Kinetics and Mechanism of Outer-Sphere Reduction of the Oxo-Bridged Trinuclear [(NH3)5RuORu(NH3)4ORu(NH3)5]7+ with Thiosulphate in Acidic Medium

• Autorzy: Banaś B.
• Języki publikacji: EN

Abstrakty

EN

The kinetics of the reduction of -oxo bridged ruthenium(III,IV) complex, [(NH3)5RuORu(NH3)4ORu(NH3)5]7+, with thiosulphate ion in acidic medium has been investigated by conventional and stopped-flow spectrophotometry in the broad range of reagents concentration, pH and temperature. The reaction follows first order kinetics with respect to the ruthenium complex concentration. The reaction order with respect to [S O ] 2 3 2- depends on the reductor concentration and changes from 1 to 2 with[S O ] 2 3 2- increase. At a sufficient excess of thiosulphate concentration over the ruthenium complex concentration, the reaction displays saturation kinetics, what can be interpreted by ion-pairs formation between the highly and oppositively charged reactants, followed by one-electron transfer from S O 2 3 2- to the ruthenium centers. The presence of the precursor outer-sphere complexes has been detected kinetically and the rate constants for intramolecular electron transfer within the ion-pairs have been calculated.

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2000
• Tom: Vol. 74, nr 10
• Strony: 1411--1419
• Opis fizyczny: Bibliogr. 34 poz., rys.

Twórcy

autor

Banaś B.

• Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland