Serendipitous Metal-Catalyzed H-H/Si-H Exchange

被引：3

作者：

Nikonov, Georgii I. ^{[1
]}

Vyboishchikov, Sergei F. ^{[2
,3
]}

Shirobokov, Oleg G. ^{[1
]}

Simionescu, Razvan ^{[1
]}

机构：

[1] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada

[2] Univ Girona, Inst Quim Computac, Girona 17071, Spain

[3] Univ Girona, Dept Quim, Girona 17071, Spain

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2014年 / 18期

基金：

加拿大自然科学与工程研究理事会; 加拿大创新基金会;

关键词：

Dihydrogen; Silanes; H-H activation; Si-H activation; Reaction mechanisms; FRUSTRATED LEWIS PAIRS; GAUSSIAN-BASIS SETS; CORRELATED MOLECULAR CALCULATIONS; FREE HYDROGEN ACTIVATION; SILYL HYDRIDE COMPLEX; SI-H; SIGMA-COMPLEXES; ORGANOSILICON COMPOUNDS; HETEROLYTIC CLEAVAGE; FACILE ACTIVATION;

D O I：

10.1002/ejic.201402202

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Various metal complexes catalyze exchange between H-2 and hydrosilanes. Catalyst screening suggests that the electron deficiency of the metal center is necessary for exchange, but silane and/or hydrogen addition or sigma-bond metathesis with the M-Si and M-H bonds are not required. Kinetic measurements for the system [(ArN=)Mo(PMe3)(3)(H)(SiH2Ph)/H-2/H3SiPh] (Ar = 2,6-iPr(2)C(6)H(3)) suggest that the reaction proceeds through activation of the silane.

引用

页码：2896 / 2901

页数：6

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