过渡金属N-杂环卡宾配合物合成.pdf.pdf

第 22 卷第 11 期化学进展 Vol. 22 No. 11
2010 年 11 月 PROGRESS IN CHEMISTRY Nov. ,2010
过渡金属 N-杂环卡宾配合物合成*
刘波张娜陈万芝
�浙江大学化学系杭州 310028�
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。
关键词咪唑盐 N-杂环卡宾过渡金属合成
中图分类号� O621. 3� O626. 23� O641. 4 文献标识码� A 文章编号� 1005-281X�2010�11-2134-13
Synthesis of Metal N-Heterocyclic plexes
Liu Bo Zhang Na Chen Wanzhi
� Department of Chemistry,Zhejiang University,Hangzhou 310028,China�
Abstract N-heterocyclic carbene ligands� NHCs� are playing an increasingly important role in many areas
such anometallic, 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
plexes. According to the nature of the NHC precursor and to the activation method employed,the
common routes for preparing NHC-plexes 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 plex having a basic ligand,thermal position of corresponding
carbene adducts,transmetallation from a silver-plex or from a gold-plex,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 plexes of N-heterocyclic carbenes can be directly synthesized by using
commercially available metal powders.
Key words imidazolium salts� N-heterocyclic carbenes� NHCs�� transition metals� synthesis
3 Synthesis of N-heterocyclic plexes from
Contents
preformed and isolate