Reactions of d0 alkylidene and amide complexes with silanes

Abstract

Abstract Reactions of silanes with d 0 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 3 SiCH 2 ) 3 Ta (PMe 3 ) [=CHSiMe 3 ] (1) with H 2 SiR'Ph (R' = Me, Ph) gave (Me 3 SiCH 2 ) 3 Ta[=C (SiMe 3 ) SiHR'Ph] (2a-b). Similar reactions of these two silanes and (H2PhSi) 2CH2 with (Me 3 SiCH 2 ) Ta (PMe 3 ) 2 [=CHR] 2 (R = SiMe 3 , 3; CMe 3 , 4) yielded novel metallasilacyclobutadienes and a metalladisilacyclohexadiene, respectively. In comparison, the reactions between M (NMe 2 ) 4 (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.