Direct vs indirect route in the activation of aroylpalladium(II) complexes by electron transfer

C. Amatore, E. Carré, A. Jutand, H. Tanaka, S. Torii, I. Chiarotto, I. Carelli

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12 Citations (Scopus)

Abstract

Based on mechanistic investigations, it is established that it is not possible to invert the reactivity of aroyl halides, ArCO-X, and make them react with electrophiles, in the presence of a palladium catalyst and a source of electron. Indeed, the key intermediate ArCO-Pd-XL2 (L = PPh3) whose activation by electron transfer in the presence of an electrophile would produce the coupling product ArCO-E, is less easily reduced than the corresponding aroyl halide. ArCO-X + E+ + 2e - ×Pd(0) → ArCO-E + X-. However, an indirect palladium catalyzed process for the synthesis of ArCO-E derivatives is proposed, from aryl halides, carbon monoxide and an electron source. Ar-X + CO + E+ + 2e →Pd(0) ArCO-E + X-. The efficiency of the second process comes from the fact that the intermediate ArCO-Pd-XL2, formed by reaction of CO with Ar-Pd-XL2, is more easily reduced than the aryl halide and the transient Ar-Pd-XL2 complex.

Original languageEnglish
Pages (from-to)2143-2152
Number of pages10
JournalElectrochimica Acta
Volume42
Issue number13-14
DOIs
Publication statusPublished - Jan 1 1997

Keywords

  • Aroyl halides
  • Aryl halides
  • Carbon monoxide
  • Electron transfer
  • Palladium

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

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    Amatore, C., Carré, E., Jutand, A., Tanaka, H., Torii, S., Chiarotto, I., & Carelli, I. (1997). Direct vs indirect route in the activation of aroylpalladium(II) complexes by electron transfer. Electrochimica Acta, 42(13-14), 2143-2152. https://doi.org/10.1016/S0013-4686(97)85491-6