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On the reaction of Co(II) cobalamin with hydrogen peroxide

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Abstract

Co(II) cobalamin (Co(IICbl) is easily oxidized to Co(III) by a variety of oxidizing agents; with hydrogen peroxide, this reaction entails oxygenation of the corrin ring to species known as stable yellow corrinoids (SYC), as described by Makarov and co-workers. Reported here is a stopped-flow UV–Vis analysis of the initial steps of the Co(II)Cbl with hydrogen peroxide, prior to formation of SYC. The earliest recorded spectra in this reaction, 2 ms after mixing, consist of a mixture of Co(II) and Co(III)-aqua cobalamin. Direct formation of SYC is observed from this stage, with no evidence of inner-sphere interaction between Co(II) and the oxidant, hydrogen peroxide. Outer-sphere monoelectronic oxidation of Co(II) by H2O2 with concerted formation of a hydroxyl radical is therefore proposed as the source of subsequent SYC formation.

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Acknowledgements

Funding from the Romanian Ministry of Education and Research (project PN-III-P4-ID-PCCF-2016-0142) is gratefully acknowledged. Prof S. V. Makarov (Ivanovo State University of Chemistry and Technology) is thanked for helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry, Babeș-Bolyai University, Str. Arany Janos Nr. 11, 400028, Cluj-Napoca, Romania

    Diana Pleșa, Maria Lehene & Radu Silaghi-Dumitrescu

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  1. Diana Pleșa
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  2. Maria Lehene
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  3. Radu Silaghi-Dumitrescu
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Correspondence to Radu Silaghi-Dumitrescu.

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Pleșa, D., Lehene, M. & Silaghi-Dumitrescu, R. On the reaction of Co(II) cobalamin with hydrogen peroxide. Reac Kinet Mech Cat 136, 1791–1799 (2023). https://doi.org/10.1007/s11144-023-02441-9

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