Hybrid macrocyclic polyoxoanions based on {Mo₃S₄}⁴⁺ and -[SiW₁₀O₃₆]^8- as inorganic ligands

The polyoxoanion [{Mo3S4(H2O)(4)(tu)}(2){Mo3S4(H2O)(3)(tu)(2)}(2)(gamma-SiW10O36)(4)](16-) was obtained by the reaction of lacunary silicotungstate [gamma-SiW10O36](8-) with the trinuclear cluster cation Mo3S4(tu)(8)(H2O)](4+) (tu is thiourea, (NH2)(2)CS)). Its reaction with copper(I) iodide in the presence of chloride anions affords tetracubane polyoxometalate [{Mo3S4Cu(H2O)(5)}(4)Cl(gamma-SiW(10)O(3)6)(4)](13-), and the reaction with silver acetate gives the previously described [{Mo3S4(H2O)(5)}(4)(gamma-SiW10O36)(4)](16-). The compounds were isolated as potassium sodium salts and structurally characterized.