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From the same journal

Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach

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Published copy (DOI)

Author(s)

  • Thomas J. Williams
  • Joshua T W Bray
  • Benjamin R M Lake
  • Charlotte E. Willans
  • Nasir A. Rajabi
  • Alireza Ariafard
  • Chiara Manzini
  • Fabio Bellina
  • Adrian C. Whitwood
  • Ian J S Fairlamb

Department/unit(s)

Publication details

JournalOrganometallics
DatePublished - 27 Jul 2015
Issue number14
Volume34
Number of pages11
Pages (from-to)3497-3507
Original languageEnglish

Abstract

Cu<sup>I</sup>(NHC)Br complexes (NHC = N-heterocyclic carbene) undergo a direct reaction with iodobenzene to give 2-arylated benzimidazolium products. The nature of the N-substituent on the NHC ligand influences the reactivity of the Cu<sup>I</sup>(NHC)Br complex toward arylation. N-Benzyl or N-phenyl substituents facilitate arylation, whereas N-mesityl substituents hinder arylation. Density functional theory calculations show that an oxidative addition/reductive elimination pathway involving Cu<sup>III</sup> species is energetically feasible. A less hindered Cu<sup>I</sup>(NHC)Br complex with N-benzyl groups is susceptible to oxidation reactions to give 1,3-dibenzylbenzimidazolium cations containing a Cu<sup>I</sup>Br anion (various polymorphs). The results described herein are of relevance to C-H functionalization of (benz)azoles. (Chemical Equation Presented).

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