Abstract
The mechanism of oxygen atom transfer between triplet molecules of a nitro compound and dimethyl sulfide is considered. This reaction pathway can be one of the possible routes in the reaction of photochemical oxidation of the sulfur compound. Quantum-chemical modeling has shown the feasibility of such a reaction as having a fairly low activation energy. The transition states of the reaction have almost the same structure in various solvents. The calculation of spin densities and charges on atoms in transition states has shown no significant charge separation. This finding is also confirmed by calculation of the activation parameters of the oxygen transfer reaction involving various solvents. The activation energies remain almost unchanged with an increase in the solvent permittivity. All the data obtained suggest the radical mechanism of oxygen atom transfer with the participation of the triplet nitro compound.
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REFERENCES
Hurley, R. and Testa, A.C., J. Am. Chem. Soc., 1968, vol. 90, no. 8, p. 1949.
Adachi, S., Kohguchi, H., and Suzuki, T., J. Phys. Chem. Lett., 2018, vol. 9, no. 2, p. 270.
Ovsyannikov, D.V. and Zelentsov, S.V., High Energy Chem., 2019, vol. 52, no. 3, p. 217.
Ovsyannikov, D.V. and Zelentsov, S.V., High Energy Chem., 2019, vol. 53, no. 2, p. 103.
Fomichev, D.A., Ovsyannikov, D.V., and Zelentsov, S.V., High Energy Chem., 2020, vol. 54, no. 4, p. 254.
Sako, M., Shimada, K., Hirota, K., and Maki, Y., J. Am. Chem. Soc., 1986, vol. 108, no. 19, p. 6039.
Noble, M., Qian, C.X.W., Reisler, H., and Wittig, C., J. Chem. Phys., 1986, vol. 85, no. 10, p. 5763.
Toniolo, A. and Persico, M., J. Chem. Phys., 2001, vol. 115, no. 4, p. 1817.
Sarkar, R., Loos, P.-F., Boggio-Pasqua, M., and Jacquemin, D., J. Chem. Theory Comput., 2022, vol. 18, no. 4, p. 2418.
Musaev, D.G., Geletii, Y.V., and Hill, C.L., J. Phys. Chem. A, 2003, vol. 107, no. 30, p. 5862.
Clarke, J.L., Kastrati, I., Johnston, L.J., and Thatcher, G.R.J., Can. J. Chem., 2006, vol. 84, p. 709.
Kulbir, K., Das, S., Devi, T., Goswami, M., Yenuganti, M., Bhardwaj, P., Ghosh, S., Sahoo, S.C., and Kumar, P., Chem. Sci., 2021, vol. 12, p. 10605.
Neese, F., Wennmohs, F., Becker, U., and Riplinger, C., J. Chem Phys., 2020, vol. 152, p. 224108.
“Lobachevsky” Supercomputer at the State University of Nizhny Novgorod. http://hpc-education.unn.ru/ru/pecypcы
The PyMOL Molecular Graphics System, Version 2.0, New York: Schrödinger, LLC, 2015.
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Translated by S. Zatonsky
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Zelentsov, S.V., Ovsyannikov, D.V. & Pyslaru, A. Photochemical Oxidation of Dimethyl Sulfide with Triplet Nitro Compounds. High Energy Chem 57, 309–312 (2023). https://doi.org/10.1134/S0018143923040161
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DOI: https://doi.org/10.1134/S0018143923040161