Reactions of thiyl radicals with transition-metal complexes

Abstract

Reactions of thiyl radicals (RS . ) were studied in aqueous solution by laser flash photolysis. Alkyl radicals, which were used to generate the thiyl radicals, were produced by the photohomolysis of the cobalt-carbon bond of RCo([14]aneN 4 )(H 2 O) 2+ complexes (R=CH 3 , C 2 H 5 ). These carbon-centered radicals abstract hydrogen atoms from thiols (C 2 H 5 SH, CysSH, or GSH), generating thiyl radicals. Thiyl radicals readily oxidize a variety of reduced transition-metal complexes