A series of tertiary amines, i.e. HAr2pyN, HArpy2N, BrAr2pyN, and BrArpy2N, containing at least one pyridyl arm were prepared, and oxidative addition of BrAr2pyN, and BrArpy2N with Ni(COD)2 afforded two diamagnetic Ni(II) complexes, ((BrAr)ArpyN)NiBr (1-Ni) and (Arpy2N)NiBr (2-Ni). The disproportionation of Fe{N(TMS)2}2(THF) in the presence of BrArpy2N afforded (Arpy2N)FeBr (2-Fe); however, C-N bond cleavage, not disproportionation, was observed upon treating Cr{N(TMS)2}2(THF)2 with BrArpy2N. Unusual optical properties were characteristic of the resulting complex, (smif)CrN(TMS)2 (4-Cr), (smif = (2-py)CHNCH(2-py)). Exposure of 1st-row transition metal complexes with the smif ligand produced a new homologous series of optically dense complexes, (smif)2M (M = V (6-V); Cr (6-Cr); Mn (6-Mn); Fe (6-Fe); Co (6-Co); Ni (6-Ni)). Oxidation chemistry afforded three (smif)2M complexes (M = Cr (7-Cr); Mn (7-Mn); Co(7-Co)). Physical and electronic properties for the series were investigated by NMR, EPR, UV-vis, and XAS (pre K-edge) spectroscopies along with X-ray crystallography, electrochemistry, and SQUID magnetometry. SQUID and XAS data helped elucidate the electronic structures obtained from the density functional theory calculations. Large absorptivities ( ~ 18,000 - 60,000 M-1cm-1) were observed in the UV-vis spectra for the complexes and have been attributed to intraligand transitions between CNazaCnb and smif * orbitals. Efforts to synthesize (smif)2Ti via salt metathesis under reducing conditions afforded varying ratios of four titanium(II) complexes: lithium[(C,Nam,Nim,Npy3-1,2-bis(pyridin-2-yl)-2-(pyridin-2-ylmethyleneamino)ethyl)(pyridin-2ylmethideyl)amido)Ti(smif)] (10-Ti), (smif)2Ti (11-Ti), (smif)(dpma)Ti (12-Ti), (Nam,Npy2-2,3,5,6-tetrakis(pyridin-2-yl)piperazin-1-yl)(smif)Ti (13-Ti). Reactivity of the coordinated azaallyl moiety in the smif ligand was probed after treatment of Fe{N(TMS)2}2(THF) with one equivalent of smifH afforded a solution of (smif)FeN(TMS)2 (14-Fe), which dimerizes in the solid state to form a bridging tetra-substituted piperazine bis-amide ligand, [14-Fe]2. Solid-state and solution dynamics indicated reversible C-C bond coupling of the smif backbone, thereby provoking an exploration of reactivity for the azaallyl moiety with unsaturated organic molecules. Exposure of 14-Fe to di-(p-tolyl)acetylene yielded the [3+2] cycloaddition product, 29-Fe. Attempts to prevent C-C bond formation by methylating the backbone led to acid-base chemistry of the azaallyl moiety.