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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

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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.

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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.

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Authors and Affiliations

  1. Faculté des Sciences Mirande, Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB) UMR CNRS 5260, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078, Dijon Cedex, France

    Sophie Fournier, Cyril Cugnet, Alain Vallat, Charles H. Devillers, Yoann Rousselin, Marek M. Kubicki, Dominique Lucas & Yves Mugnier

  2. Département de Chimie, Université de Sherbrooke, Sherbrooke, J1K 2R1, Québec, Canada

    Pierre D. Harvey

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  1. Sophie Fournier
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Fournier, S., Cugnet, C., Vallat, A. et al. 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 . J Clust Sci 21, 837–856 (2010). https://doi.org/10.1007/s10876-010-0338-2

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