Journal of Structural Chemistry

, Volume 59, Issue 6, pp 1276–1287 | Cite as

A Quantum Chemical Study of Various Intramolecular Hydrogen Bonds in 4-Amino-3-Pentene-2-Thial

  • M. PoorsargolEmail author
  • H. S. Delarami


B3LYP and MP2 methods with the most popular basis set, 6-311++G(d,p) are applied to optimize the equilibrium conformers of 4-amino-3-pentene-2-thial. Furthermore, to have more reliable energies, the total electron energies of all forms are recomputed at the CBS-4M level of theory. A theoretical investigation of the equilibrium conformers clearly shows that various intramolecular hydrogen bonds (IHBs) such as N–H...S, S–H...N, S–H...π, C–H...N, and C–H...S are the most effective factors in the conformational preference of thialamine, thiolimine, and thialimine groups. Hence, the IHB strengths are evaluated in various resonance-assisted hydrogen bond systems by geometrical factors, topological parameters, and charge transfers corresponding to orbital interactions. Also, the solvent effect on the IHB strength is considered using Tomasi′s PCM. Our results in the gas phase reveal that the thialamine group has extra stability with respect to thiolimine and thialimine ones. The population analyses of all the possible conformers by the NBO method predict that the origin of this tautomeric preference is mainly due to more significant π electron delocalization in the framework of thialamine forms, especially πC=C → π C = S* and Lp(N) → π C = C* charge transfers. Moreover, the excited state properties of IHBs in these systems are investigated theoretically using the time-dependent DFT method.


