Stoichiometric hydrosilylation of nitriles with hydrido(hydrosilylene)tungsten complexes: formation of W-Si-N three-membered ring complexes and their unique thermal behaviors.
Reactions of hydrido(hydrosilylene)tungsten complexes, Cp'(CO)2(H)W=Si(H)[C(SiMe3)3], with nitriles (MeCN, tBuCN) at 60 degrees C gave hydrosilylation products, Cp'(CO)2W[kappa2(N,Si)-Si(H)(N=CHR'){C(SiMe3)3}] (R' = Me, tBu), with a novel W-Si-N three-membered ring structure. The product of the hydrosilylation of tBuCN underwent reversible rearrangement at 70 degrees C to a silylene complex, Cp'(CO)2(H)W=Si(N=CHtBu)[C(SiMe3)3], which was a major component in equilibrium. A reaction mechanism for the hydrosilylation involving coordination of nitriles to the silylene ligand and subsequent migration of the hydrido ligand to the nitrile carbon was proposed.
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
Takahito
T
Watanabe
Hisako
H
Hashimoto
Hiromi
H
Tobita