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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Original language | English (US) |
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Pages (from-to) | 1125-1132 |
Number of pages | 8 |
Journal | Chemistry - A European Journal |
Volume | 22 |
Issue number | 3 |
DOIs | |
State | Published - Dec 13 2015 |
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Datasets
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CCDC 1030163: Experimental Crystal Structure Determination : (mu-phenolato)-bis(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)-di-gold tetrafluoroborate dichloromethane solvate
Gómez-Suárez, A. (Creator), Oonishi, Y. (Creator), Martin, A. R. (Creator), Vummaleti, S. V. C. (Creator), Nelson, D. J. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), Cavallo, L. (Creator), Nolan, S. P. (Creator) & Poater, A. (Creator), Dryad Digital Repository, 2016
DOI: 10.5517/ccdc.csd.cc13kz2q, http://hdl.handle.net/10754/624495
Dataset