CNC钳型双(氮杂环卡宾)稀土金属烃基化合物的合成与性能研究

Functionalized N-heterocyclic carbene (NHC) lanthanide complexes have undergone an upsurge research interest in the past decade. However, Kinds of Functionalized N-heterocyclic carbene (NHC) lanthanide complexes are simple. Catalytic applications of N-heterocyclic carbene (NHC) lanthanide complexes only focus on polymerization or copolymerization of lactides, isoprene and olefins. Bis(NHC) incorporated tridentate pincer ligand having strong electron-donating ylidene carbons and the precise tailoring of the metal coordination sphere could provide liable complexes and enable the complexes to be used as homogeneous catalysis. However, the bis(NHC) incorporated tridentate pincer rare-earth metal complexes are less developed. This project aims to search for the synthetic methods, reactivity and catalytic application of CNC-pincer rare-earth metal alkyl complexes incorporating diarylamido bridged bis(NHC) ligands. The electronic and steric effects on the bonding of the diarylamido bridged bis(NHC) ligands with rare-earth metals, reactivity and catalytic applications for C-C, C-N, C-P, olefins polymerization and copolymerization of the CNC-pincer diarylamido bis(NHC)-ligated rare-earth metal alkyl complexes will also be studied. It is expected that new reactivity and new catalysts for applications in organic synthesis will be developed with the accomplishment of the project.

官能化氮杂环卡宾配体近年来引起了稀土金属有机领域研究者的广泛兴趣，合成了大量官能化氮杂环卡宾稀土金属配合物，但目前存在种类比较单一且应用不够广泛等问题；钳型双(氮杂环卡宾)配体具有强供电性及空间、电子因素易调节的特点被广泛应用于配位化学和均相催化等领域，而钳型双(氮杂环卡宾)稀土金属配合物报道较少。为了丰富氮杂环卡宾稀土金属配合物的种类并拓展其应用范围，本项目拟在前期工作基础上系统开展含二苯氨基桥联双(氮杂环卡宾)CNC钳型稀土金属烃基化合物的合成方法、成键及性能研究，探索出该类稀土金属烃基化合物的有效合成方法，研究配体电子、立体因素对成键的影响，研究该类稀土金属烃基化合物与有机小分子的反应性及其在催化C-C、C-N、C-P键形成和烯烃聚合与共聚反应的应用。通过本项目研究探索出该类新型稀土金属有机配合物的合成方法，成键规律，发展新型催化剂，并为开发我国丰富的稀土金属资源提供理论依据。

系统地研究了一系列含氮杂环配体与稀土金属胺基化合物及稀土金属烃基化合物的反应性，稀土金属配合物的制备、结构表征、催化活性以及生物活性。分别探索了CNC钳型双（氮杂环卡宾）前体、NCN钳型单（氮杂环卡宾）前体及含氮杂环修饰的亚胺与稀土金属胺基化合物物及稀土金属烃基化合物的反应性研究；同时，还研究了含氮杂环修饰的亚胺稀土金属配合物的催化活性。其中，吡啶基修饰的β-烯酮亚胺稀土金属配合物在催化异戊二烯聚合方面表现优异；吲哚基修饰的芳香亚胺稀土金属配合物在催化胍化反应表现良好；此外，还初步探索了吲哚基修饰的芳香亚胺及其稀土金属配合物生物活性方面的应用。上述研究结果丰富了含氮杂环配体及其稀土金属配合物的种类，拓展了含氮杂环配体稀土金属配合物的应用。