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Relative kinetic stability towards redox decomposition of cerium(IV) complexes with some organic compounds

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Abstract

A comparative analysis is performed on the stability constants \({\upbeta }_{1yn}\) and intramolecular redox decomposition rate constants \(k_{n\; = \;1}\) obtained for intermediate cerium(IV) complexes \([{\text{CeH}}_{y} {\text{L}}_{n} ]^{4\; + \;y\; - \;nk}\) with three series of heterocyclic and aliphatic organic compounds \(R = H_{k} L\) formed during the oxidation reactions of these compounds with cerium(IV). Linear relationships are established for these complexes between \(\log k_{n\; = \;1}\) and \(\log {\upbeta }_{1yn}\). A quantitative method is proposed to examine the kinetic stabilization of unstable metal oxidation states upon complexation as well as the reactivity of these complexes on the basis of the obtained equations for these relationships.

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Notes

  1. In contrast to the pseudo-first-order rate constants that are functions of variable parameters of an experimental series, we define these constants as the rate constants of the first concentration order (\(n_{{\text{c}}} = 1)\) with respect to the complex that preserve the value constancy within the experimental series (see, e.g., [4]). They are abbreviated below as \(k_{{{{n}} = 1}}\).

  2. A reaction series consists of similar reactions proceeding through a common mechanism and obeying a common correlation.

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Authors and Affiliations

  1. Joint Institute for Nuclear Research, Dubna, Moscow region, Russia

    Olga O. Voskresenskaya

  2. Chemistry Department, Tomsk State University, Tomsk, Russia

    Nina A. Skorik

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  1. Olga O. Voskresenskaya
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  2. Nina A. Skorik
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Correspondence to Olga O. Voskresenskaya.

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Voskresenskaya, O.O., Skorik, N.A. Relative kinetic stability towards redox decomposition of cerium(IV) complexes with some organic compounds. Monatsh Chem 151, 533–542 (2020). https://doi.org/10.1007/s00706-020-02585-7

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  • DOI: https://doi.org/10.1007/s00706-020-02585-7

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