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Bis(imino) pyridines fused with 6-and 7-membered carbocylic rings as N,N,N-scaffolds for cobalt ethylene polymerization catalysts
Wang, Z; Ma, YP; Guo, JJ; Liu, QB; Solan, GA; Liang, TL; Sun, WH
2019-02-28
Source PublicationDALTON TRANSACTIONS
ISSN1477-9226
Volume48Issue:8Pages:2582-2591
AbstractThe unsymmetrical diketone, 1,2,3,7,8,9,10-heptahydrocyclohepta[b] quinoline-4,6-dione, based on a central pyridine unit fused by both 6-and 7-membered rings, has been synthesized via a sequence of reactions including ruthenium-catalyzed coupling cyclization. Templating this diketone with a mixture of cobalt(II) chloride hexahydrate and the corresponding aniline in acetic acid at reflux afforded five examples of carbocyclic-fused bis(arylimino) pyridine-cobalt(II) chlorides (aryl = 2,6-Me2Ph Co1, 2,6-Et2Ph Co2, 2,6-i-Pr2Ph Co3, 2,4,6-Me3Ph Co4, 4-Me-2,6-Et2Ph Co5) in good yield. All cobalt complexes have been fully characterized including by 1H NMR spectroscopy which reveals broad but assignable paramagnetically shifted peaks. The molecular structures of Co1, Co3 and Co4 highlight the inequivalency of the two fused rings with the cobalt center adopting a distorted trigonal bipyramidal geometry. Treatment of Co1-Co5 with MAO gave highly active catalysts (up to 5.03 x 10(6) g PE mol(-1) (Co) h(-1) at 40 degrees C, with Co4 > Co5 > Co1 > Co2 > Co3) for ethylene polymerization generating strictly linear vinyl-terminated polymers with low molecular weights (Mw range: 1.53-22.77 kg mol(-1)). By comparison, polymerizations conducted using Co1-Co5/MMAO were less active and displayed a lower selectivity for unsaturated polymers. Common to both MAO and MMAO, the most sterically hindered precatalyst Co3 gave the highest molecular weight polymer of the series (up to 22.77 kg mol(-1)) but exhibited the lowest activity.
MOST Discipline CatalogueChemistry
DOI10.1039/c8dt04892d
Indexed BySCI
Language英语
WOS SubjectChemistry ; Inorganic & Nuclear
WOS IDWOS:000459183500036
PublisherROYAL SOC CHEMISTRY
Citation statistics
Cited Times:7[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/41952
Collection工程塑料实验室
Affiliation1.Solan, GA
2.Sun, WH (reprint author), Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China.
3.Sun, WH (reprint author), Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China.
4.Liu, QB (reprint author), Univ Chinese Acad Sci, CAS Res Educ Ctr Excellence Mol Sci, Beijing 100049, Peoples R China.
5.Solan, GA (reprint author), Hebei Normal Univ, Coll Chem & Mat Sci, Shijiazhuang 050024, Hebei, Peoples R China.
6.Sun, WH (reprint author), Univ Leicester, Dept Chem, Univ Rd, Leicester LE1 7RH, Leics, England.
Recommended Citation
GB/T 7714
Wang, Z,Ma, YP,Guo, JJ,et al. Bis(imino) pyridines fused with 6-and 7-membered carbocylic rings as N,N,N-scaffolds for cobalt ethylene polymerization catalysts[J]. DALTON TRANSACTIONS,2019,48(8):2582-2591.
APA Wang, Z.,Ma, YP.,Guo, JJ.,Liu, QB.,Solan, GA.,...&Sun, WH.(2019).Bis(imino) pyridines fused with 6-and 7-membered carbocylic rings as N,N,N-scaffolds for cobalt ethylene polymerization catalysts.DALTON TRANSACTIONS,48(8),2582-2591.
MLA Wang, Z,et al."Bis(imino) pyridines fused with 6-and 7-membered carbocylic rings as N,N,N-scaffolds for cobalt ethylene polymerization catalysts".DALTON TRANSACTIONS 48.8(2019):2582-2591.
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