Regio- and stereoselective hydrosilylation of alkynes catalyzed by three-coordinate cobalt(I) alkyl and silyl complexes.

A three-coordinate cobalt(I) complex exhibits high catalytic efficiency and selectivity as well as good functional group compatibility in alkyne hydrosilylation. [Co(IAd)(PPh3)(CH2TMS)] (1) (IAd = 1,3-diadamantylimidazol-2-ylidene) facilitates regio- and stereoselective hydrosilylation of terminal, symmetrical internal, and trimethylsilyl-substituted unsymmetrical internal alkynes to produce single hydrosilylation products in the forms of β-(E)-silylalkenes, (E)-silylalkenes, and (Z)-α,α-disilylalkenes, respectively, in high yields. The comparable catalytic efficiency and selectivity of the Co(I) silyl complex [Co(IAd)(PPh3)(SiHPh2)] that was prepared from the reaction of 1 with H2SiPh2, and the isolation of an alkyne Co(I) complex [Co(IAd)(η(2)-PhC≡CPh)(CH2TMS)] from the reaction of 1 with the acetylene, point out a modified Chalk-Harrod catalytic cycle for these hydrosilylation reactions. The high selectivity is thought to be governed by steric factors.