Details
| Original language | English |
|---|---|
| Pages (from-to) | 213-225 |
| Number of pages | 13 |
| Journal | Faraday Discussions of the Chemical Society |
| Volume | 63 |
| Publication status | Published - 1977 |
| Externally published | Yes |
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.
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In: Faraday Discussions of the Chemical Society, Vol. 63, 1977, p. 213-225.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Free radical oxidation of organic sulphur compounds in aqueous solution
AU - Asmus, K. D.
AU - Bahnemann, D.
AU - Bonifačić, M.
AU - Gillis, H. A.
N1 - 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.
PY - 1977
Y1 - 1977
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=37049111106&partnerID=8YFLogxK
U2 - 10.1039/DC9776300213
DO - 10.1039/DC9776300213
M3 - Article
AN - SCOPUS:37049111106
VL - 63
SP - 213
EP - 225
JO - Faraday Discussions of the Chemical Society
JF - Faraday Discussions of the Chemical Society
SN - 0301-7249
ER -