Syntheses,Structures And Properties Of Carbonyl Metal Derivatives Of Polyoxotungstates And Polyoxovanadates

By the method of conventional aqueous solution, from simple tungstic acid salt and polyoxometalate precursor through constantly exploring reaction conditions, six novel type and structure of the polyoxotungstates and isopolyoxovanadates-based metal carbonyl derivatives were successfully synthesized, which were characterized by IR, X-ray single crystal diffraction, elemental analysis, UV-Vis and X-ray powder diffraction. At the same time, some of the compounds were discussed the electrochemical behavior and catalytic properties.1. A novel monolacunary Linqvist type isotungstate-supported metal carbonyl derivative KH[（CH₃）₄N]₃[{Re（CO）₃}₄（μ₂-OH）（μ₃-O）(W₅O₁₈)]·6H₂O（1） has been synthesized for the first time, whose anionic [W₅O₁₈]^6- carrys four rhenium carbonyl groups. And the compound carrys the highest number of metal carbonyl groups in isotungstate-supported metal carbonyl derivative.2. A novel [W₈O₃₀]^12- based metal carbonyl derivative Na₄H₂[{Re（CO）₃}₂{Re（CO）₃（H₂O）}₂(H₂W₈O₃₀)]·19H₂O（2） has been synthesized, whose polyoxoanion exists a crystallography inversion center.3. A novel heterpolytungstate-supported metal carbonyl derivative [（CH₃）₄N]H₁₁[{Mn（CO）₃}₂（H₂O）₂（W₂O₅）(HBW₁₁O₃₉)₂]·45H₂O（3） has been synthesized. The polyoxoanion of the compound consisted of two {HBW₁₁O₃₉} connect a manganese carbonyl unit respectively through two {WO₆} units together.4. A novel kind of sandwich type heterpolytungstate-supported metal carbonyl derivative K₂H₂[（CH₃）₄N]₃[{Re（CO）₃}₂（μ-OH）(HBW₁₁O₃₉)]·12H₂O（4） has been synthesized. There are two rhenium carbonyl units in the anonic, which embedded into the vacant polyoxometalate by four Re-O-W bonds.5. Two novel vanadium oxygen clusters-based metal carbonyl derivatives: H₂[Mn（CO）₃（C₃H₃N₂）₃]₂[V₂O₇]·4H₂O（5） and [Mn（CO）₃（C₃H₃N₂）₃]₆[V₁₀O₂₈]·3H₂O（6） has been synthesized for the first time, both of them represent the good activity in catalytic CO₂ cycloaddition reaction.