Abstract The 8-(arylimino)-5,6,7-trihydroquinoline-nickel(II) chlorides, [8-N{2,6-R2-4-(C15H13)C6H2}C9H8N]NiCl2 (R = Me Ni1, Et Ni2, i-Pr Ni3, F Ni4, Cl Ni5), each appended with a remote para-dibenzocycloheptyl group, have been synthesized from either the pre-formed ligand (Ni1–Ni3) or by generating the ligand in-situ during complexation (Ni4, Ni5). The molecular structures of Ni2 and Ni3 adopt dimeric or trimeric forms in the solid state, in which the chlorides can act as doubly or triply bridging ligands. On treatment with either MMAO or Et2AlCl, Ni1–Ni5 showed low (Ni4, Ni5) to high activities (Ni1–Ni3: up to 4.58 × 106 g PE mol−1 (Ni) h−1) for ethylene polymerization producing unsaturated polyethylenes of low molecular weight (1.4–2.7 kg·mol−1) and narrow dispersity ( CH CH ) with respect to terminal vinyls ( CH CH2). The ortho-substituents of the precatalyst were found to not only affect the catalytic activity but also the vinylene:vinyl ratio and the branching content. Notably, the materials generated using ortho-fluoro Ni4/Et2AlCl possessed the least number of branches and an increased vinyl contribution. Furthermore, these unsaturated polyethylenes can be readily functionalized by epoxidation with almost quantitative conversion.

中文翻译：

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远程二苯并环庚基取代亚氨基三氢喹啉-镍催化剂作为制备具有烯烃官能团的窄分散支化聚乙烯蜡的途径

摘要 8-(芳基亚氨基)-5,6,7-三氢喹啉-镍(II)氯化物，[8-N{2,6-R2-4-(C15H13)C6H2}C9H8N]NiCl2 (R = Me Ni1, Et Ni2、i-Pr Ni3、F Ni4、Cl Ni5），每个都附加一个远程对二苯并环庚基，是由预先形成的配体（Ni1-Ni3）或通过在络合过程中原位生成配体合成的（ Ni4、Ni5）。Ni2和Ni3的分子结构在固态下采用二聚体或三聚体形式，其中氯化物可以作为双重或三重桥连配体。在用 MMAO 或 Et2AlCl 处理时，Ni1-Ni5 表现出低（Ni4、Ni5）到高活性（Ni1-Ni3：高达 4.58 × 106 g PE mol-1 (Ni) h-1），用于乙烯聚合生产不饱和聚乙烯相对于末端乙烯基 (CH CH2) 而言，低分子量 (1.4–2.7 kg·mol-1) 和窄分散性 (CH CH )。发现预催化剂的邻位取代基不仅影响催化活性，而且影响亚乙烯基：乙烯基比例和支化含量。值得注意的是，使用邻氟 Ni4/Et2AlCl 生成的材料具有最少的支链数量和增加的乙烯基贡献。此外，这些不饱和聚乙烯可以很容易地通过环氧化进行功能化，转化率几乎是定量的。