From Molecule to Material: How Support Changes Heterobimetallic Catalysts in Lactide Polymerization

ABSTRACT Sustainable production of polylactide demands catalysts that are both recoverable and capable of delivering precise molar mass and stereocontrol. A series of heterobimetallic complexes (THF)NaFe(O t Bu) 3 2 , (THF) 2 KFe(O t Bu) 3 2 , KZn(O t Bu) 3 2 , (THF)KCu(O t Bu) 3 ∞ and (THF)KCo(O t Bu) 3 2 was evaluated as precursors for heterogeneous catalysts by grafting onto dehydroxylated silica. All complexes demonstrated activity in the ring‐opening polymerization of lactide. Notably, the silica‐supported (THF)KFe(O t Bu) 2 / SiO 2‐700 and (THF)NaFe(O t Bu) 2 / SiO 2‐700 systems exhibited high efficiency, promising recyclability, and afforded predictable molar masses ( M n,exp close to M n,th ) with narrow dispersities. These findings highlight new opportunities for designing recyclable catalysts for sustainable PLA synthesis.