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Potential Functions of Internal Rotation around the Csp2-S Bond and Intramolecular Interactions in Thioanisoles p-RC6H4SCH3

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Abstract

The potential functions of internal rotation around the Csp2-S bond in the compounds p-RC6H4S· CH3 (R = NH2, OCH3, CH3, H, F, Cl, CN, NO2) are studied by ab initio quantum-chemical calculations taking into account the correlation energy for all the electrons (MP2/6-31G*) and in the approximation of the density functional theory (B3LYP/6-31G*). As the electron-donor power of the p-substituents decreases and their electron-acceptor power grows, the molecular conformation changes in the sequence orthogonal-free rotation-planar. The interaction of the sulfur lone electron pairs with the aromatic ring is studied by the natural bond orbital method. The effect that the conformational changes occurring upon replacement of p-substituents exert on the electron density redistribution is demonstrated. The first Koopmans ionization potentials and the geometric parameters of the molecule are reported.

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REFERENCES

  1. Bzhezovskii, V.M., Kapustin, E.G., and Il'chenko, N.N., Zh. Obshch. Khim., 2003, vol. 73,no. 10, p. 1678.

    Google Scholar 

  2. Dewar, P.S., Ernstbrunner, E., Gilmore, J.R., Godfrey, M., and Mellor, J.M., Tetrahedron, 1974, vol. 30,no. 15, p. 2455.

    Google Scholar 

  3. Schweig, A. and Thon, N., Chem. Phys. Lett., 1976, vol. 38,no. 3, p. 482.

    Google Scholar 

  4. Degani, J., Mangini, A., Trombetti, A., and Zauli, C., Spectrochim. Acta (A), 1967, vol. 23,no. 7, p. 1351.

    Google Scholar 

  5. Katritzky, A.R., Pinzelli, R.F., and Topsom, R.D., Tetrahedron, 1972, vol. 28,no. 13, p. 3441.

    Google Scholar 

  6. Jones, I.W. and Tebby, J.C., J. Chem. Soc., Perkin Trans. 2, 1973, no. 8, p. 1125.

  7. Jones, I.W. and Tebby, J.C., J. Chem. Soc., Perkin Trans. 2, 1979, no. 2, p. 217.

  8. Ratovskii, G.V., Panov, A.M., Glukhikh, V.I., Kalabin, G.A., Dmitriev, V.I., and Aliev, I.A., Zh. Obshch. Khim., 1981, vol. 51,no. 7, p. 1504.

    Google Scholar 

  9. Panov, A.M., Ratovskii, G.V., Chuvashov, D.D., and Shivernovskaya, O.A., Zh. Obshch. Khim., 1983, vol. 53,no. 3, p. 517.

    Google Scholar 

  10. Ratovskii, G.V., Shivernovskaya, O.A., Panov, A.M., and Aliev, I.A., Zh. Obshch. Khim., 1989, vol. 59,no. 10, p. 2273.

    Google Scholar 

  11. Shivernovskaya, O.A. and Ratovskii, G.V., Zh. Obshch. Khim., 1993, vol. 63,no. 10, p. 2342.

    Google Scholar 

  12. Bzhezovskii, V.M., Kalabin, G.A., Aliev, I.A., and Trofimov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1976, no. 9, p. 1999.

  13. Bzhezovskii, V.M., Pestunovich, V.A., Kalabin, G.A., Aliev, I.A., and Trofimov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1976, no. 9, p. 2004.

  14. Mohraz, M., Jian-gi, W., Heilbronner, E., Solladie-Cavallo, A., and Matloubi-Moghadam, F., Helv. Chim. Acta, 1981, vol. 64,no. 11, p. 97.

    Google Scholar 

  15. Bzhezovskii, V.M., Kalabin, G.A., Aliev, I.A., Donskikh, V.I., and Trofimov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1987, no. 7, p. 1525.

  16. Bzhezovskii, V.M., Dolenko, G.N., Kalabin, G.A., Topchii, V.A., Aliev, I.A., Parygina, G.K., and Trofimov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1981, no. 8, p. 1784.

