Xing Qifeng, Song Kuifeng, Liang Tongling, Liu Qingbin, Sun Wen-Hua, Redshaw Carl
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Dalton Trans. 2014 Jun 7;43(21):7830-7. doi: 10.1039/c4dt00503a. Epub 2014 Apr 4.
Pyrene-4,5,9,10-tetraone was prepared via the oxidation of pyrene, and reacted with various anilines to afford a series of 4,5,9,10-tetra(arylimino)pyrenylidene derivatives (L1-L4). The tetraimino-pyrene compounds L1 and L2 were reacted with two equivalents of (DME)NiBr2 in CH2Cl2 to afford the corresponding dinickel bromide complexes (Ni1 and Ni2). The organic compounds were fully characterized, whilst the bi-metallic complexes were characterized by FT-IR spectra and elemental analysis. The molecular structures of representative organic and nickel compounds were confirmed by single-crystal X-ray diffraction studies. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me2AlCl, maintaining a high activity over a prolonged period (longer than previously reported dinickel complex pre-catalysts). The polyethylene obtained was characterized by GPC, DSC and FT-IR spectroscopy and was found to possess branched features.
通过芘的氧化反应制备了芘 - 4,5,9,10 - 四酮，并使其与各种苯胺反应，得到一系列4,5,9,10 - 四（芳基亚氨基）芘叉衍生物（L1 - L4）。四亚氨基芘化合物L1和L2在二氯甲烷中与两当量的（DME）NiBr₂反应，得到相应的二镍溴化物配合物（Ni1和Ni2）。对有机化合物进行了全面表征，而双金属配合物通过FT - IR光谱和元素分析进行表征。代表性有机化合物和镍化合物的分子结构通过单晶X射线衍射研究得以确证。这些镍配合物在MAO或Me₂AlCl存在下对乙烯聚合表现出高活性，并且在较长时间内保持高活性（比先前报道的二镍配合物预催化剂的时间更长）。通过GPC、DSC和FT - IR光谱对所得聚乙烯进行了表征，发现其具有支化结构。
