Mechanism of the Dehydrogenative Silylation of Alcohols Catalyzed by Cationic Gold Complexes: An Experimental and Theoretical Study

被引：32

作者：

Labouille, Stephanie ^{[1
]}

Escalle-Lewis, Aurelie ^{[1
]}

Jean, Yves ^{[1
]}

Mezailles, Nicolas ^{[1
]}

Le Floch, Pascal ^{[1
]}

机构：

[1] Ecole Polytech, Dept Chim, UMR CNRS DCPH 7653, Lab Heteroelements & Coordinat, F-91128 Palaiseau, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 07期

关键词：

dehydrogenative silylation; density functional calculations; gold; gold catalysis; phosphane ligands; POLARIZABLE CONTINUUM MODEL; MOLECULAR-ORBITAL METHODS; INFRARED-SPECTRA; BASIS-SETS; X-RAY; SELECTIVE HYDROSILYLATION; HYDROGENATION CATALYSTS; PHOSPHOLE LIGAND; STABILIZED GOLD; ALDOL REACTION;

D O I：

10.1002/chem.201002150

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The catalytic activity both of cationic [(XDPP)Au][X] (XDPP=bis-2,5-diphenylphosphole xantphos X= BF4) and of the isolated gold hydride complex [(XDPP)(2)Au2HR][OTf] in the dehydrogenative silylation process is presented. A parallel theoretical study using density functional theory revealed a mechanism involving the counter anion as a co-catalyst, which was experimentally confirmed by testing various counterions (X =OTf, NTf2, PF6). Finally, a "Au2H+" species was determined as the intermediate during the catalytic cycle, which correlates well with the experimental findings on the first example of catalytic activity of an isolated "Au-H" complex.

引用

页码：2256 / 2265

页数：10

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[31] AN IMPROVED ALGORITHM FOR REACTION-PATH FOLLOWING [J].