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Electron transfer at an encapsulated cobalt(III) centre: kinetics of oxidation of thiourea and 1,1,3,3-tetramethyl-2-thiourea in aqueous acidic media

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Summary

The stoichiometries, kinetics and mechanisms of oxidation of (NH2)2CS (1) and (Me2N)2CS (2) to the corresponding disulphides by CoIIIM (M = W12O40 ∞-) in aqueous HC1O4 were investigated. The reaction with (1) follows the empirical rate law- d[oxidant] = k[reductant][oxidant] where k = 12.5 ± 0.3 m−1 s−1 at 25° C, while that with (2) follows the equation- d[oxidant] = a + b [reductant] [reductant] [oxidant] where a = 5.4 × 104 M−1s−1 and b = 3.3 × 106M−2 s−1 at 25° C. Free radicals are important in the reactions and possible reaction mechanisms are suggested and discussed.

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Authors and Affiliations

  1. Department of Chemistry, Federal University of Technology, Minna, Nigeria

    Mobolanle Adegboyega Olatunji

  2. Department of Chemistry, University of Papua New Guinea, Box 320, University Post Office, PNG

    Godwin A. Ayoko

  3. National Research Institute for Chemical Technology, P.M.B 1052, Zaria, Nigeria

    Florence O. Ohiani

Authors
  1. Mobolanle Adegboyega Olatunji
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  2. Godwin A. Ayoko
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  3. Florence O. Ohiani
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Olatunji, M.A., Ayoko, G.A. & Ohiani, F.O. Electron transfer at an encapsulated cobalt(III) centre: kinetics of oxidation of thiourea and 1,1,3,3-tetramethyl-2-thiourea in aqueous acidic media. Transition Met Chem 19, 253–256 (1994). https://doi.org/10.1007/BF00161901

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  • DOI: https://doi.org/10.1007/BF00161901

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