  17. Krivdin, L.B., Kalabin, G.A., and Trofimov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1982, no. 3, p. 565.

  18. Krivdin, L.B. and Kalabin, G.A., Zh. Org. Khim., 1985, vol. 21,no. 3, p. 521.

    Google Scholar 

  19. Dolenko, G.N. and Litvin, A.L., J. Mol. Struct. (THEOCHEM), 1991, vol. 83,no. 1, p. 1.

    Google Scholar 

  20. Dolenko, G.N., Litvin, A.L., and Elin, V.P., Zh. Strukt. Khim., 1991, vol. 32,no. 6, p. 61.

    Google Scholar 

  21. Aroney, M.J., Le Fevre, R.J.W., Pierens, R.K., and The, M.G.N., J. Chem. Soc. (B), 1971, no. 6, p. 1132.

  22. Baliah, V. and Uma, M., Tetrahedron, 1963, vol. 19,no. 3, p. 455.

    Google Scholar 

  23. Lutskii, A.E., Yagupol'skii, L.M., and Obukhova, E.M., Zh. Obshch. Khim., 1964, vol. 34,no. 8, p. 2641.

    Google Scholar 

  24. Borovikov, Yu.Ya. and Topchii, V.A., Teor. Eksp. Khim., 1975, vol. 11,no. 1, p. 108.

    Google Scholar 

  25. Hess, R.E., Haas, C.K., Kaduk, B.A., Schaeffer, C.D., and Yoder, C.H., Inorg. Chim. Acta, 1971, vol. 5,no. 2, p. 161.

    Google Scholar 

  26. Buchanan, G.W., Reyes-Zamora, C., and Clarke, D.E., Can. J. Chem., 1974, vol. 52,no. 23, p. 3895.

    Google Scholar 

  27. Kalabin, G.A., Bzhezovskii, V.M., Kushnarev, D.F., Trofimov, B.A., Chmutova, G.A., and Lipovich, T.V., Izv. Akad. Nauk SSSR, Ser. Khim., 1980, no. 5, p. 1002.

  28. Baliah, V. and Premasagar, V., J. Indian Chem. Soc., 1991, vol. 68,no. 11, p. 614.

    Google Scholar 

  29. Baliah, V., Premasagar, V., Uma, M., and Mangalamudaiyar, A., Indian J. Chem. (B), 1993, vol. 32,no. 3, p. 352.

    Google Scholar 

  30. Cheryukanova, G.Ya., Chmutova, G.A., and Vereshchagin, A.N., Zh. Fiz. Khim., 1975, vol. 49,no. 1, p. 234.

    Google Scholar 

  31. Chmutova, G.A. and Podkovyrina, T.A., Zh. Obshch. Khim., 1975, vol. 45,no. 1, p. 158.

    Google Scholar 

  32. Chmutova, G.A., Vtyurina, N.N., Komina, T.V., Gazizov, I.G., and Bok, G., Zh. Obshch. Khim., 1979, vol. 49,no. 1, p. 192.

    Google Scholar 

  33. Chmutova, G.A., Stroenie i reaktsionnaya sposobnost' organicheskikh soedinenii (Structure and Reactivity of Organic Compounds), Arbuzov, B.A., Ed., Moscow: Nauka, 1978, p. 227.

    Google Scholar 

  34. Romm, I.P. and Gur'yanova, E.N., Usp. Khim., 1986, vol. 55,no. 2, p. 225.

    Google Scholar 

  35. Zaripov, N.M., Zh. Strukt. Khim., 1976, vol. 17,no. 4, p. 741.

    Google Scholar 

  36. Bzhezovskii, V.M., Kapustin, E.G., Il'chenko, N.N., Kulik, N.I., and Gorb, L.G., Zh. Obshch. Khim., 2000, vol. 70,no. 11, p. 1876.

    Google Scholar 

  37. Velino, B., Melandri, S., Caminati, W., and Favero, P.G., Gazz. Chim. Ital., 1995, vol. 125,no. 8, p. 373.

    Google Scholar 

  38. Lister, D.G., Palmieri, P., and Zauli, C., J. Mol. Struct., 1976, vol. 35,no. 2, p. 299.

    Google Scholar 

  39. Hehre, W.J., Radom, L., Schleyer, P.v.R., and Pople, J.A., Ab initio Molecular Orbital Theory, New York: Wiley, 1986.

