新型氮杂环过渡金属配合物的设计合成及应用

Amino (or imido) metal complexes have been widely used in coordination chemistry because of their unique electronic and structural features, and to build some organometallic compounds with novel structures and unique functions. For many years our group has been engaged in the synthesis of the nitrogen-based ligands and their metal comounds and further their catalytic properties in olefin polymerization. The zirconium aza-allyls, zirconium amidinates, zirconium guanidinates and zirconium β-diketiminate complexes showed similar catalytical nature to zirconocene catalysts. In this project, aniline or substituted aniline and 2-aminopyridine are used as mother materials to design and synthesize some novel metal compounds bearing aza-heterocyclic ligands by the variations of the steric hindrance at nitrogen substitutes.The coordination modes of the nitrogen atoms and the configuration of the metals can be modified by the variation of the electronic effects and steric hindrance of the ligands. The catalytical properties of the novel metal complexes on olefin polymerization are evaluated according to the bonding mode and the structures of the complexes, and are used to find good catalyst systems with high activity that can give polymers with stable properties.

胺基（或亚胺基）金属化合物由于其独特的电子和结构特征广泛应用于配位化学，构筑结构新颖和功能独特的金属有机化合物。所在课题组多年来从事氮基配体及其金属有机化合物的合成及烯烃聚合催化性能研究，合成的氮杂烯丙基锆，脒基锆，胍基锆及β-二亚胺锆配合物均具有茂锆催化的性质。本课题将利用苯胺或取代苯胺、2-氨基吡啶为母体，利用氮原子上不同立体位阻的差异，设计合成出结构新颖的含氮杂环金属化合物，通过配体上电子效应和立体位阻的变化，调控氮原子的配位状态和改变配合物中金属配位构型；针对所得新配合物成键状态和结构调控关系，进行配合物烯烃聚合性能的研究和比较，筛选出催化活性高聚合物性能稳定的催化剂体系。

胺基（或亚胺基）金属化合物由于其独特的电子和结构特征广泛应用于配位化学，构筑结构新颖和功能独特的金属有机化合物。本课题以苯胺、2, 6-二异丙基苯胺、2-氨基吡啶为母体，通过多步骤合成了其衍生物，对它们和不同无α-H腈的加成反应性、新型含氮杂环化合物的合成方法进行了研究；合成得到了胍基化合物、脒基化合物、1,3,5-三氮杂戊二烯化合物、基于吡啶的具有双环结构的1,3,5-三氮杂戊二烯系列金属配合物，研究了它们的合成机理、化合物的结构特征及性能以及在烯烃聚合、丙交酯开环聚合中的应用。研究结果表明，设计合成的含氮杂环化合在烯烃聚合、丙交酯开环聚合中显示出良好的催化活性。在此基础上，合成得到了基于吡啶的1,3,5-三氮杂戊二烯多核过渡金属化合物，该类化合物具有有趣的结构类型，对该类化合物的结构、配位化学、反应机理、性能和应用的研究还在探索中。