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Capillary electrophoresis of boron cluster compounds in aqueous and nonaqueous solvents

Valeri, Anna Lucia, Kremser, Leopold, Raggi, Maria Augusta, Grüner, Bohumir, Vespalec, Radim, Kenndler, Ernst
Electrophoresis 2008 v.29 no.8 pp. 1658-1666
acetates, acetic acid, anions, boron, capillary electrophoresis, cobalt, hydrodynamics, ionic strength, methanol, pH, perchloric acid, solvents, viscosity
The electrophoretic properties of boron cluster compounds were determined in water, methanol and ACN as solvents of the BGE and discussed based on the principles of ion migration. Two types of boron cluster compounds were investigated. One type consisted of derivatives of the nido-7,8-dicarbaundecaborate cluster, the other types are derivatized cobalt bis(dicarbollide) ions (COSANs) whose central cobalt atom is sandwiched by two 7,8-dicarbaundecaborate clusters. The BGE in all solvents was acetate/acetic acid buffer with pH 4.75 in water, 9.7 in methanol and 22.3 in ACN, respectively, at different ionic strength between 5 and 30 mM. The dependence of the mobility on ionic strength could not be explained by the theory of Debye, Hückel and Onsager, but good agreement was found upon considering an ion size parameter. Limiting mobilities were derived by curve fitting, and by the aid of the solvent viscosities the hydrodynamic radii of the analyte anions were calculated. They are between 0.25 and 0.48 nm, and were nearly independent of the solvent. Electrophoresis of the analytes in a BGE consisting of 6 mM perchloric acid in ACN allows the conclusion that the present boron cluster compounds behave as stronger acids than perchloric acid.