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Lanthanide Carboxylate Precursors for Diene Polymerization Catalysis:  Syntheses, Structures, and Reactivity with Et2AlCl
Organometallics
  • William J. Evans, University of California, Irvine
  • Dimitri Giarikos, University of California, Irvine
  • Joseph W. Ziller, University of California, Irvine
Publication Date
12-24-2001
Disciplines
Peer Reviewed
1
Abstract
Synthetic, structural, and reactivity results are presented on neodymium and lanthanum carboxylates that can function as models for diene polymerization catalysts. The neodymium and lanthanum carboxylates {Nd[O2CC(CH3)2CH2CH3]3}x (1) and {La[O2CC(CH3)2CH2CH3]3}x(2) were synthesized from the lanthanide metal and 2,2-dimethylbutyric acid in the presence of a catalytic amount of HgCl2 and Hg(OAc)2. Nd2[O2CCH(C6H5)CH2CH3]6[HO2CCH(C6H5)CH2CH3]4(3) was prepared similarly from neodymium powder and 2-phenylbutyric acid. 1 and 2 crystallize from hot pyridine as the dimeric pyridine adducts Nd2[O2CC(CH3)2CH2CH3]6[pyridine]4 (4) and La2[O2CC(CH3)2CH2CH3]6[pyridine]4 (5). 3 crystallizes from hexanes as the carboxylic acid adduct. 1 and 2 react with Et2AlCl to form the isolable solids 6 and 7, which react with Al(iBu)3 to generate catalytically active systems which polymerize isoprene, ethylene, and styrene. Although crystallization of 6 from THF forms NdCl3(THF)4 (8) and crystallization of 7 from pyridine forms [LaCl3(pyridine)4]2 (9), complexes 6 and 7 are not simply LnCl3, since elemental analyses show that they contain aluminum.
Comments

©2001 American Chemical Society

DOI
10.1021/om010887n
Citation Information
William J. Evans, Dimitri Giarikos and Joseph W. Ziller. "Lanthanide Carboxylate Precursors for Diene Polymerization Catalysis:  Syntheses, Structures, and Reactivity with Et2AlCl" Organometallics Vol. 20 Iss. 26 (2001) p. 5751 - 5758 ISSN: 0276-7333
Available at: http://works.bepress.com/dimitri-giarikos/12/