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Synthesis and characterization of the titanium complexes bearing two beta-enaminoketonato ligands with electron withdrawing groups/modified phenyls and their behaviors for ethylene (co-) polymerization
Ye, Wei-Ping; Shi, Xin-Cui; Li, Bai-Xiang; Liu, Jing-Yu; Li, Yue-Sheng; Cheng, Yan-Xiang; Hu, Ning-Hai
2010
Source PublicationDALTON TRANSACTIONS
ISSN1477-9226
Volume39Issue:38Pages:9000-9007
Abstractseries of new titanium complexes with two asymmetric bidentate beta-enaminoketonato [N,O] ligands (2b-t), [PhN=C(CF(3))CHC(Ar)O](2)TiCl(2) (2b, Ar = -C(6)H(4)F(o); 2c, Ar = -C6H4F(m); 2d, Ar = -C(6)H(4)F(p); 2e, Ar = -C(6)H(4)Cl(p); 2f, Ar = -C(6)H(4)OMe(p); 2g, Ar = -C(6)H(4)CF(3)(p); 2h, Ar = -C(6)H(4)CF(3)(m); 2i, Ar = -C(6)H(4)CF(3)(o); 2j, Ar = -C(6)H(4)Cl(o); 2k, Ar = -C(6)H(4)Br(o); 2l, Ar = -C(6)H(4)I(o); 2m, Ar = -C(6)H(3)F(2)(2,4); 2n, Ar = -C(6)H(3)F(2)(2,6); 2o, Ar = -C(6)H(3)F(2)(3,4); 2p, Ar = -C(6)H(3)F(2)(3,5); 2q, Ar = -C(6)F(5); 2r, Ar = C(6)F(4)OMe; 2s, Ar = -C(6)H(3)Cl(2)(2,6); 2t, Ar = -C(6)H(3)Cl(2)(2,5)), have been synthesized based on substituted acetophenones. X-Ray analyses reveal that complexes 2h, 2k, 2m, and 2n adopt distorted octahedral geometry around the titanium center, in which the two chloride ligands are situated in the cis-orientation. 2s also adopts distorted octahedral geometry, but the two chloride ligands in it are situated in the trans-orientation due to the increase of the steric effect of the phenyl derived from the acetophenone. The influence of the substituent effects on catalyst performance, including catalytic activities and the molecular weight distribution of the polymers obtained, was investigated in detail. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 2b-r and 2t are active catalysts for ethylene polymerization at room temperature, and produce high molecular weight polymers. It is observed that the catalytic activities are significantly enhanced by introducing some electron-withdrawing groups, such as F, Cl and CF(3), into the suitable positions of the phenyl ring close to the oxygen donor. It should be noted that complexes 2c-i, 2p, 2n and 2t are also capable of promoting the living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight copolymers with narrow molecular weight distributions (PDI = 1.05-1.30).
DOI10.1039/c001987a
Indexed BySCI
Language英语
WOS IDWOS:000282006200019
PublisherROYAL SOC CHEMISTRY
Citation statistics
Cited Times:13[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/69010
Collection中国科学院化学研究所
Corresponding AuthorLiu, Jing-Yu
AffiliationChinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
Recommended Citation
GB/T 7714
Ye, Wei-Ping,Shi, Xin-Cui,Li, Bai-Xiang,et al. Synthesis and characterization of the titanium complexes bearing two beta-enaminoketonato ligands with electron withdrawing groups/modified phenyls and their behaviors for ethylene (co-) polymerization[J]. DALTON TRANSACTIONS,2010,39(38):9000-9007.
APA Ye, Wei-Ping.,Shi, Xin-Cui.,Li, Bai-Xiang.,Liu, Jing-Yu.,Li, Yue-Sheng.,...&Hu, Ning-Hai.(2010).Synthesis and characterization of the titanium complexes bearing two beta-enaminoketonato ligands with electron withdrawing groups/modified phenyls and their behaviors for ethylene (co-) polymerization.DALTON TRANSACTIONS,39(38),9000-9007.
MLA Ye, Wei-Ping,et al."Synthesis and characterization of the titanium complexes bearing two beta-enaminoketonato ligands with electron withdrawing groups/modified phenyls and their behaviors for ethylene (co-) polymerization".DALTON TRANSACTIONS 39.38(2010):9000-9007.
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