Solvent Effects on Homolytic Bond Dissociation Energies of Hydroxylic Acids

The homolytic bond dissociation energies (BDEs) of the O−H bonds in DMSO solution for (a) phenol and a number of its derivatives, (b) three oximes, (c) three alcohols, (d) three hydroxylamines, and (e) two hydroxamic acids have been estimated by eq 1: BDEHA = 1.37pKHA + 23.1Eox(A-) + 73.3 kcal/mol. For most of these hydroxylic acids, the BDEs of the O−H bonds estimated by eq 1 are within ±2 kcal/mol of the literature values in nonpolar solvents or in the gas phase. There is no reason to believe, therefore, that these BDEs are “seriously in error because of failure to correct for solvent effects” as has been claimed on the basis that BDEs in highly polar solvents estimated for the O−H bond in phenol by photoacoustic calorimetry must be so corrected.