The enthalpy of formation of the pentane-2,4-dionate radical: A complete basis set approach

Abstract

Thermochemical properties of pentane-2,4-dione (acetylacetone, Hacac) and its radical (acac) were investigated by DFT and ab initio calculations based on complete basis set (CBS) extrapolation procedures, including CBS-QB3 and a modified CBS procedure that we named CBS-QB3-tz. We provide evidence that the most stable acac radical conformer is generated by C–H bond homolysis. The enthalpy of formation of gaseous acac, Δ f H ∘(acac,g), was estimated as −228.3 kJ/mol (CBS-QB3) and −226.7 kJ/mol (CBS-QB3-tz). Based on these results, our recommended value for Δ f H ∘(acac,g) is −227 ± 8 kJ/mol, implying that many literature values reported for metal–acac bond dissociation enthalpies in coordination complexes should be revised.