Ion solvation in 3-methyl-2-oxazolidone

Abstract

In continuing previous studies of the solvation behavior of electrolytes in nonaqueous media, a series of tetraalkylammonium tetraphenylborates, cesium and rubidium tetraphenylborates, tetraalkylammonium perchlorates, and tetraphenylarsonium chloride were investigated by proton magnetic resonance spectroscopy in 3-methyl-2-oxazolidone, a solvent with high dielectric constant, high polarity, and wide liquid range. In this study, as in a previous investigation, it was found that salt solutions containing the tetraphenylborate anion were found to shift the proton peaks upfield, indicating an increase in electron density around solvent protons. In this study the same effect has been noted for tetraphenylborate as well as tetraphenylarsonium ion and is attributed to the large diamagnetic anisotropy of the aromatic solute molecules which results in circulation of π electrons induced by the magnetic field. This ring current causes shielding of the solvent protons, and the shielding increases as the concentration of aromatic solute increases, resulting in upfield morement of chemical shift irrespective of whether the aromatic moiety is the cation or anion.