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首页> 外文期刊>Chemistry: A European journal >Highly Selective Dehydrogenative Silylation of Alkenes Catalyzed by Rhenium Complexes
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Highly Selective Dehydrogenative Silylation of Alkenes Catalyzed by Rhenium Complexes

机译：hen配合物催化烯烃的高选择性脱氢硅烷化

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摘要

Rhenium(I) complexes of type [ReBr2(L)(NO)(PR3)(2)] (L = H-2 (1), CH3CN (2), and ethylene (3): R = iPr (a) and cyclohexyl (Cy; b)) catalyze dehydrogenative silylation of alkenes in a highly selective manner to yield silyl alkenes and the corresponding alkanes. Hvdrosilylation products appear only rarely depending oil the type of olefinic substituent. and if they do appear then it is in very minor amounts. Mechanistic Studies showed that two rhenium(I) hydride species of type [ReBrH(NO)(PR3)(2)] (R=iPr (4a) and Cy (4b)) and [ReBr(eta(2)-CH2=CHR1)H(NO)(PR3)(2)] (R-1=p-CH3C6H4, R=iPr (5a), Cy (5b); R-1=H, R=iPr (5a'), Cy (5b')) are involved in the initiation pathway of the catalysis. The rate-determining steps of the catalytic cycle are the phosphine dissociation from complexes of type 5 and the reductive eliminations to form the alkane components. The catalytic cycle implies that the given rhenium systems have the ability to activate C-H and Si-H bonds through the aid of a facile redox interplay of Re-I and Re-III species. The molecular structures of 4b and 5a were established by means of X-ray diffraction studies.
机译：[ReBr2（L）（NO）（PR3）（2）]类型的hen（I）配合物（L = H-2（1），CH3CN（2）和乙烯（3）：R = iPr（a）和环己基（Cy; b））以高度选择性的方式催化烯烃的脱氢甲硅烷基化反应，生成甲硅烷基烯烃和相应的烷烃。氢甲硅烷基化产物很少出现，这取决于油的烯烃取代基的类型。如果确实出现，则数量很少。机理研究表明，两种类型的[ReBrH（NO）（PR3）（2）]氢化rh（I）（R = iPr（4a）和Cy（4b））和[ReBr（eta（2）-CH2 = CHR1 ）H（NO）（PR3）（2）]（R-1 = p-CH3C6H4，R = iPr（5a），Cy（5b）; R-1 = H，R = iPr（5a'），Cy（5b '））参与催化的引发途径。催化循环的决定速率的步骤是膦从5型络合物中解离并进行还原消除，形成烷烃组分。催化循环意味着给定的systems体系能够通过Re-I和Re-III物种的便捷氧化还原相互作用来激活C-H和Si-H键。通过X射线衍射研究确定了4b和5a的分子结构。

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