Reactions of d0 alkylidene and amide complexes with silanes

Reactions of silanes with d Ta alkylidene and Group 4 amide complexes were found to involve the initial attack on silicon atoms in the silanes by nucleophilic alkylidene carbon or amide nitrogen atoms. The reaction of (Me SiCH ) Ta (PMe ) [=CHSiMe ] (1) with H SiR'Ph (R' = Me, Ph) gave (Me SiCH ) Ta[=C (SiMe ) SiHR'Ph] (2a-b). Similar reactions of these two silanes and (H2PhSi) 2CH2 with (Me SiCH ) Ta (PMe ) [=CHR] (R = SiMe , 3; CMe , 4) yielded novel metallasilacyclobutadienes and a metalladisilacyclohexadiene, respectively. In comparison, the reactions between M (NMe ) (M = Ti, Zr, Hf) and silanes were found to give aminosilanes and metal amide hydride species which were perhaps involved in the formation of titanium-silicon-nitride (Ti-Si-N) ternary materials.