Novel Cyclophane Ligands for Late Transition Metal Olefin Polymerization Catalysis

关志斌博士，加州大学欧文分校化学系，由无机化学、生物无机化学和金属有机化学项目资助，致力于开发用于烯烃聚合的环烷基晚过渡金属催化剂。首先，对现有的和新的环芳二亚胺配体进行优化，以用于催化Ni(II)和Pd(II)的烯烃聚合。这将通过在配体中加入给电子和退出取代基，通过改变环芳二亚胺的主干结构，以及通过引入氟化苯环来实现。接下来，我们将探索环番三枝状配体的Fe(II)和Co(II)络合物作为烯烃聚合催化剂。该项目的这一部分旨在定义环番配体对三枝状后过渡金属催化剂体系的任何大环效应。最后，环番配体的后过渡金属络合物将被用于乙烯均聚和与极性共聚单体的共聚。络合物的聚合性能与催化剂的结构有关。观察到的趋势和获得的见解将指导进一步设计更好的烯烃聚合催化剂。拟议活动的更广泛影响包括对学生进行多层次的跨学科培训。该项目将雇用少数民族和女性研究生和本科生。此外，它还将对聚烯烃行业产生影响，成功开发出商业上可行的后过渡金属聚合催化剂将产生巨大的影响。

Dr. Zhibin Guan, Department of Chemistry, University of California - Irvine, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for the development of cyclophane-based late transition metal catalysts for olefin polymerization. First, current and new cyclophane diimine ligands will be optimized for Ni(II) and Pd(II) based olefin polymerization catalysis. This will be done by incorporating electron-donating and withdrawing substituents into the ligands, by changing the backbone structure of the cyclophane diimines; and by introducing fluorinated phenyl rings. Next, Fe(II) and Co(II) complexes of cyclophane tridendate ligands will be explored as olefin polymerization catalysts. This part of the project aims to define any macrocyclic effects of cyclophane ligands on tridendate late transition metal catalyst systems. Finally, late transition metal complexes of the cyclophane ligands will be tested for ethylene homopolymerization and copolymerizations with polar comonomers. The polymerization properties of the complexes will be correlated to the catalyst structures. The trends observed and insights gained will guide further design of better olefin polymerization catalysts.The broader impacts from the proposed activity include interdisciplinary training of students at multiple levels. Minority and women graduate and undergraduate students will be employed on this project. Additionally, it will impact the polyolefin industry, where the successful development of a commercially viable late transition metal polymerization catalyst would have a tremendous impact.