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

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

Research output: Contribution to journalArticle

11 Citations (Scopus)

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 C-H functionalization of (benz)azoles. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)3497-3507
Number of pages11
JournalOrganometallics
Volume34
Issue number14
Early online date7 Jul 2015
DOIs
Publication statusPublished - 27 Jul 2015

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach. / Williams, Thomas J.; Bray, Joshua T.W.; Lake, Benjamin R.M.; Willans, Charlotte E.; Rajabi, Nasir A.; Ariafard, Alireza; Manzini, Chiara; Bellina, Fabio; Whitwood, Adrian C.; Fairlamb, Ian J.S.

In: Organometallics, Vol. 34, No. 14, 27.07.2015, p. 3497-3507.

Research output: Contribution to journalArticle

Williams, TJ, Bray, JTW, Lake, BRM, Willans, CE, Rajabi, NA, Ariafard, A, Manzini, C, Bellina, F, Whitwood, AC & Fairlamb, IJS 2015, 'Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach', Organometallics, vol. 34, no. 14, pp. 3497-3507. https://doi.org/10.1021/acs.organomet.5b00093
Williams, Thomas J. ; Bray, Joshua T.W. ; Lake, Benjamin R.M. ; Willans, Charlotte E. ; Rajabi, Nasir A. ; Ariafard, Alireza ; Manzini, Chiara ; Bellina, Fabio ; Whitwood, Adrian C. ; Fairlamb, Ian J.S. / Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach. In: Organometallics. 2015 ; Vol. 34, No. 14. pp. 3497-3507.
@article{6ef8bd943b4c46a8b5d0bf65f9b7fe30,
title = "Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach",
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 C-H functionalization of (benz)azoles. (Chemical Equation Presented).",
author = "Williams, {Thomas J.} and Bray, {Joshua T.W.} and Lake, {Benjamin R.M.} and Willans, {Charlotte E.} and Rajabi, {Nasir A.} and Alireza Ariafard and Chiara Manzini and Fabio Bellina and Whitwood, {Adrian C.} and Fairlamb, {Ian J.S.}",
year = "2015",
month = "7",
day = "27",
doi = "10.1021/acs.organomet.5b00093",
language = "English",
volume = "34",
pages = "3497--3507",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Mechanistic Elucidation of the Arylation of Non-Spectator N-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach

AU - Williams, Thomas J.

AU - Bray, Joshua T.W.

AU - Lake, Benjamin R.M.

AU - Willans, Charlotte E.

AU - Rajabi, Nasir A.

AU - Ariafard, Alireza

AU - Manzini, Chiara

AU - Bellina, Fabio

AU - Whitwood, Adrian C.

AU - Fairlamb, Ian J.S.

PY - 2015/7/27

Y1 - 2015/7/27

N2 - 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 C-H functionalization of (benz)azoles. (Chemical Equation Presented).

AB - 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 C-H functionalization of (benz)azoles. (Chemical Equation Presented).

UR - http://www.scopus.com/inward/record.url?scp=84938125412&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.5b00093

DO - 10.1021/acs.organomet.5b00093

M3 - Article

VL - 34

SP - 3497

EP - 3507

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 14

ER -