Neodymium(III) Complexes with Bulky ansa-Bis(cyclopentadienyl) Ligands:  
Synthesis and Use in Olefin Oligomerization

Bogaert, Stéphane; Chenal, Thomas; Mortreux, André; Nowogrocki, Guy; Lehmann, Christian W.; Carpentier, Jean-François

doi:10.1021/om0006357

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Neodymium(III) Complexes with Bulky ansa-Bis(cyclopentadienyl) Ligands: Synthesis and Use in Olefin Oligomerization

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Lehmann, Christian W.
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Bogaert, S., Chenal, T., Mortreux, A., Nowogrocki, G., Lehmann, C. W., & Carpentier, J.-F. (2001). Neodymium(III) Complexes with Bulky ansa-Bis(cyclopentadienyl) Ligands: Synthesis and Use in Olefin Oligomerization. Organometallics, 20(1), 199-205. doi:10.1021/om0006357.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0024-65B1-F

Abstract

The trivalent neodymium complexes [rac-{Me₂Si(η⁵-2-SiMe₃-4-t-Bu-C₅H₂)₂}Nd(μ-Cl)₂Li(THF)₂] (rac-3), [rac-{Me₂Si(η⁵-2,4-(SiMe₃)₂C₅H₂)₂}Nd(μ-Cl)₂Li(THF)₂] (rac-5), and [{Me₂Si(η⁵-2,4-(SiMe₃)₂C₅H₂)(η⁵-3,4-(SiMe₃)₂C₅H₂)}Nd(μ-Cl)₂Li(THF)₂] (C₁-6) 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 C₁-6 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 [(η⁵-C₅Me₅)₂Nd(μ-Cl)₂Li(Et₂O)₂] (1) and [(η⁵-1,3-(SiMe₃)₂C₅H₃)₂Nd(μ-Cl)₂Li(THF)₂] (7). Ethylene oligomerization (Mn = 400−5000) was best achieved with complexes 1 and rac-3, as important catalyst decay occurred with bridged bis(trimethylsilyl) systems rac-5 and C₁-6.