Item


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

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Falivene, Laura
Nelson, David J.
Dupuy, Stéphanie
Nolan, Steven P.
Poater Teixidor, Albert
Cavallo, Luigi
Date: 2018 June 5
Abstract: 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)
Document access: http://hdl.handle.net/2072/319280
Language: eng
Publisher: Wiley Open Access
Rights: Attribution 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by/3.0/es/
Subject: Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Title: Mechanism of the Transmetalation of Organosilanes to Gold
Type: info:eu-repo/semantics/article
Repository: Recercat

Subjects

Authors