Stoichiometric Hydrosilylation of Nitriles with Hydrido(hydrosilylene)tungsten Complexes:  Formation of W−Si−N Three-Membered Ring Complexes and Their Unique Thermal Behaviors

Abstract

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.