Computational Study on the Bond Dissociation Enthalpies in the Enolic and Ketonic Forms of β-Diketones:  Their Influence on Metal−Ligand Bond Enthalpies

A computational study on the thermodynamic properties of 13 β-diketones is presented. The B3LYP//6-311+G(2d,2p)//B3LYP/6-31G(d) theoretical approach was employed to compute the O−H and C−H bond dissociation enthalpies and enthalpy of tautomerization and to estimate standard gas-phase enthalpies of formation for the radicals and for the parent molecules. The gas-phase enthalpies of formation for the neutral molecules are in excellent agreement with available experimental data, supporting the estimates made for the radicals. The latter are very important for the clarification of the thermochemistry of many β-diketonato metal complexes previously reported in the literature. Importantly, when substituents R = −CHR‘ are attached to the β-diketone's scaffold, C−H homolytic bond cleavage is always favored with respect to O−H bond scission.