Fluoride Affinities of Perfluorobenzenes C6F5X. Meisenheimer Complexes in the Gas Phase and Solution

Article abstract of DOI:10.1021/ja00223a001

Measurements of gas phase fluoride transfer equilibria lead to ΔG^o and ΔH^o for the reaction F^- + C6F5X = <*> where the substituents X of the perfluorobenzenes are F, H, CF3, COCH3, CN, and NO2.The relative energy changes are found to lead to an approximately linear correlation with the electron affinities of C6F5X.The gas-phase ΔG^o and ΔH^o data are used in combination with rate measurements in solution from the literature for a comparison of the reaction coordinates in the gas phase and solution and for determinations of the solvation energy of the transition state occuring in solution.