Syntheses, reactions, and ethylene polymerization of titanium complexes with [N,N,S] ligands

被引：16
|
作者：
Jia, Ai-Quan [1 ,2 ]
Wang, Jian-Qiang [3 ]
Hua, Ping [1 ,2 ]
Jin, Guo-Xin [1 ,2 ]
机构：
[1] Fudan Univ, Dept Chem, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200433, Peoples R China
[2] Fudan Univ, Key Lab Mol Engn Polymers, Chinese Minist Educ, Dept Macromol Sci, Shanghai 200433, Peoples R China
[3] Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China
来源：
DALTON TRANSACTIONS | 2011年 / 40卷 / 30期
基金：
美国国家科学基金会;
关键词：
HALF-SANDWICH IRIDIUM(III); TRANSITION-METAL CATALYSTS; ANILIDO-IMINE LIGANDS; OLEFIN POLYMERIZATION; NORBORNENE POLYMERIZATION; NICKEL(II) COMPLEXES; ADDITION POLYMERIZATION; TRIDENTATE LIGANDS; ZIEGLER CATALYSTS; ANCILLARY LIGAND;
D O I：
10.1039/c0dt01800g
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Tridentate dianionic arylsulfide free ligands [ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (3a); Ar = 2,4,6-trimethylphenyl (3b); Ar = 2,6-diisopropylphenyl (3c)) have been prepared by reduction of the corresponding imine compounds [ArN=CHC(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (2a); Ar = 2,4,6-trimethylphenyl (2b); Ar = 2,6-diisopropylphenyl (2c)) with LiAlH(4) in high yields. Reactions of TiCl(4) with the tridentate dianionic arylsulfide free ligands (3a-3c) afford five-coordinate and four-coordinate titanium complexes [kappa S, kappa(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh) TiCl(2)] (Ar = Ph (4a); Ar = 2,4,6-trimethylphenyl (4b)] and [kappa(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh) TiCl(2)] (Ar = 2,6-diisopropylphenyl (4c)], respectively. The molecular structures of compounds 2b, 2c, 3b and 3c.HCl have been characterized by single crystal X-ray diffraction analyses. Complexes 2a-4c are characterized by IR, (1)H-NMR spectra, and elemental analysis. EXAFS spectroscopy performed on complexes 4b and 4c reveals the expected different coordination geometry due to steric hindrance effect. When activated by excess methylaluminoxane (MAO), 4a-4c can be used as catalysts for ethylene polymerization and exhibit moderate to good activities.
引用
收藏
页码：7730 / 7736
页数：7
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