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Volume 63, 1977
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Free radical oxidation of organic sulphur compounds in aqueous solution


Complexed radical cations are formed as transient products in the one-electron oxidation of organic sulphides by hydroxyl radicals. Intermolecular complexes, (R2S ∴ SR2)+, are characterized by a 3-electron bond between sulphur atoms of two different molecules, absorption maxima around 500 nm and an equilibrium (R2S)2+.⇌ R2S+.+ R2S. In addition, intramolecular complex formation yielding [graphic omitted] is observed in the oxidation of 1,4-di, 1,3-di, and 1,3,5-tri-thiane. In these complexes a 3-electron-through-space-bond between two sulphur atoms of the same molecule is established. Absorption maxima are red shifted to ≥600 nm. Stabilization of an oxidized sulphur atom can also be effected by hetero-atoms other than sulphur. R2S ∴ Br(Cl) are formed in the reaction of either R2S with Br2[graphic omitted](Cl2[graphic omitted]) or the oxidized sulphide with Br(Cl). Equilibrium constants for the complexes, spectral and kinetic data on the neutral radicals and radical cations are reported and discussed.

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Article type: Paper
DOI: 10.1039/DC9776300213
Citation: Faraday Discuss. Chem. Soc., 1977,63, 213-225
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    Free radical oxidation of organic sulphur compounds in aqueous solution

    K.-D. Asmus, D. Bahnemann, M. Bonifačić and H. A. Gillis, Faraday Discuss. Chem. Soc., 1977, 63, 213
    DOI: 10.1039/DC9776300213

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