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

Marc Font, Ferran Acuña-Parés, Teodor Parella, Jordi Serra, Josep M Luis, Julio Lloret-Fillol, Miquel Costas and Xavi Ribas ()
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Marc Font: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Ferran Acuña-Parés: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Teodor Parella: Servei de RMN, Facultat de Ciències, Universitat Autònoma de Barcelona
Jordi Serra: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Josep M Luis: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Julio Lloret-Fillol: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Miquel Costas: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona
Xavi Ribas: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona

Nature Communications, 2014, vol. 5, issue 1, 1-10

Abstract: 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.

Date: 2014
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DOI: 10.1038/ncomms5373

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