A {Ti₆W₄}-Cluster-Substituted Polyoxotungstate: Synthesis, Structure, and Catalytic Oxidation Properties

A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [H₂N(CH₃)₂]₃Na₄H₉[{Ti₆W₄O₁₈(OH)(H₂O)₃}(B-α-SbW₉O₃₃)₃]·20H₂O (1), has been made by hydrothermal reactions of trivacant [B-α-SbW₉O₃₃]^9- units, Ti⁴⁺ cations, and WO₄^2- anions in the presence of [H₂N(CH₃)₂]·Cl and structurally characterized. Intriguingly, the polyoxoanion of 1 is constructed from three [B-α-SbW₉O₃₃]^9- units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [Ti₆W₄O₁₈(OH)(H₂O)₃]¹¹⁺ ({Ti₆W₄}) that is comprised of an octahedral [Ti₆WO₆(H₂O)₃]¹⁸⁺ cluster and an edge-sharing [W₃O₁₂(OH)]^7- fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that 1 possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant H₂O₂.