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Journal of Cluster Science

, Volume 21, Issue 4, pp 837–856 | Cite as

Reactivity of Pd3(dppm)3(CO) n+ and Pd3(dppm)3(CO)(RCCR) n+ (n = 0, +1, +2) Towards F. Evidence of Reactive Intermediates and X-Ray Structure of [Pd3(dppm)3(MeO2CC≡CCO2Me)(F)]PF6

  • Sophie Fournier
  • Cyril Cugnet
  • Alain Vallat
  • Charles H. Devillers
  • Yoann Rousselin
  • Marek M. Kubicki
  • Dominique Lucas
  • Yves Mugnier
  • Pierre D. Harvey
Original Paper

Abstract

The reactivity of the trinuclear palladium cluster [Pd3(dppm)3(CO)] n+ (dppm = bis(diphenylphosphinomethane); n = 2, 1) towards F was investigated by electrochemical and spectroscopic methods. The reaction depends on the charge of the cluster. The chemical reduction of the cluster dication is observed in the presence of F generating the paramagnetic monocationic cluster. Spin-trapping experiments with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) provided evidence for the radical F as an intermediate. In a similar manner to the dication, the monocationic cluster [Pd3(dppm)3(CO)]+ is also reduced, but in a slower process, by the F ion to produce [Pd3(dppm)3(CO)]0. Additionally, the alkyne cluster adducts [Pd3(dppm)3(CO)(RCCR)] n+ (n = 2, 1; R = CO2Me) are also reactive towards F. Particularly, the dication adduct leads to a metastable fluoride adduct [Pd3(dppm)3(CO)(RCCR)(F)]+. The electroreductive behavior of this adduct involves electron-transfer steps and F exchange equilibriums, for which digital simulation enables the extraction of the thermodynamic parameters (standard potentials and equilibrium constants). Concurrently, the monocation adduct [Pd3(dppm)3(CO)(RCCR)]+ with F, leads to a disproponation generating 0.5 equiv. of [Pd3(dppm)3(CO)(RCCR)(F)]+ and 0.5 equiv. of [Pd3(dppm)3(CO)(RCCR)]0. The former slowly evolves to [Pd3(dppm)3(RCCR)(F)]+, which was described by X-ray diffraction method.

Graphical Abstract

[Pd3(ddpm)3(CO)] n+ (n = 2, 1) are reduced by F to form [Pd3(dppm)3(CO)](n+)−1. Concurrently, [Pd3(dppm)3(CO)(RCCR)] n+ (n = 2, 1) with F generate the corresponding adducts [Pd3(dppm)3(CO)(RCCR)(F)](n+)−1, but, in the case of n = 1, disproponation is observed into [Pd3(dppm)3(CO)(RCCR)(F)]+ and [Pd3(dppm)3(CO)(RCCR)]0.

Keywords

Cluster Palladium Fluoride Alkyne Molecular electrochemistry 

Notes

Acknowledgments

Financial support by the Natural Sciences and Engineering Research Council (Canada), Centre National de Recherche Scientifique (CNRS, UMR 5260) and Université de Bourgogne (France) is gratefully acknowledged.

Supplementary material

10876_2010_338_MOESM1_ESM.docx (83 kb)
Supplementary material 1 (DOCX 13 kb)

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Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Sophie Fournier
    • 1
  • Cyril Cugnet
    • 1
  • Alain Vallat
    • 1
  • Charles H. Devillers
    • 1
  • Yoann Rousselin
    • 1
  • Marek M. Kubicki
    • 1
  • Dominique Lucas
    • 1
  • Yves Mugnier
    • 1
  • Pierre D. Harvey
    • 2
  1. 1.Faculté des Sciences Mirande, Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB) UMR CNRS 5260Université de BourgogneDijon CedexFrance
  2. 2.Département de ChimieUniversité de SherbrookeQuébecCanada

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