Polymerization of Norbornene and Methyl Acrylate by a Bimetallic Palladium(II) Allyl Complex

The sequential reaction of {(allyl)Pd(μ-Cl)} 2 ( 2 ) with AgPF 6 and PCy 3 in CH 2 Cl 2 generates a mixture ( 1-in situ ) of [{(allyl)Pd(PCy 3 )} 2 (μ-Cl)][PF 6 ] ( 1 ), 2, [(allyl)Pd(PCy 3 ) 2 ][PF 6 ] ( 3 ), and (allyl)PdCl(PCy 3 ) ( 4 ), which evolves to form pure 1 after 20 h at 23 °C. Complex 1 reacts with PCy 3 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.