Insight into the Decomposition Mechanism of Donor–Acceptor Complexes of EH₂ (E = Ge and Sn) and Access to Germanium Thin Films from Solution

Electron-donating N-heterocyclic carbenes (Lewis bases, LB) and electron-accepting Lewis acids (LA) have been used in tandem to yield donor–acceptor complexes of inorganic tetrelenes LB·EH₂·LA (E = Si, Ge, and Sn). Herein, we introduce the new germanium (II) dihydride adducts ImMe₂·GeH₂·BH₃ (ImMe₂ = (HCNMe)₂C:) and ImⁱPr₂Me₂·GeH₂·BH₃ (ImⁱPr₂Me₂ = (MeCNⁱPr)₂C:), with the former complex containing nearly 40 wt % germanium. The thermal release of bulk germanium from ImMe₂·GeH₂·BH₃ (and its deuterated isotopologue ImMe₂·GeD₂·BD₃) was examined in solution, and a combined kinetic and computational investigation was undertaken to probe the mechanism by which Ge is liberated. Moreover, the thermolysis of ImMe₂·GeH₂·BH₃ in solution cleanly affords conformal nanodimensional layers of germanium as thin films of variable thicknesses (20–70 nm) on silicon wafers. We also conducted a computational investigation into potential decomposition pathways for the germanium­(II)- and tin­(II)-dihydride complexes NHC·EH₂·BH₃ (NHC = [(HCNR)₂C:]; R = 2,6-ⁱPr₂C₆H₃ (Dipp), Me, and H; and E = Ge and Sn). Overall, this study introduces a mild and convenient solution-only protocol for the deposition of thin films of Ge, a widely used semiconductor in materials research and industry.