文献类型：期刊文献

英文题名：Synthesis of half-titanocenes containing phenoxy-imine ligands and their use as catalysts for olefin polymerization

作者：Zhang, Hao[1,2]; Katao, Shohei[1]; Nomura, Kotohiro[1]; Huang, Jiling[2]

机构：[1]Nara Inst Sci & Technol, Grad Sch Mat Sci, Nara 6300101, Japan;[2]E China Univ Sci & Technol, Organomet Chem Lab, Shanghai 200237, Peoples R China

年份：2007

卷号：26

期号：24

起止页码：5967

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20075010969729);WOS:【SCI-EXPANDED(收录号:WOS:000250975200029)】；

语种：英文

外文关键词：Catalysts - Copolymerization - Hexane - Ligands - Olefins - Phenols - Styrene - Synthesis (chemical) - X ray crystallography

摘要：Various half-titanocenes containing phenoxy-imine ligands of the type Cp'TiCl2[O-2-R-1-6-((RN)-N-2=CH)-(CH3)-H-6] [CP' = CP* (C5Me5) and R-1, R-2 = Me, 2,6-(Pr2C6H3)-Pr-i (1); Bu-t, 2,6-Pr2C6H3 (2); Me, Bu-t (3); Bu-t, Bu-t (4); Cp' = 1,2,4-Me3C5H2 and R-1, R-2 = Me, 2,6-(Pr2C6H3)-Pr-i (5); Cp' = Cp and R-1, R-2 = Me, 2,6-(Pr2C6H3)-Pr-i (6); Me, Bu-t (7)] were prepared by reaction of Cp'TiCl3 with LiO-2-R-1-6-((RN)-N-2 = CH)C6H3 that were prepared in situ by treating the corresponding phenol with n-BuLi. Cp*TiMe2[O-2-Me-6-{(2,6-(Pr2C6H3)-Pr-i)N = CH}C6H3](8) was prepared from Cp*TiMe3 by treating with 2-Me-6-1(2,6-(Pr2C6H3)-Pr-i)N = CH}C6H3-OH in n-hexane, and the reaction with [PhN(H)Me-2][B(C6F5)(4)] was also explored. Structures for 1-3 and 5-8 were determined by X-ray crystallography, and the imino nitrogen in the phenoxy-imine ligand was not coordinated to Ti in all cases;,the bond angles for Ti-O-C(Ph) were affected by substituents in both cyclopentadienyl and phenoxy-imine ligands. The catalytic activities for ethylene polymerization and syndiospecific styrene polymerization using 1-7-MAO catalyst systems were highly affected by the substituents in both cyclopentadienyl and phenoxy-imine ligands; the Cp* analogues (3, 4) exhibited notable activities for ethylene polymerization, whereas the Cp analogues (6, 7) showed significant activities for syndiospecific styrene polymerization. The Cp analogue 6 was also an effective catalyst precursor for copolymerization of ethylene with norbornene.