Solvation of tetraalkylammonium chlorides in acetonitrile-water mixtures: mass spectrometry and molecular dynamics simulations

The salvation of tetromethylommonium chloride (Me4NCl) and tetra-n-butylommonium chloride (Bu4NCl) in water-acetonitrile mixtures was investigated by mass spectrometry of clusters isolated from the solution. As for as the positive ions ore concerned, clusters composed of alkylammonium ions and acetonitrile molecules only were observed, even for mixtures with high water content. In contrast, for the negative ions, clusters composed of chloride with both water and/or ocetonitrile molecules were observed. For the smaller system (Me4NCl) we performed quantum chemical calculations and molecular dynamics simulations. It was found that even though water is present in the salvation shelf of Me4N+ only acetonitrile has a strong electrostatic interaction with the cation. Water molecules around Me4N+ form hydrogen bonds with other water molecules, and they interact with Me4N+ mainly via dispersive interactions. These results indicate that Me4N+ behoves like a hydrophobic solute. On the other hand, the interaction of Cl- with water and acetonitrile is of comparable strength and, in both cases, the electrostatic interaction dominates. Herein we demonstrate experimentally and theoretically that positive and negative ions give rise to characteristic solvation structures in mixed solvents: even a relatively small organic cation, such as Me4N+, exhibits a hydrophobic-like salvation shell.