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The nature of the O—O bond in hydroperoxides

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Abstract

Quantum-chemical calculations of the H2O2 and F2 molecules using different computational schemes, basis sets, and procedures for the inclusion of electron correlation were performed. High-resolution X-ray diffraction study of the electron density distribution in the crystals of 2,5-dimethyl-2,5-dihydroperoxyhexane and 2,5-dimethyl-2,5-dihydroperoxyhex-3-yne was carried out. Joint analysis of the results obtained showed that the formally covalent O—O and F—F bonds correspond to a specific type of interatomic interaction. This type is intermediate between the shared and closed-shell interactions (the latter are typical of the ionic systems and van der Waals molecules).

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow,p

    K. A. Lysenko, M. Yu. Antipin & V. N. Khrustalev

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  1. K. A. Lysenko
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  2. M. Yu. Antipin
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  3. V. N. Khrustalev
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Lysenko, K.A., Antipin, M.Y. & Khrustalev, V.N. The nature of the O—O bond in hydroperoxides. Russian Chemical Bulletin 50, 1539–1549 (2001). https://doi.org/10.1023/A:1013013930181

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