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

A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [HN(CH)]NaH[{TiWO(OH)(HO)}(B-α-SbWO)]·20HO (), has been made by hydrothermal reactions of trivacant [B-α-SbWO] units, Ti cations, and WO anions in the presence of [HN(CH)]·Cl and structurally characterized. Intriguingly, the polyoxoanion of is constructed from three [B-α-SbWO] units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [TiWO(OH)(HO)] ({TiW}) that is comprised of an octahedral [TiWO(HO)] cluster and an edge-sharing [WO(OH)] fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant HO.