An acetate-bridged Ru-substituted arsenotungstate [H N(CH ) ] [As W O {Ru (CH COO)} ]⋅22 H O (1) has been synthesized and structurally characterized. Four Ru atoms occupy the respective lacunary S2 sites of the crown-shaped polyanion [As W O ] , and each Ru atom is coordinated by one As atom and five μ -O atoms, comprising four from the S2 site and one from the acetate ligand. To the best of our knowledge, this coordination of the Ru atom, with an Ru-As bond length of 2.377(3)-2.387(3) Å, is unprecedented in polyoxometalate (POM) chemistry. Notably, 1 exhibits high efficiency, excellent selectivity, and good recyclability for the oxidation of sulfides with hydrogen peroxide (H O ). Catalytic oxidation of various sulfides in the presence of 1 gives superior conversion and selectivity for sulfones in acetonitrile, whereas sulfoxides are obtained in methanol.

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Two novel trans-isomers of 1 : 2-type lanthanide-containing monolacunary Dawson-type tungstophosphates [Ln(α-PWO)] (Ln = La (1), Ce (2)) were successfully isolated and characterized by elemental analysis, IR, TG, and P NMR studies. Both polyanions 1 and 2 consist of one Ln ion sanwiched between two monolacunary Dawson-type tungstophosphates fragments [α-PWO] oriented at 180° with respect to each other. The solid-state and solution P NMR spectroscopy revealed that the trans-[Ce(α-PWO)] species probably quickly isomerizes to the cis-isomer species in solution.

The first example of wholly inorganic ruthenium-containing polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH)2]·24H2O (1) was isolated and systematically characterized by element analysis, infrared spectroscopy (IR), thermogravimetric analyses (TGA), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX) and single-crystal X-ray diffraction. Compound 1 is composed of an unprecedented {Mo14}-type isopolymolybdate with a di-ruthenium core precisely encapsulated in its center, exhibiting a three-tiered ladder-like structure. The title compound can act as an efficient heterogeneous catalyst in the transformation of 1-phenylethanol to acetophenone. This catalyst is also capable of being recycled and reused for at least ten cycles with its activity being retained under the optimal conditions.

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