The effects of halogenation on the tautomeric and conformational equilibria of the model system 2-hydroxypyridine/2-pyridone have been investigated through chlorine substitution at positions 3, 4, 5, and 6. In the gas phase, the lactim syn-periplanar tautomer (OH ) was the predominant species for all compounds over the lactam form (C=O) and the less abundant anti-periplanar lactim (OH ). However, the population of the three species was shown to be dependent on the position of the chlorine substitution. Chlorination in position 5 or 6 strongly stabilizes the OH tautomer, whereas the C=O form has a significant population when the ring is chlorinated in positions 3 or 4. Overall, the OH form is the least favourable form, although the 3-substitution favours the population of this tautomer. In addition, the C=O tautomer is strongly stabilized in the solvent, which makes it the dominant form in some substituted species. This study has been performed by means of rotational spectroscopy in the gas phase and/or theoretical calculations in the isolated phase and in solution. Both the OH and C=O forms of 5-chloro-2-hydroxypyridine and the OH form of 6-chloro-2-hydroxypyridine were experimentally observed. All transitions displayed a complex nuclear hyperfine structure owing to the presence of the chlorine and nitrogen nuclei. For all species, a full quadrupolar hyperfine analysis has been performed. This has provided crucial information for the unambiguous identification of tautomers.
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