Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers

Yusuke Mitsushige, Hina Yasuda, Brad P. Carrow, Shingo Ito, Minoru Kobayashi, Takao Tayano, Yumiko Watanabe, Yoshishige Okuno, Shinya Hayashi, Junichi Kuroda, Yoshikuni Okumura, Kyoko Nozaki

Research output: Contribution to journalArticlepeer-review

73 Scopus citations

Abstract

A series of palladium complexes bearing a bisphosphine monoxide with a methylene linker, that is, [κ2-P,O-(R12P)CH2P(O)R22]PdMe(2,6-lutidine)][BArF4] (Pd/BPMO), were synthesized and evaluated as catalysts for the homopolymerization of ethylene and the copolymerization of ethylene and polar monomers. X-ray crystallographic analyses revealed that these Pd/BPMO complexes exhibit significantly narrower bite angles and longer Pd-O bonds than Pd/BPMO complexes bearing a phenylene linker, while maintaining almost constant Pd-P bond lengths. Among the complexes synthesized, menthyl-substituted complex 3f (R1 = (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-yl; R2 = Me) showed the best catalytic performance in the homo- and copolymerization in terms of molecular weight and polymerization activity. Meanwhile, complex 3e (R1 = t-Bu; R2 = Me) exhibited a markedly higher incorporation of comonomers in the copolymerization of ethylene and allyl acetate (≤12.0 mol %) or methyl methacrylate (≤0.6 mol %). The catalytic system represents one of the first examples of late-transition-metal complexes bearing an alkylene-bridged bidentate ligand that afford high-molecular-weight copolymers from the copolymerization of ethylene and polar monomers.

Original languageEnglish (US)
Pages (from-to)305-311
Number of pages7
JournalACS Macro Letters
Volume7
Issue number3
DOIs
StatePublished - Mar 20 2018

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers'. Together they form a unique fingerprint.

Cite this