title: Anion partitioning and ion-pairing behavior of anions in the extraction of cesium salts by 4,5' '-Bis(tert-octylbenzo)dibenzo-24-crown-8 in 1,2-dichloroethane.
abstract: A systematic study of anion partitioning and ion pairing was performed for an extraction of individual cesium salts into 1,2-dichloroethane (1,2-DCE) using 4,5' '-bis(tert-octylbenzo)dibenzo-24-crown-8 as the cesium receptor. Equilibrium constants corresponding to the extraction of ion pairs and dissociated ions, formation of the 1:1 cesium/crown complex (confirmed by electrospray mass spectrometry), and dissociation of the ion pairs in water-saturated 1,2-DCE at 25 degrees C were obtained from equilibrium modeling using the SXLSQI program. The standard Gibbs energy of partitioning between water and water-saturated 1,2-DCE was determined for picrate, permanganate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, and acetate anions. The dissociation of the organic-phase complex ion pair [Cs(4,4' '-bis(tert-octylbenzo)dibenzo-24-crown-8]+NO3- observed in the extraction experiments was shown to be consistent with the dissociation constant determined independently by conductance measurements. As attributed to the large effective radius of the complex cation, the evident anion discrimination due to ion pairing in the 1,2-DCE phase was relatively small, by comparison only a tenth of the discrimination exhibited by the anion partitioning. Only chloride and picrate exhibit evidence for significantly greater-than-expected ion-pairing tendency. These results provide insight into the inclusion properties of the clefts formed by opposing arene rings of the crown ether upon encapsulation of the Cs+ ion, whose weak anion recognition likely reflects the preferential inclusion of 1,2-DCE molecules in the clefts. Observed anion extraction selectivity in this system, which may be ascribed predominantly to solvent-induced Hofmeister bias selectivity toward large charge-diffuse anions, was nearly the same whether cesium salts were extracted as dissociated ions or ion pairs.
authors.affiliation: Chemical Sciences Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37830-6119, USA.
authors.forename: Tatiana G
authors.initials: TG
authors.lastname: Levitskaia
authors.forename: Leon
authors.initials: L
authors.lastname: Maya
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Van Berkel
authors.forename: Bruce A
authors.initials: BA
authors.lastname: Moyer