B-type Anderson Heteropoly Acid And Lindqvist Heteropoly Acid Derivatives:Synthesis, Preliminary Study On Catalytic Performance

Polyoxmetalates （POMs） is a kind of special nature and structure of the metal oxygencluster compounds. Due to the potential value at catalytic, pharmacology and material science,becoming one of research hot spots in recent years.In this thesis, we design and compose six new Polyoxmetalates derivatives from the rawmaterials Anderson-skeleton and Lindqvist-skeleton.Na₃[Cr（OH）₆Mo₆O₁₈] as raw material reacting at aqueous solution, three Anderson-typeorganic derivatives Na₂(C₄H₁₂O₃N)[Cr（OH）₆Mo₆O₁₈]·C₄H₁₁O₃N·6H₂O （1）、[（C₄H₉）₄N]₇[HOCH₂C（CH₂）₃Cr（OH）₃Mo₆O₂₁]₂Br·20H₂O （2） and [（C₄H₉）₄N]₆{H_4-[HOCH₂C（CH₂）₃（CrO₆）Mo₆O₁₈]}₂（C₆H₅COO）₂·2.5C₆H₅COOH·5H₂O （3） had beensynthesized. They structures were characterized by IR,1HNMR and TG-DTA （or TGA-DSC）.And their crystal datas were determined by X-ray diffraction. The compound1, which was acharge transfer complex of [Cr（OH）₆Mo₆O₁₈]^3- and Tris, stabilized by hydrogen bonds.Compound2was single facet methylated by pentaerythritol and the next side was linked withBr-or water molecule through hydrogen bonds. Three-dimensional network structure wasformed from hydrogen bonds between each component. Compound3is obtained from the[（C4H₉）₄N]₇[HOCH₂C（CH₂）₃Cr（OH）₃Mo₆O₂₁]₂Br aqueous solution of CoCl₂and sodiumbenzoate with heating. H+can be hydrolyzed from hot CoCl2aqueous to make the POMsorganoimido derivative change in structure. Pentaerythritol linking with three μ-3-O changedto linking two μ-3-O and one μ-2-O.Lindqvist-type organoimido derivative （n-Bu₄N）₂[Mo₆O₁₈（NR）]（R=o-CH₃C₆H₃（OH））had been synthesized from [α-Mo₈O₂₆]^4- and4-amino-3-methylphenol hydrochloride andcharacterized by IR and TG-DTA. There were two new isomers of （n-Bu₄N）₂[Mo₆O₁₈（NR）]characterized by X-ray diffraction. However, there were not got Lindqvist complexes fromthe complexation reaction of Lindqvist-tape POMs and metal ions (Co²⁺, Fe³⁺), but a new[α-Mo₈O₂₆]^4- was occasionally obtained, and characterized by X-ray diffraction.We studied the catalytic performance of compound2and4in differenttemperatures because of their good thermostability. The experimental datas show thatboth the two compounds had good thermocatalytic activities, and compound4had thebest catalytic at170℃. Thephotocatalytic activities were much poor comparing with thethermocatalytic activities. This paper provided certain theory basis for the study of POMs in synthesis andperformance.