Reactivity of carbene•phosphine dimers: proton affinity revisited
Reactivity of carbene•phosphine dimers: proton affinity revisited
复制标题
DOI：
10.1002/poc.1890
复制
发表时间：
2011-10-01
影响因子：
1.8
通讯作者：
Lee, Jeehiun K.
中科院分区：
文献类型：
--
作者：
Liu, Min;Chen, Mu;Lee, Jeehiun K.
通过计算和实验考察了N-杂环卡宾与三环己基膦(PCy3)的气相反应性。新的测量表明，二甲基咪唑和1-乙基-3-甲基咪唑-2-亚甲基比PCy3更碱性，这与我们和其他人以前的测量结果相反。还发现卡宾和PCy3的质子结合二聚体表现出有趣的反应活性，包括膦氢烷基化、环己烯消除和/或乙烯消除。这一新的反应性被进一步探讨和讨论。版权所有(C)2011 John Wiley&Sons，Ltd.
The gas phase reactivity of N-heterocyclic carbenes versus tricyclohexylphosphine (PCy3) is examined computationally and experimentally. New measurements indicate that dimethylimidazol- and 1-ethyl-3-methylimidazol-2-ylidene are more basic than PCy3, in contrast to previous measurements made by us and by others. Proton-bound dimers of the carbenes and PCy3 are also found to exhibit interesting reactivity involving phosphine alkylation, cyclohexene elimination, and/or ethylene elimination. This novel reactivity is further probed and discussed. Copyright (C) 2011 John Wiley & Sons, Ltd.