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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 alky...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4906480/ https://www.ncbi.nlm.nih.gov/pubmed/27308213 http://dx.doi.org/10.1002/open.201500172 |
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author | Falivene, Laura Nelson, David J. Dupuy, Stéphanie Nolan, Steven P. Poater, Albert Cavallo, Luigi |
author_facet | Falivene, Laura Nelson, David J. Dupuy, Stéphanie Nolan, Steven P. Poater, Albert Cavallo, Luigi |
author_sort | Falivene, Laura |
collection | PubMed |
description | 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. |
format | Online Article Text |
id | pubmed-4906480 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-49064802016-06-15 Mechanism of the Transmetalation of Organosilanes to Gold Falivene, Laura Nelson, David J. Dupuy, Stéphanie Nolan, Steven P. Poater, Albert Cavallo, Luigi ChemistryOpen Full Papers 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. John Wiley and Sons Inc. 2015-09-10 /pmc/articles/PMC4906480/ /pubmed/27308213 http://dx.doi.org/10.1002/open.201500172 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Falivene, Laura Nelson, David J. Dupuy, Stéphanie Nolan, Steven P. Poater, Albert Cavallo, Luigi Mechanism of the Transmetalation of Organosilanes to Gold |
title | Mechanism of the Transmetalation of Organosilanes to Gold |
title_full | Mechanism of the Transmetalation of Organosilanes to Gold |
title_fullStr | Mechanism of the Transmetalation of Organosilanes to Gold |
title_full_unstemmed | Mechanism of the Transmetalation of Organosilanes to Gold |
title_short | Mechanism of the Transmetalation of Organosilanes to Gold |
title_sort | mechanism of the transmetalation of organosilanes to gold |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4906480/ https://www.ncbi.nlm.nih.gov/pubmed/27308213 http://dx.doi.org/10.1002/open.201500172 |
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