Molecular complexes and solvation interactions in the reaction of quinone imines with thiols
- 4 Downloads
This study aims to investigate the role of complexation between reagents and the role of solvation of reagents by solvents in the kinetics of chain reactions of quinone imines with thiols. The thermodynamic characteristics of the complexation of quinone imines with thiophenol in CCl4, chlorobenzene, and ethanol, as well as of the complexation of quinone imines and thiophenol with these solvents were calculated by quantum chemical methods (DFT calculations at the PBE/cc-pVDZ level of theory) and in terms of the additive-multiplicative model. Both approaches give consistent results. The formation of molecular complexes in quinone imine–thiphenol systems is accompanied by a 10–30 kJ mol–1 decrease in enthalpy and has only a slight effect on the reaction mechanism.
Key wordsquinone imines thiophenol quantum chemical calculations DFT method PBE/cc-pVDZ additive-multiplicative model hydrogen bonding complexation solvation
Unable to display preview. Download preview PDF.
- 1.The Chemistry of the Quinoid Compounds, Ed. S. Patai, Vol. 1, Parts 1–2, John Wiley and Sons, London–New York–Sydney–Toronto, 1974, 1247 pp.Google Scholar
- 2.The Chemistry of the Quinoid Compounds, Eds S. Patai, Z. Ruppoport, Vol. 2, Parts 1–2, John Wiley and Sons, Chichester–New York–Brisbane–Toronto–Singapore, 1988, 1675 pp.Google Scholar
- 4.G. B. Afanas´eva, E. V. Tsoi, O. N. Chupakhin, E. O. Sidorov, S. V. Konovalov, Zh. Org. Khim. [J. Org. Chem. USSR], 1985, 21, 1926 (in Russian).Google Scholar
- 11.D. W. Potter, J. A. Hinson, Mol. Pharmacol., 1986, 30,33.Google Scholar
- 13.Methods in Enzymology, Vol. 378, 382, Eds H. Sies, L. Packer, Elsevier Acad. Press, San Diego–London, 2004.Google Scholar
- 26.Spravochnik khimika [Chemist's Handbook], 2nd ed., Ed. B. P. Nikol´skii, Khimiya, Leningrad–Moscow, 1962, Vol. 1, 963–974 (in Russian).Google Scholar
- 27.L. Taimr, J. Rotschova, J. Pospisil, Chem. Ind., 1979, No. 12,413.Google Scholar
- 28.O. A. Raevsky, V. Yu. Grigor´ev, S. V. Trepalin, Svidetel´stvo ob ofitsial´noi registratsii programmy dlya EVM HYBOT (Hydrogen Bond Thermodynamics) No. 990090 ot 26 fevralya 1999 [Certificate of State Registration of a Computer Program HYBOT (Hydrogen Bond Thermodynamics) No. 990090 dated February 26, 1999], Moscow, Federal´naya sluzhba po intellektual´noi sobstvennosti, patentam i tovarnym znakam [Federal Service for Intellectual Property, Patents, and Trademarks] (in Russian).Google Scholar