MECHANISM OF A COBALT(III)-CATALYZED OLEFIN HYDROSILATION REACTION - DIRECT EVIDENCE FOR A SILYL MIGRATION PATHWAY

被引：150
作者：
BROOKHART, M
GRANT, BE
机构：
[1] Department of Chemistry, The University of North Carolina, Chapel Hill
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 06期
关键词：
D O I：
10.1021/ja00059a008
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The electrophilic Co(III) complex [Cp*(P(OMe)3)CoCH2CH2-mu-H]+ BAr'4- (1; BAr'4- = B[3,5-(CF3)2C6H3]4-) has been demonstrated to be an efficient catalyst for the regiospecific hydrosilation of 1-hexene. The spectroscopic detection of the catalyst resting state species [Cp*(P(OMe)3)CoCH(Bu)CH(SiEt3)-mu-H]+ (2) in solutions of working catalyst systems has provided direct evidence for a silyl migration pathway. The spectroscopic detection of [Cp*(P(OMe)3)CoCH2CH-{(CH2)4SiEt3}-mu-H]+ (6), along with supporting kinetics and deuterium labeling experiments, established the turnover-limiting step as the isomerization of 2 to 6.
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页码：2151 / 2156
页数：6
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