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Ring-Opening Polymerization of ε-Caprolactone by Using Aluminum Complexes Bearing Aryl Thioether Phenolates: Labile
Someswara Rao Kosuru1, Yu-Lun Chang1, Po-Yu Chen1
1Department of Medicinal and Applied Chemistry, Drug Development and Value Creation Research Center, Kaohsiung Medical University, Kaohsiung, Taiwan 80708, ROC.
Abstract:
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 fcOAlMe (75 min, conversion = 100%) was higher than that of the oxidized form fcOAlMe (4320 min, conversion = 45%), and the CL polymerization rate of fc(OAlMe) (40 min, conversion = 100%) was higher than that of fc(OAlMe) (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(OAlMe) exhibited weaker thioether coordination and higher activation energy in TS1 compared with those of the reduced form fcOAlMe. 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.
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