Ion-dipole SN2 reaction in acetone-water mixtures. Electrostatic and specific solute-solvent interactions

The rate constants of the S(N)2 reaction of sodium 4-nitrophenoxide (1) and iodomethane were determined by UV-visible spectrophotometry in acetone-wat er mixtures at 25, 30, and 35 degreesC. The rate-X-water (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-water = 0.4, whereas the observed second-order rate constants k'(2) in creases again in the water-rich region. In pure acetone, in the presence of dicyclohexano-[18]-crown-6, k'(2) increases linearly with the concentratio n of the crown ether as a result of the complexation of the sodium ion (K-S = 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 sp ecies. Ion-pairing was also detected at X-water = 0.65 with a dissociation constant K-d = 7.82 x 10(-4) M-1. The solvatochromic behaviors of 2,6-diphe nyl-4-(2,4,6-triphenyl-1-pyridinio)-1-phenoxide (2), 4-[(1-methyl-4(1H)-pyr idinylidene)ethylidene]-2,5-cyclohexadien-1-one (3), and 1-methyl-8-oxy-qui nolinium betaine (4) were investigated in the entire range of acetone-water mixtures. The dyes presented an increasing order of hydrophilicity compati ble with their chemical structure, i.e., 2 < 3 < 4. Kinetic parameters for the methylation of 1 and the ET values of the dyes show a linear correlatio n of the polarity in the region of X-water = 1.0-0.40 for 3 and 4, and it w as observed that the more hydrophilic the dye the better the correlation co efficient, because of the structural similarity with 1. The activation para meter-X-water profile shows extrema at X-water < 0.4, reflecting an importa nt change in the structure of the Solvent that is responsible for the chang es in the solvation of the reactive species including ion-pairs. These resu lts suggest that the addition of water to acetone reduces abruptly the rate of substitution due to the preferential solvation (PS) of the phenoxide io n by the hydrogen-bonding donor (HBD) solvent. Nevertheless, the real secon d-order rate constant is "masked" by the association involving Na+ and 4-ni trophenoxide that extends even to water-rich mixtures. A model, based on th e assumption that the free-energy terms involved in the second-order rate c onstant and the dissociation constant of the ion-pair have two components, is invoked to explain the kinetic data. One of the components depends on el ectrostatic interactions for which the main variable is the dielectric cons tant of the solvent mixture, and the other depends on the specific solute-s olvent interactions, expressed by the activity coefficients of transfer of the species involved. The model indicates that in the range of X-water = 1. 0-0.40 the interactions are exclusively electrostatic, while for the rest o f the acetone-rich region they are specific with a large contribution of th e 4-nitrophenoxide ion.