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2-亚氨基吡啶镍卤化物配合物引发的乙烯聚合:苄基的合成、表征和催化影响。

Ethylene polymerization by 2-iminopyridylnickel halide complexes: synthesis, characterization and catalytic influence of the benzhydryl group.

机构信息

Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

出版信息

Dalton Trans. 2012 Oct 21;41(39):11999-2010. doi: 10.1039/c2dt30989k.

Abstract

A series of 2-(2-benzhydrylbenzenamino)pyridine ligands (L1–L13) was synthesized and used as bidentate N^N ligands with nickel halides to afford the corresponding nickel dihalide complexes L(2)Ni(2)Cl(4) C1–C13 and L(2)NiBr(2) D1–D13. All ligands and complexes were characterized by IR and NMR spectroscopy, and by elemental analysis. The molecular structures of the representative complexes C1·2CH(3)OH, C5·2H(2)O, D4, D7 and D9 were confirmed by single-crystal X-ray diffraction studies. Upon activation with either methylaluminoxane (MAO) or ethylaluminium sesquichloride (Et(3)Al(2)Cl(3), EASC), these nickel pre-catalysts exhibited high activities (up to the range of 10(7) g mol(-1) (Ni) h(-1)) towards ethylene polymerization, producing branched polyethylenes with narrow polydispersity.

摘要

一系列 2-(2-二苯甲基苯氨基)吡啶配体 (L1–L13) 被合成出来,并作为双齿 N^N 配体与镍卤化物一起使用,得到相应的镍二卤化物配合物 L(2)Ni(2)Cl(4) C1–C13 和 L(2)NiBr(2) D1–D13。所有的配体和配合物都通过红外和核磁光谱以及元素分析进行了表征。代表性配合物 C1·2CH(3)OH、C5·2H(2)O、D4、D7 和 D9 的分子结构通过单晶 X 射线衍射研究得到了证实。用甲基铝氧烷 (MAO) 或乙基铝倍半氯化物 (Et(3)Al(2)Cl(3), EASC) 活化后,这些镍预催化剂在乙烯聚合方面表现出很高的活性(高达 10(7) g mol(-1) (Ni) h(-1)),得到了具有较窄多分散性的支化聚乙烯。

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