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Effect of ligand nonplanarity and solvent nature on the kinetic stability of zinc porphyrin complexes

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Abstract

Planarity disturbance in metal porphyrin macrorings produces destabilization of complexes in dimethyl sulfoxide-acetic acid and benzene-acetic acid systems, except for cases where the coordination center is additionally stabilized by endocyclic substituents and/or extra ligands. The first dissociation stage of complexes with N-substituted analogs of porphyrins involves substitution of the acido ligand in the strongly shielded coordination sphere by an electron-donor solvent molecule. The revealed dependences of dissociation rate constants on acid concentration in DMSO, untypical of most metal porphyrins, are explained by a change in the type of the attacking species with changing solvent composition. The dissociation rate constants of complexes in an electron donor solvent can be lower by several orders of magnitude than in a weakly solvating medium.

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Authors and Affiliations

  1. Ivanovo State University of Chemical Technology, pr. F. Engel’sa 7, Ivanovo, 153000, Russia

    D. B. Berezin, O. V. Shukhto & P. A. Shatunov

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  1. D. B. Berezin
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  2. O. V. Shukhto
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  3. P. A. Shatunov
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Correspondence to D. B. Berezin.

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Original Russian Text © D.B. Berezin, O.V. Shukhto, P.A. Shatunov, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 854–861.

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Berezin, D.B., Shukhto, O.V. & Shatunov, P.A. Effect of ligand nonplanarity and solvent nature on the kinetic stability of zinc porphyrin complexes. Russ J Gen Chem 78, 997–1004 (2008). https://doi.org/10.1134/S1070363208050277

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  • DOI: https://doi.org/10.1134/S1070363208050277

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