钒卤过氧化酶：多齿螯合型钒配合物分子设计、合成及仿生催化溴化活性

Using hydrothermal,solution, ionic liquid, etc.various synthetical experiment techniques, a series of oxovanadium-amino super-molecular complexes containing the series of poly(pyrazolyl)borate or polydentate N-heterocyclic ligands as supporting ligands and the amino acid small molecules with biology-activity as the second ligands are designed and synthesized, examining on synthesis regulation of the reaction system. Based on the molecular spectra and structure,we will study the polarization and coupling actions between the conduction electrons from the center vanadium atom to the steric hindrance N-heterocyclic ligands, coordinated environment, bond-forming characters, electron and energy transfer of the center vanadium atom, as well as the electron transfer mechanism and the reaction process about different oxidation states of the vanadium atom.In the neutral water system, we will also carry out the bromination reaction using phenol red as a organic substrate which is shown by the conversion of phenol red to bromophenol blue with the oxovanadium complex as a catalysis, it is investigated at molecular level that oxovanadium complexes with different substituted group on the polypyrazolylborate N-heterocyclic ligands have influenced on the bromination reaction activities using phenol red as organic substrate. There are wide application prospects in the aspect of innovative drugs and precursor compounds with synthesis, structure and bromination reaction activities of oxovanadium complexes are studied. Especially, the reference information about achieving to inertia C-H bonding activity in catalytic bromination reaction under mild conditions to decrease waste of energy resources and to discharge pollution is provided.

采用水热、溶液、离子液体等多种合成方法，以聚吡唑硼酸盐（蝎型或类蝎型配体）及多齿富氮杂环化合物为支撑配体，有机羧酸或生物小分子化合物为可修饰配体，设计合成系列含有混合聚吡唑硼酸盐配体的钒氧类氨基酸（或类谷胱氨肽）超分子化合物，并考察体系的合成规律。基于分子光谱与结构，研究体系内中心原子与障碍性富氮杂环配体之间的金属d电子与π传导电子的相互极化和耦合作用，以及配位环境、成键特性、电子跃迁、能量转移及不同价态钒氧电子传递机制和反应过程。在中性水溶液中以溴化钾为溴化剂进行苯酚红溴化成苯酚蓝的催化溴化反应，在分子水平上研究这些由不同取代基的多吡唑富氮杂环配体支撑的钒（氧）配合物催化溴化活性的影响规律。开拓钒氧小分子配合物合成、结构及催化溴化功能在创新药物和先导化合物研究方面具有广阔的应用前景。尤其是实现温和条件下惰性C-H键的活化溴化反应新途径，进而为减少能源的消耗和污染物的排放提供有价值的参考。

利用配位键和共价键的强度、饱和性和方向性，系统研究了功能基元的组装方法和技术，通过功能基元的结构优化和裁剪，从分子水平上研究这些不同取代基的富氮杂环配体支撑的钒（氧）配合物或超分子化合物催化溴化活性的影响因素和催化溴化机制。首次建立了一套评价钒氧化合物催化溴化活性的反应体系和稳定的评估方法。设计了新型氮杂环配体15个；合成了新颖的模型钒氧化合物19个；考察了这些化合物的催化溴化活性并推测了催化机理。研究结果发表在国内外期刊上，并且在国内相关化学会上进行了交流。四年间，以通信作者共发表SCI论文35篇，代表作有ACS Applied Materials & Interface，Inorg. Chem., Cryst. Growth Des., Dalton Transactions, CrystEngComm.,等。中国发明专利２件。上述研究成果，为进一步开发新的绿色环保型均相溴化有机化合物催化剂，深入了解有机化合物的C-H 断裂机制提供了有价值的参考。