Addition of oxygen to organic sulfur radicals

verfasst von: K. Schäfer, M. Bonifačić, D. Bahnemann, K. D. Asmus
Abstract: Addition reactions of molecular oxygen to organic sulfur radicals generally appear to be slower than to cor-responding carbon centered radicals. No reaction at all has been found to occur between O₂ and the radical cations RSSR⁺·, R2S⁺·, and (R₂S)₂⁺·. The rate constant for the reaction of oxygen with the thiyl radicals from penicillamine k(PenS· + O₂) = 4.0 × 10⁷ M^-1 s^-1 has been determined from direct pulse radiolysis experiments, and k = 3.4 × 10⁸, 7.8 × 10⁸, and 2.3 × 10⁸ M^-1 s^-1 have been evaluated by a competition method for the addition of O₂ to C₂H₅S·, t-Bu-S·, and HOCH₂CH₂S·, respectively. Higher rate constants up to 10⁹ M^-1 s^-1 were measured for the addition of O₂ to mesomeric carbon-sulfur radical centers, 〉Ċ-S- ↔ 〉C=Ṡ-. The results are discussed in terms of other O₂ addition reactions to various organic and inorganic radicals.
Externe Organisation(en): Helmholtz-Zentrum Berlin für Materialien und Energie GmbH
Ruder Boskovic Institute
Typ: Artikel
Journal: Journal of Physical Chemistry
Band: 82
Seiten: 2777-2780
Anzahl der Seiten: 4
ISSN: 0022-3654
Publikationsdatum: 1978
Publikationsstatus: Veröffentlicht
Peer-reviewed: Ja
ASJC Scopus Sachgebiete: Allgemeiner Maschinenbau, Physikalische und Theoretische Chemie
Elektronische Version(en): https://doi.org/10.1021/j100515a005 (Zugang: Unbekannt)

BibTeX

@article{2610d12887cf451f8bb5aac146e76f55,
title = "Addition of oxygen to organic sulfur radicals",
abstract = "Addition reactions of molecular oxygen to organic sulfur radicals generally appear to be slower than to cor-responding carbon centered radicals. No reaction at all has been found to occur between O2 and the radical cations RSSR+·, R2S+·, and (R2S)2+·. The rate constant for the reaction of oxygen with the thiyl radicals from penicillamine k(PenS· + O2) = 4.0 × 107 M-1 s-1 has been determined from direct pulse radiolysis experiments, and k = 3.4 × 108, 7.8 × 108, and 2.3 × 108 M-1 s-1 have been evaluated by a competition method for the addition of O2 to C2H5S·, t-Bu-S·, and HOCH2CH2S·, respectively. Higher rate constants up to 109 M-1 s-1 were measured for the addition of O2 to mesomeric carbon-sulfur radical centers, 〉Ċ-S- ↔ 〉C=Ṡ-. The results are discussed in terms of other O2 addition reactions to various organic and inorganic radicals.",
author = "K. Sch{\"a}fer and M. Bonifa{\v c}i{\'c} and D. Bahnemann and Asmus, {K. D.}",
note = "Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",
year = "1978",
doi = "10.1021/j100515a005",
language = "English",
volume = "82",
pages = "2777--2780",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "26",
}