Mechanism of the Transmetalation of Organosilanes to Gold

Handle URI:
http://hdl.handle.net/10754/577254
Title:
Mechanism of the Transmetalation of Organosilanes to Gold
Authors:
Falivene, Laura ( 0000-0003-1509-6191 ) ; Nelson, David J. ( 0000-0002-9461-5182 ) ; Dupuy, Stéphanie; Nolan, Steven P.; Poater, Albert ( 0000-0002-8997-2599 ) ; Cavallo, Luigi ( 0000-0002-1398-338X )
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Mechanism of the Transmetalation of Organosilanes to Gold 2015:n/a ChemistryOpen
Publisher:
Wiley-Blackwell
Journal:
ChemistryOpen
Issue Date:
Sep-2015
DOI:
10.1002/open.201500172
Type:
Article
ISSN:
21911363
Additional Links:
http://doi.wiley.com/10.1002/open.201500172
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorNelson, David J.en
dc.contributor.authorDupuy, Stéphanieen
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorPoater, Alberten
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-09-13T12:13:39Zen
dc.date.available2015-09-13T12:13:39Zen
dc.date.issued2015-09en
dc.identifier.citationMechanism of the Transmetalation of Organosilanes to Gold 2015:n/a ChemistryOpenen
dc.identifier.issn21911363en
dc.identifier.doi10.1002/open.201500172en
dc.identifier.urihttp://hdl.handle.net/10754/577254en
dc.description.abstractDensity 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.en
dc.language.isoenen
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://doi.wiley.com/10.1002/open.201500172en
dc.rightsThis is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.en
dc.subjectDFT calculationsen
dc.subjectfluoride-freeen
dc.subjectgold catalysisen
dc.subjecthomogeneous catalysisen
dc.subjectorganosilanesen
dc.subjecttransmetalationen
dc.titleMechanism of the Transmetalation of Organosilanes to Golden
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistryOpenen
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionWestCHEM Department of Pure & Applied Chemistry; University of Strathclyde; Thomas Graham Building 295 Cathedral Street Glasgow G1 1XL UKen
dc.contributor.institutionEaStCHEM School of Chemistry; University of St. Andrews; North Haugh St. Andrews Fife KY16 9ST UKen
dc.contributor.institutionEaStCHEM School of Chemistry; University of St. Andrews; North Haugh St. Andrews Fife KY16 9ST UKen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química; Universitat de Girona; Campus Montilivi 17071 Girona Catalonia Spainen
dc.contributor.institutionChemistry Department, College of Science, King Saud University, Riyadh, Saudi Arabiaen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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