4-amino-3-pentene-2-thial intramolecular hydrogen bond resonance AIM NBO 


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  1. 1.
    L. A. Allison, J. Keddington, and R. E. Shoup. J. Liq. Chromatogr., 1983, 6, 1785–1798.CrossRefGoogle Scholar
  2. 2.
    G. Yamashita and D. Rabenstein. J. Chromatogr., 1989, 491, 341–354.CrossRefGoogle Scholar
  3. 3.
    Y. Sun, D. L. Smith, and R. E. Shoup. Anal. Biochem., 1991, 197, 69–76.CrossRefGoogle Scholar
  4. 4.
    M. Cappiello, P. G. Vilardo, V. Micheli, et al. Exp. Eye. Res., 2000, 70, 795–803.CrossRefGoogle Scholar
  5. 5.
    W. L. Banwart and J. M. Bremner. Soil. Biol. Biochem., 1975, 7, 359–364.CrossRefGoogle Scholar
  6. 6.
    J. Terpinski and J. Dabrowski. J. Mol. Struct., 1969, 4, 285–291.CrossRefGoogle Scholar
  7. 7.
    S. F. Tayyari, M. Fazli, and F. Milani–nejad. J. Mol. Struct. (THEOCHEM.), 2001, 541, 11–15.CrossRefGoogle Scholar
  8. 8.
    A. Nowroozi, H. Raissi, and F. Farzad. J. Mol. Struct. (THEOCHEM.), 2005, 730, 161–169.CrossRefGoogle Scholar
  9. 9.
    I. Jimenez–Fabian, A. F. Jalbout, E. Moshfeghi, et al. Int. J. Quan. Chem., 2008, 108, 383–390.CrossRefGoogle Scholar
  10. 10.
    H. Raissi, A. F. Jalbout, M. Fazli, et al. Int. J. Quan. Chem., 2009, 109, 1497–1504.CrossRefGoogle Scholar
  11. 11.
    A. Nowroozi, M. Sheibaninia, H. Roohi, et al. Int. J. Quan. Chem., 2011, 111, 586–595.CrossRefGoogle Scholar
  12. 12.
    A. Nowroozi, H. Roohi, M. Poorsargol, et al. Int. J. Quan. Chem., 2011, 111, 3008–3016.CrossRefGoogle Scholar
  13. 13.
    M. Shahabi, H. Raissi, and F. Mollania. Struct. Chem., 2015, 26, 491–506.CrossRefGoogle Scholar
  14. 14.
    G. Gilli and P. Gilli. The Nature of Hydrogen Bond. Oxford: Oxford University, Press, 2009.CrossRefGoogle Scholar
  15. 15.
    P. Sanz, O. Mό, M. Yáñez, et al. ChemPhysChem., 2007, 8, 1950–1958.CrossRefGoogle Scholar
  16. 16.
    I. Alkorta, J. Elguero, O. Mό, et al. Mol. Phys., 2004, 102, 2563–2574.CrossRefGoogle Scholar
  17. 17.
    G. J. Zhao and K. L. Han. Acc. Chem. Res., 2012, 45, 404–413.CrossRefGoogle Scholar
  18. 18.
    G. Zhao, F. Yu, M. Zhang, et al. J. Phys. Chem. A, 2011, 115, 6390–6393.CrossRefGoogle Scholar
  19. 19.
    A. E. Reed, L. A. Curtis, and F. A. Weinhold. Chem. Rev., 1988, 88, 899–926.CrossRefGoogle Scholar
  20. 20.
    R. F. W. Bader. Atoms in Molecules: A Quantum Theory. Clarendon, Oxford, 1990.Google Scholar
  21. 21.
    M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al. Gaussian 03 Program Package. Gaussian, Inc, Pittsburgh, 2003.Google Scholar
  22. 22.
    E. D. Glendening, A. E. Reed, J. E. Carpenter, et al. NBO Version 3.1, Theoretical Chemistry Institute and Department of Chemistry. Madison, Wisconsin: University of Wisconsin, 1995.Google Scholar
  23. 23.
    M. Cossi, V. Barone, and J. Cammi. Chem. Phys. Lett., 1996, 255, 327–335.CrossRefGoogle Scholar
  24. 24.
    S. Miertus, E. Scrocco, and J. Tomasi. Chem. Phys., 1981, 55, 117–129.CrossRefGoogle Scholar
  25. 25.
    P. Schuster and G. Zundel. The Hydrogen Bond, Recent Development in Theory and Experiment. Nourth–Holland, Amesterdam, 1976.Google Scholar
  26. 26.
    I. Rozas, I. Alkorta, and J. Elguero. J. Phys. Chem. A, 2001, 105, 10462–10467.CrossRefGoogle Scholar
  27. 27.
    E. Espinosa and M. Molins. J. Chem. Phys., 2000, 113, 5686–5694.CrossRefGoogle Scholar
  28. 28.
    M. Jablonski, A. Kaczmarek, and A. J. Sadlej. J. Phys. Chem. A, 2006, 110, 10890–10898.CrossRefGoogle Scholar
  29. 29.
    G. Buemi and F. Zuccarello. J. Mol. Struct. (THEOCHEM.), 2002, 581, 71–85.CrossRefGoogle Scholar
  30. 30.
    A. Nowroozi. PhD thesis. Mashhad, Iran: Ferdowsi University, 2002.Google Scholar
  31. 31.
    E. Espinosa, E. Molins, and C. Lecomte. Chem. Phys. Lett., 1998, 285, 170–173.CrossRefGoogle Scholar
  32. 32.
    E. Espinosa, M. Souhassou, H. Lachekar, et al. Acta Crystallogr. B, 1999, 55, 563–572.CrossRefGoogle Scholar
  33. 33.
    H. S. Biswal and S. J. Wategaonkar. Phys. Chem. A, 2009, 113, 12763–12773.CrossRefGoogle Scholar
  34. 34.
    P. V. R. Schleyer. Chem. Rev., 2005, 105, 3433–3435.CrossRefGoogle Scholar
  35. 35.
    T. M. Krygowski and M. K. Cyranski. Chem. Rev., 2001, 101, 1385–1420.CrossRefGoogle Scholar
  36. 36.
    S. J. Grabowski. J. Phys. Org. Chem., 2003, 16, 797–802.CrossRefGoogle Scholar

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© Pleiades Publishing, Ltd. 2018

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of ScienceUniversity of ZabolZabolIran

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