High-Pressure NMR Studies on the Alternating Copolymerization of Styrene with Carbon Monoxide Catalyzed by a Palladium(II)−(R,S)-BINAPHOS Complex

Autor:	and Tamejiro Hiyama, Kyoko Nozaki, Jonathan A. Iggo, Yasutoyo Kawashima, Jianke Liu
Rok vydání:	2003
Předmět:	Diffusion Organic Chemistry Inorganic chemistry chemistry.chemical_element Nuclear magnetic resonance spectroscopy Catalysis Styrene Inorganic Chemistry chemistry.chemical_compound chemistry Polymer chemistry Copolymer Gaseous diffusion Physical and Theoretical Chemistry Carbon monoxide Palladium
Zdroj:	Organometallics. 22:5418-5422
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om0304917
Popis:	The asymmetric copolymerization of styrene with CO catalyzed by Pd−(R,S)-BINAPHOS complexes has been studied using in situ NMR spectroscopy under both diffusion- and reaction-controlled conditions. While a study conducted in a conventional zirconia tube suffered from gas diffusion limitation, use of a high-pressure NMR flow cell allows the observation of potential catalytic intermediates. The formation of Pd−alkyl complexes via 1,2-insertion of styrene into Pd−acyl complexes is confirmed to be the most active catalytic pathway. The 2,1-insertion complexes were found to be quite inactive to further insertion and remarkably stable toward β-hydride elimination, in contrast to our previous expectations.
Databáze:	OpenAIRE
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