Theoretical ab initio calculations are performed to provide support for our hypothesis that the gas phase ratio of the 2-hydroxypyridine/2(1H)-pyridinone tautomers results from the thermodynamic equilibrium which exists between cyclic hydrogen-bonded oxo-oxo and hydroxy-hydroxy dimers. We therefore, disprove the monomolecular mechanism of the tautomerization process, which has frequently been assumed in the past to estimate the free energy difference between the monomeric tautomers based on the experimentally determined tautomer ratio.
ASJC Scopus subject areas
- Condensed Matter Physics
- Physical and Theoretical Chemistry