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 Pr3iGeGePh3 and Bu3tGe[NHC(CH3)CHCN]

The alpha-germylated nitriles R(3)GeCH(2)CN ( R = Ph, Pr(i), Bu(t)) and germanium amides R(3)GeNMe(2) (R = Pr(i) and Bu(t)) have been prepared and characterized and their reactivity with Ph(3)GeH in CH(3)CN 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 R(3)GeGePh(3) (R = Ph, Pr(i)) where the amide reagents are converted to R(3)GeCH(2)CN in situ which subsequently react with Ph(3)GeH. 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 Bu(3)(t)GeGePh(3) by these methods did not result in the desired product but rather in isolation of the 3-amidocrotononitrile species Bu(3)(t)Ge[NHC(CH(3))CHCN]. The crystal structures of Pr(3)(i)GeGePh(3) and Bu(3)(t)Ge[NHC(CH(3))CHCN] have been determined. (C) 2008 Elsevier B. V. All rights reserved.