利用银卡宾法制备N-杂环卡宾铑配合物及其反应性的研究  

Reactivity study of silver carbene complexes in preparing rhodium complexes of N-heterocyclic carbenes

作　　者：彭学刚[1] 于晓燕[1] 张庆新[1] 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《河北工业大学学报》2013年第6期51-55,共5页Journal of Hebei University of Technology

基　　金：国家自然科学基金(21001039);河北省自然科学基金(B2011202081)

摘　　要：利用银卡宾法通过金属交换转移反应制备N-杂环卡宾铑配合物,N-杂环卡宾银配合物AgCl(IPr)(IPr=1,3-双(2,6-二异丙基苯基)咪唑-2-亚基)和氯化降冰片二烯铑二聚体[RhCl(NBD)]2(NBD=2,5-降冰片二烯)反应得到了铑的N-杂环卡宾降冰片二烯基化合物RhCl(NBD)(IPr).探究了反应温度对制备RhCl(NBD)(IPr)的影响并分析了N-杂环卡宾银配合物(Ag(I)-NHC)N-取代基结构对制备N-杂环卡宾铑配合物(Rh(I)-NHC)的影响.结果表明:作为卡宾转移试剂,Ag(I)-NHC制备Rh(I)-NHC的反应活性取决于卡宾N-取代基的结构,若与N相连的位存在酸性质子如亚甲基质子,则C-Ag键在相对温和的温度(如室温)下就能断裂,反应活性较高;若与N相连的位无酸性质子,则C-Ag键在相对较高的温度才能断裂,反应活性较低.RhCl(NBD)(IPr)(IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) has been prepared by reaction of AgCl(IPr) with [RhCl(NBD)] 2(NBD = 2,5-norbornadiene). In the reaction, Ag(I)-NHC was used as a carbene transfer reagent. Investigation on the effects of different temperatures and different N- substituent groups of Ag(I)-NHC in synthesizing Rh(I)-NHC was carried out and a conclusion was obtained as follows, the reactivity of Ag(I)-NHC to prepare Rh(I)-NHC depended on N- substituent groups of NHC. N- acidic protons made C-Ag bond fragile, and thus provided Ag(I)-NHC with high reactivity. For NHC without N- acidic protons, high temperature was needed to break C-Ag bond of Ag(I)-NHC.

关 键 词：N-杂环卡宾 银卡宾法 铑配合物 N-取代基 温度因素 

分 类 号：T-55[一般工业技术]