A Metallacage Encapsulating Chloride as a Probe for a Solvation Scale in Ionic Liquids

With 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.


Published in:
INORGANIC CHEMISTRY, 46, 2, 403-408
Year:
2007
Other identifiers:
Laboratories:




 Record created 2007-01-17, last modified 2018-03-17


Rate this document:

Rate this document:
1
2
3
 
(Not yet reviewed)