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

Citation

Williams, TJ and Bray, JTW and Lake, BRM and Willans, CE and Rajabi, NA and Ariafard, A and Manzini, C and Bellina, F and Whitwood, AC and Fairlamb, IJS, Mechanistic elucidation of the arylation of non-spectator N-heterocyclic carbenes at copper using a combined experimental and computational approach, Organometallics, 34, (14) pp. 3497-3507. ISSN 0276-7333 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 American Chemical Society

DOI: doi:10.1021/acs.organomet.5b00093

Abstract

CuI(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 CuI(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 CuIII species is energetically feasible. A less hindered CuI(NHC)Br complex with N-benzyl groups is susceptible to oxidation reactions to give 1,3-dibenzylbenzimidazolium cations containing a CuIBr anion (various polymorphs). The results described herein are of relevance to CH functionalization of (benz)azoles.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:105895
Year Published:2015
Web of Science® Times Cited:4
Deposited By:Chemistry
Deposited On:2016-01-19
Last Modified:2016-09-20
Downloads:0

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