Tautomerism of Neutral α-Tropolone and its Protonated and Deprotonated Forms

Abstract

Abstract Possible structures of α-tropolone (2-hydroxy-2,4,6-cycloheptatrien-1-one) tautomers: four neutral, thirteen protonated, and four deprotonated, are studied at the B3LYP/6-311++G∗∗ computational level. The energies and the free energies calculated for the studied tautomers show that for each of the three forms, among all the possible tautomers in the tautomeric mixture, only one structure is expected: a keto-enol structure with an intramolecular hydrogen bond (neutral α-tropolone molecule), the structure with two deprotonated exocyclic oxygen atoms (tropolonate, deprotonated tropolone), and the structure with two hydroxyl group forming an intramolecular hydrogen bond (protonated tropolone). The relative energies of the studied tautomers are rationalized based on the results from the atomic energy integration performed within the frame of the Quantum Theory of Atoms in Molecules.