Abstract
Para-substituted phenoxide ions are characterized by a strong resonance interaction between the oxygen and the substituent when the substituent is electron-accepting. We have modeled these interactions by computing the minima of the electrostatic potential, Vmin, and the average local ionization energy, ĪS,min, near the unprotonated oxygens of para-substituted phenoxide ions. The calculations of Vmin and ĪS,min were carried out at different levels of theory using both ab initio and density functional methods. Vmin and ĪS,min have been found to correlate well with the empirical substituent constant, σp-. The calculated energy differences for the acidic dissociation of phenols and the corresponding experimental gas-phase acidities were found to agree very well. A close linear relationship was found between Vmin and the gas-phase acidities. The findings suggest that through-resonance is accounted for in our calculations and that Vmin and ĪS,min can be used as tools for predicting σp-.
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