 2.56000 H 0.22300 -0.15600 2.17800 C -1.90900 -2.14900 -1.85800 1305 C -0.62700 -2.83600 -2.35500 C -2.27600 -1.01000 -2.81800 H 0.22200 -2.13200 -2.40500 H -0.75500 -3.26500 -3.36200 H -0.34000 -3.65400 -1.67600 H -2.71700 -2.91300 -1.95800 H -2.32100 -1.34100 -3.86700 H -1.51300 -0.21500 -2.74600 H -3.26000 -0.57600 -2.56600 Si -2.06800 -2.67600 0.84900 C -2.96500 -1.68400 2.20400 C -0.45400 -3.26400 1.68400 C -3.03900 -4.26100 0.47100 H -2.37400 -0.78900 2.46700 H -3.10200 -2.26300 3.13000 H -3.96000 -1.34700 1.86900 H 0.12200 -2.42800 2.11600 H 0.20500 -3.79000 0.97200 H -0.66300 -3.96000 2.51200 H -3.23100 -4.82700 1.39500 H -2.45600 -4.91200 -0.20100 H -4.00600 -4.06800 -0.01700 C 7.31400 -0.49600 -0.26000 C 6.64400 0.38800 0.58700 C 6.58000 -1.37200 -1.05800 C 5.25100 0.39300 0.63200 C 5.18500 -1.36800 -1.00600 C 4.50900 -0.48700 -0.16100 H 8.40500 -0.49800 -0.29900 H 7.21100 1.07900 1.21400 H 4.72700 1.08800 1.28800 H 4.57800 -2.03900 -1.61500 H 7.09700 -2.06400 -1.72600 C 2.96300 -0.53500 -0.12900 O 2.53800 -0.89500 1.25500 O 2.46000 -1.34300 -1.00900 C 3.08500 -2.09800 1.72800 H 3.01600 -2.88400 0.95600 H 2.51100 -2.41000 2.61200 H 4.14400 -1.97700 2.01500 O -5.09200 -0.22200 -0.38500 O -4.22600 2.05300 0.72500 O -1.91500 2.45500 -0.69600 C -5.92600 0.41600 0.54700 C -5.60900 1.89300 0.51900 H -5.75500 0.00300 1.55900 1306 H -6.99100 0.26900 0.29200 H -6.19100 2.41900 1.29600 H -5.88600 2.31200 -0.46700 C -3.75700 3.37100 0.56800 C -2.25300 3.29800 0.38500 H -4.00400 3.99000 1.44800 H -4.23700 3.83400 -0.31400 H -1.79000 2.85700 1.28000 H -1.82800 4.30700 0.24600 C -5.41400 -1.57900 -0.60500 H -6.39400 -1.66900 -1.10300 H -5.43700 -2.13600 0.34700 H -4.62800 -2.00500 -1.24100 C -1.97400 3.07000 -1.96400 H -1.70500 2.31300 -2.71100 H -1.25200 3.90100 -2.02500 H -2.98500 3.45100 -2.18800 1307 Table C.2.222. Atomic coordinates and single point energies for E18. G = –2409.746208 GSP = –2411.766531 Na 0.53300 -0.60500 -0.01600 Na -2.80700 0.28900 -0.15400 N 1.55700 1.40000 -0.29100 N -1.56800 -1.60700 -0.40800 Si 1.67500 2.02500 1.27900 C 1.03900 3.80100 1.60000 C 3.42100 1.99800 2.04900 C 0.55700 0.95000 2.39400 C 2.41500 1.79600 -1.38300 C 1.89000 1.22600 -2.70500 H 2.56800 1.43300 -3.55000 H 0.90200 1.66100 -2.93800 H 1.76400 0.13400 -2.63100 C 2.58800 3.31600 -1.53900 H 3.44900 1.39200 -1.26400 H 3.20900 3.57200 -2.41300 H 3.06900 3.75000 -0.64900 H 1.60400 3.80200 -1.65600 H 1.57300 4.55400 1.00000 H 1.15500 4.07200 2.66200 H -0.03200 3.86700 1.35200 H 4.14000 2.52200 1.39600 H 3.78600 0.96700 2.17200 H 3.44500 2.48800 3.03500 H -0.48200 1.00400 2.02600 H 0.55900 1.30500 3.43600 H 0.86700 -0.10800 2.41000 C -1.40000 -2.13800 -1.74700 C 0.00100 -2.71500 -2.01700 1308 C -1.70200 -1.05800 -2.79300 H 0.75400 -1.90700 -2.04100 H 0.05800 -3.22600 -2.99100 H 0.29000 -3.42700 -1.22900 H -2.10500 -2.98000 -1.94500 H -1.55800 -1.41700 -3.82500 H -1.02700 -0.19800 -2.63700 H -2.74200 -0.70100 -2.70300 Si -1.96400 -2.61000 0.91800 C -3.17500 -1.64100 2.03200 C -0.52300 -3.07200 2.06800 C -2.76500 -4.26300 0.43400 H -2.70400 -0.70500 2.38500 H -3.45700 -2.20800 2.93200 H -4.10600 -1.38000 1.50000 H -0.06000 -2.17300 2.50600 H 0.26600 -3.61000 1.52000 H -0.86800 -3.71000 2.89900 H -3.07400 -4.81800 1.33400 H -2.04200 -4.89300 -0.10900 H -3.64800 -4.14500 -0.21100 C 5.80700 -0.20000 -2.36700 C 6.20500 0.09900 -1.06400 C 4.64600 -0.93800 -2.59600 C 5.44500 -0.33900 0.01700 C 3.87500 -1.36700 -1.52000 C 4.27200 -1.06500 -0.21500 H 6.40600 0.14700 -3.21100 H 7.11200 0.68000 -0.88900 H 5.74100 -0.11100 1.04000 H 2.96000 -1.94100 -1.67500 H 4.33400 -1.16900 -3.61500 C 3.40900 -1.52200 0.90600 O 4.02700 -1.51000 2.08000 O 2.25900 -1.88700 0.77800 C 3.24900 -1.86800 3.21600 H 2.72200 -2.81500 3.04000 H 2.51400 -1.08000 3.42900 H 3.95200 -1.96200 4.04900 O -4.85400 -0.44000 -1.04500 O -4.54300 1.86200 0.27800 O -1.86000 2.36900 0.33200 C -5.99600 0.19700 -0.53400 C -5.71600 1.67900 -0.47400 H -6.22600 -0.18900 0.47700 H -6.87400 0.01200 -1.18100 1309 H -6.57000 2.20500 -0.01100 H -5.57500 2.07900 -1.49500 C -4.12600 3.20000 0.41100 C -2.75300 3.17300 1.05500 H -4.83300 3.77400 1.03700 H -4.08400 3.68200 -0.58400 H -2.82900 2.73200 2.06100 H -2.36100 4.20100 1.15900 C -5.02600 -1.82300 -1.25500 H -5.78700 -2.00800 -2.03300 H -5.33400 -2.32600 -0.32200 H -4.05800 -2.22900 -1.57200 C -1.34700 2.93300 -0.86600 H -0.39800 2.40700 -1.06300 H -1.13400 4.00600 -0.72200 H -2.06100 2.81800 -1.70300 1310 Table C.2.223. Atomic coordinates and single point energies for T8. G = –2409.725364 GSP = –2411.742756 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.63700 N 2.09800 0.00000 -1.09000 N -1.43400 0.24000 1.89700 Si 2.96200 -1.41300 -0.62800 C 4.19600 -1.22200 0.82100 C 3.96500 -2.31300 -1.96300 C 1.70200 -2.62900 0.11800 C 2.62900 1.34300 -1.22800 C 1.57300 2.37200 -0.80600 H 1.89100 3.40600 -1.01100 H 1.37800 2.28500 0.28000 H 0.63100 2.19600 -1.34600 C 3.93100 1.63400 -0.47700 H 2.86300 1.56700 -2.28900 H 4.23500 2.68100 -0.63100 H 4.75000 0.99200 -0.83400 H 3.81000 1.46400 0.60400 H 5.14700 -0.74800 0.54200 H 4.42200 -2.22600 1.21800 H 3.73000 -0.63000 1.62200 H 4.69900 -1.62700 -2.41600 H 3.31100 -2.69300 -2.76100 H 4.52300 -3.15900 -1.53100 H 1.32200 -2.22600 1.07500 H 2.16400 -3.60400 0.33800 H 0.84400 -2.80900 -0.54200 C -2.04600 1.55000 1.76000 1311 C -2.27400 1.97800 0.30200 C -1.20900 2.61700 2.47700 H -1.31400 2.13900 -0.21800 H -2.83900 2.92100 0.23200 H -2.82600 1.20200 -0.25000 H -3.05500 1.57700 2.23500 H -1.63300 3.62700 2.37000 H -0.19100 2.63200 2.05300 H -1.13100 2.40100 3.55700 Si -2.39400 -1.17700 1.85500 C -1.74400 -2.38800 3.18000 C -2.26700 -2.15900 0.23500 C -4.24400 -0.87800 2.15200 H -0.68200 -2.62900 2.99300 H -2.28800 -3.34500 3.16500 H -1.82600 -1.97500 4.19900 H -1.25500 -2.58400 0.13100 H -2.45400 -1.52300 -0.64500 H -2.97500 -3.00200 0.20900 H -4.78300 -1.83700 2.19600 H -4.67400 -0.29500 1.32200 H -4.45100 -0.32900 3.08200 C 2.39700 2.15900 -5.60800 C 3.01400 0.94100 -5.31200 C 1.21600 2.51400 -4.95900 C 2.45700 0.08600 -4.36500 C 0.65700 1.65800 -4.00900 C 1.28200 0.45100 -3.70000 H 2.83600 2.82800 -6.35000 H 3.93500 0.65800 -5.82300 H 2.93200 -0.86200 -4.11500 H -0.27400 1.90800 -3.49800 H 0.72400 3.45900 -5.19700 C 0.65400 -0.44300 -2.66800 O 1.01200 -1.75600 -2.87000 O -0.44100 -0.17600 -2.16200 C -0.04400 -2.69200 -2.90000 H -0.69900 -2.60800 -2.02300 H 0.42100 -3.68400 -2.92300 H -0.65900 -2.55500 -3.80400 O -1.34800 0.33500 5.50600 O 1.03800 -0.87300 