Polymerization of norbornene and methyl acrylate by a bimetallic palladium(II) allyl complex

Article abstract of DOI:10.1021/om700921f

The sequential reaction of {(allyl)Pd(μ-Cl)}₂ (2) with AgPF₆ and PCy3 in CH₂Cl₂ generates a mixture (1-in situ) of [{(allyl)Pd(PCy₃)}₂(μ-Cl)][PF ₆] (1), 2, [(allyl)Pd(PCy₃)₂][PF₆] (3), and (allyl)PdCl(PCy₃) (4), which evolves to form pure 1 after 20 h at 23 °C. Complex 1 reacts with PCy₃ to generate 3 and 4 and undergoes facile exchange of Pd units with 4. Both 1 and 1-in situ polymerize mixtures of norbornene (NB) and methyl acrylate (MA) to a mixture of poly(NB) and poly(MA) via competing NB insertion polymerization and MA radical polymerization.