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Catalytic Epoxidations with Peroxides: Molybdenum Trioxide Species as the Origin of Allylic Byproducts

Authors

  • Dr. Ulrich Neuenschwander,

    1. Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich (Switzerland), Fax: (+41) 44-633-1514
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  • Emanuel Meier,

    1. Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich (Switzerland), Fax: (+41) 44-633-1514
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  • Prof. Dr. Ive Hermans

    Corresponding author
    1. Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich (Switzerland), Fax: (+41) 44-633-1514
    • Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich (Switzerland), Fax: (+41) 44-633-1514
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Abstract

Molybdenum(VI)peroxide species, formed in the reaction of MoVI complexes with peroxides, are able to epoxidize >C[DOUBLE BOND]C< double bonds heterolytically. In this study, theoretical and experimental evidence is provided for a kinetically competing reaction reaction of such molybdenum(VI)peroxide species with additional peroxide reagent, leading to molybdenum(VI)trioxide species, which easily decompose into radicals. Under epoxidation conditions, those radicals will reduce the selectivity, due to the formation of allylic byproducts. The involved reaction pathways are characterized by DFT calculations, providing kinetic parameters that are in good agreement with the experimental observations.

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