5.59500 O 2.30000 0.16300 3.40000 C -1.05400 -0.47900 6.61200 C 0.44300 -0.48000 6.80700 H -1.41800 -1.50800 6.43300 1312 H -1.54300 -0.09500 7.52600 H 0.71400 -1.17000 7.62600 H 0.78700 0.53500 7.08000 C 2.44600 -0.83600 5.58200 C 2.87600 -0.89900 4.13000 H 2.87200 -1.68300 6.14900 H 2.80100 0.10100 6.05200 H 2.51400 -1.83400 3.67600 H 3.97600 -0.88700 4.04200 C -2.73100 0.51500 5.28900 H -3.18100 1.09600 6.11100 H -3.24500 -0.45800 5.20900 H -2.85000 1.05400 4.34000 C 3.05500 1.35500 3.38900 H 2.51800 2.07900 2.76400 H 4.04900 1.17600 2.94700 H 3.17600 1.77100 4.40300 1313 Table C.2.224. Atomic coordinates and single point energies for T18. G = –2409.709937 GSP = –2411.728771 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.01000 N 2.45200 0.00000 -0.10500 N -1.91100 0.11100 1.74900 Si 2.81800 1.64200 0.33300 C 2.36200 2.98000 -0.94600 C 4.65200 1.99500 0.75300 C 1.74800 2.17300 1.81200 C 3.28600 -0.63700 -1.12900 C 2.52400 -1.66200 -1.98400 H 3.22800 -2.32000 -2.51700 H 1.91100 -1.14600 -2.74000 H 1.85200 -2.28900 -1.38500 C 4.01500 0.29200 -2.11700 H 4.10300 -1.19100 -0.61800 H 4.64500 -0.30700 -2.79200 H 4.66800 1.02000 -1.61700 H 3.29900 0.84800 -2.74300 H 2.86500 2.86200 -1.91600 H 2.65700 3.96100 -0.53400 H 1.27300 2.99100 -1.10100 H 5.11100 2.61700 -0.03100 H 5.22900 1.06100 0.82400 H 4.76000 2.54000 1.70400 H 1.98300 1.63600 2.74000 H 0.67400 2.07900 1.56800 H 1.91600 3.24800 1.99000 C -2.84700 -0.82600 1.12500 C -2.23200 -2.21200 0.92900 C -3.39900 -0.33300 -0.22400 1314 H -1.38000 -2.15800 0.23200 H -2.95600 -2.92600 0.50500 H -1.86800 -2.61300 1.88800 H -3.74000 -0.99600 1.76700 H -4.07300 -1.07500 -0.68300 H -2.57100 -0.13900 -0.92700 H -3.96600 0.60100 -0.09700 Si -2.67100 1.15200 2.89500 C -3.77800 2.57900 2.29700 C -1.35400 2.03600 3.96300 C -3.75400 0.20000 4.13900 H -3.16700 3.41200 1.92100 H -4.37600 2.95000 3.14500 H -4.48000 2.27300 1.50500 H -0.60400 2.56800 3.35500 H -0.84000 1.40600 4.71400 H -1.87900 2.80300 4.55300 C 1.87500 -5.01900 -0.11600 C 3.19500 -4.57700 -0.04000 C 0.85200 -4.24200 0.43400 C 3.49800 -3.35400 0.56000 C 1.15600 -3.01800 1.02200 C 2.47000 -2.55100 1.06000 H 1.64500 -5.97800 -0.58200 H 4.00000 -5.19400 -0.44400 H 4.52900 -3.01300 0.64600 H 0.37000 -2.41500 1.47400 H -0.18200 -4.59500 0.41700 C 2.72900 -1.23400 1.73000 O 4.05300 -1.03800 1.92600 O 1.90500 -0.77000 2.53500 C 4.40800 -0.24800 3.04300 H 5.50100 -0.16800 3.03000 H 4.07500 -0.73100 3.97300 H 3.96800 0.75500 2.98700 H -4.70600 -0.13400 3.70000 H -4.00200 0.84500 4.99700 H -3.23400 -0.69300 4.52300 O -1.00700 3.44000 0.50900 O -0.52200 1.59000 -1.57000 O -0.54700 -1.09200 -2.09500 C -0.61000 4.76700 0.30300 C -2.00100 2.97500 -0.36300 C -1.47500 2.61100 -1.73500 C 0.06900 1.09200 -2.74600 C -0.61400 -0.19100 -3.17300 1315 C -0.83800 -2.41700 -2.46000 H 0.13700 5.01000 1.06900 H -1.46600 5.45900 0.40600 H -0.14700 4.92000 -0.68700 H -2.82000 3.71200 -0.46600 H -2.39600 2.06300 0.10100 H -1.00600 3.47400 -2.24500 H -2.32100 2.26700 -2.36000 H 1.12200 0.88000 -2.50200 H 0.03600 1.84000 -3.55600 H -0.09000 -0.60600 -4.05500 H -1.67000 -0.01300 -3.45600 H -0.67200 -3.05400 -1.58400 H -0.16600 -2.75400 -3.26800 H -1.88600 -2.51700 -2.79400 1316 Table C.2.225. Atomic coordinates and single point energies for E17. G = –xx GSP = –xx C -3.90000 -0.79700 -0.08900 C -5.25300 -0.85000 0.24900 C -3.07200 0.19900 0.43800 C -5.79500 0.10100 1.11200 C -3.61900 1.12900 1.32800 C -4.97300 1.09200 1.65100 H -3.47800 -1.54700 -0.76000 H -5.88500 -1.63900 -0.16200 H -6.85400 0.06500 1.37200 H -5.39000 1.83200 2.33700 H -2.95500 1.87400 1.77000 C -1.58000 0.25000 0.16800 N -1.05400 0.11200 -1.02700 C -1.80000 0.07900 -2.26200 C -1.30100 1.20400 -3.17300 C -1.61900 -1.27400 -2.95400 H -1.83300 1.21400 -4.13700 H -0.22400 1.07400 -3.36900 H -1.44100 2.17800 -2.68300 H -2.15300 -1.31500 -3.91600 H -1.98200 -2.09500 -2.31800 H -0.54700 -1.44900 -3.14300 H -2.88100 0.24600 -2.10300 O -0.85800 0.42400 1.20000 Na 0.99600 0.08400 -0.00700 N 2.11400 2.18900 0.31100 N 3.40800 -0.33200 -0.11500 N 1.37300 -2.19000 0.70200 C 1.40200 3.27100 -0.34500 C 1.86600 2.18900 1.74400 H 0.32700 3.17300 -0.13500 H 1.54300 3.20900 -1.43300 1317 H 1.74100 4.27100 -0.00200 H 0.78500 2.10600 1.92600 H 2.26200 3.10300 2.23500 H 2.34200 1.31600 2.21500 C 3.52600 2.15000 -0.02300 C 4.18400 0.81300 0.33400 H 4.09600 2.96100 0.48000 H 3.62300 2.33600 -1.10400 H 4.29100 0.73500 1.42600 H 5.21400 0.80900 -0.08200 C 3.34600 -0.43700 -1.56100 H 4.33800 -0.64200 -2.01500 H 2.95400 0.49300 -1.99700 H 2.65900 -1.24300 -1.85700 C 3.77800 -1.58300 0.52600 C 2.70400 -2.66600 0.37400 H 3.94100 -1.37500 1.59400 H 4.73800 -1.98500 0.13600 H 3.00100 -3.53700 0.99900 H 2.68700 -3.03100 -0.66500 C 0.32200 -3.06200 0.21000 C 1.20300 -1.90900 2.11900 H 0.42100 -3.19400 -0.87700 H -0.65400 -2.59500 0.40600 H 0.34200 -4.06200 0.69200 H 1.95100 -1.17700 2.45700 H 1.31100 -2.82400 2.73900 H 0.21200 -1.46100 2.28100 1318 Table C.2.226. Atomic coordinates and single point energies for E16. G = –1725.939666 GSP = –1725.286498 Na 1.77600 -0.25600 -0.37400 N -1.61000 0.65900 0.42700 Si -2.53600 2.13100 0.15800 C -2.10400 3.10000 -1.40400 C -4.41900 1.92900 0.11500 C -2.17700 3.37100 1.55300 H -4.79400 1.34100 0.96400 H -4.75500 1.43200 -0.80500 H -4.88900 2.92400 0.15100 H -1.11500 3.66000 1.57600 H -2.45500 3.02500 2.55800 H -2.76100 4.28200 1.34500 H -2.65400 4.05400 -1.36600 H -2.40300 2.55800 -2.31100 H -1.03200 3.34000 -1.48100 C -1.48200 0.09800 1.77900 C -0.34300 0.73100 2.58200 C -2.79100 0.04400 2.57500 H -0.21000 0.21900 3.54800 H -0.51900 1.79700 2.78200 H 0.59500 0.64000 2.01100 H -1.18400 -0.94700 1.63100 H -3.17600 1.04400 2.82500 H -2.64100 -0.49800 3.52100 H -3.55800 -0.48700 1.99200 N 2.58600 2.07700 -0.15200 N 4.31300 -0.34800 -0.39800 N 2.39400 -2.41100 0.51900 C 1.68600 2.95100 0.59100 C 2.78800 2.59800 -1.49700 1319 H 2.04400 4.00100 0.59400 H 1.60600 2.61100 1.63200 H 0.67800 2.91400 0.15200 H 1.81800 2.86500 -1.93400 H 3.25200 1.84600 -2.15200 H 3.42600 3.50600 -1.49700 C 3.84500 1.90600 0.56500 C 4.83700 0.99400 -0.14900 H 4.34200 2.88800 0.73100 H 3.61100 1.50200 1.56400 H 5.77300 0.95900 0.44300 H 5.11000 1.44700 -1.11200 C 4.83800 -0.92300 -1.62800 H 5.92000 -1.15800 -1.55900 H 4.69100 -0.21900 -2.45800 H 4.30000 -1.84600 -1.88300 C 4.54400 -1.22000 0.75300 C 3.83000 -2.56600 0.66100 H 5.63300 -1.39900 0.89100 H 4.19900 -0.69000 1.65600 H 4.09900 -3.16700 1.55500 H 4.21300 -3.12700 -0.20400 C 1.71800 -2.23800 1.79600 C 1.75000 -3.45700 -0.26200 H 1.78000 -4.44100 0.25000 H 2.25100 -3.55800 -1.23600 H 0.70800 -3.15500 -0.44300 H 0.67000 -1.97000 1.60100 H 2.18100 -1.42100 2.37300 H 1.76200 -3.15800 2.41400 O -0.20600 -1.01500 -0.41900 H 0.27600 1.42800 -1.53200 O -1.41600 0.29500 -1.89200 C -1.34500 -0.40700 -0.62700 C -0.20400 0.81600 -2.31900 H -0.40200 1.47000 -3.18000 H -1.55900 -2.81900 0.57400 C -2.49000 -2.56700 0.06400 C -2.54800 -1.37400 -0.66200 C -3.58700 -3.42800 0.11700 C -3.71200 -1.08800 -1.38200 H -3.52500 -4.35200 0.69600 H -3.74100 -0.18800 -1.99600 C -4.75500 -3.11800 -0.57800 C -4.80800 -1.94900 -1.33900 H 0.50100 0.02700 -2.64200 1320 H -5.61400 -3.79000 -0.54000 H -5.70800 -1.71000 -1.90900 1321 Table C.2.227. Atomic coordinates and single point energies for E15. G = –1723.688898 GSP = –1725.279056 Na -0.92500 -0.07800 0.21200 N 1.07100 0.88400 -0.49800 Si 1.95500 2.33600 -0.54800 C 1.97800 3.15900 1.16900 C 3.81300 2.25500 -0.99500 C 1.31700 3.68100 -1.75300 H 3.97700 2.11600 -2.07400 H 4.33400 1.43800 -0.47300 H 4.29500 3.20400 -0.70800 H 0.28500 3.99600 -1.53700 H 1.34200 3.31300 -2.79200 H 1.95600 4.57800 -1.70900 H 2.52500 4.11300 1.10100 H 2.51100 2.51800 1.88800 H 0.98500 3.38700 1.58600 C 1.01500 -0.07000 -1.58000 C -0.12000 0.22100 -2.58800 C 2.31200 -0.26600 -2.38000 H -0.20900 -0.56300 -3.36000 H 0.07000 1.18300 -3.08900 H -1.10500 0.31600 -2.09500 H 0.78900 -1.08100 -1.15300 H 2.51700 0.62400 -2.99800 H 2.24200 -1.13500 -3.05400 H 3.16600 -0.41500 -1.70400 N -2.66700 1.73800 0.47300 N -4.51800 -0.50000 -0.06700 N -2.01400 -2.24500 -0.30400 C -1.74600 2.83300 0.19000 C -3.00700 1.69300 1.88600 1322 H -2.19700 3.81900 0.42800 H -1.46400 2.81300 -0.87100 H -0.81800 2.71400 0.76200 H -2.08500 1.65400 2.48500 H -3.59800 0.79300 2.10500 H -3.57900 2.58800 2.20800 C -3.85300 1.89700 -0.36100 C -4.96000 0.88000 -0.11500 H -4.30000 2.90300 -0.20000 H -3.52700 1.87900 -1.41200 H -5.73300 1.03600 -0.90100 H -5.45300 1.10300 0.84400 C -5.60600 -1.37100 0.32700 H -6.42800 -1.38700 -0.42100 H -6.02500 -1.03300 1.28600 H -5.25000 -2.40100 0.46300 C -3.89700 -0.92300 -1.30900 C -3.12800 -2.23600 -1.24800 H -4.65400 -1.00400 -2.12300 H -3.18300 -0.14800 -1.61700 H -2.71500 -2.39100 -2.25600 H -3.80400 -3.09600 -1.05900 C -1.01600 -3.22600 -0.71300 C -2.44300 -2.53700 1.06200 H -2.93100 -3.53300 1.12800 H -3.15100 -1.77300 1.40300 H -1.56300 -2.53700 1.72000 H -0.20300 -3.22400 0.02200 H -0.60200 -2.96000 -1.69600 H -1.44700 -4.24800 -0.77100 O 0.52500 -1.37000 1.44300 H 0.19400 1.26300 2.21800 O 1.86700 0.10200 2.45400 C 1.63000 -0.87300 1.58500 C 0.73400 0.73000 3.01600 H 1.10700 1.45500 3.74600 H 1.82400 -3.04800 0.05800 C 2.78400 -2.54300 0.15700 C 2.86400 -1.38300 0.93200 C 3.91900 -3.03200 -0.48400 C 4.08700 -0.72300 1.08100 H 3.85400 -3.93400 -1.09500 H 4.13200 0.18400 1.68300 C 5.13600 -2.36400 -0.34900 C 5.22000 -1.21300 0.43700 H 0.07700 -0.00600 3.50000 1323 H 6.02500 -2.74200 -0.85700 H 6.17100 -0.68900 0.53800 1324 Table C.2.228. Atomic coordinates and single point energies for T7. G = –1723.684626 GSP = –1725.272813 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.39400 Si 1.11200 0.00000 3.71300 C 2.41400 1.37200 3.54500 C 0.45200 0.29500 5.48300 C 2.08600 -1.63400 3.90300 H -0.50200 -0.20700 5.69100 H 0.31700 1.36600 5.69500 H 1.19800 -0.08500 6.20100 H 2.56400 -1.96400 2.96900 H 1.43300 -2.45000 4.25100 H 2.87700 -1.50500 4.65900 H 3.10100 1.28900 4.40200 H 1.93400 2.36000 3.59800 H 3.02700 1.33400 2.63200 C -0.97800 -1.06300 2.24600 C -0.42000 -2.34200 1.58000 C -1.70400 -1.49800 3.53100 H -1.22000 -3.07100 1.37200 H 0.31600 -2.82300 2.24100 H 0.10100 -2.14800 0.62500 H -1.77600 -0.68400 1.56500 H -1.00900 -2.03200 4.20100 H -2.53900 -2.18000 3.30500 H -2.10200 -0.63000 4.07300 N 2.24600 -0.58300 -0.94600 N 0.59900 -1.32000 -3.27900 N -1.82400 -0.59400 -1.56200 C 2.92300 -0.72300 0.33700 C 2.62400 0.66100 -1.60100 H 4.02600 -0.72100 0.22500 1325 H 2.62000 -1.66800 0.80900 H 2.62900 0.08600 1.02000 H 2.45600 1.50400 -0.91600 H 2.00800 0.81800 -2.49700 H 3.69500 0.67100 -1.89100 C 2.55600 -1.74400 -1.77300 C 1.99800 -1.69200 -3.19000 H 3.65700 -1.86600 -1.86500 H 2.19600 -2.63900 -1.24200 H 2.19100 -2.68300 -3.65900 H 2.57300 -0.96100 -3.78000 C 0.21100 -1.12200 -4.66100 H 0.27100 -2.05900 -5.25500 H 0.87000 -0.37800 -5.13000 H -0.81800 -0.74400 -4.72500 C -0.26500 -2.26400 -2.59500 C -1.69900 -1.80100 -2.37200 H -0.29500 -3.23800 -3.13600 H 0.16100 -2.46500 -1.60300 H -2.20200 -2.62000 -1.83700 H -2.24400 -1.68600 -3.33300 C -3.11300 -0.56500 -0.88300 C -1.67000 0.62800 -2.34900 H -2.44000 0.69600 -3.14600 H -0.67700 0.65300 -2.81500 H -1.77900 1.49500 -1.68200 H -3.17000 0.35500 -0.28900 H -3.20700 -1.42800 -0.20800 H -3.95700 -0.58500 -1.60400 O -1.35700 1.62800 0.66700 H 1.43500 2.01500 0.99900 O -0.09600 2.75400 2.15600 C -1.08800 1.89000 1.84400 C 0.87400 2.95100 1.16200 H 1.56700 3.71300 1.53600 H -3.57500 0.95200 1.61000 C -3.37200 1.28200 2.62800 C -2.11600 1.81400 2.92800 C -4.34400 1.17300 3.62100 C -1.85700 2.28600 4.21700 H -5.32000 0.74700 3.38300 H -0.88400 2.72800 4.43000 C -4.06900 1.60800 4.91600 C -2.82500 2.17400 5.20900 H 0.41800 3.28200 0.21700 H -4.82500 1.51700 5.69700 1326 H -2.61000 2.52800 6.21900 1327 Table C.2.229. Atomic coordinates and single point energies for T16. G = –1589.956058 GSP = –1591.39318 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.28800 Si 1.34800 0.00000 3.35700 C 2.66200 1.24300 2.78100 C 1.06100 0.47500 5.18000 C 2.24100 -1.68500 3.46500 H 0.22500 -0.07400 5.63700 H 0.85700 1.55000 5.29500 H 1.97100 0.25000 5.75900 H 2.51500 -2.07800 2.47300 H 1.61600 -2.44400 3.96100 H 3.16600 -1.58400 4.05500 H 3.54500 1.16000 3.43400 H 2.28000 2.27200 2.86300 H 3.00400 1.08600 1.74500 C -1.04000 -1.01200 2.35700 C -0.68000 -2.33500 1.64600 C -1.53700 -1.34600 3.77200 H -1.50700 -3.06000 1.71000 H 0.21200 -2.79200 2.10100 H -0.47100 -2.19200 0.57100 H -1.92300 -0.61800 1.80500 H -0.75600 -1.88300 4.33600 H -2.43000 -1.98900 3.74200 H -1.78800 -0.42900 4.32300 N 1.85700 -0.51700 -1.48200 N -1.41200 -0.68100 -1.79000 C 2.55600 -1.28900 -0.45800 C 2.67400 0.62000 -1.88000 H 3.52800 -1.67400 -0.82800 H 1.95000 -2.14300 -0.12600 1328 H 2.74000 -0.66000 0.42500 H 2.94400 1.21600 -0.99700 H 2.11900 1.26400 -2.57800 H 3.61400 0.29900 -2.37500 C 1.54100 -1.34900 -2.64800 H 1.29500 -0.68200 -3.49000 H 2.45400 -1.90200 -2.95300 C 0.39400 -2.33800 -2.43300 C -1.02800 -1.81100 -2.63800 H 0.53000 -3.17300 -3.13800 H 0.47100 -2.78200 -1.42900 H -1.71400 -2.64500 -2.43100 H -1.17700 -1.55100 -3.70600 C -2.76700 -0.80400 -1.26400 C -1.24500 0.60000 -2.46600 H -1.88500 0.67800 -3.36900 H -0.20000 0.73300 -2.77800 H -1.50600 1.41400 -1.77500 H -2.96900 0.05000 -0.60300 H -2.85300 -1.72600 -0.67200 H -3.52900 -0.82700 -2.07000 O -1.47000 1.56900 0.60000 H 1.31000 2.06700 0.49100 O -0.05300 2.75400 1.88900 C -1.08400 1.89000 1.72900 C 0.74200 2.97600 0.75300 H 1.45900 3.76200 1.01500 H -3.59000 1.01600 1.76600 C -3.28600 1.36900 2.75200 C -1.99700 1.88200 2.91100 C -4.15700 1.31500 3.84000 C -1.60100 2.39300 4.15100 H -5.15900 0.90300 3.71500 H -0.60400 2.81900 4.25100 C -3.74700 1.78900 5.08500 C -2.47000 2.33900 5.23500 H 0.13100 3.28800 -0.10700 H -4.42500 1.74200 5.93800 H -2.15300 2.72500 6.20500 1329 Table C.2.230. Atomic coordinates and single point energies for T15. G = –1668.423245 GSP = –1669.948861 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.38100 Si 1.21400 0.00000 3.60800 C 2.60700 1.21800 3.18500 C 0.73300 0.50900 5.38300 C 2.05200 -1.69900 3.87800 H -0.23400 0.09900 5.70600 H 0.69000 1.60200 5.49600 H 1.50700 0.14100 6.07600 H 2.43700 -2.15900 2.95600 H 1.35500 -2.41700 4.33900 H 2.89900 -1.57800 4.57200 H 3.40400 1.11900 3.93800 H 2.23000 2.25000 3.23300 H 3.06800 1.06500 2.19700 C -1.03500 -1.02100 2.35900 C -0.60600 -2.33300 1.66500 C -1.64400 -1.38700 3.72200 H -1.43300 -3.06100 1.64200 H 0.23900 -2.79200 2.19900 H -0.28500 -2.18800 0.61600 H -1.87700 -0.62300 1.75100 H -0.90700 -1.91900 4.34600 H -2.51900 -2.04600 3.60400 H -1.96300 -0.48600 4.26400 N 2.39400 -0.73300 -0.90600 N -1.88700 -0.38400 -1.67200 C 2.80300 -1.40800 0.32000 C 3.08100 0.54500 -1.02400 H 3.89500 -1.60200 0.34000 H 2.27800 -2.37000 0.40900 1330 H 2.53300 -0.79800 1.19000 H 2.95900 1.12000 -0.09600 H 2.67200 1.13800 -1.85500 H 4.17000 0.41200 -1.19500 C 2.68800 -1.58400 -2.05800 C 2.15700 -1.04200 -3.38200 H 3.78500 -1.74300 -2.13700 H 2.24800 -2.57300 -1.85900 H 2.30700 -1.82200 -4.14600 H 2.75800 -0.18000 -3.71000 C -0.21600 -1.79500 -2.86400 C -1.68300 -1.42600 -2.68700 H -0.13800 -2.62800 -3.58300 H 0.14100 -2.18600 -1.89600 H -2.22800 -2.33000 -2.37700 H -2.12600 -1.11500 -3.65300 C -3.01600 -0.69600 -0.80200 C -2.09600 0.93200 -2.27100 H -3.04100 0.96400 -2.85200 H -1.27500 1.18100 -2.95500 H -2.13800 1.68700 -1.47600 H -3.11500 0.10700 -0.06200 H -2.83600 -1.64100 -0.27000 H -3.96400 -0.78300 -1.37100 O -1.36900 1.63100 0.70400 H 1.37700 2.11100 0.80600 O -0.05100 2.75800 2.14500 C -1.05900 1.89400 1.87200 C 0.82300 3.02300 1.07900 H 1.53800 3.77500 1.43100 H -3.57100 1.01200 1.71400 C -3.33300 1.34200 2.72400 C -2.06000 1.85200 2.98500 C -4.28100 1.26200 3.74300 C -1.76200 2.34300 4.25900 H -5.27000 0.85100 3.53600 H -0.78100 2.77800 4.44000 C -3.96500 1.71000 5.02500 C -2.70700 2.26300 5.27700 H 0.27700 3.39800 0.20100 H -4.70300 1.64300 5.82600 H -2.46200 2.63300 6.27400 C 0.68400 -0.65100 -3.31700 H 0.57800 0.19900 -2.62300 H 0.35100 -0.28600 -4.30300 1331 Table C.2.231. Atomic coordinates and single point energies for T17. G = –1550.723519 GSP = –1552.117016 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.27900 Si 1.42400 0.00000 3.24300 C 2.79400 0.99900 2.39000 C 1.30200 0.73800 4.99200 C 2.18400 -1.73200 3.49900 H 0.40400 0.39300 5.52700 H 1.27300 1.83800 4.96000 H 2.18500 0.44900 5.58400 H 2.38300 -2.23300 2.53900 H 1.53600 -2.39300 4.09400 H 3.14200 -1.64000 4.03600 H 3.73900 0.87500 2.94200 H 2.55700 2.07200 2.37200 H 2.96900 0.66000 1.35500 C -1.04900 -0.99100 2.43100 C -0.73100 -2.34700 1.76700 C -1.49500 -1.25100 3.87900 H -1.60100 -3.02200 1.79900 H 0.10800 -2.84500 2.27500 H -0.44200 -2.23200 0.70700 H -1.94500 -0.60700 1.89500 H -0.68600 -1.74100 4.44600 H -2.37700 -1.90900 3.91800 H -1.74400 -0.30900 4.38600 O -1.46000 1.57400 0.60400 H 1.31200 2.14200 0.34200 O 0.01500 2.73500 1.85500 C -1.03800 1.88600 1.72400 1332 C 0.72800 3.01700 0.67900 H 1.43600 3.81800 0.92100 H -3.56300 1.07900 1.80900 C -3.23900 1.44100 2.78500 C -1.93500 1.92300 2.92100 C -4.09900 1.43100 3.88300 C -1.51500 2.45100 4.14400 H -5.11300 1.04300 3.77600 H -0.50700 2.85400 4.22800 C -3.66500 1.92100 5.11300 C -2.37400 2.44200 5.23800 H 0.05300 3.33600 -0.12800 H -4.33500 1.91000 5.97400 H -2.03700 2.84300 6.19600 N -1.24800 -0.18300 -2.04800 N 1.32200 -1.44100 -1.43300 C -1.68500 1.08700 -2.60400 C -2.35800 -0.86300 -1.39400 H -2.09600 1.70600 -1.79400 H -2.45600 0.95700 -3.39100 H -0.82900 1.61900 -3.04500 H -3.17300 -1.10100 -2.10800 H -2.75400 -0.21700 -0.59700 H -2.02200 -1.80400 -0.93400 C 2.12300 -2.46100 -0.77400 C 2.16900 -0.44300 -2.06600 H 2.76900 -1.99600 -0.01700 H 2.76100 -3.01600 -1.49100 H 1.46700 -3.18000 -0.26300 H 2.72300 -0.85100 -2.93800 H 2.90500 -0.07400 -1.33800 H 1.57400 0.41600 -2.40900 C 0.37100 -2.04200 -2.36300 C -0.56600 -1.02700 -3.01600 H 0.01300 -0.37800 -3.69000 H -1.28200 -1.57600 -3.66200 H 0.90000 -2.59500 -3.16900 H -0.21200 -2.79100 -1.80200 1333 Table C.2.232. Atomic coordinates and single point energies for E12. G = –1888.084762 GSP = –1889.724458 Na -0.79100 1.44900 -0.21700 Na -0.88500 -1.22800 0.50200 O 0.73500 0.32800 1.19300 N -2.64800 0.08600 -0.15900 O 0.29100 3.41400 -0.20400 C 1.61200 3.37500 0.35400 C -0.13100 4.76200 -0.41300 C 1.85100 4.78100 0.88500 C 1.09900 5.62600 -0.14400 H 1.70000 5.73100 -1.05900 H 0.83700 6.63000 0.21300 H 1.39700 4.89300 1.88100 H 2.91800 5.02700 0.96200 H 1.64100 2.58400 1.11700 H 2.33200 3.12000 -0.44300 H -0.51700 4.86400 -1.43800 H -0.94700 4.99500 0.29100 O -0.01600 -3.30400 0.55100 C 1.39800 -3.47800 0.67800 C -0.64700 -4.52300 0.15600 C 1.69200 -4.84500 0.06800 C 0.40200 -5.60700 0.37700 H 1.82900 -4.75400 -1.02000 H 2.59200 -5.31000 0.49000 H 0.39500 -5.93700 1.42700 H 0.24400 -6.48400 -0.26200 1334 H -1.55700 -4.66000 0.75600 H -0.93300 -4.45400 -0.90700 H 1.90700 -2.64900 0.16300 H 1.66800 -3.44300 1.74700 C -3.01600 0.06100 -1.55900 C -3.96200 1.19500 -1.98200 C -3.60600 -1.28700 -1.99800 H -4.93400 1.09300 -1.47100 H -4.15000 1.19600 -3.06800 H -3.54500 2.17600 -1.70100 H -4.54900 -1.47900 -1.46200 H -2.90900 -2.10400 -1.75000 H -3.80800 -1.32200 -3.08100 H -2.09200 0.19100 -2.17300 Si -3.71300 0.28700 1.15600 C -4.20100 2.09200 1.52800 C -5.34900 -0.68400 1.11000 C -2.76900 -0.32100 2.69300 H -2.63800 -1.41800 2.66700 H -3.30600 -0.08700 3.62500 H -1.77100 0.14400 2.76000 H -5.16100 -1.76200 0.98400 H -5.99600 -0.35800 0.28000 H -5.91300 -0.54300 2.04600 H -4.77600 2.52900 0.69700 H -3.29900 2.71200 1.67200 H -4.81200 2.17400 2.44100 C 1.42900 0.03900 0.16000 N 0.82300 -0.21300 -0.97500 C 1.45000 -0.70600 -2.18200 C 0.66500 -1.92700 -2.66800 C 1.44900 0.37700 -3.26300 H -0.38100 -1.64200 -2.86100 H 0.66200 -2.71200 -1.89700 H 1.09400 -2.34300 -3.59200 H 2.49200 -1.03000 -2.00400 H 0.41000 0.66700 -3.48700 H 1.91700 0.02100 -4.19300 H 1.97900 1.28000 -2.92600 C 2.92800 0.00100 0.37700 C 3.39100 -0.45800 1.61700 C 4.75400 -0.48900 1.90000 C 5.67400 -0.02800 0.95700 C 3.85700 0.47400 -0.55600 C 5.22200 0.46400 -0.26600 H 2.65300 -0.77500 2.35600 1335 H 5.10100 -0.86000 2.86600 H 6.74200 -0.04100 1.18100 H 5.93400 0.84500 -0.99900 H 3.51400 0.87200 -1.51200 1336 Table C.2.233. Atomic coordinates and single point energies for E11. G = –1888.079005 GSP = –1889.718908 Na 1.25100 1.18800 1.35000 Na 0.78700 -1.44700 0.08400 O -0.46700 -0.09200 1.31700 N 2.73300 -0.20000 0.27700 O 0.25400 3.17200 1.04500 C -1.09800 3.21600 1.52300 C 0.42900 4.19000 0.07000 C -1.90200 4.01100 0.47600 C -0.90100 4.21400 -0.66900 H -1.06500 5.14200 -1.23100 H -0.93900 3.36900 -1.37400 H -2.80000 3.46800 0.15400 H -2.21700 4.98100 0.88500 H -1.43800 2.17700 1.63000 H -1.11700 3.70600 2.50900 H 0.63100 5.15800 0.56500 H 1.29300 3.92600 -0.55400 O -0.51700 -2.56000 -1.33500 C -1.84600 -3.03600 -1.11000 C -0.34500 -2.51000 -2.74300 C -2.69600 -2.44200 -2.25000 C -1.65000 -1.90300 -3.25100 H -3.33400 -3.21300 -2.70100 H -3.34500 -1.63600 -1.88600 H -1.59700 -0.80700 -3.18900 H -1.86200 -2.17900 -4.29200 H 0.55300 -1.91700 -2.96500 H -0.19800 -3.53400 -3.13300 H -1.83400 -4.13900 -1.15700 1337 H -2.15700 -2.72300 -0.10400 C 3.70500 -0.92100 1.08400 C 5.10300 -0.29100 1.10500 C 3.82500 -2.40000 0.68000 H 5.56600 -0.34900 0.10600 H 5.77300 -0.80400 1.81300 H 5.04400 0.77100 1.38700 H 4.15500 -2.47800 -0.36800 H 2.85500 -2.91800 0.76800 H 4.54200 -2.94700 1.31200 H 3.35900 -0.92600 2.14200 Si 3.06400 0.49600 -1.24700 C 4.14100 2.06600 -1.25600 C 3.81600 -0.64700 -2.56900 C 1.37100 1.06800 -1.92300 H 0.67300 0.23000 -2.09700 H 1.48500 1.59900 -2.88100 H 0.87300 1.76100 -1.22300 H 3.22000 -1.56500 -2.69200 H 4.83700 -0.95500 -2.29300 H 3.87600 -0.14300 -3.54700 H 5.18900 1.84300 -1.00700 H 3.77800 2.79600 -0.51400 H 4.12800 2.55100 -2.24500 C -1.65900 -0.59100 1.39000 N -2.08700 -1.52700 2.16600 C -1.20400 -2.09800 3.16800 C 0.09300 -2.71800 2.62100 C -0.90000 -1.10100 4.29000 H 0.85800 -1.95000 2.43300 H -0.11300 -3.28400 1.69600 H 0.51700 -3.42700 3.34700 H -1.77000 -2.92900 3.62200 H -0.33500 -0.24600 3.88900 H -0.30800 -1.57200 5.09000 H -1.83600 -0.72300 4.72300 C -2.66400 -0.04700 0.39400 C -2.23300 0.73800 -0.67900 C -3.14500 1.21800 -1.62200 C -4.50300 0.93200 -1.48800 C -4.03000 -0.33300 0.52100 C -4.94200 0.15800 -0.40900 H -1.16900 0.96300 -0.76600 H -2.79200 1.82000 -2.46400 H -5.21900 1.31000 -2.22000 H -6.00500 -0.06400 -0.29800 1338 H -4.34100 -0.95100 1.36400 1339 Table C.2.234. Atomic coordinates and single point energies for E14. G = –2643.988335 GSP = –2646.262109 Na -0.62200 1.66200 -0.17600 Na 2.53700 -0.18900 -0.13800 N -3.18700 -0.90300 -0.13900 N 1.70300 1.95700 -0.27400 Si -2.24100 -1.77800 1.05500 C -1.38500 -3.36100 0.41500 C -3.21000 -2.41000 2.54400 C -0.71000 -0.78200 1.60000 C -3.76600 -1.31900 -1.41900 C -3.39600 -0.38900 -2.58200 H -3.88000 -0.74100 -3.50600 H -2.30800 -0.37000 -2.74200 H -3.70700 0.64200 -2.38800 C -3.45400 -2.76100 -1.80000 H -4.86700 -1.26900 -1.33000 H -3.98700 -3.00800 -2.72900 H -3.78500 -3.46700 -1.02500 H -2.37900 -2.91900 -1.97600 H -2.05900 -4.16300 0.08600 H -0.82400 -3.74700 1.28300 H -0.65300 -3.16400 -0.38300 H -3.99600 -3.10300 2.20200 H -3.69100 -1.58100 3.07800 H -2.55900 -2.96300 3.23900 H -0.00700 -0.69300 0.75200 H -0.18200 -1.31400 2.40800 H -0.98600 0.21200 1.97300 C 2.01200 2.71000 -1.47700 C 0.79200 3.44500 -2.05700 C 2.61400 1.81100 -2.56700 H 0.02500 2.72400 -2.39500 1340 H 1.05000 4.06600 -2.92800 H 0.33800 4.10100 -1.29700 H 2.77200 3.50000 -1.28000 H 2.86000 2.37300 -3.48200 H 1.90000 1.01600 -2.84200 H 3.53100 1.32100 -2.20700 Si 1.97900 2.59900 1.28600 C 2.69100 1.22000 2.39500 C 0.39300 3.16000 2.18300 C 3.13900 4.09900 1.35000 H 2.00100 0.35800 2.41700 H 2.82000 1.55400 3.43700 H 3.67300 0.87100 2.03100 H -0.29500 2.32200 2.38400 H -0.15800 3.91700 1.59900 H 0.62500 3.61100 3.16100 H 3.28700 4.41300 2.39400 H 2.70200 4.95200 0.80700 H 4.13100 3.90200 0.91600 C -7.70500 1.46400 -0.34500 C -7.33600 0.33900 0.39800 C -6.71900 2.27200 -0.90800 C -5.99000 0.02800 0.57000 C -5.36900 1.95500 -0.73300 C -4.99700 0.82900 -0.00400 H -8.76000 1.71000 -0.47900 H -8.10500 -0.29400 0.84700 H -5.68400 -0.84500 1.15300 H -4.57100 2.57400 -1.14600 H -7.00200 3.15700 -1.48100 C -3.49900 0.52000 0.24100 O -3.39100 0.42500 1.70400 O -2.68900 1.40900 -0.26700 C -3.44400 1.64700 2.37600 H -2.67400 2.35000 2.01800 H -3.28300 1.44500 3.44500 H -4.42900 2.13400 2.25400 C 6.45300 1.49100 -1.34000 C 5.35500 1.42600 -0.28400 O 4.78100 0.12200 -0.41700 C 5.58300 -0.70400 -1.25800 C 6.91100 0.03200 -1.40000 H 7.25300 2.19400 -1.07500 H 6.03000 1.79800 -2.30800 H 4.55600 2.16900 -0.42100 H 5.76500 1.53500 0.73500 1341 H 5.08500 -0.81600 -2.23800 H 5.67000 -1.69900 -0.79600 H 7.44300 -0.22600 -2.32400 H 7.56800 -0.19700 -0.54800 C 3.80900 -2.20100 3.23100 C 4.35800 -2.12200 1.79900 O 3.21300 -2.05600 0.96300 C 2.26500 -2.95200 1.52400 C 2.37600 -2.75000 3.04100 H 3.78300 -1.20400 3.68800 H 4.43000 -2.84800 3.86400 H 4.93700 -3.03100 1.54900 H 4.97300 -1.23700 1.59400 H 2.53200 -3.98800 1.24400 H 1.28000 -2.71400 1.10100 H 2.20000 -3.68600 3.58600 H 1.63400 -2.01900 3.38800 C 0.61800 -3.18300 -2.97800 C 1.67000 -2.80800 -1.93500 O 1.23100 -1.57500 -1.36300 C 0.08700 -1.07100 -2.06200 C 0.07300 -1.81600 -3.39100 H -0.18000 -3.78500 -2.51800 H 1.04200 -3.75800 -3.81200 H 2.66100 -2.65400 -2.39500 H 1.77200 -3.55700 -1.13600 H 0.20300 0.01800 -2.17500 H -0.82500 -1.26200 -1.47200 H 0.75200 -1.32900 -4.10800 H -0.92900 -1.86000 -3.83700 1342 Table C.2.235. Atomic coordinates and single point energies for E13. G = –2643.987264 GSP = –2646.267372 Na -1.15400 0.85900 -0.61500 Na 2.20200 -0.08100 -0.07300 N -2.10900 -1.12600 -0.05600 N 1.01600 1.62100 -1.12900 Si -1.84600 -1.27400 1.60300 C -0.88200 -2.82000 2.19400 C -3.38200 -1.17100 2.72700 C -0.71400 0.17900 2.12800 C -3.03800 -1.93400 -0.81000 C -2.79200 -1.78400 -2.31600 H -3.55700 -2.30700 -2.91400 H -1.80400 -2.19300 -2.58500 H -2.80300 -0.72100 -2.60400 C -3.01200 -3.43200 -0.45900 H -4.09200 -1.61000 -0.64000 H -3.69400 -4.01600 -1.09900 H -3.31200 -3.59800 0.58700 H -1.99100 -3.83200 -0.58100 H -1.44800 -3.74800 2.02600 H -0.62800 -2.77000 3.26600 H 0.05700 -2.89500 1.61900 H -4.12500 -1.93200 2.43900 H -3.86600 -0.18700 2.62900 H -3.13400 -1.32800 3.78900 H 0.26800 0.12500 1.62600 H -0.52900 0.17000 3.21400 H -1.14900 1.16100 1.87900 C 1.06800 1.62100 -2.58100 C -0.26100 1.17800 -3.21400 1343 C 2.19400 0.72100 -3.11300 H -0.51500 0.15100 -2.89800 H -0.22100 1.18100 -4.31400 H -1.07700 1.85700 -2.91400 H 1.27300 2.63400 -2.99000 H 2.22400 0.68800 -4.21500 H 2.06100 -0.31100 -2.74400 H 3.16600 1.08100 -2.74800 Si 1.39700 3.02700 -0.23800 C 2.44200 2.54700 1.28800 C -0.09000 3.96100 0.49000 C 2.37200 4.33200 -1.22000 H 1.89800 1.81700 1.91300 H 2.65300 3.42300 1.92100 H 3.40900 2.09900 1.00100 H -0.66700 3.32000 1.17600 H -0.78000 4.28000 -0.30800 H 0.23000 4.85500 1.04900 H 2.73900 5.12300 -0.54700 H 1.73000 4.81400 -1.97400 H 3.23800 3.90800 -1.75300 C -6.70900 -0.51600 -1.72900 C -6.85000 -0.42500 -0.34300 C -5.67700 0.16300 -2.37700 C -5.96100 0.34900 0.39900 C -4.77900 0.92600 -1.63700 C -4.91900 1.01800 -0.25100 H -7.40800 -1.12300 -2.30700 H -7.65500 -0.96000 0.16100 H -6.05900 0.43000 1.48100 H -3.96000 1.45900 -2.12400 H -5.56500 0.08700 -3.45900 C -3.93800 1.84300 0.50200 O -4.35100 2.14800 1.72800 O -2.88100 2.23200 0.05500 C -3.47700 2.93800 2.52400 H -3.12500 3.81100 1.95900 H -2.61100 2.34100 2.84100 H -4.05800 3.24700 3.39800 C 6.05000 0.80200 -2.14700 C 5.15200 1.29200 -1.01800 O 4.39600 0.15100 -0.62600 C 4.99900 -1.05100 -1.10100 C 6.34200 -0.63100 -1.69600 H 6.95100 1.41600 -2.27300 H 5.49400 0.79800 -3.09600 1344 H 4.45100 2.08800 -1.30900 H 5.74900 1.65200 -0.16000 H 4.33400 -1.50300 -1.85800 H 5.09200 -1.75500 -0.26000 H 6.66800 -1.29100 -2.51000 H 7.12200 -0.63200 -0.92000 C 3.93100 0.37800 3.76500 C 4.31600 -0.33200 2.45700 O 3.09900 -0.84000 1.93000 C 2.37800 -1.32500 3.05300 C 2.56200 -0.24500 4.12300 H 3.83800 1.46000 3.60500 H 4.68600 0.21300 4.54500 H 5.00000 -1.17800 2.65600 H 4.76800 0.31700 1.69800 H 2.81600 -2.28700 3.38100 H 1.33700 -1.49700 2.75600 H 2.52900 -0.66200 5.13700 H 1.76200 0.50300 4.03800 C 1.46800 -4.54400 -0.40100 C 2.45800 -3.41500 -0.12500 O 1.86900 -2.23900 -0.67400 C 0.73500 -2.58000 -1.49600 C 0.83800 -4.08500 -1.71600 H 0.70400 -4.58600 0.38800 H 1.95800 -5.52400 -0.46400 H 3.42200 -3.60700 -0.62800 H 2.65400 -3.24400 0.94400 H 0.79600 -2.00300 -2.43000 H -0.18800 -2.28900 -0.96300 H 1.50500 -4.31200 -2.56200 H -0.14000 -4.54200 -1.91600 1345 Table C.2.236. Atomic coordinates and single point energies for T4. G = –2643.966174 GSP = –2646.241329 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.05700 N 2.38700 0.00000 1.13300 N -1.78000 0.03700 1.54500 Si 2.91000 -1.23500 2.23900 C 2.85400 -0.77000 4.10600 C 4.67100 -1.92500 2.10900 C 1.71200 -2.70300 2.15200 C 2.74000 1.41600 1.22500 C 1.65000 2.27100 0.57000 H 1.93900 3.33200 0.51400 H 0.71400 2.20600 1.15100 H 1.44600 1.92600 -0.45500 C 3.02400 1.95800 2.63000 H 3.67200 1.62100 0.66500 H 3.15600 3.05100 2.58700 H 3.94700 1.52900 3.04500 H 2.20400 1.73500 3.33100 H 3.67800 -0.10000 4.38600 H 3.00500 -1.70800 4.66600 H 1.92000 -0.31800 4.47200 H 5.41800 -1.11700 2.13400 H 4.80800 -2.50300 1.18500 H 4.86700 -2.58700 2.96700 H 0.68500 -2.44500 2.46800 H 2.06200 -3.51100 2.81500 H 1.64500 -3.11700 1.13800 C -2.66600 1.15800 1.81300 C -2.00700 2.49500 1.46500 1346 C -3.16000 1.21700 3.26800 H -1.15600 2.67800 2.14000 H -2.70400 3.34100 1.57300 H -1.61800 2.48600 0.43500 H -3.58700 1.10300 1.18800 H -3.87600 2.03800 3.43400 H -2.30000 1.37200 3.94400 H -3.64700 0.27000 3.55000 Si -2.50800 -1.48200 1.20900 C -2.70600 -2.66200 2.69300 C -1.42400 -2.42200 -0.03700 C -4.25100 -1.35700 0.46500 H -1.75200 -2.77100 3.23300 H -3.03500 -3.66300 2.37000 H -3.45600 -2.27400 3.40000 H -0.39900 -2.55700 0.34700 H -1.36800 -1.89300 -1.00300 H -1.82400 -3.43000 -0.22600 H -4.61700 -2.36300 0.20800 H -4.27000 -0.74800 -0.45200 H -4.96500 -0.91600 1.17800 C 6.01500 1.88800 -1.92100 C 6.23500 0.75400 -1.13700 C 4.72500 2.18400 -2.35800 C 5.17000 -0.06900 -0.78000 C 3.66000 1.36000 -1.99800 C 3.87000 0.24200 -1.18800 H 6.85000 2.53200 -2.20000 H 7.24500 0.50600 -0.80800 H 5.33600 -0.96000 -0.17700 H 2.64800 1.57000 -2.34600 H 4.54800 3.05700 -2.98900 C 2.68200 -0.62100 -0.82300 O 3.08700 -1.91600 -0.55100 O 1.60300 -0.44300 -1.41100 C 2.38600 -2.92800 -1.24100 H 1.30900 -2.91100 -1.02200 H 2.81700 -3.88100 -0.90900 H 2.51600 -2.82500 -2.32900 C -1.11200 -1.54200 7.10200 C -1.50700 -1.06100 5.69100 O -0.39900 -1.37400 4.85500 C 0.11500 -2.60800 5.33200 C 0.11600 -2.44400 6.85000 H -1.93800 -2.09400 7.57100 H -0.86300 -0.70100 7.76300 1347 H -1.69300 0.01700 5.61400 H -2.39600 -1.59800 5.32100 H 1.10300 -2.76400 4.88800 H -0.55300 -3.43100 5.01700 H 1.04300 -1.94200 7.16600 H 0.06000 -3.40600 7.37500 C 1.33000 3.59700 5.41500 C 0.24600 3.04200 4.46500 O 0.17900 1.63700 4.71000 C 0.57700 1.42800 6.05700 C 1.76000 2.36900 6.23800 H 0.91300 4.38300 6.05900 H 2.17200 4.03000 4.86100 H 0.49100 3.18700 3.40500 H -0.74200 3.49100 4.66100 H 0.81300 0.36400 6.18100 H -0.25500 1.69400 6.73700 H 2.65700 1.90500 5.80400 H 1.96300 2.60300 7.29000 C -0.95400 2.54800 -3.12200 C -0.56100 1.07100 -3.04500 O -1.17700 0.62300 -1.85000 C -2.48900 1.15400 -1.86300 C -2.35300 2.56900 -2.46300 H -0.95600 2.93000 -4.15000 H -0.24300 3.15000 -2.53800 H 0.51100 0.86100 -2.96400 H -0.97400 0.50900 -3.90300 H -2.87300 1.12600 -0.83500 H -3.13200 0.51900 -2.49900 H -2.41700 3.34100 -1.68500 H -3.15100 2.76800 -3.19000 1348 Table C.2.237. Atomic coordinates and single point energies for T5. G = –2643.967935 GSP = –2646.244173 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.66600 N 2.16200 0.00000 -1.01300 N -1.46000 0.12900 1.87200 Si 3.06100 -1.19200 -0.15800 C 4.16700 -0.57700 1.28100 C 4.22100 -2.31100 -1.15800 C 1.80500 -2.27300 0.78500 C 2.67800 1.25100 -1.54300 C 1.60000 2.34200 -1.49000 H 1.88900 3.23400 -2.06800 H 1.41700 2.66100 -0.44900 H 0.65400 1.96300 -1.90300 C 3.97300 1.77500 -0.90700 H 2.93600 1.14000 -2.61500 H 4.26200 2.73200 -1.36800 H 4.80200 1.06700 -1.06000 H 3.86700 1.93600 0.17700 H 5.05100 -0.01000 0.95900 H 4.52600 -1.46400 1.83200 H 3.59200 0.04300 1.98800 H 4.93900 -1.69800 -1.72900 H 3.65500 -2.92700 -1.87000 H 4.80100 -2.97400 -0.49700 H 1.32700 -1.68400 1.59100 H 2.30400 -3.13200 1.26200 H 1.01300 -2.66600 0.13300 C -2.22000 1.36000 1.70700 C -1.89100 2.08800 0.39500 C -2.02600 2.31700 2.89400 H -0.83300 