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Journal of Cluster Science

, Volume 17, Issue 1, pp 5–12 | Cite as

Electrochemical Dissociative Oxidation of the Unsaturated Pd3(dppm)3(CO)2+ Cluster; An Astonishing Resemblance with the Photo-Oxidative Analogue

  • David Brevet
  • Dominique Lucas
  • Yves Mugnier
  • Pierre Harvey
Article

Abstract

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) 2 2+ 4 complex is generated among the first intermediates, and the d8 Pd(dppm)(NCCH3) 2 2+ 3 is formed as the final product. The intermediacy of “Pd3(dppm)3(CO)4+” and “Pd3(dppm) 3 4+ ” 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.

KEY WORDS:

Cluster palladium electrochemistry oxidation dissociation 

Notes

ACKNOWLEDGMENTS

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.

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Copyright information

© Springer 2005

Authors and Affiliations

  • David Brevet
    • 1
  • Dominique Lucas
    • 1
  • Yves Mugnier
    • 1
  • Pierre Harvey
    • 2
  1. 1.Laboratoire de Synthèse et Electrosynthèse Organométalliques, CNRS UMR 5188, Faculté des Sciences MirandeUniversité de BourgogneDijonFrance
  2. 2.Département de ChimieUniversité de SherbrookeSherbrookeCanada

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