Redox-Controlled Polymerization and Copolymerization

Redox control is an attractive strategy for modulating polymerization processes as well as the compositions, microstructures, and properties of polymer products. This perspective summarizes recently reported catalytic systems that possess redox-switching capabilities and their applications to the ring-opening polymerizations of cyclic esters, ring-opening-metathesis polymerizations of cyclic olefins, and coordination–insertion polymerizations of olefins. Redox-induced switching between catalytically active states enables the generation of unique polymer microstructures that are difficult to access otherwise.