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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Synthesis of functional polyolefins using cationic bisphosphine monoxide-palladium complexes
1Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Journal of the American Chemical Society
|May 18, 2012
Summary
New cationic palladium complexes enable ethylene copolymerization with diverse polar monomers, yielding linear polymers with random functional groups. This expands catalytic options beyond existing phosphine-sulfonate systems for functional polyolefins.
Area of Science:
- Polymer Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Copolymerization of ethylene with polar vinyl monomers is challenging due to catalyst incompatibility with polar functional groups.
- Existing catalysts, like Brookhart-type α-diimine palladium complexes, have limited applicability to industrially relevant polar monomers.
- Phosphine-sulfonate ligated palladium complexes are a known class of catalysts for such reactions.
Purpose of the Study:
- To explore the efficacy of cationic palladium complexes ligated by bisphosphine monoxide (BPMO) in ethylene copolymerization with various polar vinyl monomers.
- To demonstrate an alternative catalytic system for producing linear functional polyolefins.
- To compare the performance of BPMO-ligated palladium catalysts with existing systems.
Main Methods:
- Synthesis and characterization of cationic palladium complexes featuring bisphosphine monoxide (BPMO) ligands.
- Copolymerization reactions of ethylene with polar vinyl monomers (vinyl acetate, acrylonitrile, vinyl ethers, allyl monomers) using the developed catalysts.
- Analysis of copolymer microstructure, including linearity and distribution of polar groups.
Main Results:
- Cationic palladium-BPMO complexes effectively catalyzed the copolymerization of ethylene with a range of polar vinyl monomers.
- The resulting copolymers exhibited highly linear microstructures and a random distribution of polar functional groups.
- These catalysts showed good activity, outperforming certain established systems for specific monomer combinations.
Conclusions:
- Cationic palladium-BPMO complexes represent a viable and active catalytic system for the synthesis of linear functional polyolefins.
- This work expands the scope of palladium-catalyzed ethylene copolymerization with polar monomers.
- Bisphosphine monoxide ligated palladium complexes offer a new alternative to phosphine-sulfonate systems for producing functional polyolefins.
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