Mechanistic elucidation of the arylation of non-spectator N-heterocyclic carbenes at copper using a combined experimental and computational approach

Cu^I(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^I(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^III species is energetically feasible. A less hindered Cu^I(NHC)Br complex with N-benzyl groups is susceptible to oxidation reactions to give 1,3-dibenzylbenzimidazolium cations containing a Cu^IBr anion (various polymorphs). The results described herein are of relevance to C–H functionalization of (benz)azoles.