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Solvation of Tetraalkylammonium Chlorides in Acetonitrile–Water Mixtures: Mass Spectrometry and Molecular Dynamics Simulations
Author(s) -
Saielli Giacomo,
Scorrano Gianfranco,
Bagno Alessandro,
Wakisaka Akihiro
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500050
Subject(s) - solvation , acetonitrile , chemistry , solvation shell , molecule , chloride , hydrogen bond , tetramethylammonium , ion , molecular dynamics , inorganic chemistry , mass spectrometry , computational chemistry , organic chemistry , chromatography
The solvation of tetramethylammonium chloride (Me 4 NCl) and tetra‐ n ‐butylammonium chloride (Bu 4 NCl) in water–acetonitrile mixtures was investigated by mass spectrometry of clusters isolated from the solution. As far as the positive ions are 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 acetonitrile molecules were observed. For the smaller system (Me 4 NCl) we performed quantum chemical calculations and molecular dynamics simulations. It was found that even though water is present in the solvation shell of Me 4 N + , only acetonitrile has a strong electrostatic interaction with the cation. Water molecules around Me 4 N + form hydrogen bonds with other water molecules, and they interact with Me 4 N + mainly via dispersive interactions. These results indicate that Me 4 N + behaves 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 Me 4 N + , exhibits a hydrophobic‐like solvation shell.