Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R = Ph, Pri, But) and germanium amides R3GeNMe2 (R = Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

The α-germylated nitriles R3GeCH2CN (R = Ph, Pri, But) and germanium amides R3GeNMe2 (R = Pri and But) have been prepared and characterized and their reactivity with Ph3GeH in CH3CN has been explored to investigate their utility for the construction of Ge–Ge bonds. In each case the phenyl and iso-propyl derivatives furnish the corresponding digermanes R3GeGePh3 (R = Ph, Pri) where the amide reagents are converted to R3GeCH2CN in situ which subsequently react with Ph3GeH. The rate of the Ge–C bond cleavage reactions was found to depend on the steric and electronic properties of the organic substituents. Attempted synthesis of But3GeGePh3 by these methods did not result in the desired product but rather in isolation of the 3-amidocrotononitrile species But3Ge[NHC(CH3)CHCN]. The crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN] have been determined.