Naslov
Kinetics of the Reactions between Sulfide Radical Cation Complexes,[S(S]^+^ and [S(N]^+^, and Superoxide or Carbon Dioxide Radical Anions
(Kinetics of the Reactions Between Sulfide Radical Cation Complexes,[S(S]^+^ and [S(N]^+^, and Superoxide or Carbon Dioxide Radical Anions)

Autori
Bonifačić, Marija ; Hug, Gordon L. ; Schoneich, Christian

Izvornik
Journal of Physical Chemistry A (1089-5639) 104 (2000), 6; 1240-1245

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
carbon dioxide radical anion; pulse radiolysis; rate constants; reaction mechanism; sulfide radical cation; superoxide

Sažetak
The reaction of superoxide radical anions with sulfide radical cation complexes represents an important sulfoxide forming process. Here, absolute rate constants for the reaction of sulfur-sulfur ([>S(S<]^+^) and sulfur-nitrogen ([>S(NH"2"R]^+^ three-electron bonded sulfide radical cation complexes with superoxide and, for comparison, carbon dioxide radical anion have been measured by pulse radiolysis. For two different sulfur-sulfur bonded species, the intermolecular complex from dimethylsulfide and the intramolecular complex from 1,5-dithia-3-hydroxycyclooctane, the rate constant for the reaction with superoxide are on the order of (6.5 ( 0.2)x10^9^ M^–1^s^–1^. The fact that the stronger reducing carbon dioxide radical anion shows the lower rate constant can be interpreted by different reaction mechanisms, electron transfer for the carbon dioxide radical anion and addition by the superoxide radical anion. The latter is consistent with earlier product studies on the reaction of superoxide radical anion with sulfide radical cation complexes.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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