Water Elimination from Phosphorus–Oxygen Compounds: The Formation of 2-Phosphapropene by Thermolysis of Dimethylphosphane Oxide

Authors

  • Prof. Dr. Hans Bock,

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    1. Institut für Anorganische Chemie der Universität, Niederurseler Hang, D-6000 Frankfurt am Main 50 (FRG)
    • Institut für Anorganische Chemie der Universität, Niederurseler Hang, D-6000 Frankfurt am Main 50 (FRG)
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  • Dipl.-Chem. Martin Bankmann

    1. Institut für Anorganische Chemie der Universität, Niederurseler Hang, D-6000 Frankfurt am Main 50 (FRG)
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  • Gas-Phase Reactions, Part 75. This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, Hoechst AG, and the Land Hessen. We thank Prof. K. Kühelin (Hoechst AG) for donation of chemicals. Part 74: H. Bock, B. Solouki S. Patai; Z. Rappoport (Eds.): The Chemistry of Organic Silicon Compounds, Wiley, Chichester 1989, pp. 555–653.

  • Dedicated to Professor Gottfried Märkl on the occasion of his 60th birthday

Abstract

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The cleavage of the P [DOUBLE BOND] O bond in the title reaction is an unusual finding – this bond, however, is still generally considered as energetically preferred. The course of the reaction is explained on the basis of an MNDO energy hypersurface by entropy-favored dissipation of the activation energy stored in the “chemically activated” isomerization intermediate (H3C)2P[BOND]OH.

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