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)

Abstract

Chloro and azido germanium(II) and tin(II) 1,5-diazapentadienyl complexes have been investigated. The treatment of GeCl2·(1,4-dioxane) or SnCl2 with [(Mes)2DAP]Li in a 1:1 molar ratio gave the corresponding germanium(II) or tin(II) chloro complexes [(Mes)2DAP]MCl (where [(Mes)2DAP] = 2,4-dimethyl-N,N‘-bis(2,4,6-trimethylphenyl)-1,5-diazapentadienyl; M = Ge or Sn). [(Mes)2DAP]GeCl and [(Mes)2DAP]SnCl are monomeric in the solid state. The C3N2M rings adopt a flattened boat conformation. The metathesis reaction between [(Mes)2DAP]MCl and sodium azide affords the azido compounds [(Mes)2DAP]MN3 in excellent yield. X-ray analysis revealed that [(Mes)2DAP]GeN3 features an essentially linear azide moiety and a nearly planar heterocyclic C3N2Ge ring system. The azide group occupies a site above the C3N2Ge ring. The solid-state structure of the tin azide [(Mes)2DAP]SnN3 shows weak intermolecular Sn···N contacts. It features a linear azide moiety and a planar heterocyclic C3N2Sn ring system. Both azides have long (M...