• Open Access

Gas-Phase Reactions of Cationic Vanadium-Phosphorus Oxide Clusters with C2Hx (x=4, 6): A DFT-Based Analysis of Reactivity Patterns

Authors

  • Dipl.-Chem. Nicolas Dietl,

    1. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
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  • Dr. Xinhao Zhang,

    1. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
    2. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Dipl.-Chem. Christian van der Linde,

    1. Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstraße 40, 24098 Kiel (Germany)
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  • Prof. Dr. Martin K. Beyer,

    1. Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstraße 40, 24098 Kiel (Germany)
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  • Dr. Maria Schlangen,

    Corresponding author
    1. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
    • Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
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  • Prof. Dr. Helmut Schwarz

    Corresponding author
    1. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
    2. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)
    • Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-21102
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Abstract

The reactivities of the adamantane-like heteronuclear vanadium-phosphorus oxygen cluster ions [VxP4−xO10].+ (x=0, 2–4) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas-phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT-based calculations; homolytic C[BOND]H bond activation constitutes the initial step, and for all systems the P[BOND]O. unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen-atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e reduction of the cationic clusters.

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