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[O 2 CC(CH 3 ) 2 CH 2 CH 3 ] 3 } x ( 1 ) and {La[O 2 CC(CH 3 ) 2 CH 2 CH 3 ] 3 } x ( 2 ) were synthesized from the lanthanide metal and 2,2-dimethylbutyric acid in the presence of a catalytic amount of HgCl 2 and Hg(OAc) 2 . Nd 2 [O 2 CCH(C 6 H 5 )CH 2 CH 3 ] 6 [HO 2 CCH(C 6 H 5 )CH 2 CH 3 ] 4 ( 3 ) was prepared similarly from neodymium powder and 2-phenylbutyric acid. 1 and 2 crystallize from hot pyridine as the dimeric pyridine adducts Nd 2 [O 2 CC(CH 3 ) 2 CH 2 CH 3 ] 6 [pyridine] 4 ( 4 ) and La 2 [O 2 CC(CH 3 ) 2 CH 2 CH 3 ] 6 [pyridine] 4 ( 5 ). 3 crystallizes from hexanes as the carboxylic acid adduct. 1 and 2 react with Et 2 AlCl to form the isolable solids 6 and 7 , which react with Al( i Bu) 3 to generate catalytically active systems which polymerize isoprene, ethylene, and styrene. Although crystallization of 6 from THF forms NdCl 3 (THF) 4 ( 8 ) and crystallization of 7 from pyridine forms [LaCl 3 (pyridine) 4 ] 2 ( 9 ), complexes 6 and 7 are not simply LnCl 3 , since elemental analyses show that they contain aluminum.
| Original language | American English |
|---|---|
| Pages (from-to) | 5751-5758 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 20 |
| Issue number | 26 |
| DOIs | |
| State | Published - Nov 29 2001 |
| Externally published | Yes |
ASJC Scopus Subject Areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Disciplines
- Chemistry
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