Al(<sc>iii</sc>) and Ga(<sc>iii</sc>) triflate complexes as solvate ionic liquids: speciation and application as soluble and recyclable Lewis acidic catalysts

This work reports on the first solvate ionic liquids (SILs) based on aluminium(iii) and gallium(iii) triflates, M(OTf)(3), and triglyme (G3). Liquid-phase speciation of these new SILs was studied by multinuclear NMR spectroscopy. Across the compositional range of G3 : M(OTf)(3) mixtures, both metals were found to be in a hexacoordinate environment, with both G3 and [OTf](-) ligands present in the first coordination sphere, and apparently exchanging through a dynamic equilibrium. The Lewis acidity was quantified by the Gutmann acceptor number (AN) and compared to the performance of SILs as Lewis acidic catalysts in model [3 + 3] cycloadditions. Despite saturated coordination, AN values were relatively high, reaching AN = ca. 71-83 for Al-SILs and ca. 80-93 for Ga-SILs, corroborating the labile nature of the metal-ligand bonding. In a model catalytic reaction, SILs were fully soluble in the reaction mixtures, in contrast to the corresponding triflate salts. The catalytic performance of SILs exceeded that of the corresponding triflate salts, and Ga-SILs were more active than Al-SILs, in agreement with AN measurements. In conclusion, the new Group 13 SILs can be considered as soluble and catalytically active forms of their corresponding metal triflates, with potential uses in catalysis.