Mechanistic studies of Alkene/CO polymerization with palladium complexes promoted by B(C6F5)(3)

GK Barlow, JD Boyle, NA Cooley*, T Ghaffar, DF Wass

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

37 Citations (Scopus)

Abstract

The reaction of Pd(dppp)(OAc)(2) [dppp = 1,3-bis(diphenylphosphino)propane] with B(C6F5)(3) in situ gives an efficient catalyst for alkene/CO polymerization in aprotic media. The borane is consumed during the polymerization, and its fluoroaryl groups are incorporated into the polymer chain ends. In the absence of the monomers the catalyst components react to give palladium(II)-pentafluoroaryl complexes formulated as Pd(dppp)(C6F5){[B(C6F5)(3)](y)OH} (y = 1, 3a; y = 2, 3b). Complex 3a can be isolated, albeit as an impure solid, and is itself a catalyst for the reaction. In light of these results a novel chain initiation process for the polymerization is proposed, involving insertion of monomers into a fluoroarylpalladium complex formed by aryl transfer from the borane to a palladium(II) complex. This facile initiation step, combined with the catalyst stability engendered by the presence of strong Bronsted acids, explains the effectiveness of this catalyst system in aprotic media.

Original languageEnglish
Pages (from-to)1470-1476
Number of pages7
JournalOrganometallics
Volume19
Issue number8
Publication statusPublished - 17 Apr 2000

Keywords

  • CATALYZED ALTERNATING COPOLYMERIZATION
  • CROSS-COUPLING REACTION
  • CARBON-MONOXIDE
  • PALLADIUM(II)-CATALYZED COPOLYMERIZATION
  • ORGANOBORON COMPOUNDS
  • OLEFIN POLYMERIZATION
  • SYNTHETIC REACTIONS
  • ARYL CHLORIDES
  • ALPHA-OLEFINS
  • ETHYLENE

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