Ab initio and density functional theory study of keto-enol equilibria of deltic acid in gas and aqueous solution phase: a bimolecular proton transfer mechanism

J Org Chem. 2012 Oct 5;77(19):8621-6. doi: 10.1021/jo301575c. Epub 2012 Sep 13.

Abstract

Keto-enol tautomerism in deltic acid (2,3-dihydroxycycloprop-2-en-1-one) has been studied using ab initio methods and the B3LYP functional of density functional theory, as well as complete basis set (CBS-QB3 and CBS-APNO) and G4 methods. Relative and absolute energies were calculated with each of the methods, whereas computations of geometries and harmonic frequencies for dihydroxycyclopropenone and hydroxycyclopropanedione were computed in the gas phase but were limited to HF, MP2, and the B3LYP functional, in combination with the 6-31++G(3df,3pd) basis set. Using the MP2/6-31++G(3df,3pd) gas phase optimized structure, each species was then optimized fully in aqueous solution by using the polarizable continuum model (PCM) self-consistent reaction field approach, in which HF, MP2, and B3LYP levels of theory were utilized, with the same 6-31++G(3df,3pd) basis set. In both gas and aqueous solution phases, the keto form is higher in energy for all of the model chemistries considered. From the B3LYP/6-31++G(3df,3pd) Gibbs free energy, the keto-enol tautomeric equilibrium constant for 2,3-dihydroxycycloprop-2-en-1-one/3-hydroxy-1,2-cyclopropanedione is computed to be K(T)(gas) = 2.768 × 10(-12) and K(T)(aq) = 5.469 × 10(-14). It is concluded that the enol form is overwhelmingly predominant in both environments.