Cyclic voltammetry (CV), rotating disk electrode voltammetry (RDE) and bulk electrolysis were used to investigate the electrochemical oxidation of the title cluster in acetonitrile (CH3CN). Two irreversible 2-electron oxidation processes occur at +0.95 V and +1.15 V vs. SCE. Bulk electrolysis demonstrates that the d9–d9 Pd2(dppm)2(NCCH3)22+4 complex is generated among the first intermediates, and the d8 Pd(dppm)(NCCH3)22+3 is formed as the final product. The intermediacy of “Pd3(dppm)3(CO)4+” and “Pd3(dppm)34+” is suspected but not confirmed. This oxidation process exhibits a close resemblance to the photo oxidative reactivity of the title cluster in the presence of chlorocarbons (R–Cl) for which the sole observed product is Pd(dppm)Cl2.
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P.D.H. thanks NSERC (Natural Sciences and Engineering Research Council) and FCAR (Fonds Concertés pour l’Avancement de la Recherche) for funding. Y.M. is grateful to CNRS (Centre National de la Recherche Scientifique) and Conseil Régional de Bourgogne for funding.