Chatterjee, Debabrata and Paul, Barnali and Mukherjee, Rupa (2013) Oxidation of thiocyanate with H2O2 catalyzed by [Ru(III)(edta)(H2O)](-). Dalton Transactions, 42 (27). pp. 10056-10060.

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The [Ru(III)(edta)(H2O)](-) (edta(4-) = ethylenediaminetetraacetate) complex is shown to catalyze the oxidation of thiocyanate (SCN(-)) with H2O2 mimicking the action of peroxidases. The kinetics of the catalytic oxidation process was studied by using stopped-flow and rapid scan spectrophotometry as a function of [Ru(III)(edta)], [H2O2], [SCN(-)], pH (3.2-9.1) and temperature (15-30 °C). Spectral analyses and kinetic data are suggestive of a catalytic pathway in which hydrogen peroxide reacts directly with thiocyanate coordinated to the Ru(III)(edta) complex. Catalytic intermediates such as [Ru(III)(edta)(OOH)](2-) and [Ru(V)(edta)(O)](-) were found to be non-reactive in the oxidation process under the specified conditions. Formation of SO4(2-) and OCN(-) was identified as oxidation products in ESI-MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.

Item Type: Article
Subjects: Chemistry
Depositing User: Dr. Sarita Ghosh
Date Deposited: 21 Sep 2016 11:43
Last Modified: 21 Sep 2016 11:43

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