2.39900 0.36700 1349 H -2.49500 2.99900 0.26300 H -2.08300 1.43300 -0.47000 H -3.31200 1.16400 1.66500 H -2.58700 3.25700 2.77500 H -0.95900 2.57200 3.01700 H -2.35700 1.83000 3.82400 Si -2.29200 -1.35800 2.03400 C -1.47200 -2.40100 3.41400 C -2.20700 -2.48900 0.51400 C -4.13400 -1.18500 2.46400 H -0.40300 -2.56500 3.18800 H -1.93700 -3.39700 3.48000 H -1.54800 -1.93200 4.41000 H -1.17800 -2.86300 0.38800 H -2.48100 -1.94900 -0.40700 H -2.86500 -3.36600 0.61400 H -4.55200 -2.16700 2.73400 H -4.70500 -0.81000 1.60100 H -4.31700 -0.49400 3.30200 C 2.47600 0.88500 -5.98600 C 3.16400 -0.16600 -5.37600 C 1.26100 1.31900 -5.45800 C 2.64300 -0.77600 -4.23800 C 0.73800 0.70900 -4.31700 C 1.43300 -0.32900 -3.69600 H 2.88600 1.36200 -6.87800 H 4.11200 -0.51200 -5.79100 H 3.17300 -1.59000 -3.74300 H -0.21700 1.02100 -3.89400 H 0.71400 2.13100 -5.93900 C 0.84200 -0.96500 -2.47100 O 1.32900 -2.24500 -2.29300 O -0.29400 -0.68300 -2.08200 C 0.36300 -3.27400 -2.28400 H -0.46200 -3.05400 -1.59500 H 0.88100 -4.18800 -1.96700 H -0.05300 -3.42600 -3.29300 C -2.81500 1.44000 6.78800 C -2.43300 0.20700 5.97800 O -1.06400 0.40200 5.62700 C -0.47600 1.43800 6.41300 C -1.49900 1.75300 7.50200 H -3.65500 1.25800 7.46900 H -3.08800 2.26600 6.11300 H -3.01400 0.07800 5.05300 H -2.52700 -0.71400 6.58000 1350 H -0.29200 2.31400 5.76800 H 0.49000 1.08000 6.80000 H -1.42700 2.78700 7.86300 H -1.36300 1.07800 8.36100 C 1.17000 -3.41900 5.66600 C 1.01800 -1.95600 6.11600 O 1.43600 -1.17400 5.00900 C 2.55200 -1.85100 4.45200 C 2.16700 -3.33400 4.48700 H 0.20700 -3.82300 5.33100 H 1.53800 -4.05100 6.48400 H 1.67500 -1.74000 6.97800 H -0.00700 -1.65800 6.36700 H 3.44600 -1.65900 5.07500 H 2.73400 -1.45200 3.44500 H 3.04500 -3.97900 4.61900 H 1.68100 -3.61900 3.54400 C 3.73500 2.65000 3.29500 C 2.89600 1.68300 4.13100 O 1.77500 1.33500 3.31700 C 1.76600 2.11200 2.11400 C 2.67900 3.29700 2.39700 H 4.45800 2.09200 2.68000 H 4.28800 3.36800 3.91300 H 2.52800 2.15900 5.05500 H 3.43800 0.76600 4.40500 H 0.72800 2.39500 1.89300 H 2.14100 1.49500 1.28000 H 2.13100 4.08000 2.94300 H 3.09100 3.73600 1.48000 1351 Table C.2.238. Atomic coordinates and single point energies for T3. G = –2643.961344 GSP = –2646.240879 Na 0.00000 0.00000 0.00000 Na 0.00000 0.00000 3.44100 N 2.49700 0.00000 -0.12100 N -1.72100 -0.09500 1.90700 Si 2.62000 1.67500 -0.50700 C 2.16600 2.11300 -2.30900 C 4.33700 2.49500 -0.26200 C 1.38200 2.65500 0.55800 C 3.44800 -0.92700 -0.72700 C 2.82300 -2.29200 -1.04200 H 3.58300 -3.00700 -1.39700 H 2.07000 -2.16900 -1.83500 H 2.32200 -2.73100 -0.17300 C 4.14400 -0.46300 -2.02000 H 4.28100 -1.11600 -0.01200 H 4.87600 -1.21800 -2.34700 H 4.68600 0.48500 -1.89000 H 3.41100 -0.33000 -2.83200 H 2.99700 1.90400 -2.99700 H 1.92700 3.18600 -2.39300 H 1.29200 1.53500 -2.64200 H 4.76000 2.79300 -1.23300 H 5.04100 1.79100 0.20700 H 4.28700 3.40000 0.36400 H 1.62400 2.56700 1.62600 H 0.32900 2.34300 0.43700 H 1.42700 3.71900 0.27300 C -2.61000 -1.24400 1.80000 1352 C -1.84000 -2.56300 1.89200 C -3.45100 -1.25900 0.51900 H -1.13900 -2.64800 1.04400 H -2.51400 -3.43500 1.86200 H -1.25000 -2.60700 2.82100 H -3.34400 -1.26900 2.64000 H -4.11400 -2.13900 0.46800 H -2.78300 -1.26900 -0.35900 H -4.08000 -0.35700 0.45600 Si -2.43200 1.39600 2.38300 C -2.89800 2.64700 1.03200 C -1.20700 2.35700 3.49600 C -4.00800 1.18300 3.42500 H -2.06000 2.78700 0.33300 H -3.14600 3.62300 1.47800 H -3.77600 2.31100 0.45700 H -0.20700 2.46100 3.04200 H -1.10200 1.90300 4.49900 H -1.58100 3.37700 3.66500 C 2.57200 -4.49600 2.14000 C 3.82600 -3.88800 2.16700 C 1.42100 -3.70400 2.11000 C 3.93500 -2.49600 2.17000 C 1.53100 -2.31800 2.10600 C 2.78700 -1.70300 2.13000 H 2.49000 -5.58400 2.13400 H 4.72800 -4.50100 2.18900 H 4.91100 -2.01200 2.20300 H 0.62900 -1.70900 2.02700 H 0.43400 -4.16900 2.06300 C 2.86700 -0.20900 2.19700 O 4.13700 0.22700 2.22300 O 1.96100 0.46200 2.69800 C 4.33700 1.50400 2.80100 H 5.40100 1.73400 2.68200 H 4.06700 1.48300 3.86700 H 3.73300 2.26800 2.29900 C -0.40900 -3.80500 5.37100 C 0.45400 -2.56600 5.58900 O -0.31900 -1.50800 5.04500 C -1.68200 -1.73500 5.38800 C -1.84600 -3.26400 5.50600 H -0.18100 -4.60600 6.08600 H -0.23300 -4.19400 4.35800 H 1.41700 -2.59200 5.06100 H 0.63300 -2.38100 6.66400 1353 H -2.50100 -3.66000 4.72000 H -2.29000 -3.53200 6.47400 C -0.23400 -3.38100 -3.10500 C -0.60800 -2.84700 -1.72000 O -0.43800 -1.43000 -1.78000 C -0.02400 -1.03000 -3.08600 C -0.47500 -2.16300 -3.99800 H -0.82800 -4.25900 -3.38900 H 0.82900 -3.66200 -3.13000 H 0.03400 -3.25600 -0.92400 H -1.66000 -3.06000 -1.46600 H 0.08100 -2.19600 -4.94300 H -1.54700 -2.05800 -4.22900 C -2.46100 3.27300 -2.54200 C -1.06000 2.83200 -2.13700 O -1.19900 1.50100 -1.63200 C -2.48800 0.98300 -1.97200 C -3.06500 1.94700 -3.00300 H -2.44700 4.04700 -3.32000 H -3.01100 3.66000 -1.67200 H -0.59800 3.45900 -1.36000 H -0.38800 2.82100 -3.01000 H -2.37000 -0.04600 -2.33800 H -4.16300 1.94000 -3.01600 H -2.70500 1.69500 -4.01300 H -0.48000 -0.05700 -3.30800 H 1.07200 -0.90300 -3.10300 H -1.90600 -1.23200 6.34400 H -2.30000 -1.28300 4.59700 H -3.10600 0.95200 -1.06400 H -4.82400 0.72200 2.84600 H -4.36500 2.16500 3.77400 H -3.83500 0.55500 4.31400 1354 Table C.2.239. Atomic coordinates and single point energies for E4. G = –1785.568615 GSP = –1787.00989 Na 0.99500 0.38200 -0.92900 N -1.18400 -0.46800 0.36500 Si -1.04800 -2.21700 0.24200 C -0.36200 -2.96400 1.84900 C -2.67100 -3.15400 -0.02700 C 0.19700 -2.74100 -1.07900 H -3.39200 -2.92100 0.77200 H -2.48100 -4.23900 -0.00500 H -3.11700 -2.89100 -0.99500 H 0.31900 -3.83600 -1.09100 H 1.19000 -2.30900 -0.86800 H -0.12900 -2.41200 -2.07500 H -0.43100 -4.05900 1.74300 H -0.92600 -2.68100 2.74900 H 0.69600 -2.71500 2.00900 C -0.96600 0.34700 1.56600 C -2.07500 0.20100 2.61600 C 0.40400 0.15500 2.23300 H -1.88200 0.85900 3.47900 H -2.11700 -0.83500 2.98600 H -3.05800 0.45700 2.19800 H -0.98500 1.38800 1.20100 H 0.43100 -0.75100 2.85300 H 0.61400 1.00800 2.89700 H 1.23200 0.08500 1.50700 H -3.39300 0.13300 -3.02500 C -5.47400 0.63400 0.20000 C -4.25300 0.08900 -0.19300 C -5.59500 2.01100 0.40500 C -3.13800 0.91000 -0.39000 1355 C -4.49000 2.83600 0.19300 C -1.75200 0.33700 -0.79000 C -3.27300 2.28600 -0.21400 C -2.37200 -0.29500 -3.01600 O -0.94800 1.24800 -1.24200 O -2.01400 -0.74300 -1.74300 H -6.33800 -0.01700 0.35200 H -4.14700 -0.98600 -0.34700 H -6.54900 2.43800 0.72100 H -4.58000 3.91400 0.34100 H -2.39200 2.89900 -0.41200 H -2.35000 -1.16100 -3.69500 H -1.67200 0.47600 -3.37300 H 1.64800 2.45000 