[(t-Bu2PCH2SiMe2)2N]RuCH3:: The origin of extremely facile, double H-C(sp3) activation generating a "hydrido-carbene" complex

被引：27

作者：

Ingleson, MJ

Yang, XF

Pink, M

Caulton, KG ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

[2] Indiana Univ, Ctr Mol Struct, Bloomington, IN 47405 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 31期

关键词：

D O I：

10.1021/ja052973a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The four-coordinate compound [(tBu2PCH2SiMe2)2N]RuCH3 undergoes rapid double H-C(sp3) activation at -78 °C to generate a "hydrido-carbene" complex. DFT calculations suggest that the origin of the low barrier to methane elimination is an α-agostic interaction in the low-lying singlet state of the highly unsaturated (PNP)RuMe. The hydrido-carbene complex can be viewed as a "masked" resting state of the four-coordinate cyclometalated alkyl complex, [(tBu2PCH2SiMe2)N(Me2SiCH2P(tBu)(C(CH3)2CH2)]Ru, where hydride migration from metal to carbon occurs before any subsequent reactivity. Copyright © 2005 American Chemical Society.

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页码：10846 / 10847

页数：2

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