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

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 hyd...

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Published in:Journal of structural chemistry 2023-02, Vol.64 (2), p.227-239
Main Authors: Ulitin, N. V., Anisimova, V. I., Khursan, S. L., Baldinov, A. A., Suvorova, I. A., Nurullina, N. M., Shiyan, D. A., Tereshchenko, K. A., Badrtdinova, A. I., Denisova, M. N., Kharlampidi, K. E., Grzhegorzhevskii, K. V., Abramov, P. A.
Format: Article
Language:English
Subjects:
Adducts
Atomic
Atomic/Molecular Structure and Spectra
Catalytic activity
Chemistry
Chemistry and Materials Science
Cumene
Cumene hydroperoxide
Density distribution
Electron density
Free radicals
Inorganic Chemistry
Molecular
Optical and Plasma Physics
Oxidation
Physical Chemistry
Quantum chemistry
Reaction kinetics
Solid State Physics
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Summary: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.
ISSN:0022-4766
1573-8779
DOI:10.1134/S0022476623020075