Addition of oxygen to organic sulfur radicals

authored by

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.

External Organisation(s)

Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)
Ruder Boskovic Institute

Type

Article

Journal

Journal of Physical Chemistry

Volume

82

Pages

2777-2780

No. of pages

4

ISSN

0022-3654

Publication date

1978

Publication status

Published

Peer reviewed

Yes

ASJC Scopus subject areas

General Engineering, Physical and Theoretical Chemistry

Electronic version(s)

https://doi.org/10.1021/j100515a005 (Access: Unknown)