Cobalt‐Mediated Switchable Catalysis for the One‐Pot Synthesis of Cyclic Polymers

A cobalt salen pentenoate complex [salen=(R,R)-N,N'-bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediamine] is rationally designed as the catalyst for the ring-opening copolymerization (ROCOP) of epoxides/anhydrides/CO₂ . Via migratory insertion of carbon monoxide (CO) into the Co-O bonds, the ROCOP-active species α-alkene-ω-O-Co^III (salen) can be rapidly and quantitatively transformed into α-alkene-ω-O₂ C-Co^III (salen) telechelic linear precursors. Upon dilution of reaction mixtures, the homolytic cleavage of Co-C bonds induced by visible light generates α-alkene acyl radicals that spontaneously undergo intramolecular radical addition to afford organocobalt-functionalized cyclic polyesters and CO₂ -based polycarbonates with excellent regioselectivity. The cyclic products can either react with radical scavengers to generate metal-free cyclic polymers or serve as photo-initiators for organometallic-mediated radical polymerization (OMRP) to produce tadpole-shaped copolymers.