Free radical oxidation of organic sulphur compounds in aqueous solution

authored by: K. D. Asmus, D. Bahnemann, M. Bonifačić, H. A. Gillis
Abstract: 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 (R ₂S)_22.⁺ ⇌ R ₂S. In addition, intramolecular complex formation yielding (diagram presented)⁺ 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 ^.-(Cl₂^.-) 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.
External Organisation(s): Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)
National Research Council of Canada
Type: Article
Journal: Faraday Discussions of the Chemical Society
Volume: 63
Pages: 213-225
No. of pages: 13
ISSN: 0301-7249
Publication date: 1977
Publication status: Published
Peer reviewed: Yes
ASJC Scopus subject areas: General Physics and Astronomy, Physical and Theoretical Chemistry
Electronic version(s): https://doi.org/10.1039/DC9776300213 (Access: Unknown)

BibTeX

@article{8d87fd53baa94750ba687ad27c8c03c1,
title = "Free radical oxidation of organic sulphur compounds in aqueous solution",
abstract = "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 (R 2S)22.+ ⇌ R 2S. In addition, intramolecular complex formation yielding (diagram presented)+ 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 .-(Cl2.-) 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.",
author = "Asmus, {K. D.} and D. Bahnemann and M. Bonifa{\v c}i{\'c} and Gillis, {H. A.}",
note = "Funding information: The latter appears to be reflected in the energy of maximum absorption with A, ranging from -350 to 650 nm in the series R2SX *, RSSR?, (R,S),t, and the intramolecular radical cations from 1,3-di-, 1,3,5-tri- and 1,4-di-thiane. Part of this work was carried out during a visit by K.-D. Asmus to the National Research Council in Ottawa. The financial support received for this purpose from the NRC Canada is gratefully acknowledged. The authors would also like to thank G. G. Teather for his technical assistance. G. MeiDner, A. Henglein and G. Beck, 2. Naturforsch., 1967, 22b, 13. B. C. Gilbert, J. P. Larkin and R.",
year = "1977",
doi = "10.1039/DC9776300213",
language = "English",
volume = "63",
pages = "213--225",
journal = "Faraday Discussions of the Chemical Society",
issn = "0301-7249",
publisher = "Royal Society of Chemistry",
}