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

The formation of 3-aminocrotononitrile and 4-amino-2,6-dimethylaminopyrimidine has been observed during the course of the hydrogermolysis reaction between a germanium amide and a germanium hydride, either as the free amines or bound to germanium as ligands consisting of their conjugate bases. These species arise from the dimerization or trimerization of acetonitrile, and have only been detected when germanium amides having substantial steric bulk at the germanium center are employed in the reaction. The isolation of germanium-bound 3-aminocrotononitrile compounds suggests that α-germyl nitrile species R3GeCH2CN that result from the reaction of the germanium amides R3GeNMe2 with CH3CN solvent also can further react with CH3CN to generate the 3-aminocrotononitrile and 4-amido-2,6-dimethylaminopyrimidine species. The two germanes Ph3Ge[NHC(CH3)double bond; length as m-dashCHCN] and 2,6-dimethyl-4-(triphenylgermylamino)pyrimidine have been prepared and structurally characterized, and the conversion of Ph3GeCH2CN to Ph3Ge[NHC(CH3)double bond; length as m-dashCHCN] and 2,6-dimethylamino-4-(triphenylgermylamino)pyrimidine as well as the conversion of Ph3Ge[NHC(CH3)double bond; length as m-dashCHCN] to 2,6-dimethyl-4-(triphenylgermylamino)pyrimidine in acetonitrile solvent has been observed using 1H NMR spectroscopy.