Citation: Ya-lin Qiao, Ping Hu, Guo-xin Jin. SYNTHESES, CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS[J]. Chinese Journal of Polymer Science, ;2013, 31(5): 760-768. doi: 10.1007/s10118-013-1265-0 shu

SYNTHESES, CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS

Corresponding author: Guo-xin Jin,
Received Date: 4 December 2012
Revised Date: 1 January 2013

Fund Project: This work was financially supported by the Shanghai Science and Technology Committee (08DZ2270500, 08DJ1400103), Shanghai Leading Academic Discipline Project (B108) and the National Basic Research Program of China (2009CB825300, 2010DFA41160).

A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-But4-Me-6-((2-(SC6H5)C6H4N＝CHC6H2O)]- (La) and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-But4-Me-6-((2-(SC6H5)C6H4N-CH2C6H2O)]2- (Lb) have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group IV metal complexes CpTi[O-NS]Cl2 (1a), CpZr[O-NS]Cl2 (1b), CpTi[O-N-S]Cl (2a), CpZr[O-N-S]Cl (2b) and Cp*Zr[O-N-S]Cl (2c) were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp*ZrCl3, and characterized by IR, 1H-NMR, 13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO) as co-catalyst up to 1.58 107 g-PEmol-Zr-1h-1. The good catalytic activities can be maintained even at high temperatures such as 100℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.
- Half-sandwich group IV metal complexes,
- Tridentate dianionic ligands,
- Phenoxy-imine arylsulfide ligands,
- Catalyst,
- Ethylene polymerization
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