项目名称: 新型三元卟啉金属配合物的合成与催化性能研究
项目编号: No.21301074
项目类型: 青年科学基金项目
立项/批准年度: 2014
项目学科: 数理科学和化学
项目作者: 薛兆历
作者单位: 江苏大学
项目金额: 24万元
中文摘要: 三元卟啉是新型的由三个吡咯环通过次甲基桥相连而成的具有14-π电子共轭的卟啉衍生物。与卟啉相比,三元卟啉的内环半径较小,因此金属离子与其配位时只能位于其大环平面的上方,这种特殊的配位构型导致其金属配合物具有较为独特的性质。将它们用作催化剂时,可极大地增加活性中心与反应底物接触的几率、有效地提高催化效率。本项目拟设计合成一系列新型的含有铁、钴、锰等过渡金属离子的三元卟啉配合物,并在配合物中引入不同的具有吸电子或给电子特性的取代基团以调控它们的结构和性质。将采用各种光谱技术对配合物的性质进行详细研究,着重研究它们作为催化剂催化环氧化烯烃的性能。系统研究配合物中金属离子和取代基的种类、配合物的结构对烯烃催化环氧化性能的影响,总结对于烯烃环氧化具有优良催化性能的配合物所应具有的结构特征。确定配合物催化环氧化烯烃的适宜实验条件并提出相应的催化机理,为三元卟啉配合物的定向合成与应用研究提供理论基础。
中文关键词: 三元卟啉;过渡金属;配位;电化学;催化
英文摘要: Triphyrins are a new kind of porphyrin derivatives. They are composed by three pyrrole rings and meso-carbon bridges to form a 14-π electronic aromatic conjugated system. The contraction of the ring center and the reducing of the symmetry, making triphyrins show a special coordination mode. For example, when a metal ion is coordinated to triphyrin, the only coordination position for the metal ion is the axial direction, meanwhile the metal ion can not insert into the triphyrin main plane but sit on top. This coordination mode is totally different from that of the normal metalloporphyrins. when they are used as catalyst, it might greatly increase the reaction probability between the activity center and substrate and will effectively improve the catalytic efficiency. In this project we intend to design and synthesis a series of novel metallotriphyrins which contain transition metals such as iron, coblat and manganese. The structures and properties of the synthesized comounds will be characterized by a variety of spectral and electrochemical thechniques. Different electron-withdrawing or electron-donating substituents will be introduced to the triphyrin macrocycle in order to adjust and control the structure and properties of the compounds. Our study will focuse on the performance and properties of the metallotriph
英文关键词: triphyrin;transition metal;coordination;electrochemistry;catalysis