Ligand-controlled insertion regioselectivity accelerates copolymerisation of ethylene with methyl acrylate by cationic bisphosphine monoxide-palladium catalysts

Yusuke Mitsushige, Brad P. Carrow, Shingo Ito, Kyoko Nozaki

Research output: Contribution to journalArticle

39 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)737-744
Number of pages8
JournalChemical Science
Volume7
Issue number1
DOIs
StatePublished - Jan 1 2016

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Ligand-controlled insertion regioselectivity accelerates copolymerisation of ethylene with methyl acrylate by cationic bisphosphine monoxide-palladium catalysts'. Together they form a unique fingerprint.

  • Cite this