Abstract
It was shown that the rate and selectivity of irreversible processes of electrochemical and chemical reduction of onium cations of elements of groups V-VII, containing alkyl and aryl substituents, increase with increasing principal quantum number of the central atom of the cation. This pattern is explained on the basis of the Marcus theory by a decrease in the energy of heterolytic dissociation of the bonds of the substituent to the central atom of the cation, leading to a decrease in the free energy and energy of reorganization of the reaction, as well as to an increase in their rate and selectivity.
This is a preview of subscription content, log in via an institution to check access.
Literature cited
V. I. Bogillo, A. F. Levit, N. V. Kondratenko, al. “Kinetics of the reduction of onium salts by stable radicals and radical anions,” Teor. Éksp. Khim., 19, No. 4, 508–512 (1983).
M. Beiser (ed.), Electrochemistry of Organic Compounds [Russian translation], Mir, Moscow (1976).
O. A. Ptitsyna, T. V. Levashova, K. P. Butin, and O. A. Reutov, “Polarography of diarylhalogenonium salts,” Dokl. Akad. Nauk SSSR, 201, No. 2, 372–374 (1971).
R. A. Marcus, “Theoretical relations among rate constants, barriers, and Bronsted slopes of chemical reactions,” J. Phys. Chem., 72, No. 3, 891–899 (1968).
V. G. Mairanovsky, “Electrode processes with a fast and ultrafast bond cleavage. Correlations with gas-phase reactions of dissociative electron capture,” J. Electroanal. Chem., 125, No. 1, 231–235 (1981).
F. D. Seava and B. P. Morgan, “Mechanism of one-electron electrochemical reductivecleavage of sulfonium salts,” J. Am. Chem. Soc., 106, No. 15, 4121–4125 (1984).
R. A. Marcus, “Chemical and electrochemical electron-transfer theory,” Annu. Rev. Phys. Chem., 15, 155–196 (1964).
M. K. Kroeger and R. S. Drago, “Quantitative prediction and analysis of enthalpies for the interaction of gas-phase ion-ion gas-phase ion-molecule and molecule-molecule Lewis acid-base systems,” J. Am. Chem. Soc., 103, No. 12, 3250–3262 (1981).
L. Eberson, “Electron-transfer theory in organic chemistry. 2. An analysis of alkyl halide reduction by electron transfer reagents on the basis of the Marcus theory,” Acta Chem. Scand. B, 36, No. 8, 533–543 (1982).
Author information
Authors and Affiliations
Additional information
Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 4, pp. 468–470, July–August 1987.
Rights and permissions
About this article
Cite this article
Bogillo, V.I., Gragerov, I.P. Influence of the nature of the central atom of onium cations on the rate and selectivity of processes of their one-electron reduction. Theor Exp Chem 23, 439–441 (1988). https://doi.org/10.1007/BF00536364
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00536364