Structural Chemistry

, Volume 26, Issue 3, pp 639–645 | Cite as

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

Original Research

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.

Keywords

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

Supplementary material

11224_2015_581_MOESM1_ESM.doc (7.2 mb)
Supplementary material 1 (DOC 7348 kb)

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Marta Marín-Luna
    • 1
    • 2
  • Ibon Alkorta
    • 1
  • José Elguero
    • 1
  1. 1.Instituto de Química Médica (CSIC)MadridSpain
  2. 2.MurciaSpain

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