Ring-Opening Polymerization of ε-Caprolactone by Using Aluminum Complexes Bearing Aryl Thioether Phenolates: Labile Thioether Chelation.

In this study, aluminum complexes bearing ferrocene-based and arylthiomethylphenolate ligands were synthesized, and their catalytic activity for ε-caprolactone (CL) polymerization was investigated. The catalytic activity of the reduced form of Al complexes was higher than that of the oxidized form. The CL polymerization rate of the reduced form fcO 2 AlMe (75 min, conversion = 100%) was higher than that of the oxidized form fc ox O 2 AlMe (4320 min, conversion = 45%), and the CL polymerization rate of fc(OAlMe 2 ) 2 (40 min, conversion = 100%) was higher than that of fc ox (OAlMe 2 ) 2 (60 min, conversion = 97%). Electron deficiency substituents on phenolate decreased the catalytic activity of Al complexes bearing arylthiomethylphenolate ligands. Density functional theory calculations revealed that thioether coordination stabilized the transition state ( TS1 ) and that the oxidized form fc ox (OAlMe 2 ) 2 exhibited weaker thioether coordination and higher activation energy in TS1 compared with those of the reduced form fcO 2 AlMe . In addition, our study determined that the thioether group is a suitable chelating group for Al catalysts in CL polymerization due to its labile nature.