Substituent effects on the acidity of weak acids. 3. Phenols and benzyl alcohols

The gas-phase acidities of meta- and para-substituted phenols have been calculated at the B3LYP/6-311+G, MP2/6-311+G, MP2/6-311++G, and MP2/6-311+G(2df,2pd) theoretical levels. The larger basis sets give the more satisfactory DeltaHacid values that are correlated with the observed acidities with a slope close to unity. They are systematically about 2 kcal/mol too small. The acidities of most substituted phenols are linearly related to those of the corresponding substituted benzoic acids and benzyl alcohols. Here, the substituent effect is a Coulombic interaction (field effect) of the distributed charge in the benzene ring with the negative charge of the anionic center. The exceptions are strong para-substituted pi-acceptors such as NO(2) and CHO, and to a smaller extent, CN and CF(3). Here there is direct charge transfer from the phenoxide oxygen to the substituent.