A series of six nickel and two palladium novel complexes bearing α-diimine ligands with fluorinated alkyl substituents in para-aryl positions was prepared. Two nickel complexes were structurally characterized by X-ray diffraction. Upon activation by methylaluminoxane or borate, the complexes were tested in ethene, propene, and hex-1-ene polymerization using toluene and chlorobenzene. Propene and hex-1-ene polymerization initiated by nickel complexes and ethene polymerization initiated by palladium complexes showed living/controlled character and yielded high molar mass polyolefins with narrow molar mass dispersity (Đ < 1.2). The effect of fluoroalkyl substituents on catalyst activity, thermal stability and chain-walking is only minor. The branching density of polyolefins can be regulated more efficiently by the variation of ortho-aryl and backbone substituents of α-diimine ligands. The topology of polyethylenes prepared by palladium complexes at low ethene pressure is dendritic as shown by Mark–Houwink plots and g′ values obtained from SEC with viscometric detection. The solubility of most of the complexes in fluorinated solvents is limited with the exception of palladium methyl chloride derivatives which suggest the promising method for further design of catalysts suitable for interphase polymerization.

中文翻译：

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带有氟化烷基取代的α-二亚胺配体的镍和钯配合物，用于活性/受控烯烃聚合†

制备了一系列六个带有α-二亚胺配体的镍和两个钯新颖的配合物，它们在对芳基的位置带有氟化的烷基取代基。通过X射线衍射在结构上表征了两种镍配合物。在被甲基铝氧烷或硼酸盐活化后，在甲苯，氯苯和乙烯，丙烯和1-己烯的聚合反应中测试了配合物。镍配合物引发的丙烯和己烯1-己烯聚合反应和钯配合物引发的乙烯聚合表现出活性/可控性，并得到了摩尔质量分散较窄的高摩尔质量聚烯烃（Đ<1.2）。氟代烷基取代基对催化剂活性，热稳定性和链行走的影响很小。聚烯烃的支化密度可以通过改变α-二亚胺配体的邻芳基和骨架取代基来更有效地调节。如Mark–Houwink图所示，由钯络合物在低乙烯压力下制备的聚乙烯的拓扑结构是树枝状的，并且通过粘度检测从SEC获得的g ′值。除钯甲基氯衍生物外，大多数配合物在氟化溶剂中的溶解度均受到限制，这暗示了进一步设计适用于相间聚合的催化剂的有前途的方法。