还原态联吡啶有机铈化合物的合成、结构及反应性研究

The organometallic complexes with a reduced 2,2'-bipyridyl ligand have received increasing attention since they are widely used in many fields such as medicine, biology, and chemical engineering, and it becomes one of the most significant research fields in organometallic chemistry. So far, reduced bipyridyl organolanthanide complexes have been reported rarely, and this research work is at the beginning. According to their special properties in magnetism and reactivity, carrying out the research work in reduced bipyridyl organolanthanide complexes is a desirable goal, which is not only in academic study but also in industry. A series of reduced bipyridyl organocerium complexes would be designed and prepared, and their use in activation of small molecules would be studied. The electron interaction between the cerium ion and bipyridyl ligand would be investigated by magnetic susceptibility studies, and their reactivity would be further investigated by computational studies. A relationship between the electronic structure and the reactivity would be established, which would provide an academic theory for their potential application in biology, medicine, chemical engineering, and organic synthesis. For comparison, organocerium complexes drived from the substituted bipyridyl and 1,10-phenanthroline would be included in this proposal.

2,2'-联吡啶（简称联吡啶）金属有机化合物（本项目中指还原态联吡啶金属有机化合物）在医药、生物及化工等领域具有广阔的应用前景，是金属有机化学的前沿研究课题。目前，对联吡啶稀土金属有机化合物的研究还处于起步阶段，而稀土金属有机化合物又具有独特的磁性及反应性。因此，开展联吡啶稀土金属有机化合物的研究具有重要的科学意义和潜在的应用价值。 本项目拟设计并合成出一系列联吡啶有机铈化合物，并将其应用于小分子的活化反应，进行反应性能测试。通过磁性研究揭示这些联吡啶有机铈化合物中心金属离子与联吡啶配体之间的电子作用关系，并借助分子计算与模拟，对其反应性能进行探讨，研究电子结构与反应性能之间的关系，为这类化合物在生物、医药、化工及有机合成方面的潜在应用提供理论依据。同时，为了探讨电子效应对联吡啶有机铈化合物磁性及反应性的影响，本项目还将在取代联吡啶和1,10-菲罗啉衍生的有机铈化合物方面做部分工作。

设计合成新型金属配合物，并研究他们的反应性是有机、金属有机和无机化学中的重要研究领域之一，它不仅有助于深入理解这些化合物的性质，同时有助于设计新反应，建立新方法。本研究设计并合成了铈联吡啶化合物，以及其他IIA、IIIB族金属配合物，并研究了它们的反应性能。实验结果表明，偶氮苯镁自由基化合物是有用的单电子转移试剂，可以与一系列化合物发生反应，分离得到一些用常规方法难以合成的金属镁配合物。手性稀土金属络合物可以有效的催化外消旋丙交酯的开环聚合。有机金属钍化合物在小分子以及Si-H键、C-H键活化方面也表现了独特的反应性能。在研究的过程中我们发表相关研究论文5篇，其中影响因子介于4-10者2篇，影响因子大于10者2篇。