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

The sequential reaction of {(allyl)Pd(mu-Cl)}(2) (2) with AgPF6 and PCy3 in CH2Cl2 generates a mixture (1-in situ) of [{(allyl)Pd(PCy3)}(2)(mu-Cl)][PF6] (1), 2, [(allyl)Pd(PCy3)(2)][PF6] (3), and (allyl)PdCl(PCy3) (4), which evolves to form pure 1 after 20 h at 23 degrees 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.