Neodymium(III) complexes with bulky ansa-bis(cyclopentadienyl) ligands:: Synthesis and use in olefin oligomerization

被引：36
作者：
Bogaert, S
Chenal, T
Mortreux, A
Nowogrocki, G
Lehmann, CW
Carpentier, JF
机构：
[1] ENSCL, CNRS, UPRESA 8010, Lab Catalyse Lille, F-59652 Villeneuve Dascq, France
[2] ENSCL, CNRS, UPRESA 8012, Lab Cristallochim & Physicochim Solide, F-59652 Villeneuve Dascq, France
[3] Max Planck Inst Kohlenforsch, D-45466 Mulheim, Germany
来源：
ORGANOMETALLICS | 2001年 / 20卷 / 01期
关键词：
D O I：
10.1021/om0006357
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The trivalent neodymium complexes [rac-{Me2Si(eta (5)-2-SiMe3-4-t-Bu-C5H2)(2))Nd(mu -Cl)(2)Li(THF)(2)] (rac-3),[rac-{Me2Si(eta (5)-2,4-(SiMe3)(2)C5H2)(2)}Nd(mu -Cl)(2)Li(THF)(2)] (rac-5), and [(Me2Si(eta (5)-2,4-(SiMe3)(2)C5H2)((eta (5)-3,4-(SiMe3)(2)C5H2)}Nd(mu -Cl)(2)Li(THF)(2)] (C-1-6) have been prepared and their structures investigated by NMR and X-ray crystallography. These new chlorolanthanocenes, when combined in situ with a dialkylmagnesium cocatalyst, initiate the polymerization of ethylene and 1-octene to yield di(oligoalkyl)magnesium species, which can be finally hydrolyzed to oligomers. Bulky bridged complexes rac-3, rac-5, and C-1-6 gave significantly more active catalysts for 1-octene oligomerization (M-n = 400-1300, M-w/M-n = 1.11-1.65) than systems based on nonbridged complexes [(eta (5)-C5Me5)(2)Nd(mu -Cl)(2)Li(Et2O)(2)] (1) and [(eta (5)-1,3-(SiMe3)(2)C5H3)(2)Nd(mu -Cl)(2)Li(THF)(2)] (7). Ethylene oligomerization (M-n = 400-5000) was best achieved with complexes 1 and rac-3, as important catalyst decay occurred with bridged bis(trimethylsilyl) systems rac-5 and C-1-6.
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页码：199 / 205
页数：7
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