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oai:recercat.cat:10256/121052024-06-18T13:50:49Zcom_2072_452955com_2072_2054col_2072_453073

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis Font Molins, Marc Acuña-Parés, Ferran Parella Coll, Teodor Serra Parareda, Jordi Luis Luis, Josep Maria Lloret Fillol, Julio Costas Salgueiro, Miquel Ribas Salamaña, Xavi Ministerio de Economía y Competitividad (Espanya) Ministerio de Ciencia e Innovación (Espanya) Mecanismes de reacció (Química) Reaction mechanisms (Chemistry) Catàlisi homogènia Homogeneous 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) info:eu-repo/date/embargoEnd/2026-01-01 info:eu-repo/date/embargoEnd/2026-01-01 2014 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://hdl.handle.net/10256/12105 http://hdl.handle.net/10256/12105 eng info:eu-repo/semantics/altIdentifier/doi/10.1038/ncomms5373 info:eu-repo/semantics/altIdentifier/issn/2041-1723 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 info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3 Tots els drets reservats info:eu-repo/semantics/embargoedAccess application/pdf Macmillan Publishers © Nature Communications, 2014, vol. 5, núm. art. 4373 Articles publicats (D-Q)