Facile Activation of H-H and Si-H Bonds by Boranes

被引:62
作者
Nikonov, Georgii I. [1 ]
Vyboishchikov, Sergei F. [2 ,3 ]
Shirobokov, Oleg G. [1 ]
机构
[1] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada
[2] Univ Girona, Dept Quim, Girona 17071, Spain
[3] Univ Girona, Inst Quim Computac, Girona 17071, Spain
基金
加拿大自然科学与工程研究理事会;
关键词
FRUSTRATED LEWIS PAIRS; FREE CATALYTIC-HYDROGENATION; DIHYDROGEN ACTIVATION; MECHANISM; HYDROSILATION; INTERMEDIATE; BOROHYDRIDE; HYDROLYSIS; IMINES; H-2;
D O I
10.1021/ja300365s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The borane B(C6F5)(3) is a precatalyst for H/D exchange between H-2 and deuterium-labeled silanes (D3SiPh, D2SiMePh, DSiMe2Ph, DSiEt3). Experimental and DFT studies reveal that B(C6F5)(3) itself cannot activate dihydrogen but converts to HB(C6F5)(2) under the action of hydrosilane. The latter species easily activates H-H and Si-H bonds by a sigma-bond metathesis mechanism, which was further confirmed by the reactions of BD3 center dot THF with H-2.
引用
收藏
页码:5488 / 5491
页数:4
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