Synthesis and characterization of novel titanium complexes bearing [ONX]-type β-enaminoketonato ligands and their application to ethylene (co)polymerization

Dalton Transactions : an International Journal of Inorganic Chemistry
Ping TaoYue-Sheng Li

Abstract

A series of novel titanium complexes bearing tridentate β-enaminoketonato chelating ligands of type, [R(2)NC(CF(3))C(H)CR(1)O]TiCl(3) (2a: R(1) = Ph, R(2) = -C(6)H(4)OMe(o); 2b: R(1) = Ph, R(2) = -C(9)H(6)N; 2c: R(1) = Ph, R(2) = -C(6)H(4)SMe(o); 2d: R(1) = Ph, R(2) = -C(6)H(4)SPh(o); 2e: R(1) = (t)Bu, R(2) = -C(6)H(4)SPh(o)) and [R(2)NC(R(1))C(H)C(CF(3))O]TiCl(3) (2f: R(1) = Ph, R(2) = -C(6)H(4)PPh(2)(o)) were prepared from TiCl(4) by treating with one equiv of deprotonated ligands in toluene. The reaction of 1a with equivalent of TiCl(4) in THF afforded another complex, C(6)H(4)OMeNC(CF(3))C(H)CPhO]TiCl(3)(thf) (3a), in addition to formation of the dichloride complex 4a, [C(6)H(4)(OMe)NC(CF(3))C(H)CPhO](2)TiCl(2). After deprotonation by alkali-metal hydride at -78 °C in diethyl ether, ligand 1a could react with 0.5 equiv of TiCl(4) to form the exclusive and clean dichloride complex 4a in high yield. These complexes were identified by NMR and mass spectra as well as elemental analyses. X-ray diffraction studies on these new trichloride complexes revealed a distorted octahedral coordination of the central metal with three chlorine atoms in a mer disposition. Dichloride complex 4a also adopted a distorted octahedral geometry aro...Continue Reading

References

Dec 26, 2001·Chemical Reviews·S D IttelM Brookhart
Mar 28, 2002·Journal of the American Chemical Society·Makoto MitaniTerunori Fujita
Sep 26, 2002·Journal of the American Chemical Society·Phillip D Hustad, Geoffrey W Coates
Jan 9, 2003·Chemical Reviews·Vernon C Gibson, Stefan K Spitzmesser
Oct 15, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiao-Hong YangYong Tang
Mar 15, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Ai-Quan JiaGuo-Xin Jin
Feb 15, 1999·Angewandte Chemie·George J P BritovsekDuncan F Wass

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