Computational study of the intramolecular proton transfer between 6-hydroxypicolinic acid tautomeric forms and intermolecular hydrogen bonding in their dimers

Abstract

This paper is a density functional theory (DFT) calculation of intramolecular proton transfer (IPT) in 6-hydroxypicolinic acid (6HPA, 6-hydroxypyridine-2-carboxylic acid) tautomeric forms. The transition state for the enol-to-keto transition is reported in the gas phase and in four different solvents. The planar and non-planar dimer forms of 6HPA keto and enol, respectively, were also studied in the gas phase The IPT reactions and dimerization processes were studied at the B3LYP/6-31++G(d) level of the theory. The influence of the solvent on the tautomerization reaction of 6HPA was examined using the conductor-polarizable continuum model (CPCM). The IPT reaction in the gas phase is almost the same as in solution. The calculated dimerization energies show that the stability of 6HPA tautomer dimer structures is directly affected by the distance of intermolecular hydrogen bonding and electrostatic potential (ESP) value in the tautomer dimer.