Thermochemistry of arylselanyl radicals and the pertinent ions in acetonitrile.

Reduction and oxidation potentials of a series of parasubstituted phenylselanyl radicals, XC(6)H(4)Se(*), have been measured using photomodulated voltammetry in acetonitrile. The thermodynamic significance of these data was substantiated through a study of the oxidation process of the pertinent selenolates in linear sweep voltammetry. Both the reduction and the oxidation potentials correlate linearly with the Hammett substituent coefficients sigma and sigma(+) leading in the latter case to slopes, rho(+), of 2.5 and 3.8, respectively. Through comparison of these slopes with those published previously for the O- and S-centered analogues, it is revealed that the pi-interaction becomes progressively smaller as the size of the radical center increases in the order O, S, and Se. Solvation energies of the pertinent selenolates and selanylium ions have been extracted from thermochemical cycles incorporating the measured electrode potentials for XC(6)H(4)Se(*) as well as electron affinities and ionization potentials obtained from theoretical calculations at the B3LYP/6-31+G(d) level. The extracted data show the expected overall substituent dependency for both kinds of ions; that is, the absolute value of the solvation energy decreases as the charge becomes more delocalized. The data have also been compared with solvation energies computed using the polarizable continuum model (PCM). Interestingly, we find that, while the model seems to work well for selenolates, it underestimates the solvation of selanylium ions in acetonitrile by as much as 25 kcal mol(-)(1). These large deviations are ascribed to the fact that the PCM method does not take specific solvent effects into account as it treats the solvent as a continuum described solely by its dielectric constant. Gas-phase calculations show that the arylselanylium ions can coordinate covalently to one or two molecules of acetonitrile in strong Ritter-type adducts. When this strong interaction is included in the solvation energy calculations by means of a combined supermolecule and PCM approach, the experimental data are reproduced within a few kcal mol(-)(1). Although the energy difference of the singlet and triplet spin states of the arylselanylium ions is small for the gas-phase structures, the singlet cation is undoubtedly the dominating species in solution because the triplet cation lacks the ability to form covalent bonds.