Linear solvation energy relations

Solvents have been parameterized by scales of dipolarity/polarizability π*, hydrogen-bond donor (HBD) strength α, and hydrogen-bond acceptor strength β. Linear dependence (LSER's) on these solvent parameters are used to correlate and predict a wide variety of solvent effects, as well as to provide an analysis in terms of knowledge and theoretical concepts of molecular structural effects. Some recent applications utilizing this approach are presented. Included are analyses of solvent effects on (a) the free energies of transfer of tetraalkylammonium halide ion pairs and dissociated ions, (b) rates of nucleophilic substitution reactions, (c) the contrast in solvent effects of water (HBD) and dimethyl sulfoxide (non-HBD) on the acidities of m- and p-substituted phenols, (d) partition coefficients of non-HBD solutes between solvent bilayers, and (e) family relationships between proton transfer (and non-protonic Lewis acid) basicities and corresponding β values for monomer HBA. A comprehensive summary of LSER with references is given. © 1985 Plenum Publishing Corporation.