Perspective on metal-mediated polar monomer/alkene copolymerization

A major unsolved problem in polymer synthesis is the design of efficient metal-mediated systems for the copolymerization of alkenes with polar vinyl monomers, such as acrylates and methacrylates. There are several reasons for the absence of efficient transition metal-based insertion copolymerization catalysts. First, following insertion, the ester group of the acrylate coordinates to the metal thereby hindering subsequent monomer coordination. A second reason stems from the preferred 2,1-insertion of acrylates into metal–carbon bonds resulting in the placement of the ester group on the α-carbon. This makes the metal–alkyl species particularly prone to homolysis because of the enhanced stability of the resultant alkyl radical, one that is essentially the same as the propagating species in radical-initiated acrylate polymerization. In this perspective we focus on this issue of facile metal–carbon bond homolysis, especially following acrylate insertion, using examples from our own work. We suggest ways to circumvent these issues, for example forcing 1,2-insertion by imposing steric crowding at the metal. Finally, we discuss the danger of relying on radical traps as probes for polymerization mechanism. Radical traps can react with metal-hydrides and attenuate metal-centered nonradical reactions. However, even when radical traps fail to stop an observed polymerization, it may be wrong to conclude that a nonradical mechanism is at work since the traps can be destroyed under certain reaction conditions.

The preferred 2,1-insertion of acrylates into metal–carbon bonds results in the placement of the ester group on the α-carbon, making the metal–alkyl species particularly prone to homolysis because of the enhanced stability of the resultant alkyl radical. We suggest ways to circumvent this problem, for example forcing 1,2-insertion by imposing steric crowding at the metal. We also discuss the danger of relying on radical traps as probes for polymerization mechanism.Figure optionsDownload as PowerPoint slide