Free radical oxidation of organic sulphur compounds in aqueous solution

verfasst von: 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.
Externe Organisation(en): Helmholtz-Zentrum Berlin für Materialien und Energie GmbH
National Research Council of Canada
Typ: Artikel
Journal: Faraday Discussions of the Chemical Society
Band: 63
Seiten: 213-225
Anzahl der Seiten: 13
ISSN: 0301-7249
Publikationsdatum: 1977
Publikationsstatus: Veröffentlicht
Peer-reviewed: Ja
ASJC Scopus Sachgebiete: Allgemeine Physik und Astronomie, Physikalische und Theoretische Chemie
Elektronische Version(en): https://doi.org/10.1039/DC9776300213 (Zugang: Unbekannt)

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",
}