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首页> 外文期刊>RSC Advances >Synthesis and structural analysis of aryloxo-modified trinuclear half-titanocenes, and their use as catalyst precursors for ethylene polymerisation
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Synthesis and structural analysis of aryloxo-modified trinuclear half-titanocenes, and their use as catalyst precursors for ethylene polymerisation

机译：芳氧基改性三核半滴度的合成与结构分析及其作为乙烯聚合催化剂前体的用途

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摘要

A series of trinuclear half-titanocenes, [Cp'TiX2{(O-2,4-R2C6H2)-6-CH2}](3)N [X - Cl, R - Me, Cp' - Cp (1); X = Cl, R = Bu-t, Cp' = Cp (4), Cp* (5), (BuC5H4)-Bu-t (6), 1,2,4-Me3C5H2 (7); X = Me, Cp' = Cp*, R = Me (8), Bu-t (9)] and the related bimetallic complexes, [Cp'TiCl2{(O-2,4-Me2C6H2)-6-CH2}][Cp'TiCl{(O-2,4-Me2C6H2)-6-CH2}(2)]N [Cp' = Cp* (2), 1,2,4-Me3C5H2 (3)], have been prepared and identified. Structures of 1-5, 7 and 9 were determined by X-ray crystallography, and all complexes fold with distorted tetrahedral geometries around titanium. These complexes (2-9) are stable in solution except the Cp analogue (1), which presents as a mixture of the trinuclear analogue (1) and the (proposed) binuclear analogue, CpTiCl3, and CpTi[{(O-2,4-Me2C6H2)-6-CH2}](3)N in solution; there is an equilibrium between 1 and the binuclear analogue (and CpTiCl3) depending on the temperature, solvent and concentration. The Cp* analogues (2, 8, 9), exhibited high catalytic activities for ethylene polymerisation in the presence of MAO cocatalyst, affording ultrahigh molecular weight polymers with uniform molecular weight distributions in most cases. [Cp*TiMe2{(O-2,4-Me2C6H2)-6-CH2}](3)N (8) showed the higher catalytic activities than the related mononuclear analogue, Cp*TiCl2(O-2-R-4,6-Me3C6H2) (R - Me, Bu-t); the activity by 8 in the presence of AliBu(3)-[Ph3C][B(C6F5)(4)] cocatalysts was higher than that in the presence of MAO.
机译：一系列三核半茂钛的，[Cp'TiX2 {（O-2,4-R2C6H2）-6-CH 2}]（3）N [X - 氯，R - Me中，CP” - CP（1）; X =氯，R =卜的t，Cp” = CP（4）中，Cp *（5），（BuC5H4）-Bu-T（6），1,2,4- Me3C5H2（7）; X = Me中的Cp” =的Cp *，R =我（8），卜-T（9）]和相关的双金属络合物，[Cp'TiCl2 {（O-2,4-Me2C6H2）-6-CH 2}] [Cp'TiCl {（O-2,4-Me2C6H2）-6-CH 2}（2）] N [CP” =的Cp *，1,2,4- Me3C5H2（3）（2）]，已经制备和鉴定。 1-5，7和9的结构通过X射线晶体学确定，并且所有的复合物折叠周围钛扭曲的四面体几何形状。这些配合物（2-9）是在除的Cp类似物（1）中，溶液中稳定，其呈现为三核类似物的（1）的混合物和（提出）双核类似物，CpTiCl3，和CPTI [{（O-2， 4- Me2C6H2）-6-CH 2}]（3）N在溶液中;有并且取决于温度，溶剂和浓度的双核类似物（和CpTiCl3）1之间的平衡。在CP *类似物（2，8,9），表现出高的催化活性在MAO助催化剂存在下乙烯聚合，得到超高与在大多数情况下均匀的分子量分布的高分子量聚合物。的[Cp * TIME2 {（O-2,4-Me2C6H2）-6-CH 2}]（3）N（8）表现出较高的催化活性比相关单核类似物中，Cp *生成TiCl2（O-2-R-4， 6- Me3C6H2）（R - Me中，卜-T）;由8 AliBu的存在（3）的活性 - [Ph3C] [B（C 6 F 5）（4）]的助催化剂比在MAO存在下更高。

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  • 来源
    《RSC Advances》 |2017年第66期|共14页
  • 作者

    Yan Qing; Tsutsumi Ken; Nomura Kotohiro;

  • 作者单位

    Tokyo Metropolitan Univ Dept Chem 1-1 Minami Osawa Hachioji Tokyo 1920397 Japan;

    Tokyo Metropolitan Univ Dept Chem 1-1 Minami Osawa Hachioji Tokyo 1920397 Japan;

    Tokyo Metropolitan Univ Dept Chem 1-1 Minami Osawa Hachioji Tokyo 1920397 Japan;

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  • 正文语种 eng
  • 中图分类 化学;
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