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Oxidation of thiourea by peroxomonosulfate ion catalyzed by a ruthenium(III) complex: kinetic and mechanistic studies

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The complex [RuIII(edta)(H2O)] (edta4− = ethylenediaminetetraacetate) catalyzes the oxidation of thiourea (TU) by peroxomonosulfate ion (HSO5 ). The kinetics of the catalytic oxidation process was studied by using stopped-flow and rapid-scan spectrophotometry as a function of [RuIII(edta)(H2O)], [HSO5 ] and [TU] at a constant pH of 6.2 (phosphate buffer) and temperature of 25 °C. Spectral and kinetic data are suggestive of a catalytic pathway involving rapid formation of a [RuIII(edta)(TU)] intermediate complex by reaction of [RuIII(edta)(H2O)] with TU, followed by the oxidation of the coordinated TU in which HSO5 reacts directly with the S atom of TU coordinated to the RuIII(edta) complex. Analysis of the reaction mixture at the end of the reaction revealed the formation of formamidine disulfide (TU2) as a major product; however, thiourea dioxide (TUO2) and sulfate were also observed if the reaction mixture was kept for longer time periods. A detailed mechanism in agreement with the spectral and kinetic data is presented.

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Papiya Sarkar thanks CSIR, New Delhi, for junior research fellowship (CSIR-JRF).

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Correspondence to Debabrata Chatterjee.

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Sarkar, P., Chatterjee, D. Oxidation of thiourea by peroxomonosulfate ion catalyzed by a ruthenium(III) complex: kinetic and mechanistic studies. Transition Met Chem 41, 9–13 (2016). https://doi.org/10.1007/s11243-015-9991-5

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  • Ruthenium
  • Thiourea
  • H2O2 System
  • Hedta
  • Kinetic Trace