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Kinetic model and mechanism of the acid dissociation of d-metal bis(dipyrrolylmethenates)

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Abstract

A kinetic model and a mechanism have been developed by quantum chemical simulation for the protolytic dissociation of dinuclear homoleptic bis(dipyrrolylmethenates) of d-metals (M) with the general formula [M2L2] and a double-helix structure. The reaction is described by a third-order equation that is first-order with respect to the complex and second-order with respect to the acid. The main contribution to the total dissociation rate is made by the rate-determining step, specifically, attack of the second acetic acid molecule on the nitrogen atom of one of the coordination sites of the helicate. The dinuclear helicates of 3,3′-bis(dipyrrolylmethenes) are more inert in an acidic medium than 2,3′- and 2,2′-bis(dipyrrolylmethenes).

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Authors and Affiliations

  1. G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, 153045, Russia

    G. B. Guseva, E. V. Antina, A. A. Ksenofontov & A. I. V’yugin

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  1. G. B. Guseva
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  2. E. V. Antina
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  3. A. A. Ksenofontov
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  4. A. I. V’yugin
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Correspondence to G. B. Guseva.

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Original Russian Text © G.B. Guseva, E.V. Antina, A.A. Ksenofontov, A.I. V’yugin, 2014, published in Kinetika i Kataliz, 2014, Vol. 55, No. 4, pp. 411–420.

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Guseva, G.B., Antina, E.V., Ksenofontov, A.A. et al. Kinetic model and mechanism of the acid dissociation of d-metal bis(dipyrrolylmethenates). Kinet Catal 55, 391–400 (2014). https://doi.org/10.1134/S0023158414040053

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  • DOI: https://doi.org/10.1134/S0023158414040053

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