Azido Derivatives of Low-Valent Group 14 Elements: Synthesis, Characterization, and Electronic Structure of [(<i>n</i>-Pr)<sub>2</sub>ATI]GeN<sub>3</sub> and [(<i>n</i>-Pr)<sub>2</sub>ATI]SnN<sub>3</sub> Featuring Heterobicyclic 10-π-Electron Ring Systems
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Treatment of THF solutions of [(n-Pr)2ATI]MCl (where [(n-Pr)2ATI]- = N-(n-propyl)-2-(n-propylamino)troponiminate; M = Ge and Sn) with sodium azide affords the compounds [(n-Pr)2ATI]MN3 in excellent yield. X-ray analyses revealed that these Ge(II) and Sn(II) compounds feature linear azide moieties and planar heterobicyclic C7N2M ring systems. Germanium and tin atoms adopt a pyramidal geometry. IR spectra of [(n-Pr)2ATI]GeN3 and [(n-Pr)2ATI]SnN3 display a νasym(N3) band at 2048 and 2039 cm-1, respectively. DFT calculations on the corresponding methyl-substituted species demonstrate that the geometrical and electronic structure of these two species are very similar, and the dominant canonical form of the metal−azide moiety is M−N−N⋮N. The tin system is, as expected, slightly more ionic. A comparative CASSCF/DFT study on the model system H−Sn−N3 illustrates that the DFT approach is viable for the calculation of the structures of these species.
