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The influence of halogen bonds on tautomerism: the case of 3-mercapto-1,2-azoles (pyrazoles, isoxazoles, isothiazoles)

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Abstract

DFT calculations at the B3LYP/6-311++G(d,p) computational level have been carried out on three tautomeric pairs of 3-mercapto-1,2-azoles (pyrazoles, isoxazoles, and isothiazoles) to study the effect of halogen bonds (XBs) on the position of the equilibrium. As halogen bond donors, we have selected Br2, Cl2, BrCl, ClF and BrF and compare them with HF as a hydrogen bond donor. Several linear relationships were found between binding energies of different halogen bond donors. The main conclusion of this study is that the XB inverts the tautomeric equilibrium while an HB does not.

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Acknowledgments

This work has been supported by the Spanish Ministerio de Economía y Competitividad (CTQ2012-35513-C02-02) and Comunidad Autónoma de Madrid (S2013/MIT-2841, Fotocarbon). Computer, storage, and other resources from the CTI (CSIC) are gratefully acknowledged. One of us (M.M.-L.) benefits from a contract from the Ministerio de Economía y Competitividad.

Conflict of interest

The authors declare no conflict of interest.

Author information

Correspondence to Ibon Alkorta.

Additional information

Marta Marín-Luna was on leave from Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain.

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Marín-Luna, M., Alkorta, I. & Elguero, J. The influence of halogen bonds on tautomerism: the case of 3-mercapto-1,2-azoles (pyrazoles, isoxazoles, isothiazoles). Struct Chem 26, 639–645 (2015). https://doi.org/10.1007/s11224-015-0581-0

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Keywords

  • Tautomerism
  • Halogen bonds
  • Molecular electrostatic potentials
  • Binding energies
  • Stabilizing charge-transfer energies