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Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

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

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)

© Nature Communications, 2014, vol. 5, núm. art. 4373

Macmillan Publishers

Author: Font Molins, Marc
Acuña-Parés, Ferran
Parella Coll, Teodor
Serra i Parareda, Jordi
Luis Luis, Josep Maria
Lloret Fillol, Julio
Costas Salgueiro, Miquel
Ribas Salamaña, Xavi
Date: 2014
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
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)
Format: application/pdf
ISSN: 2041-1723
Document access: http://hdl.handle.net/10256/12105
Language: eng
Publisher: Macmillan Publishers
Collection: MINECO/PN 2013-2015/CTQ2012-37420-C02-01
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
Reproducció digital del document publicat a: http://dx.doi.org/10.1038/ncomms5373
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/277801
Is part of: © Nature Communications, 2014, vol. 5, núm. art. 4373
Rights: Tots els drets reservats
Subject: Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Catàlisi homogènia
Homogeneous catalysis
Title: Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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