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

• Published in: Journal of structural chemistry Vol. 64; no. 2; pp. 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: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.02.2023; Springer Nature B.V
• 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; quantum chemical simulation; intermediate catalytic adduct; cumene oxidation; cumene hydroperoxide
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476623020075

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.