Redox reactions of a pyrazine-bridged RuIII(edta) binuclear complex: spectrochemical, spectroelectrochemical and theoretical studies.

Abstract

The redox reactions of a pyrazine-bridged binuclear [(edta)RuIIIpzRuIII(edta)]2- (edta4- = ethylenediaminetetraacetate; pz = pyrazine) have been investigated spectrochemically and spectroelectrochemically for the first time. The kinetics of the reduction of [(edta)RuIIIpzRuIII(edta)]2- (RuIII-RuIII) with the ascorbic acid anion (HA-) was studied as a function of ascorbic concentration and temperature at a fixed pH 6.0. The overall reaction of RuIII-RuIII was found to consist of two-steps involving the initial formation of the mixed-valence [(edta)RuIIpzRuIII(edta)]3- (RuII-RuIII) intermediate complex (λmax = 462 nm, εmax = 10 000 M-1 cm-1), which undergoes further reduction by ascorbic acid to produce the [(edta)RuIIpzRuII(edta)]4-(RuII-RuII) ultimate product complex (λmax = 540 nm, εmax = 20 700 M-1 cm-1). Our studies further revealed that the RuII-RuIII and RuII-RuII species are formed in the electrochemical reduction of the RuIII-RuIII complex at 0.0 and -0.4 V (vs. SHE), respectively. Formation of RuII-RuIII and RuII-RuII was further corroborated by magnetic moment measurements and DFT calculations. Kinetic data and activation parameters are interpreted in terms of a mechanism involving rate-determining outer-sphere electron transfer between Ru(III) and the ascorbate monoanion (HA-) at pH 6.0. A detailed reaction mechanism in agreement with the spectral, spectro-electrochemical and kinetic data is presented. The results of the spectral and kinetic studies of the reaction of the RuII-RuII complex with molecular oxygen (O2) reveal the ability of the RuII-RuII species to effect the oxygen reduction reaction (ORR) leading to the formation of H2O2, a partial reduction product of dioxygen (O2).