title: Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at Cu(III), Ag(III) and Au(III).
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.
authors.affiliation: Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Shahrak Gharb, Tehran, Iran.
authors.forename: Yasamin
authors.initials: Y
authors.lastname: Younesi
authors.forename: Bahare
authors.initials: B
authors.lastname: Nasiri
authors.forename: Rasool
authors.initials: R
authors.lastname: BabaAhmadi
authors.forename: Charlotte E
authors.initials: CE
authors.lastname: Willans
authors.forename: Ian J S
authors.initials: IJ
authors.lastname: Fairlamb
authors.forename: Alireza
authors.initials: A
authors.lastname: Ariafard