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：
加拿大创新基金会; 加拿大自然科学与工程研究理事会;
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
收藏
页码：2896 / 2901
页数：6
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