Nitrite reduction mediated by the complex RuIII(EDTA)

Reported is the first example of a ruthenium(III)-complex, RuIII(EDTA) (EDTA4− = ethylenediaminetetraacetate), that mediates O-atom transfer from nitrite to the biological thiols cysteine and glutathione, leading to the formation of [RuIII(EDTA)(NO+)]0. However, at pH below 5.0, the coordinated nitrite ion in the [RuIII(EDTA)(NO2)]2− complex undergoes proton-assisted decomposition, resulting in the formation of a [RuIII(EDTA)(NO+)]0 species

Mechanism of the oxidation of thiosulfate with hydrogen peroxide catalyzed by aqua-ethylenediaminetetraacetatoruthenium(III)

Catalytic ability of [RuIII(edta)(H2O)]− (edta4− = ethylenediaminetetraacetate) complex toward oxidation of thiosulfate (S2O32−) in presence of H2O2 has been explored in the present work. The kinetics of the catalytic oxidation of thiosulfate (S2O32−) has been studied spectrophotometrically as a function of [RuIII(edta)], [H2O2], [S2O32−] and pH. Spectral analyses and kinetic data indicate a catalytic pathway involving activation of both substrate (S2O32−) and oxidant (H2O2). Substrate activation pathway involves the formation of a red [RuIII(edta)(S2O3)]3− species through the reaction of the [RuIII(edta)(H2O)]− catalyst complex and the substrate (S2O32−). Hydrogen peroxide reacts directly with thiosulfate coordinated to the RuIII(edta) complex to yield sulfite as immediate oxidation product. Peroxide activation pathway is governed by the formation of [RuV(edta)(O)]− catalytic intermediate which oxidize thiosulfate, however, at slower rate (View the MathML source at 25 °C) as compared to the rate of oxidation of the coordinated thiosulfate (View the MathML source at 25 °C). Sulfite and sulfate were found to be the oxidation products of the above described catalytic oxidation process. A detailed mechanism in agreement with the spectral and kinetic data is presented