Daguenet, CDyson, PJ2007-01-172007-01-172007-01-17200710.1021/ic060631fhttps://infoscience.epfl.ch/handle/20.500.14299/239506WOS:0002434847000169993With the purpose of assessing the reactivity of chloride ions dissolved in ionic liquids (ILs), a relative scale for the solvation of chloride is given for a series of ILs based on the bis(trifluoromethane)sulfonimide ([Tf<SUB>2</SUB>N]) anion and different cations, 1-butyl-3-methylimidazolium ([bmim]), 1-butyl-2,3-dimethylimidazolium ([bdmim]), 1-butyl-1-methylpyrrolidinium ([bmpy]), 1-butylpyridinium ([bpy]), 1-pentyl-1,1,1-triethylammonium ([C<SUB>5</SUB>e<SUB>3</SUB>am]), and 1-(2-hydroxy)ethyl-3-methylimidazolium ([mimeOH]). Insights into the solvation of chloride are achieved by the thermodynamic study of the reaction of dissociation of a chloride-templated nickel(II) metallacage performed at various temperatures by UV-visible spectroscopy in each IL. The order of chloride solvation [C<SUB>5</SUB>e<SUB>3</SUB>am][Tf<SUB>2</SUB>N] &lt; [bmpy][Tf<SUB>2</SUB>N] &lt; [bmim][Tf<SUB>2</SUB>N] &le; [bdmim][Tf<SUB>2</SUB>N] &lt; [bpy][Tf<SUB>2</SUB>N] &lt;&lt; [mimeOH][Tf<SUB>2</SUB>N] was ascertained from the reaction enthalpies determined in the different ILs. The reaction entropies display a concentration-dependent behavior, which has highlighted a correlated motion of the ions in these ILs.text::journal::journal article::research article