Reduction of some Pt(iv) complexes with biologically important sulfur-donor ligands

摘要

The reduction of the Pt(iv) complexes [PtCl_4(bipy)], [PtCl _4(dach)] and [PtCl_4(en)] by glutathione (GSH), l-cysteine (l-Cys) and l-methionine (l-Met) was investigated by stopped-flow spectrophotometry at pH 2.0 (in 0.01 M perchloric acid) and at pH 7.2 (in 25 mM Hepes buffer). Kinetic measurements were performed under pseudo-first order conditions with an excess of the reducing agent. The order of the reactivity of the studied complexes was [PtCl_4(bipy)] > [PtCl_4(dach)] > [PtCl_4(en)], and reactivity of investigated reducing agents followed the order GSH > l-Cys > l-Met. All the reactions between the selected Pt(iv) complexes and the sulfur donor biomolecules proceeded by a reductive elimination process that included nucleophilic attack by the reducing agent on one of the mutually trans-coordinated chloride ligands, which led to a two-electron transfer process. The final products of the redox reactions were the corresponding reduced Pt(ii) complexes and the oxidized form of the reducing agents.