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

Synthetic, Structural, and Physical Investigations of the Large Linear and Branched Oligogermanes Ph3GeGePh2GePh2GePh2H, Ge5Ph12, and (Ph3Ge)4Ge

“…Instead, we isolated 3-aminocrotononitrile and 2,6-dimethylpyrimidine, which are oligomers of acetonitrile, and identified Ph 3 GeGePh 3 as a product of the reaction. , Several other unidentified germanium-containing products were also generated, suggesting that (Ph 3 Ge) 3 GeNMe 2 had decomposed during the course of the reaction. We subsequently demonstrated that that Ph 3 GeCH 2 CN could be converted to Ph 3 Ge­[NHC­(CH 3 )­CHCN] and 2,6-dimethyl-4-(triphenylgermylamino)­pyrimidine upon prolonged heating of Ph 3 GeCH 2 CN in CH 3 CN in the presence of HNMe 2 , which explains how the aforementioned products were formed.…”

A Germanium Isocyanide Complex Featuring (n → π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C–H Bond Activation under Mild Conditions

“…5 Although the possibility of π-back-bonding in these adducts has not been explored, there have been numerous recent reports of the activation of small molecules such as H2, NH3, or C2H4, via synergistic pathways in which a main group atom(s) behaves as both electron donor and acceptor. [6][7][8] We now report that the addition of tert-butylisocyanide to a diarylgermylene leads to the formation of a Lewis adduct, (Ar Me 6) 2GeCNBu t (1) [Ar Me 6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2]. Further analysis of the metalisocyanide bonding mode in 1 by density functional theory (DFT) indicates that 1 displays back-bonding from the lone pair on germanium to the π* orbital of the isocyanide ligand.…”