Interaction of dodecaborate cluster compounds on hydrophilic column materials in water

The interaction of a series of dodecaborate cluster compounds B12X122− and B12X11Y2− (X = H, Cl, Br, I and Y = SH, OH, NR3) with hydrophilic column materials (Superdex 200, Sepharose 4B, Sephadex G-50, Sephadex G-100, alumina, silica gel and anion exchange material) was studied. Almost all the dodecaborate cluster compounds were retained strongly on Superdex 200. The halogenated cluster compounds interacted with Sepharose 4B, Sephadex G-50, Sephadex G-100 and alumina; on alumina, also the non-halogenated clusters were retained. Silica gel showed the least interaction with all compounds. The thermodynamic parameters were investigated for a selection of compounds on Superdex 200 and Sephadex G-100. Values for ΔH° were found to be negative on both gels. As the change in entropy ΔS° was also negative, it compensated ΔH° to a large extent. The clusters interacted also strongly with anion exchange material in ion chromatography; the interaction decreased with increasing acetonitrile concentration, implying a large contribution from solvent effects.

► Dodecaborate clusters are retained on hydrophilic matrices used for gel filtration.
► Interaction is driven by enthalpy, with entropy partly counter-acting the affinity.
► With alumina as matrix, retention is observed for some of the clusters.
► Silica retains the clusters the least, Superdex 200 the strongest.
► The phenomenon might be used to separate different dodecaborate clusters.