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Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles
Published on: June 25, 2018
Ligand-controlled insertion regioselectivity accelerates copolymerisation of ethylene with methyl acrylate by
Yusuke Mitsushige1, Brad P Carrow2, Shingo Ito1
1Department of Chemistry and Biotechnology , Graduate School of Engineering , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku , Tokyo 113-8656 , Japan .
Abstract:
A new series of palladium catalysts ligated by a chelating bisphosphine monoxide bearing diarylphosphino groups (aryl-BPMO) exhibits markedly higher reactivity for ethylene/methyl acrylate copolymerisation when compared to the first generation of alkyl-BPMO-palladium catalysts that contain a dialkylphosphino moiety. Mechanistic studies suggest that the origin of this disparate catalyst behavior is a change in regioselectivity of migratory insertion of the acrylate comonomer as a function of the phosphine substituents. The best aryl-BPMO-palladium catalysts for these copolymerisations were shown to undergo exclusively 2,1-insertion, and this high regioselectivity avoids formation of a poorly reactive palladacycle intermediate. Furthermore, the aryl-BPMO-palladium catalysts can copolymerise ethylene with other industrially important polar monomers.
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