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Bis(Imino)Pyridine Iron And Cobalt Complexes: Preparation, Electronic Structure Determination And Reactivity Of Metal-Ligand Multiple Bonds
The synthesis, reactivity and electronic structures of a series of bis(imino)pyridine iron and cobalt complexes was investigated. A series of monomeric bis(imino)pyridine cobalt dinitrogen complexes was investigated using a combination of 1H NMR and infrared spectroscopies, X-ray crystallography, EPR spectroscopy, solution and solid state magnetic measurements and density functional theory. The neutral bis(imino)pyridine cobalt dinitrogen complexes have doublet ground states and are best described as low-spin cobalt(I) centers with an unpaired electron on the singly reduced chelate, while the anionic bis(imino)pyridine cobalt dinitrogen complexes are also best described as low-spin cobalt(I) centers with dianionic chelates. These investigations established that reduction of monochloride precursors occurs at the metal center, in contrast to the related bis(imino)pyridine iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2, where reduction of the chelate is observed. A series of bis(imino)pyridine iron imide complexes was also investigated. A combination of Xray crystallography, variable temperature SQUID magnetization data and Mössbauer spectroscopy was used to elucidate the electronic structures of these complexes. In contrast to the previously reported N-aryl substituted bis(imino)pyridine iron imide complexes, where an iron(III) metal center and a singly reduced chelate was observed, an iron(IV) metal center and a triplet diradical chelate was observed for N-alkyl substituted bis(imino)pyridine iron imide complexes. For (iPrPDI)FeN(2Ad) (iPrPDI = 2,6-(2,6-iPr2-C6H3-N=CMe)2C5H3N), thermal spin crossover from S = 0 to S = 1 was observed when warming from 15 K to 200 K. (ArPDI)FeNR compounds with an S = 0 ground state promoted C-H bond activation of both imine methyl groups of the bis(imino)pyridine ligand. The C-H bond activation with (iPrPDI)FeN(CyOct) was firstorder in iron with a rate constant of k = 3.4(2)x10-5 s-1 at 25 °C and a primary kinetic isotope effect of 3.3(2), consistent with a rate-determining step of intramolecular C-H bond activation. In contrast, no C-H bond activation of the ligand was observed for the iron imide complexes that are S = 1 at 23 °C. The reactivity of bis(imino)pyridine iron imide compounds with hydrogen, silanes, terminal alkynes and organic azides, and the electronic structures of the resulting iron complexes, was also investigated.
dissertation or thesis