Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at CuIII, AgIII and AuIII. Issue 28 (18th March 2016)

• Record Type: Journal Article
• Authors: Younesi, Yasamin; Nasiri, Bahare; BabaAhmadi, Rasool; Willans, Charlotte E.; Fairlamb, Ian J. S.; Ariafard, Alireza
• Is Part Of: Chemical communications. Volume 52:Issue 28(2016)
• Page Start: 5057
• Page End: 5060
• Publication Date: 2016-03-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c6cc01299j
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : A dichotomy in carbon versus bromide reductive elimination in Cu III –NHC complexes is rationalized by computational methods (DFT). 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.