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Issue 3, 1998
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Electroreduction of Pd2(dppm)2Cl2 and Pd(dppm)Cl2 [dppm=bis(diphenylphosphino)methane] in aprotic medium under carbon dioxide: electrogeneration of Pd33-CO)(µ-dppm)3

Abstract

The electroreduction of the – Pd2(dppm)2Cl2 and monomeric Pd(dppm)Cl2 complexes in aprotic medium (such as DMF, THF and acetonitrile) has been performed under CO2 atmosphere. In all cases the final products are CO32- anion, CO and the neutral Pd33-CO)(µ-dppm)3 cluster. This electroreduction is not catalytic but rather stoichiometric. The electroreduction mechanisms have been addressed experimentally by electrochemical methods and IR spectroscopy, and theoretically by density functional methods via the geometry optimizations of the proposed intermediates. The intermediates "‘Pd2(dppm)2’' and "‘Pd(dppm)’' are assumed to be active towards the binding of CO2 prior to its reduction. E′lectrore′duction de Pd2(dppm)2Cl2 et de Pd(dppm)Cl2 [dppm=bis(diphe′nylphosphino)me′thane] en milieu aprotique sous dioxyde de carbone: E′lectroge′ne′ration de Pd33-CO)(µ-dppm)3. L'e′lectrore′duction du complexe - Pd2(dppm)2Cl2 et du monomère Pd(dppm)Cl2 en milieu aprotique (DMF, THF et ace′tonitrile) a e′te′ effectue′e sous atmosphère de CO2. Dans tous les cas les produits finaux sont l'anion CO32-, CO et le cluster neutre Pd33-CO)(µ-dppm)3. Cette e′lectrore′duction n'est pas catalytique mais stoechiome′trique. Les me′canismes d'e′lectrore′duction ont e′te′ e′tudie′s expe′rimentalement par des me′thodes e′lectrochimiques et par spectroscopie IR, et the′oriquement par les me′thodes de la fonctionnelle de la densite′ via les optimisations ge′ometriques des interme′diaires propose′s. Les interme′diaires "‘Pd2(dppm)2’' et "‘Pd(dppm)’' sont suppose′s être actifs vis à vis de la fixation du CO2 avant sa re′duction.

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Article type: Paper
DOI: 10.1039/A708331I
Citation: New J. Chem., 1998,22, 237-246
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    Electroreduction of Pd2(dppm)2Cl2 and Pd(dppm)Cl2 [dppm=bis(diphenylphosphino)methane] in aprotic medium under carbon dioxide: electrogeneration of Pd33-CO)(µ-dppm)3

    I. Gauthron, Y. Mugnier, K. Hierso and P. D. Harvey, New J. Chem., 1998, 22, 237
    DOI: 10.1039/A708331I

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