Synthesis and Structure of Ti-, Zr- and Hf-Containing Polyoxotungstates and Study of their Oxidation Catalysis Properties

我们计划合成由高氧化态的早期过渡金属取代的新型的、离散的分子多氧钨酸盐，如TiVI，ZrVI，HfVI。Kortz小组在含钛多氧钨酸盐的合成和结构表征方面拥有丰富的经验。最近，我们还分离出了一些含过氧基的锆基和氟化氢取代的衍生物。Kortz集团的这一合成技术与Kholdeeva集团在均相选择氧化催化方面的丰富经验完美地结合在一起，该催化使用了含钛和锆的多氧钨酸盐。合成了新型聚阴离子，并在固态下进行了结构表征(红外光谱、拉曼光谱、电子能谱等)。新西伯利亚的Kholdeeva小组将研究不来梅Kholdeeva小组在溶液中(UV-Vis、电化学、多核核磁共振)的均匀催化潜力(特别是在环境友好的氧化剂-过氧化氢水中氧化烯烃和芳烃)。

We plan to synthesize novel, discrete-molecular polyoxotungstates substituted by early transition metals in high oxidation states, such as TiVI, ZrVI, HfVI. The Kortz group has documented experience in the synthesis and structural characterization of Ti containing polyoxotungstates. Very recently, we have also isolated some Zr- and Hf-substituted derivatives including peroxo-species. This synthesis know-how of the Kortz group matches perfectly with the extensive experience of the Kholdeeva group in homogeneous selective oxidation catalysis using Ti- and Zr-containing polyoxotungstates. The novel polyanions synthesized and structurally characterized in the solid state (IR, Raman, elem. analysis, TGA, single-crystal XRD) and in solution (UV-vis, electrochemistry, multinuclear NMR) by the Kortz group in Bremen will be investigated for their homogeneous catalysis potential (in particular oxidation of olefins and aromatics with environmentally benign oxidant - aqueous hydrogen peroxide) by the Kholdeeva group in Novosibirsk.