Solvent effect on keto–enol tautomerism in a new β-diketone: a comparison between experimental data and different theoretical approaches

Abstract

The novel β-diketo compound (3-acetyl-4-oxopentanoic acid) OPAA is here synthesized and completely characterized in the solid state by means of X-ray crystallography and in solution by potentiometry and ¹H and ¹³C NMR spectroscopy. In the solid state, OPAA exhibits the di-keto (DK) structure, however, in solution, we can observe a strong solvent dependent tautomeric equilibrium. Theoretical ab initio calculations employing DFT at the B3LYP/6-311G** level, and different methods of theoretical model chemistry (CBS-4M, G3MP2, CBS-QB3) are used to extensively investigate the tautomeric equilibrium and compare it with experimental data. Solvent effects are evaluated using a CPCM continuum solvation method; among all applied methods, CBS-4M is the one that better predicts experimental data and is able to qualitatively describe tautomeric equilibrium in solution, allowing thermodynamic calculations of pK_a. Furthermore a supermolecular solvent approach is used to better analyze solvent–solute interactions in order to predict chemical properties.