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Progress in Chemistry 2009, Vol. 21 Issue (6): 1229-1240 Previous Articles   Next Articles

• Review •

Synthesis of N-heterocyclic Carbenes and Metal Complexes

Jiang Lan1,2 ;  |Li Zhengning2** ;  |Zhao Defeng1**   

  1.  (1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China;
    2. Liaoning Key Laboratory of Bioorganic Chemistry, College of Environment and Chemical Engineering, Dalian University, Dalian 116622, China）
  • Received: Revised: Online: Published:
  • Contact: Li Zhengning; Zhao Defeng E-mail:znli@dl.cn; zhaodfg@sina.com
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Due to the strong electronic donor properties and the versatile structure which can be readily modified, as well as the distinct topography, N-heterocyclic carbene（NHC）is a new class of ligands as an alternative to traditional phosphine ones. Therefore, it is attractive to use NHC as ligand in catalysis. In fact, the catalytic properties of NHC-metal (NHC-M) complexes in homogeneous and asymmetric catalysis has been a focused research field and many successful results have been reported in recent years. In this paper, the syntheses of NHC, NHC-M complexes and their major precursor imidazolium salts are reviewed. The synthetic methods for NHC-M complexes include: (a) reaction of metal complexes with pre-formed NHC ligands; (b) reaction of metal complexes with NHC precursor such as imidazolium salts and a strong base; (c) interaction between metal halide and NHC-Ag complexes. For the synthesis of NHC precursors, there are also several routes: (a) condensation of glyoxal, amines and paraformaldehyde; (b) alkylation of imidazole or monosubstituted imidazole with alkyl halide; (c) annulation of ortho esters and 1,2-diamines; (d) ring closure of hydrazines or amides with acetic anhydride; (e) reduction of thiones with Na/K in THF.

Contents
1 Introduction
2 The classification and structure of NHC
3 Synthesis of NHC and their metal complexes
3.1 Synthesis of NHC
3.2 Synthesis of NHC-metal complexes
4 Synthesis of NHC precursors
4.1 Synthesis of imidazolium salts
4.2 Synthesis of imidazolinyllium salts
4.3 Synthesis of triazolium salts
4.4 Synthesis of benzoimidazolium salts
4.5 Synthesis of bis-NHC precursors
5 Epilogue

Key words: N-heterocyclic carbene (NHC), NHC-metal complexes, imidazolium salts, synthesis

CLC Number: 

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