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Lanthanide Metallocene Reactivity with Dialkyl Aluminum Chlorides: Modeling Reactions Used to Generate Isoprene Polymerization Catalysts
Organometallics
  • William J. Evans, University of California, Irvine
  • Timothy M. Champagne, University of California, Irvine
  • Dimitri Giarikos, University of California, Irvine
  • Joseph W. Ziller, University of California, Irvine
Publication Date
2-14-2005
Disciplines
Peer Reviewed
1
Abstract
The well-defined coordination environment of trivalent [(C5Me5)2Ln]+ complexes has been used to examine the reaction chemistry of the lanthanide carboxylate and R2AlCl (R = Me, Et, iBu) components used in the preparation of lanthanide-based diene polymerization catalysts. Each of the R2AlCl reagents can replace a carboxylate ligand with chloride in reactions with [(C5Me5)2Sm(O2CC6H5)]2, but instead of forming a simple chloride complex like [(C5Me5)2SmCl]3, bimetallic lanthanide aluminum dichloro complexes (C5Me5)2Sm(μ-Cl)2AlR2are generated by ligand redistribution. These bis(chloride)-bridged complexes are also readily formed from the divalent precursor (C5Me5)2Sm(THF)2 and R2AlCl. However, the analogous reaction between (C5Me5)2Sm(THF)2 and Et3Al gives (C5Me5)2Sm(THF)(μ-η2-Et)AlEt3, which contains the first Ln(III)−(η2-Et) linkage, a coordination mode that differentiates Et from Me. To determine if mixed mono-chloride/alkyl-bridged (C5Me5)2Ln(μ-Cl)(μ-R)AlR2 complexes can be isolated, (C5Me5)2Y(μ-Cl)YCl(C5Me5)2 was reacted with R3Al. These reactions form [(C5Me5)2Y(μ-Cl)(μ-R)AlR2]x complexes, but again there is a differentiation on the basis of R:  the Me complex is a dimer and the others are monomers. (C5Me5)2Y(μ-Cl)2AlR2 complexes were similarly prepared for comparison with the mixed ligand species and for additional Me, Et, and iBu comparisons.
Comments

©2005 American Chemical Society

DOI
10.1021/om049484o
Citation Information
William J. Evans, Timothy M. Champagne, Dimitri Giarikos and Joseph W. Ziller. "Lanthanide Metallocene Reactivity with Dialkyl Aluminum Chlorides: Modeling Reactions Used to Generate Isoprene Polymerization Catalysts" Organometallics Vol. 24 Iss. 4 (2005) p. 570 - 579 ISSN: 0276-7333
Available at: http://works.bepress.com/dimitri-giarikos/17/