Ion-dipole S2 reaction in acetone - Water mixtures. Electrostatic and specific solute - Solvent interactions

The rate constants of the S2 reaction of sodium 4-nitrophenoxide (1) and iodomethane were determined by UV - visible spectrophotometry in acetone - water mixtures at 25, 30, and 35 °C. The rate - X (mole fraction of water) profile shows that the reaction depends strongly on the medium. The fastest rate constant was obtained in pure acetone, and a minimum occurred at X = 0.4, whereas the observed second-order rate constants k′ increases again in the water-rich region. In pure acetone, in the presence of dicyclohexano-[18]-crown-6, k′ increases linearly with the concentration of the crown ether as a result of the complexation of the sodium ion (K = 104.8 M) of the ion-pair and the increase in the effective concentration of free 4-nitrophenoxide ion, which was assumed to be the only reactive species. Ion-pairing was also detected at X = 0.65 with a dissociation constant K = 7.82 × 10 M. The solvatochromic behaviors of 2,6-diphenyl-4-(2,4,6triphenyl-1-pyridinio)-1-phenoxide(2),4- [(1-methyl-4(1H)-pyridinylidene)ethylidene]-2,5-cyclohexadien-1-one (3), and 1-methyl-8-oxy-quinolinium betaine (4) were investigated in the entire range of acetone - water mixtures. The dyes presented an increasing order of hydrophilicity compatible with their chemical structure, i.e., 2 < 3 < 4. Kinetic parameters for the methylation of 1 and the E values of the dyes show a linear correlation of the polarity in the region of X = 1.0-0.40 for 3 and 4, and it was observed that the more hydrophilic the dye the better the correlation coefficient, because of the structural similarity with 1. The activation parameter - X profile shows extrema at X < 0.4, reflecting an important change in the structure of the solvent that is responsible for the changes in the solvation of the reactive species including ion-pairs. These results suggest that the addition of water to acetone reduces abruptly the rate of substitution due to the preferential solvation (PS) of the phenoxide ion by the hydrogen-bonding donor (HBD) solvent. Nevertheless the real second-order rate constant is "masked" by the association involving Na and 4-nitrophenoxide that extends even to water-rich mixtures. A model, based on the assumption that the free-energy terms involved in the second-order rate constant and the dissociation constant of the ion-pair have two components, is invoked to explain the kinetic data. One of the components depends on electrostatic interactions for which the main variable is the dielectric constant of the solvent mixture, and the other depends on the specific solute - solvent interactions, expressed by the activity coefficients of transfer of the species involved. The model indicates that in the range of X = 1.0-0.40 the interactions are exclusively electrostatic, while for the rest of the acetone-rich region they are specific with a large contribution of the 4-nitrophenoxide ion.