The organic carboxylic acid coordinated monomeric peroxoniobate-based ionic liquids (ILs) [TBA]­[NbO­(OH)2(R)] (TBA = tetrabutylammonium; R = lactic acid (LA), glycolic acid (GLY), malic acid (MA)) were prepared and fully characterized by elemental analysis, NMR, IR, Raman, TGA, 93Nb NMR, and HRMS. These IL catalysts exhibited not only high catalytic activity for the epoxidation of olefins under very mild reaction conditions, as the turnover frequency of [TBA]­[NbO­(OH)2(LA)] reached up to 110 h–1, but also satisfactory recyclability in the epoxidation by using only 1 equiv of hydrogen peroxide as an oxidant. Meanwhile, this work revealed that the ILs underwent structural transformation from [NbO­(OH)2(R)]− to [Nb­(O–O)2(R)]− (R = LA, GLY, MA) in the presence of H2O2 by a subsequent activity evaluation, characterization, and first-principles calculations. Moreover, the organic carboxylic acid coordinated monomeric peroxoniobate-based ILs were investigated using density functional theory (DFT) calculations, which identified that [Nb­(O–O)2LA]− was more advantageous than [Nb­(O–O)2(OOH)2]− for the epoxidation of olefins. Due to the coordination between the α-hydroxy acids and the monomeric peroxoniobate anions, the functionalized ILs can efficiently catalyze the epoxidation of a wide range of olefins and allylic alcohols under very mild conditions. Additionally, the effect of solvents on the reaction is illustrated. It was found that methanol can lower the epoxidation barriers by forming a hydrogen bond with a peroxo ligand attached to the niobium center.

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Transesterification can be accelerated under pressurized CO2 and satisfactory activity and selectivity to unsymmetrical organic carbonate can be obtained.

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