User-Friendly, Living Coordination–Insertion Polymerizations with Broad Functional Group Tolerance

The development of new user-friendly polymerizations for the synthesis of advanced functional materials has the ability to significantly accelerate discovery in materials science. However, it is often difficult to develop robust methodologies that overcome the sensitivities of many polymerization types and enable well-controlled polymerizations of diverse functional monomers. Herein, we introduce (Ad₃P)Pd(Me)SbF₆ as a bench-stable, single-component catalyst that is capable of living coordination-insertion polymerization of substituted norbornenes conducted in air, at room temperature, and with broad tolerance to over 30 different functional groups. Our studies revealed that the electron-donating phosphine ligand, tri(1-adamantyl)phosphine (Ad₃P), and a silver salt activating species were pivotal for maintaining well-controlled polymerizations in the presence of coordinating functionalities. We demonstrated the livingness of this catalytic system and generated block copolymers, ultrahigh molecular weight polymers, and functional polymers from a range of substituted norbornenes. Overall, this work enables coordination-insertion polymerization as a user-friendly technique for the direct synthesis of advanced functional materials.