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On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

KGaA, Weinheim.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

A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

Wiley

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Gómez-Suárez, Adrián
Oonishi, Yoshihiro
Martin, Anthony R.
Vummaleti, Sai Vikrama Chaitanya
Nelson, David J.
Cordes, David B.
Slawin, Alexandra M. Z.
Cavallo, Luigi
Nolan, Steven P.
Poater Teixidor, Albert
Data: 18 gener 2016
Resum: KGaA, Weinheim.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
A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
Accés al document: http://hdl.handle.net/10256/13297
Llenguatge: eng
Editor: Wiley
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201503097
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Drets: Tots els drets reservats
Matèria: Funcional de densitat, Teoria del
Density functionals
Catàlisi homogènia
Homogeneous catalysis
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Alquins
Alkynes
Títol: On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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