title: On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes.
abstract: Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2 (μ-OH)][BF4 ] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate.
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.
authors.forename: Adrián
authors.initials: A
authors.lastname: Gómez-Suárez
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.|Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo, 060-0812, Japan.
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Oonishi
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.|Institut de Chimie de Nice, UMR 7272, Université de Nice Sophia Antipolis, CNRS, Parc Valrose, 06108, Nice cedex 2, France.
authors.forename: Anthony R
authors.initials: AR
authors.lastname: Martin
authors.affiliation: KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Sai V C
authors.initials: SV
authors.lastname: Vummaleti
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.|WestCHEM Department of Pure & Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: David J
authors.initials: DJ
authors.lastname: Nelson
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.
authors.forename: David B
authors.initials: DB
authors.lastname: Cordes
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, UK.
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.affiliation: KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia. luigi.cavallo@kaust.edu.sa.
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.affiliation: Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia. stevenpnolan@gmail.com.
authors.forename: Steven P
authors.initials: SP
authors.lastname: Nolan
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. albert.poater@udg.edu.
authors.forename: Albert
authors.initials: A
authors.lastname: Poater
keywords: alkynes; density functional calculations; gold; homogeneous catalysis; hydrophenoxylation; reaction mechanisms