Regio- and Stereoselective Hydrosilylation of Alkynes Catalyzed by Three-Coordinate Cobalt(I) Alkyl and Silyl Complexes

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• 作者：Zhenbo Mo ; Jie Xiao ; Yafei Gao ; Liang Deng
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：December 17, 2014
• 年：2014
• 卷：136
• 期：50
• 页码：17414-17417
• 全文大小：296K
• ISSN：1520-5126

文摘

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 尾-(E)-silylalkenes, (E)-silylalkenes, and (Z)-伪,伪-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)(畏²-PhC鈮Ph)(CH₂TMS)] from the reaction of 1 with the acetylene, point out a modified Chalk鈥揌arrod catalytic cycle for these hydrosilylation reactions. The high selectivity is thought to be governed by steric factors.