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Mechanism of the Transmetalation of Organosilanes to Gold

Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the first transmetalation of organosilanes to gold as a cheap fluoride-free process. The versatile gold(I) complex [Au(OH)(IPr)] permits very straightforward access to a series of aryl-, vinyl-, and alkylgold silanolates by reaction with the appropriate silane reagent. These silanolate compounds are key intermediates in a fluoride-free process that results in the net transmetalation of organosilanes to gold, rather than the classic activation of silanes as silicates using external fluoride sources. However, here we propose that the gold silanolate is not the active species (as proposed during experimental studies) but is, in fact, a resting state during the transmetalation process, as a concerted step is preferred

A. P. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

Wiley Open Access

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Falivene, Laura
Nelson, David J.
Dupuy, Stéphanie
Nolan, Steven P.
Poater Teixidor, Albert
Cavallo, Luigi
Data: febrer 2016
Resum: Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the first transmetalation of organosilanes to gold as a cheap fluoride-free process. The versatile gold(I) complex [Au(OH)(IPr)] permits very straightforward access to a series of aryl-, vinyl-, and alkylgold silanolates by reaction with the appropriate silane reagent. These silanolate compounds are key intermediates in a fluoride-free process that results in the net transmetalation of organosilanes to gold, rather than the classic activation of silanes as silicates using external fluoride sources. However, here we propose that the gold silanolate is not the active species (as proposed during experimental studies) but is, in fact, a resting state during the transmetalation process, as a concerted step is preferred
A. P. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
Accés al document: http://hdl.handle.net/10256/13309
Llenguatge: eng
Editor: Wiley Open Access
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.1002/open.201500172
info:eu-repo/semantics/altIdentifier/eissn/2191-1363
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: Attribution 3.0 Spain
URI Drets: http://creativecommons.org/licenses/by/3.0/es/
Matèria: Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Títol: Mechanism of the Transmetalation of Organosilanes to Gold
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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