Azido Derivatives of Germanium(II) and Tin(II): Syntheses and Characterization of [(Mes)2DAP]GeN3, [(Mes)2DAP]SnN3, and the Corresponding Chloro Analogues Featuring Heterocyclic Six-π-Electron Ring Systems (where [(Mes)2DAP] = {N(Mes)C(Me)}2CH)

Chloro and azido germanium(II) and tin(II) 1,5-diazapentadienyl complexes have been investigated. The treatment of GeCl 2 ·(1,4-dioxane) or SnCl 2 with [(Mes) 2 DAP]Li in a 1:1 molar ratio gave the corresponding germanium(II) or tin(II) chloro complexes [(Mes) 2 DAP]MCl (where [(Mes) 2 DAP] = 2,4-dimethyl- N,N ‘ -bis(2,4,6-trimethylphenyl)-1,5-diazapentadienyl; M = Ge or Sn). [(Mes) 2 DAP]GeCl and [(Mes) 2 DAP]SnCl are monomeric in the solid state. The C 3 N 2 M rings adopt a flattened boat conformation. The metathesis reaction between [(Mes) 2 DAP]MCl and sodium azide affords the azido compounds [(Mes) 2 DAP]MN 3 in excellent yield. X-ray analysis revealed that [(Mes) 2 DAP]GeN 3 features an essentially linear azide moiety and a nearly planar heterocyclic C 3 N 2 Ge ring system. The azide group occupies a site above the C 3 N 2 Ge ring. The solid-state structure of the tin azide [(Mes) 2 DAP]SnN 3 shows weak intermolecular Sn···N contacts. It features a linear azide moiety and a planar heterocyclic C 3 N 2 Sn ring system. Both azides have long (M)N−N(N) bonds and short (MN)N−N bonds. IR spectra of [(Mes) 2 DAP]GeN 3 and [(Mes) 2 DAP]SnN 3 display ν asym (N 3 ) bands at 2062 and 2060 cm - 1, respectively. 14 N NMR spectroscopic data show three well-separated signals for the nitrogen atoms of the azide moieties. Structural and spectroscopic data suggest the presence of very similar azide groups in the Ge(II) and Sn(II) adducts. The dominant canonical form of the metal−azide moiety is M−N−N⋮N.