Novel Cyclophane Ligands for Late Transition Metal Olefin Polymerization Catalysis

加州-尔湾大学化学系管智斌博士得到了无机、生物无机和有机化学项目的支持，用于开发用于烯烃聚合的环芳基后过渡金属催化剂。首先，当前和新的环蕃二亚胺配体将被优化用于Ni（II）和Pd（II）基烯烃聚合催化。这将通过将给电子和吸电子取代基并入配体中，通过改变环蕃二亚胺的骨架结构;以及通过引入氟化苯环来实现。接下来，将探索环蕃三齿配体的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蕃配体对三齿后过渡金属催化剂体系的任何大环效应。最后，后过渡金属配合物的环蕃配体将被测试为乙烯均聚和共聚与极性共聚单体。配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更好的烯烃聚合催化剂的进一步设计。拟议活动的更广泛影响包括多层次学生的跨学科培训。 该项目将雇用少数民族和女研究生和本科生。此外，它还将影响聚烯烃行业，成功开发商业上可行的后过渡金属聚合催化剂将产生巨大影响。

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.