Microwave-Assisted Synthesis of Tris-Anderson Polyoxometalates for Facile CO₂ Cycloaddition

Four new tris-Anderson polyoxometalates (POMs), (NH₄)₄[ZnMo₆O₁₈(C₄H₈NO₃)(OH)₃]·4H₂O (1), (NH₄)₄[CuMo₆O₁₈(C₄H₈NO₃)(OH)₃]·4H₂O (2), (TBA)₃(NH₄)[ZnMo₆O₁₇(C₅H₉O₃)₂(OH)]·10H₂O (3) (TBA = n-C₁₆H₃₆N), and (NH₄)₄[CuMo₆O₁₈(C₅H₉O₃)₂]·16H₂O (4), were synthesized by a microwave-assisted method. Single-crystal X-ray diffraction revealed that 1 and 2 contained a tris (trihydroxyl organic compounds) ligand grafted on one side, while two tris ligands were grafted on two sides to form χ/δ and δ/δ isomers in 3 and 4, respectively. ¹H and ¹³C NMR spectra of the χ/δ isomer 3 were obtained for the first time, with six methylenes showing six peaks in the ¹H NMR spectrum and only four peaks in the ¹³C NMR spectrum. Mass spectrometry monitoring revealed that during the microwave-assistant process the tris ligand can graft onto POMs to form 1, while tris directly coordinates with metallic heteroatoms to form isopolymolybdates during the conventional reflux synthesis process. In addition, 1-4 can catalyze CO₂ with epoxides into cyclic carbonates with high selectivity and yields at an atmospheric pressure of CO₂, which is lower than the pressure of CO₂ in other catalysis using POMs as catalysts. Furthermore, 1-4 showed good catalytic stability and cycling properties. Mechanism studies substantiated POMs cocatalyzed with Br^- to improve the catalytic yields.