Mechanism of Insertion Polymerization of Allyl Ethers

Florian P. Wimmer, Lucia Caporaso, Luigi Cavallo, Stefan Mecking, Laura Falivene*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Scopus citations


The copolymerization of ethylene (E) with allyl ethyl ether (AEE) by [di(2-dianisyl)phosphine-2-yl]benzenesulfonato Pd(II) as a catalyst is investigated by DFT calculations and compared with the copolymerization of E with diallyl ether (DAE). For AEE, both 1,2- and 2,1-monomer insertions lead to a very stable O-Chelate product (a five-membered and a four-membered ring, respectively) that hinders any further ethylene insertion. As for DAE, a first 2,1-insertion (favored by 1.8 kcal mol-1 vs the 1,2-insertion) leads to the four-membered O-Chelate product that easily evolves to the most stable intermediate with the second DAE C=C bond coordinated to the metal promoting the following 1,2-insertion. The 2,1 + 1,2 DAE insertion product, bearing a five-membered cyclic unit, is stabilized by a β-agostic interaction that easily opens in favor of E coordination and insertion. Based on the proposed copolymerization mechanism, the stereochemistry of the E/DAE copolymer is studied and the experimental microstructure explained. Finally, [di(2-anisyl)phosphine-2-yl]benzenesulfon(methyl)amido Pd(II) species showing a greater regioselectivity toward a first DAE 2,1-insertion (Δ ΔG of -3.6 kcal mol-1) are suggested to be a promising catalyst.

Original languageEnglish (US)
Pages (from-to)4525-4531
Number of pages7
Issue number12
StatePublished - Jun 26 2018

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

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


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