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STRUCTURE AND THERMODYNAMIC CHARACTERISTICS OF INTERMEDIATE CATALYTIC ADDUCTS IN CUMENE OXIDATION IN THE PRESENCE OF 2-ETHYLHEXANOATES OF GROUP 2 METALS

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Abstract

The kinetics of cumene oxidation in the presence of Mg, Ca, Sr, Ba 2-ethylhexanoates is studied experimentally. It is established that the Mg 2-ethylhexanoate exhibits the highest catalytic performance. It is shown by the PBEPBE-GD3/def2TZVP method that the intermediate adducts of cumene, cumene hydroperoxide (gauche- and trans-conformers), and dimethyl phenyl carbinol with Mg 2-ethylhexanoate are thermodynamically possible. The data on the structure of intermediate adducts and electron density distribution were obtained by conducting PBEPBE-GD3/def2TZVP quantum chemical calculations. The totality of structural data, energy parameters of the adducts, nature of the electron density distribution, and the strength of the O–O bond show that the intermediate adduct of cumene hydroperoxide (trans-conformer) with Mg 2-ethylhexanoate most rapidly decomposes into free radicals. A mechanism of catalytic activity of Mg 2-ethylhexanoate in cumene oxidation is proposed based on the results of quantum chemical simulation.

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Funding

All the quantum chemical calculations were carried out on the equipment of the Khimia Common Use Center of the Ufa Institute of Chemistry of UFRC RAS and the Agidel Regional Common Use Center of UFRC RAS.

The study was funded by the Russian Science Foundation (project No. 22-13-00461, https://rscf.ru/project/22-13-00461/).

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Authors and Affiliations

  1. Kazan National Research Technological University, Kazan, Russia

    N. V. Ulitin, V. I. Anisimova, A. A. Baldinov, I. A. Suvorova, N. M. Nurullina, D. A. Shiyan, K. A. Tereshchenko, A. I. Badrtdinova, M. N. Denisova & K. E. Kharlampidi

  2. Ufa Institute of Chemistry, Federal Ufa Research Center, Russian Academy of Sciences, Ufa, Russia

    S. L. Khursan

  3. Ural Federal University, Ekaterinburg, Russia

    K. V. Grzhegorzhevskii & P. A. Abramov

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  1. N. V. Ulitin
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Correspondence to K. A. Tereshchenko.

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Russian Text © The Author(s), 2023, published in Zhurnal Strukturnoi Khimii, 2023, Vol. 64, No. 2, 105891.https://doi.org/10.26902/JSC_id105891

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Ulitin, N.V., Anisimova, V.I., Khursan, S.L. et al. STRUCTURE AND THERMODYNAMIC CHARACTERISTICS OF INTERMEDIATE CATALYTIC ADDUCTS IN CUMENE OXIDATION IN THE PRESENCE OF 2-ETHYLHEXANOATES OF GROUP 2 METALS. J Struct Chem 64, 227–239 (2023). https://doi.org/10.1134/S0022476623020075

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