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Quantum chemical investigation of intramolecular thione-thiol tautomerism of 1,2,4-triazole-3-thione and its disubstituted derivatives

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Abstract

The one step intramolecular thione-thiol tautomerism of 1,2,4-triazole-3-thione and its disubstituted derivatives has been studied through the use of electronic structure methods. Due to the absence of experimental data for the parent molecule of 1,2,4-triazole-3-thione the structure and energetics of aforementioned tautomers were derived using various basis sets and levels including HF, B3LYP, and MP2 methods. The gas phase results show that in all different levels of theory the most stable tautomer is the thione form. It has also been revealed that B3LYP/6-31G(d,p) level is quite well suited and reliable to investigate these kinds of tautomerism. To account the influence of substituents on the mentioned tautomerization, the tautomerism and conformational properties as well as vibrational analysis of 20 halophenyl and isopyridyl derivatives were investigated using B3LYP/6-31G(d,p) calculations. In all cases the calculations indicate that substituents have no considerable effects on relative stabilities and energy barriers for the thione-thiol proton transfer and the thione forms are the predominant species in the gas phase. In order to figure out the relative stabilities of the species involved in the tautomerism, geometrical and natural bond orbital (NBO) analyses have been employed. It has also been shown that the computed vibrational frequencies of tautomers with different scaling factors could be used to interpret the vibrational frequencies in IR spectrum of similar species.

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Acknowledgments

We are grateful to Professor Seik Weng Ng for making his software (G98W) and hardware (machine time) facilities available to us. The financial support of the Research Councils of Shahid Beheshti University is also gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, Shahid Beheshti University, G.C., Evin, 19839-6313, Tehran, Iran

    Mehdi D. Davari, Homayoon Bahrami, Zahra Zolmajd Haghighi & Mansour Zahedi

Authors
  1. Mehdi D. Davari
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  2. Homayoon Bahrami
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  3. Zahra Zolmajd Haghighi
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  4. Mansour Zahedi
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Correspondence to Mansour Zahedi.

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ESM 1

The calculated average errors in bond distances and bond angles of 2,4-dihydro-3H-5-phenyl-4-amino-1,2,4-triazole-3-thione as well as vibrational frequency of disubstituted derivatives have been supplied in Tables T1-T19 (DOC 456 kb)

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Davari, M.D., Bahrami, H., Haghighi, Z.Z. et al. Quantum chemical investigation of intramolecular thione-thiol tautomerism of 1,2,4-triazole-3-thione and its disubstituted derivatives. J Mol Model 16, 841–855 (2010). https://doi.org/10.1007/s00894-009-0585-z

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  • DOI: https://doi.org/10.1007/s00894-009-0585-z

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