    Google Scholar 

  40. Møller, Ch. and Plesset, M.S., Phys. Rev., 1934, vol. 46,no. 4, p. 618.

    Google Scholar 

  41. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Stratmann, R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Gonzalez, C., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Andres, J.L., Head-Gordon, M., Replogle, E.S., and Pople, J.A., GAUSSIAN 98W, Rev. A.7, Pittsburgh: Gaussian, 1998.

    Google Scholar 

  42. Parr, R.G. and Yang, W., Density Functional Theory of Atoms and Molecules, New York: Oxford Univ. Press, 1989.

    Google Scholar 

  43. Becke, A.D., J. Chem. Phys., 1993, vol. 98,no. 7, p. 5648.

    Google Scholar 

  44. Stephens, P.J., Delvin, C.F., Chabalowski, C.F., and Frisch, M.J., J. Phys. Chem., 1994, vol. 98,no. 45, p. 11 623.

    Google Scholar 

  45. Frisch, M.J., Trucks, G.W., Head-Gordon, M., Gill, P.M.W., Wong, M.W., Foresman, J.B., Johnson, B.G., Schlegel, H.B., Robb, M.A., Replogle, E.S., Gomperts, R., Andres, J.L., Raghavachari, K., Binkley, J.S., Gonzalez, C., Martin, R.L., Fox, D.J., Defrees, D.J., Baker, J., Stewart, J.J.P., and Pople, J.A., GAUSSIAN 92/DFT, Rev. G.3. Pittsburgh: Gaussian, 1993.

    Google Scholar 

  46. Reed, A.E., Curtiss, L.A., and Weinhold, F., Chem. Rev., 1988, vol. 88,no. 6, p. 899.

    Google Scholar 

  47. Weinhold, F. and Carpenter, J.E., The Structure of Small Molecules and Ions, Naaman, R. and Vager, Z., Eds., New York: Plenum, 1988, p. 227.

    Google Scholar 

  48. Nemukhin, A.V. and Veinkhol'd, F., Ross. Khim. Zh., 1994, vol. 38,no. 6, p. 5.

    Google Scholar 

  49. Glendening, A.D., Reed, A.E., Carpenter, J.E., and Weinhold, F., GAUSSIAN 98W, Rev. A.7, NBO Ver. 3.1, Pittsburgh: Gaussian, 1998.

    Google Scholar 

  50. Internal Rotation of Molecules, Orville-Thomas, W.J., Ed., London: Wiley, 1974.

    Google Scholar 

  51. Reed, A.E., Weinstok, R.B., and Weinhold, F., J. Chem. Phys., 1985, vol. 83,no. 2, p. 735.

    Google Scholar 

  52. Kapustin, E.G., Cand. Sci. (Chem.) Dissertation, Kiev, 2001.

  53. Leenuwen, R. van and Baerends, E.J., Phys. Rev. (A), 1994, vol. 49,no. 4, p. 2421.

    Google Scholar 

  54. Bzhezovskii, V.M., Kapustin, E.G., and Il'chenko, N.N., Ukr. Khim. Zh., 2001, vol. 67,no. 1/2, p. 50.

    Google Scholar 

  55. Bzhezovskii, V.M., Il'chenko, N.N., Kulik, N.I., and Yagupol'skii, L.M., Zh. Obshch. Khim., 1997, vol. 67,no. 10, p. 1694.

    Google Scholar 

  56. Bzhezovskii, V.M., Il'chenko, N.N., Kulik, N.I., and Yagupol'skii, L.M., Ukr. Khim. Zh., 1997, vol. 63,no. 9, p. 43.

    Google Scholar 

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  1. Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine

    V. M. Bzhezovskii & E. G. Kapustin

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  1. V. M. Bzhezovskii
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Bzhezovskii, V.M., Kapustin, E.G. Potential Functions of Internal Rotation around the Csp2-S Bond and Intramolecular Interactions in Thioanisoles p-RC6H4SCH3 . Russian Journal of General Chemistry 74, 74–82 (2004). https://doi.org/10.1023/B:RUGC.0000025172.49653.1f

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