过渡金属N-杂环卡宾配合物合成  

Synthesis of Metal N-Heterocyclic Carbene Complexes

作　　者：刘波[1] 张娜[1] 陈万芝[1] 

机构地区：[1]浙江大学化学系,杭州310028

出　　处：《化学进展》2010年第11期2134-2146,共13页Progress in Chemistry

基　　金：国家自然科学基金项目(No.20872129)资助

摘　　要：由于N-杂环卡宾配体(NHCs)的独特性能,N-杂环卡宾过渡金属配合物在均相催化等方面取得了重要应用,但是其合成方法却发展缓慢。本文综述了N-杂环卡宾过渡金属配合物合成方法的最新研究进展,介绍了富电子烯烃裂解反应、游离NHC直接配位反应、配体底物的脱质子原位反应、卡宾加合物热解反应、金属交换转移反应和C2-X(X为甲基、卤原子或氢原子)键氧化加成反应等合成N-杂环卡宾过渡金属配合物的主要方法,此外本课题组还首次发现了金属粉末法,该法可用于规模化合成铁、钴、镍、铜等第一过渡系金属NHC配合物。N-heterocyclic carbene ligands（NHCs） are playing an increasingly important role in many areas such as organometallic,organic synthetic,pharmaceutical and polymer chemistry.While numerous powerful catalytic systems incorporating NHC ligands have been described,methods of synthesizing them have advanced more slowly.This review describes the recent progress of the methods used in the preparation of N-heterocyclic carbene complexes.According to the nature of the NHC precursor and to the activation method employed,the common routes for preparing NHC-metal complexes are insertion of metal ions into the carbon-carbon double bonds of highly electron-rich alkenes,coordination of preformed,isolated free carbenes,deprotonation of an Imidazolium salt with an external base or with metal complex having a basic ligand,thermal decomposition of corresponding carbene adducts,transmetallation from a silver-NHC complex or from a gold-NHC complex,oxidative addition of the C2-X （X = Me,halogen,H） bond of an imidazolium precursor.In addition,our research group firstly found that iron,cobalt,nickel,and copper complexes of N-heterocyclic carbenes can be directly synthesized by using commercially available metal powders.

关 键 词：咪唑盐 N-杂环卡宾 过渡金属 合成 

分 类 号：O621.3[理学—有机化学] O626.23[理学—化学]