Lanthanide Carboxylate Precursors for Diene Polymerization Catalysis:  Syntheses, Structures, and Reactivity with Et2AlCl

Authors

William J. Evans, University of California, Irvine
Dimitri Giarikos, University of California, IrvineFollow
Joseph W. Ziller, University of California, Irvine

Document Type

Article

Publication Title

Organometallics

ISSN

0276-7333

Publication Date

2001

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.

DOI

10.1021/om010887n

Volume

20

Issue

26

First Page

5751

Last Page

5758

Comments

©2001 American Chemical Society

NSUWorks Citation

Evans, W. J., Giarikos, D., & Ziller, J. W. (2001). Lanthanide Carboxylate Precursors for Diene Polymerization Catalysis:  Syntheses, Structures, and Reactivity with Et2AlCl. Organometallics, 20, (26), 5751 - 5758. https://doi.org/10.1021/om010887n. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/59