Reactivity of α-germyl nitriles with acetonitrile: Synthesis, structures, and generation of Ph3Ge[NHC(CH3)CHCN] and 2,6-dimethyl-4-(triphenylgermylamino)pyrimidine from Ph3GeCH2CN

► Dimerization or trimerization of CH3CN has been observed during the hydrogermolysis reaction. ► This provides the free amines or germanes containing these amines as ligands. ► Two new germanes with the conjugate bases of di- and triacetonitrile as ligands have been prepared and structurally characterized. ► The pathway for the reaction R3GeCH2CN with CH3CN to provide di- and triacetonitrile-substituted germanes has been elucidated.