共轭η3氮杂烯丙基和η5β-二亚胺系列配体的合成及其金属络合物催化性能关联影响的研究

Azaally and the derived β-diketiminate ligands are important components in the non-cyclopentadienyl array. They were paid innumerous attentions due to their unique features in structural and catalytic properties. However, β-diketiminate ligand prepared by condensation of β-diketone and amine are limited due to the symmetric terminal groups. Moreover, the research about them with chiral specificity is rare. The synthetic methods of this research will make a breakthough and the asymmetric or chiral groups could be introduced into the terminal position easily. This project covers the research of synthetic methods for η3,η5-featured conjugated ligand systems including azaally and β-diketiminate ligands (including the chiral species), as well as the corresponding metal complexes. The relevance between the structrue and olefin polymerization property of the zirconium, titanium complexes will be studied. The catalytic properties of the chiral species in asymmetric synthesis will be explored as well. It focuses on the following aspects: (1) systematically establish a synthetic pathway to azaallyl and β-diketiminate ligands from the imines; (2) summerize the relationship between the microstructure and the macro catalytic property for related complexes, select the potentially applicable catalysts and explore the way of transforming organometallic products into application in industry; (3) study the catalytic behaviors of imine, azaally, β-diketiminate ligands and related metal complexes with chirality in the asymmetric synthesis reactions.

氮杂烯丙基及衍生体β-二亚胺作为非茂环配体，因在金属有机化合物结构和催化方面的独特性质,得到了非常广泛的关注。不过，由β-二酮与胺缩合的传统方法得到的β-二亚胺局限于对称末端取代基的范围内，而且具有手性取代基的相应物质及催化研究也鲜有报道，本研究的合成方法突破了此类限制，方便了不对称取代基和手性基团的引入。申请课题研究具有η3 、η5共轭氮杂烯丙基和β-二亚胺（包括手性）配体和相应金属有机化合物的合成方法，重点考查其锆、钛化合物结构与烯烃聚合催化性能方面的关系以及手性化合物的不对称催化性能。包括以下内容：（1）系统建立由亚胺制备氮杂烯丙基到β-二亚和手性配体的制备方法；（2）通过结构表征研究微观结构与催化性能的关联性，筛选出有实际应用前景的高效烯烃聚合催化剂，积极开辟金属有机化学研究向应用型转化的道路；（3）考查由亚胺、氮杂烯丙基和β-二亚胺手性配体及相应金属络合物催化的不对称合成反应。

氮杂烯丙基及衍生体β-二亚胺作为非茂环配体，在金属有机化合物结构和催化方面的独特性质得到了非常广泛的关注。由β-二酮与胺缩合的传统方法得到的β-二亚胺局限于对称末端取代基的范围内，而且具有手性取代基的相应物质及催化研究也鲜有报道，本研究的合成方法突破了此类限制，方便了不对称取代基和手性基团的引入。按照课题计划研究了具有η3 、η5 共轭氮杂烯丙基和β-二亚胺（包括手性）配体和相应金属有机化合物的合成方法，重点考查锆、钛化合物结构与烯烃聚合催化性能方面的关系以及手性化合物的不对称催化性能。包括以下内容：（1）系统建立由亚胺制备氮杂烯丙基到β-二亚和手性配体的制备方法；（2）通过结构表征研究微观结构与催化性能的关联性，筛选出有实际应用前景的高效烯烃聚合催化剂，积极开辟金属有机化学研究向应用型转化的道路；（3）考查由亚胺、氮杂烯丙基和β-二亚胺手性配体及相应金属络合物催化的不对称合成反应。