New divalent samarocenes for butadiene polymerisation: influence of the steric effect and the electron density on the catalytic activity

被引：22

作者：

Bonnet, F ^{[1
]}

Visseaux, M ^{[1
]}

Barbier-Baudry, D ^{[1
]}

机构：

[1] Univ Bourgogne, Dept Chim, Lab Synth & Electrosynthese Organomet, CNRS,UMR 5188, F-21078 Dijon, France

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2004年 / 689卷 / 01期

关键词：

lanthanides; diene polymerisation; samarocenes;

D O I：

10.1016/j.jorganchem.2003.10.011

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two new divalent samarocenes, (Cp2Sm)-Sm-*/(THF) (1) and (Cp-Ph3)(2)Sm(THF) (2) (Cp-*/ = (C5Me4Pr)-Pr-n, Cp-Ph3 = H2C5Ph3-1,2,4), were synthesized and characterized by H-1 NMR and elemental analysis. The activity of 1 and 2 as butadiene polymerisation catalysts was studied, in the presence of MAO and MMAO, and compared to this of Cp-2(*) Sm(THF)(2) (3) and (Cp-4i)(2)Sm (4) (Cp-* = C5Me5, Cp-4i = (C5HPr4)-Pr-i), in the same conditions. The 1/MAO system presents the highest activity. The less active 2/MAO system leads to a high cis-1,4 regular structure up to 97%. The MMAO cocatalyst is found very sensitive to the steric hindrance of the samarocenes: the activity decreases from 1/MAO to 1/MMAO, and no activity is observed in the case of complexes 2 and 4, associated to MMAO. Complexes 1 and 2 can be both oxidized with AlMe3 to give the corresponding Sm/Al bimetallics 1' and 2' respectively. (C) 2003 Elsevier B.V. All rights reserved.

引用

页码：264 / 269

页数：6

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