Phenylene-Bridged Cp/Carboxamide Ligands for Titanium Complexes of Various Binding Modes and Their Ethylene/1-Octene Copolymerization
详细信息 查看全文
- 作者：Ui Gab Joung ; Chun Ji Wu ; Sang Hoon Lee ; Choong Hoon Lee ; Eun Jung Lee ; Won-Sik Han ; Sang Ook Kang ; Bun Yeoul Lee
- 刊名：Organometallics
- 出版年：2006
- 出版时间：October 9, 2006
- 年：2006
- 卷：25
- 期：21
- 页码：5122 - 5130
- 全文大小：181K
- 年卷期：v.25,no.21(October 9, 2006)
- ISSN：1520-6041
文摘
o-Phenylene-bridged or substituted o-phenylene-bridged di- or trimethylcyclopentadienyl/carboxamideligands 2-(RMe2C5H2)-4,6-R'2C6H2NHC(O)tBu (R = Me or H; R' = Me, H, or F) are prepared. WhenR' is methyl or H, unbridged trichlorotitanium complexes containing a chloroimine unit as a pendantgroup, 2-[(
5-RMe2C5H)TiCl3]-4,6-R'2C6H2N=C(Cl)tBu (7, R = H, R' = H; 8, R = Me, R' = H; 9, R= H, R' = Me; 10, R = Me, R' = Me), are unexpectedly afforded through the successive addition ofTi(NMe2)4 and SiCl4 to the ligands. The same treatment to the ligands where R' = F affords oxygen-coordinated bridged complexes [2-(5-RMe2C5H)-4,6-F2C6H2N=C(O)tBu-
O]TiCl2 (11, R = H; 12, R= Me). The desired nitrogen-coordinated bridged complexes [2-(5-RMe2C5H)C6H4NC(O)tBu-2N,O]TiMe2 (13, R = H; 14, R = Me) are obtained by reacting the corresponding dilithium compound withMe2TiCl2. The binding modes of 7, 8, 9, 11, and 14 are confirmed by X-ray crystallography.Trichlorotitanium complex 8 shows high activity in ethylene/1-octene copolymerization (activity, 100 ×106 g/molTi·h at 13 bar ethylene). Trimethylcyclopentadienyl complexes show higher activity than thedimethylcyclopentadienyl analogues, and the activities of 12 and 14 reach ~65 × 106g/molTi·h. Complex12 is excellent in incorporating 1-octene.
5-RMe2C5H)TiCl3]-4,6-R'2C6H2N=C(Cl)tBu (7, R = H, R' = H; 8, R = Me, R' = H; 9, R= H, R' = Me; 10, R = Me, R' = Me), are unexpectedly afforded through the successive addition ofTi(NMe2)4 and SiCl4 to the ligands. The same treatment to the ligands where R' = F affords oxygen-coordinated bridged complexes [2-(5-RMe2C5H)-4,6-F2C6H2N=C(O)tBu-O]TiCl2 (11, R = H; 12, R= Me). The desired nitrogen-coordinated bridged complexes [2-(5-RMe2C5H)C6H4NC(O)tBu-2N,O]TiMe2 (13, R = H; 14, R = Me) are obtained by reacting the corresponding dilithium compound withMe2TiCl2. The binding modes of 7, 8, 9, 11, and 14 are confirmed by X-ray crystallography.Trichlorotitanium complex 8 shows high activity in ethylene/1-octene copolymerization (activity, 100 ×106 g/molTi·h at 13 bar ethylene). Trimethylcyclopentadienyl complexes show higher activity than thedimethylcyclopentadienyl analogues, and the activities of 12 and 14 reach ~65 × 106g/molTi·h. Complex12 is excellent in incorporating 1-octene.