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Mechanism of iridium(III) catalysis in the oxidation of diols by N-bromoacetamide

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Summary

The kinetics of iridium(III)-catalysed oxidation of 1,2-ethanediol and 1,4-butanediol by N-bromoacetamide (NBA) in HClO4 in the presence of [Hg(OAc)2] as a scavenger for Br− have been investigated. The reactions are zero-order with respect to both diols, and first-order in NBA at low NBA concentrations, tending to zero order at high concentrations. The order in IrIII decreases from unity to zero at high iridium(III) concentrations. A positive effect on the oxidation rate is observed for [H+] and [HgII] whereas a negative effect is observed for acetamide and [Cl−]. Ionic strength does not influence the oxidation rate. (H2OBr)+ is postulated as the oxidizing species. A mechanism consistent with the observed kinetic data is proposed.

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Authors and Affiliations

  1. Department of Chemistry, University of Allahabad, 211002, Allahabad, India

    Ashok K. Singh, Alka Srivastava, Ashutosh Kumar & Bharat Singh

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  1. Ashok K. Singh
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  2. Alka Srivastava
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  3. Ashutosh Kumar
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  4. Bharat Singh
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Singh, A.K., Srivastava, A., Kumar, A. et al. Mechanism of iridium(III) catalysis in the oxidation of diols by N-bromoacetamide. Transition Met Chem 18, 427–430 (1993). https://doi.org/10.1007/BF00208187

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  • DOI: https://doi.org/10.1007/BF00208187

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