MECHANISM OF A COBALT(III)-CATALYZED OLEFIN HYDROSILATION REACTION - DIRECT EVIDENCE FOR A SILYL MIGRATION PATHWAY
MECHANISM OF A COBALT(III)-CATALYZED OLEFIN HYDROSILATION REACTION - DIRECT EVIDENCE FOR A SILYL MIGRATION PATHWAY
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DOI：
10.1021/ja00059a008
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发表时间：
1993-03-24
影响因子：
15
通讯作者：
GRANT, BE
中科院分区：
文献类型：
--
作者：
BROOKHART, M;GRANT, BE
亲电Co（III）配合物[Cp*（P（OMe）3）CoCH 2CH 2-mu-H]+ BAr '4-（1; BAr' 4- = B[3，5-（CF 3）2C 6 H 3]4-）已被证明是1-己烯区域特异性硅氢化反应的有效催化剂。工作催化剂体系溶液中催化剂静止态物质[Cp*（P（OMe）3）CoCH（Bu）CH（SiEt 3）-mu-H]+（2）的光谱检测为甲硅烷基迁移途径提供了直接证据。[Cp*（P（OMe）3）CoCH 2CH-{（CH 2）4SiEt 3}-μ-H]+（6）的光谱检测，沿着支持动力学和氘标记实验，建立了作为2至6的异构化的转换限制步骤。
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.