Reactivity of Rare-Earth Oxides in Anhydrous Imidazolium Acetate Ionic Liquids

Rare-earth metal sesquioxides (RE2O3) are stable compounds that require high activation energies in solid-state reactions or strong acids for dissolution in aqueous media. Alternatively, dissolution and downstream chemistry of RE2O3 have been achieved with ionic liquids (ILs), but typically with additional water. In contrast, the anhydrous IL 1-butyl-3-methylimidazolium acetate [BMIm][OAc] dissolves RE2O3 for RE = La-Ho and forms homoleptic dinuclear metal complexes that crystallize as [BMIm](2)[RE2(OAc)(8)] salts. Chloride ions promote the dissolution without being included in the compounds. Since the lattice energy of RE2O3 increases with decreasing size of the RE3+ cation, Ho2O3 dissolves very slowly, while the sesquioxides with even smaller cations appear to be inert under the applied conditions. The Sm and Eu complex salts show blue and red photoluminescence and Van Vleck paramagnetism. The proton source for the dissolution is the imidazolium cation. Abstraction of the acidic proton at the C-2-atom yields an N-heterocyclic carbene (imidazole-2-ylidene). The IL can be regenerated by subsequent reaction with acetic acid. In the overall process, RE2O3 is dissolved by anhydrous acetic acid, a reaction that does not proceed directly.

Automated summary

Rare-earth metal sesquioxides (RE2O3) are stable compounds that require high activation energies or strong acids for dissolution. However, these compounds can be dissolved and processed with anhydrous ionic liquid [BMIm][OAc]. The dissolution is promoted by chloride ions and results in the formation of homoleptic dinuclear metal complexes. Photoluminescence and paramagnetism are observed in the complex salts of Sm and Eu.