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 weight percent of 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, thermolysis of ImMe2•GeH2•BH3 in solution cleanly affords conformal nanodimensional layers of germanium as thin films of variable thicknesses (20 to 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- Pr2C6H3 (Dipp), Me and H; 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.