Redox reactions of a Ru-III-edta complex with thioamino acids. Kinetic and mechanistic studies

The kinetics of reduction of [Ru-III(edta)pz](-) (edta(4-) = ethylenediaminetetraacetate; pz = pyrazine) by thioamino acids (RSH = cysteine, glutathione) resulting in the formation of a red [Ru-II(edta)pz](2-) species (lambda(max) = 462 nm) has been studied spectrophotometrically using both conventional mixing and stopped-flow techniques. The time course of the reaction was followed as a function of [RSH], pH, temperature and pressure. Alkali metal ions were found to have a positive influence (K+ > Na+ > Li+) on the reaction rate. Kinetic data and activation parameters are interpreted in terms of a mechanism involving outer-sphere electron transfer between the reaction partners. A detailed reaction mechanism in agreement with the spectral and kinetic data is presented.