Irreversible cleavage of a carbene-rhodium bond in Rh-N-heterocyclic carbene complexes:: implications for catalysis

被引:55
作者
Allen, DP
Crudden, CM [1 ]
Calhoun, LA
Wang, RY
机构
[1] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada
[2] Univ New Brunswick, Dept Chem, Fredericton, NB E3B 6E2, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
N-heterocyclic carbene; catalysis; hydrogenation; rhodium complex;
D O I
10.1016/j.jorganchem.2004.07.021
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Despite the generally accepted belief that carbene-metal bonds are strong and do not dissociate, the reaction of Rh-N-heterocyclic carbene complexes with triphenylphosphine in dichloroethane was determined to take place via cleavage of the Rh-carbene bond. The products of this reaction are Wilkinson's catalyst and a bisimiclazolium salt derived from reaction between dichloroethane and two equivalents of the carbene. The implications of this reaction for catalysis are significant since the carbene complex shows lower activity than Wilkinson's catalyst in hydrogenation reactions. In non-halogenated solvents, the catalyst shows higher stability, such that the rate of exchange with free phosphine could be measured, and was determined to be ca. 10 times slower than in Wilkinson's catalyst. (C) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:3203 / 3209
页数:7
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