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Energetic, structural and tautomeric analysis of 2-mercaptobenzimidazole

An experimental and computational approach

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Abstract

This paper reports an experimental and theoretical study about the energetic and structural characteristics of the 2-mercaptobenzimidazole (MBI) tautomeric forms (thione and thiol). The standard (p° = 0.1 MPa) molar enthalpy of formation, at T = 298.15 K, in the gaseous phase, for MBI was derived from its enthalpies of combustion and sublimation, obtained by rotating-bomb calorimetry and by the Knudsen effusion technique, respectively. The results are compared with the corresponding data for MBI thione/thiol tautomers calculated by the G3(MP2)//B3LYP approach that suggest the thione form as the preferred form of MBI in gaseous phase. Computationally, the molecular structures of both tautomers were established and the geometrical parameters were determined at the B3LYP/6-31G(d) level of theory. In addiction, the G3(MP2)//B3LYP tautomerization energy at 0 K for thione/thiol forms of MBI was calculated and also evidences that the tautomeric equilibrium favours the thione tautomer. The standard Gibbs energy of formation in crystalline and gaseous phases was also derived, allowing an analysis of the thermodynamic stability of MBI in comparison with other related compounds.

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Acknowledgements

This work was supported by the Foundation for Science and Technology (FCT) of Portugal, Project UID/QUI/UI0081/2013, and FEDER, Projects POCI-01-0145-FEDER-006980 and NORTE-01-0145-FEDER-000028. ALRS thanks FCT for the award of a Ph.D. Grant (SFRH/BD/69606/2010).

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  1. Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 687, 4169-007, Porto, Portugal

    Ana L. R. Silva & Maria D. M. C. Ribeiro da Silva

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  1. Ana L. R. Silva
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Correspondence to Maria D. M. C. Ribeiro da Silva.

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Silva, A.L.R., Ribeiro da Silva, M.D.M.C. Energetic, structural and tautomeric analysis of 2-mercaptobenzimidazole. J Therm Anal Calorim 129, 1679–1688 (2017). https://doi.org/10.1007/s10973-017-6353-x

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