Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at CuIII, AgIII and AuIII

Yasamin Younesi; Bahare Nasiri; Rasool Babaahmadi; Charlotte E. Willans; Ian J.S. Fairlamb; Alireza Ariafard

doi:10.1039/c6cc01299j

Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at Cu^III, Ag^III and Au^III

Yasamin Younesi, Bahare Nasiri, Rasool Babaahmadi, Charlotte E. Willans^*, Ian J.S. Fairlamb, Alireza Ariafard

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

Abstract

Reductive elimination of imidazolium salts from Cu^III is extremely sensitive to the anionic ligand (X or Y) type on Cu (e.g. ΔG^‡ ranges from 4.7 kcal mol^-1 to 31.8 kcal mol^-1, from chloride to benzyl). Weakly σ-donating ligands dramatically accelerate reductive elimination. Comparison with Ag/Au shows that the HOMO energy, strength of M-NHC and M-Y bonds and inherent stability of M^III with respect to M^I are critical to governing reaction feasibility.

Original language	English
Pages (from-to)	5057-5060
Number of pages	4
Journal	Chemical Communications
Volume	52
Issue number	28
DOIs	https://doi.org/10.1039/c6cc01299j
Publication status	Published - 11 Apr 2016
Externally published	Yes

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title = "Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at CuIII, AgIII and AuIII",

abstract = "Reductive elimination of imidazolium salts from CuIII is extremely sensitive to the anionic ligand (X or Y) type on Cu (e.g. ΔG‡ ranges from 4.7 kcal mol-1 to 31.8 kcal mol-1, from chloride to benzyl). Weakly σ-donating ligands dramatically accelerate reductive elimination. Comparison with Ag/Au shows that the HOMO energy, strength of M-NHC and M-Y bonds and inherent stability of MIII with respect to MI are critical to governing reaction feasibility.",

author = "Yasamin Younesi and Bahare Nasiri and Rasool Babaahmadi and Willans, {Charlotte E.} and Fairlamb, {Ian J.S.} and Alireza Ariafard",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2016.",

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T1 - Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at CuIII, AgIII and AuIII

AU - Younesi, Yasamin

AU - Nasiri, Bahare

AU - Babaahmadi, Rasool

AU - Willans, Charlotte E.

AU - Fairlamb, Ian J.S.

AU - Ariafard, Alireza

PY - 2016/4/11

Y1 - 2016/4/11

N2 - Reductive elimination of imidazolium salts from CuIII is extremely sensitive to the anionic ligand (X or Y) type on Cu (e.g. ΔG‡ ranges from 4.7 kcal mol-1 to 31.8 kcal mol-1, from chloride to benzyl). Weakly σ-donating ligands dramatically accelerate reductive elimination. Comparison with Ag/Au shows that the HOMO energy, strength of M-NHC and M-Y bonds and inherent stability of MIII with respect to MI are critical to governing reaction feasibility.

AB - Reductive elimination of imidazolium salts from CuIII is extremely sensitive to the anionic ligand (X or Y) type on Cu (e.g. ΔG‡ ranges from 4.7 kcal mol-1 to 31.8 kcal mol-1, from chloride to benzyl). Weakly σ-donating ligands dramatically accelerate reductive elimination. Comparison with Ag/Au shows that the HOMO energy, strength of M-NHC and M-Y bonds and inherent stability of MIII with respect to MI are critical to governing reaction feasibility.

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U2 - 10.1039/c6cc01299j

DO - 10.1039/c6cc01299j

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VL - 52

SP - 5057

EP - 5060

JO - Chemical Communications

JF - Chemical Communications

IS - 28

ER -

Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at Cu^III, Ag^III and Au^III

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