Rigid geometry 8-arylimino-7,7-dimethyl-5,6-dihydroquinolyl nickel bromides: single-site active species towards ethylene polymerization | |
Department | OSSO国家重点实验室 |
Huang, Chuanbing1; Zhang, Youfu2; Liang, Tongling1; Zhao, Zhijuan1; Hu XQ(胡信全)2; Sun WH(孙文华)1,3; Sun WH(孙文华) | |
2016 | |
Source Publication | New Journal of Chemistry |
ISSN | 1144-0546 |
Volume | 40Issue:11Pages:9329-9336 |
Abstract | The fused ring heterocyclic ketone, 5,6-dihydro-7,7-dimethylquinolin-8-one, was prepared and employed for the synthesis of a series of 8-arylimino-7,7-dimethyl-5,6-dihydroquinoline derivatives (aryl = 2,6-Me2Ph (L1), 2,6-Et2Ph (L2), 2,4,6-Me3Ph (L3), 2,6-Et2-4-MePh (L4), 2,6-i-Pr2Ph (L5)). The reaction of L1–L4 with (DME)NiBr2 (DME = 1,2-dimethoxyethane) gave the corresponding cationic bis-chelates, [(Lx)2NiBr][Br] (Lx = L1 (Ni1), L2 (Ni2), L3 (Ni3), L4 (Ni4)), as bromide salts; no such complex could be isolated with the most sterically bulky L5. All new compounds were characterized using IR spectroscopy, elemental analysis and in the case of L1–L5 using 1H and 13C NMR spectroscopy. Furthermore, the molecular structures of Ni1 and Ni3 have been determined and they reveal cation–anion pairs based on a trigonal bipyramidal nickel-containing cation charge balanced by a bromide counterion. In addition, X-ray photoelectron spectroscopy (XPS) was used to probe the solid state structures of L1, L3 and Ni1–Ni4; this technique provided valuable information regarding the net charge on nickel within the complexes. Upon activation with either methylaluminoxane (MAO) or ethylaluminium sesquichloride (EASC), all nickel complexes exhibited high activities towards ethylene polymerization and produced polyethylene waxes with low molecular weights. The catalytic activities, Ni1 [2,6-di(Me)] > Ni3 [2,4,6-tri(Me)] > Ni4 [2,6-di(Et)-4-Me] > Ni2 [2,6-di(Et)], correlated well with the trend in net charges observed in XPS analysis. The polydispersities (1.7–2.0) obtained for polyethylenes are narrow and indicate genuinely single-site active species for these catalysts. These performance characteristics have been attributed to the influence of the rigid geometry imparted by L1–L5 that, due to the presence of 7,7-dimethyl-substituents, prevents imine–enamine tautomerization. |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1039/c6nj02464e |
Funding Organization | National Natural Science Foundation of China (No. U1362204;21374123;21473160) |
Indexed By | SCI |
If | 3.269 |
Language | 英语 |
compositor | 第三作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/21098 |
Collection | 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Sun WH(孙文华) |
Affiliation | 1.Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China 2.College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China 3.State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China |
Recommended Citation GB/T 7714 | Huang, Chuanbing,Zhang, Youfu,Liang, Tongling,et al. Rigid geometry 8-arylimino-7,7-dimethyl-5,6-dihydroquinolyl nickel bromides: single-site active species towards ethylene polymerization[J]. New Journal of Chemistry,2016,40(11):9329-9336. |
APA | Huang, Chuanbing.,Zhang, Youfu.,Liang, Tongling.,Zhao, Zhijuan.,Hu XQ.,...&孙文华.(2016).Rigid geometry 8-arylimino-7,7-dimethyl-5,6-dihydroquinolyl nickel bromides: single-site active species towards ethylene polymerization.New Journal of Chemistry,40(11),9329-9336. |
MLA | Huang, Chuanbing,et al."Rigid geometry 8-arylimino-7,7-dimethyl-5,6-dihydroquinolyl nickel bromides: single-site active species towards ethylene polymerization".New Journal of Chemistry 40.11(2016):9329-9336. |
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