0.80900 H 2.86400 3.71200 0.53000 C 2.47400 2.75600 0.14600 H 2.04700 2.95800 -0.85100 H 4.92000 2.35900 2.18100 H 3.85000 0.97500 2.54200 C 4.59400 1.36600 1.83000 Si 3.85400 1.44400 0.06500 H 5.48300 3.27700 -0.56700 N 3.17300 0.02500 -0.54700 H 5.46900 0.69600 1.86300 C 5.23600 2.27900 -0.96700 H 4.90900 2.40000 -2.01200 H 6.16100 1.68100 -0.97500 C 3.82900 -1.25200 -0.64400 H 5.91300 -0.68200 -0.34400 C 5.29400 -1.18700 -1.10700 H 5.36900 -0.60700 -2.03900 H 5.72000 -2.19000 -1.27600 H 3.30900 -1.87500 -1.40700 H 2.70200 -2.14600 0.98600 C 3.75200 -2.04900 0.66900 H 4.28800 -1.50800 1.46600 H 4.18600 -3.06100 0.57800 1356 Table C.2.240. Atomic coordinates and single point energies for E3. G = –1785.550006 GSP = –1786.998065 Na 0.58600 -0.27500 -0.68900 N -1.22100 -0.68200 0.66300 Si -1.73700 -2.27900 0.49500 C -1.31900 -3.53100 1.88300 C -3.62900 -2.52100 0.26000 C -0.85900 -3.00200 -1.04000 H -4.13200 -2.47000 1.24000 H -3.88300 -3.49400 -0.19500 H -4.05100 -1.71600 -0.36200 H -1.34200 -3.92200 -1.41100 H 0.17700 -3.26500 -0.76700 H -0.80900 -2.28600 -1.87600 H -1.65900 -4.54500 1.61200 H -1.80100 -3.26000 2.83700 H -0.23200 -3.56900 2.05500 C -1.31100 0.11000 1.86200 C -2.64900 -0.02200 2.61000 C -0.15200 -0.16200 2.83600 H -2.72800 0.68700 3.45100 H -2.76100 -1.04300 3.01600 H -3.48700 0.15800 1.92000 H -1.22700 1.18700 1.59200 H -0.19800 -1.20400 3.19300 H -0.17600 0.50800 3.71300 H 0.81300 -0.03200 2.32100 H -4.35200 -1.17900 -3.06900 C -3.22200 3.23200 0.74400 C -3.23300 2.14000 -0.11800 C -2.07700 4.02300 0.86300 1357 C -2.09000 1.83200 -0.86000 C -0.93800 3.71800 0.11800 C -2.04200 0.66000 -1.77700 C -0.94800 2.62600 -0.74600 C -3.29100 -0.97600 -2.88800 O -1.04200 0.28200 -2.34900 O -3.24500 0.13500 -2.00900 H -4.10800 3.46100 1.33900 H -4.11200 1.50100 -0.20800 H -2.07000 4.87100 1.54900 H -0.03100 4.31700 0.21700 H -0.06400 2.37900 -1.33800 H -2.81600 -1.84900 -2.42300 H -2.77400 -0.74200 -3.82900 H 1.67000 2.19800 0.82300 H 3.05500 3.31200 0.67700 C 2.54800 2.45300 0.20600 H 2.19300 2.77700 -0.78700 H 4.97500 1.62600 2.13100 H 3.71600 0.40800 2.49000 C 4.48900 0.70600 1.76300 Si 3.71400 0.95700 0.02800 H 5.58700 2.55600 -0.59500 N 2.83000 -0.32000 -0.61600 H 5.25200 -0.09100 1.74500 C 5.17600 1.62400 -1.02000 H 4.83900 1.83300 -2.04800 H 5.99600 0.89200 -1.08200 C 3.24900 -1.69000 -0.74100 H 5.40100 -1.48600 -0.47300 C 4.69500 -1.87100 -1.23000 H 4.85100 -1.30100 -2.15800 H 4.94400 -2.93000 -1.41500 H 2.61600 -2.20000 -1.50500 H 2.00500 -2.39700 0.90300 C 3.04800 -2.48900 0.56000 H 3.69100 -2.07400 1.35400 H 3.28600 -3.56100 0.43900 1358 Table C.2.241. Atomic coordinates and single point energies for T6, T13. G = –1785.541509 GSP = –1786.98598 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.36200 Si 1.67600 0.00000 2.74100 C 2.50500 1.70700 2.92000 C 2.16300 -0.90800 4.35000 C 2.60800 -0.77100 1.26900 H 1.95600 -0.25700 5.21400 H 3.23700 -1.15700 4.37000 H 1.57900 -1.82900 4.48000 H 3.62000 -1.10200 1.55500 H 2.73000 0.00000 0.48900 H 2.08000 -1.62300 0.81800 H 3.58700 1.56400 3.08200 H 2.11500 2.29000 3.76900 H 2.37600 2.30500 2.00500 C -0.92400 0.93500 2.98200 C -0.79800 1.03000 4.51100 C -0.85700 2.34000 2.36300 H -1.60800 1.63500 4.95000 H 0.16100 1.49600 4.79500 H -0.83000 0.02500 4.95800 H -1.95600 0.58600 2.78900 H 0.11700 2.81300 2.56200 H -1.64400 2.99600 2.77300 H -0.98300 2.29200 1.26900 H 1.05900 -4.50400 2.94200 C -3.73500 -1.65600 4.11200 C -2.43000 -1.92600 3.70700 C -4.69000 -1.24000 3.18100 C -2.06600 -1.77100 2.36700 1359 C -4.33300 -1.10600 1.84000 C -0.66400 -2.02100 1.88700 C -3.02700 -1.37700 1.43400 C 1.09100 -3.56700 2.37100 O -0.39600 -2.10900 0.68600 O 0.01400 -2.77400 2.81100 H -4.01100 -1.76800 5.16300 H -1.67300 -2.24500 4.42300 H -5.71000 -1.02200 3.50200 H -5.07200 -0.78500 1.10300 H -2.73600 -1.28000 0.38700 H 2.05200 -3.06600 2.56500 H 1.00400 -3.77700 1.29600 H -2.63700 0.89900 -0.79500 H -3.33600 0.64300 -2.41100 C -2.40100 0.59700 -1.83000 H -2.07300 -0.45700 -1.82000 H -2.78300 3.46800 -3.18100 H -2.00000 3.85400 -1.62100 C -1.82300 3.47100 -2.63800 Si -1.04600 1.72100 -2.56700 H -1.92700 1.23700 -4.89900 N 0.33000 1.51600 -1.62100 H -1.15200 4.18100 -3.14900 C -0.93900 1.20100 -4.40800 H -0.55100 0.17300 -4.49000 H -0.25800 1.85800 -4.97300 C 1.53500 2.29600 -1.65800 H 1.35600 3.22300 -3.62100 C 2.06300 2.57300 -3.07500 H 2.15200 1.62900 -3.63400 H 3.04500 3.07700 -3.06500 H 2.35000 1.73800 -1.14100 H 1.05400 3.43500 0.12800 C 1.40300 3.62700 -0.89800 H 0.65200 4.26600 -1.39000 H 2.35700 4.18200 -0.85100 1360 Table C.2.242. Atomic coordinates and single point energies for T6-2. G = –1785.541661 GSP = –1786.986268 Na 0.00000 0.00000 0.00000 N 0.00000 0.00000 2.34500 Si 1.62000 0.00000 2.92200 C 2.42000 1.71300 3.18000 C 1.90700 -0.87300 4.59800 C 2.72800 -0.80000 1.59600 H 1.63400 -0.19200 5.42000 H 2.96500 -1.15500 4.73500 H 1.28200 -1.77200 4.69100 H 3.68900 -1.13900 2.01600 H 2.96100 -0.04300 0.82800 H 2.23900 -1.64600 1.09500 H 3.47800 1.57200 3.46100 H 1.93600 2.29500 3.97800 H 2.39000 2.31000 2.25500 C -0.98800 0.94000 2.85600 C -1.06000 1.00400 4.38900 C -0.83400 2.35300 2.26800 H -1.91500 1.60900 4.73200 H -0.14200 1.45500 4.80500 H -1.15700 -0.01000 4.80600 H -1.98800 0.60700 2.52300 H 0.10100 2.82500 2.60700 H -1.67200 3.00000 2.57700 H -0.82100 2.31200 1.16600 H 0.91600 -4.38000 3.38600 C -4.06400 -1.59800 3.38200 C -2.71000 -1.89700 3.24500 C -4.79100 -1.11500 2.29200 1361 C -2.07000 -1.71200 2.01700 C -4.15800 -0.94300 1.06100 C -0.60100 -1.98500 1.83400 C -2.80500 -1.24900 0.92300 C 0.97900 -3.55900 2.65900 O -0.11200 -2.13600 0.70800 O -0.12900 -2.72500 2.89300 H -4.55500 -1.73700 4.34700 H -2.12900 -2.26700 4.08900 H -5.85000 -0.87100 2.40300 H -4.71100 -0.56100 0.20100 H -2.31100 -1.11200 -0.04200 H 1.92800 -3.02300 2.81300 H 0.95900 -3.95700 1.63500 H 1.31100 -0.17700 -2.51600 H 2.19100 1.15100 -3.30500 C 1.49400 0.91100 -2.48600 H 2.01600 1.15100 -1.54300 H 0.02600 1.88900 -5.16400 H -1.05500 0.59000 -4.57900 C -0.75000 1.63700 -4.42200 Si -0.13500 1.89600 -2.62700 H 1.21800 3.91600 -3.34700 N -1.13000 1.36400 -1.37900 H -1.62700 2.27300 -4.62800 C 0.42700 3.72700 -2.60100 H 0.82400 3.98400 -1.60500 H -0.40700 4.41400 -2.81300 C -2.48700 1.74500 -1.10600 H -2.63900 3.57300 -2.28300 C -2.76000 3.25300 -1.23300 H -2.04000 3.82000 -0.62400 H -3.78200 3.51900 -0.91400 H -2.73400 1.48700 -0.05000 H -3.34300 -0.10600 -1.87000 C -3.50100 0.97800 -1.97400 H -3.34800 1.23000 -3.03600 H -4.54700 1.21400 -1.70900