Chloroaluminate ionic liquids as reagents for isolating soluble hexanuclear zirconium halide cluster compounds

Ambient-temperature chloroaluminate molten salts, mixtures of aluminum trichloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride (ImCl), have been used as solvents to excise and isolate centered hexanuclear zirconium halide clusters from their solid-state precursors. Cluster compounds synthesized via high-temperature reactions, KZr6CCl15 and Li2Zr6MnCl15, were dissolved into basic molten salts at 100-110 degrees C The C-centered cluster compound, Im(4)Zr(6)CCl(18), was isolated in 70% yield, and the Mn-centered cluster compound, Im(5)Zr(6)MnCl(18) C7H8. 2CH(3)CN, was isolated in 54% yield. Im(5)Zr(6)BCl(18) is efficiently oxidized by ferrocenium tetrafluoroborate, and one-electron-oxidized B-centered cluster, [(Zr6B)Cl-18](4-), was isolated in 90% yield as the salt Im(4)Zr(6)BCl(18).