Novel Cyclophane Ligands for Late Transition Metal Olefin Polymerization Catalysis

关志斌博士，加州大学尔湾分校化学系，受无机、生物无机和有机金属化学项目支持，从事环烷基烯烃聚合迟过渡金属催化剂的开发。首先，对现有的和新的环烷二亚胺配体进行优化，以催化Ni（II）和Pd（II）基烯烃聚合。这将通过在配体中加入供电子和吸电子取代基，通过改变环烷二亚胺的主链结构；通过引入氟化苯环。下一步，Fe（II）和Co（II）配合物环烷三叉戟配体将探索作为烯烃聚合催化剂。该项目的这一部分旨在定义环烷配体对三叉戟晚期过渡金属催化剂体系的任何大环效应。最后，将测试环烷配体的晚期过渡金属配合物的乙烯均聚合和与极性共聚单体的共聚。配合物的聚合性能与催化剂的结构有关。所观察到的趋势和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在多个层次上对学生进行跨学科培训。本项目将雇用少数民族和女性研究生和本科生。此外，它将影响聚烯烃行业，在商业上可行的后过渡金属聚合催化剂的成功开发将产生巨大的影响。

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.