Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis
dc.contributor.author
dc.date.accessioned
2016-02-19T11:12:16Z
dc.date.available
2016-02-19T11:12:16Z
dc.date.issued
2014
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2041-1723
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dc.description.abstract
Silver is extensively used in homogeneous catalysis for organic synthesis owing to its Lewis acidity, and as a powerful one-electron oxidant. However, two-electron redox catalytic cycles, which are most common in noble metal organometallic reactivity, have never been considered. Here we show that a Ag(I)/Ag(III) catalytic cycle is operative in model C–O and C–C cross-coupling reactions. An aryl-Ag(III) species is unequivocally identified as an intermediate in the catalytic cycle and we provide direct evidence of aryl halide oxidative addition and C–N, C–O, C–S, C–C and C–halide bond-forming reductive elimination steps at monometallic silver centres. We anticipate our study as the starting point for expanding Ag(I)/ Ag(III) redox chemistry into new methodologies for organic synthesis, resembling well-known copper or palladium cross-coupling catalysis. Furthermore, findings described herein provide unique fundamental mechanistic understanding on Ag-catalysed cross-coupling reactions and dismiss the generally accepted conception that silver redox chemistry can only arise from one-electron processes
dc.description.sponsorship
This work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2012-37420-C02-01/BQU, CTQ2012-32436, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637)
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application/pdf
dc.language.iso
eng
dc.publisher
Macmillan Publishers
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
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Reproducció digital del document publicat a: http://dx.doi.org/10.1038/ncomms5373
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© Nature Communications, 2014, vol. 5, núm. art. 4373
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
021300
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dc.relation.FundingProgramme
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