Hydroxometalates from anion exchange reactions of [BF4]−based ionic liquids: Formation of [M(OH)6)]2−(M = Ti, Zr) and [Zr(OH)5]−

The hydrolysis reactions of Ti(OiPr)4in the presence of different ionic liquids using ethanol as solvent were investigated. The reaction in the presence of [BMIM][BF4] gave rise to the anion exchange reaction product [BMIM]2[Ti(OH)6] in moderate yield. On the contrary, Ti7O4(OEt)20 was obtained in ionic liquids with other anions. The anion exchange reaction has a broad capacity for group functionalization. It can be used to synthesize both imidazolium and pyridium [Ti(OH)6]2− salts. In contrast, under the similar reaction conditions, the reactions of zirconium alcoholate gave rise to [Zr(OH)5]− or [Zr(OH)6]2− intermediates depending on the counter cations. Under the solvothermal reaction conditions, [PF6]− based ionic liquids can also undertake the similar anion exchange reactions.