Electron spin resonance and pulse radiolysis studies on the spin trapping of sulphur-centered radicals

Abstract

Thiyl radicals are shown to be readily trapped with the spin traps 5,5-dimethyl-1-pyrroline- N-oxide (DMPO) and 3,3,5,5-tetramethyl-1-pyrroline- N-oxide (TMPO) giving characteristic spin adducts with hyperfine coupling constants a N 1.52–1.58, a H 1.52–1.80 mT, and g values in the range 2.0065–2.0067 for the DMPO adducts and a N 1.50–1.56, a H 1.70–1.92 mT, g 2.0049–2.0051 for the TMPO adducts. Kinetic data obtained from pulse radiolysis studies show that, in general, thiyl radicals react rapidly with these spin traps with rate constants of the order of 10 7–10 8 dm 3 mol −1 s −1. The tetramethylated spin trap TMPO though giving slightly less intense electron spin resonance (ESR) spectra, produces longer lived adducts, and is suggested to be of greater utility due to the more characteristic nature of the coupling constants of the observed adducts; reaction of certain thiyl radicals with DMPO produces adducts which are superficially similar to the hydroxyl radical adduct to the same trap.