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Progress in Chemistry 2010, Vol. 22 Issue (11): 2134-2146 Previous Articles   Next Articles

• Review •

Synthesis of Metal N-Heterocyclic Carbene Complexes

Liu Bo  Zhang Na   Chen  Wanzhi**   

  1. (Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, China)
  • Received: Revised: Online: Published:
  • Contact: Chen Wanzhi E-mail:chenwzz@yahoo.com
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N-Heterocyclic carbene ligands(NHCs) are playing an increasingly important role in many areas such as organometallic, organic synthetic, pharmaceutical, and polymer chemistry since the discovery of the first N-heterocyclic carbene complexes in 1968 by Öfele and by Wanzlick and the isolation of the first stable free carbene in 1991 by Arduengo III et al. 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.

Contents
1 Introduction
2 Synthesis of N-heterocyclic carbene complexes by the cleavage of electron-rich olefins
3 Synthesis of N-heterocyclic carbene complexes from preformed, isolated free carbenes
4 Synthesis of N-heterocyclic carbene complexes by deprotonation of an Imidazolium salt with a base
4.1 Deprotonation with an external base
4.2 Deprotonation with metal complex having a basic ligand
5 Synthesis of N-heterocyclic carbene complexes by thermal decomposition of carbene adducts
5.1 Alcohol adduct of N-heterocyclic carbene
5.2 Triethylborane adduct of N-heterocyclic carbene
5.3 Pentafluorobenzene adduct of N-heterocyclic carbene
5.4 CO2 adduct of N-heterocyclic carbene
5.5 Cyanide adduct of N-heterocyclic carbene
6 Synthesis of N-heterocyclic carbene complexes by transmetallation
6.1 Transmetallation from a silver-NHC complex
6.2 Transmetallation from a gold-NHC complex
7 Synthesis of N-heterocyclic carbene complexes by oxidative addition through activating of the C2-X bond
8 Direct synthesis of N-heterocyclic carbene complex by using metal powders
9 Synthesis of N-heterocyclic carbene complexes by other special methods
9.1 Direct synthesis of N-heterocyclic carbene copper complexes via Cu2O.
9.2 Transmetallation of lithiated heterocycles
9.3 Transmetallation from group VI metal carbonyl carbene complexes
10 Conclusions and Outlook

Key words: imidazolium salts, N-heterocyclic carbenes(NHCs), transition metal, synthesis

CLC Number: 

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