Abstract
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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Curtis WE, Muldrow ME, Parker NB, Barkley R, Linas SL, Repine JE (1988) Proc Natl Acad Sci 85:3422
Sprong RC, Aarsman CJM, van Oirschot JFLM, van Asbeck BS (1997) J Lab Clin Med 129:470
Kelner MJ, Bagnell R, Welch KJ (1990) J Biol Chem 265:1306
Lai Y-L, Wu H-D, Chen CF (1998) J Cardiovasc Pharmacol 32:714
Wang W, Schuchmann MN, Schuchmann H-P, Knolle W, von Sonntag J, von Sonntag C (1999) J Am Chem Soc 121:238
Simoyi RH, Epstein IR, Kustin K (1994) J Phys Chem 98:551
Sharma V, Joshi WV, Millero FJ, Connor D (1999) Environ Sci Technol 33:2645
Kudrik EV, Theodoridis AK, van Eldik R, Makarov SV (2005) Dalton Trans 6:1117–1122
Henry NPO, Harutyuneran KY, Byrd JE (1979) Inorg Chem 18:197
Chatterjee D, Paul B, Mukherjee R (2013) Dalton Trans 42:10056–10060
Baly J (1986) J Electroanal Chem 214:481–483
Diamantis AA, Dubrwaski JV (1981) Inorg Chem 20:1142
Matsubara T, Creutz C (1979) Inorg Chem 18:1956–1966
Bajaj HC, van Eldik R (1988) Inorg Chem 27:4052–4055
Chatterjee D, Sikdar A, Patnam VR, Theodoridis A, van Eldik R (2008) Dalton Trans 29:3851–3856
Gao Q, Wang G, Sun Y, Epstein IR (2008) J Phys Chem A 112:5771
Acknowledgments
Papiya Sarkar thanks CSIR, New Delhi, for junior research fellowship (CSIR-JRF).
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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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DOI: https://doi.org/10.1007/s11243-015-9991-5