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Collaboration between Trinuclear Aluminum Complexes Bearing Bipyrazoles in the Ring-Opening Polymerization of
Someswara Rao Kosuru1, Feng-Jie Lai2,3, Yu-Lun Chang1
1Department of Medicinal and Applied Chemistry, Drug Development and Value Creation Research Center, Kaohsiung Medical University, Kaohsiung 80708, Taiwan, Republic of China.
Abstract:
Trinuclear aluminum complexes bearing bipyrazoles were synthesized, and their catalytic activity for ε-caprolactone (CL) polymerization was investigated. DAlMe exhibited higher catalytic activity than did the dinuclear aluminum complex LAlMe (16 times as high for CL polymerization; [CL]:[DAlMe]:[BnOH] = 100:0.5:5, [DAlMe] = 10 mM, conversion 93% after 18 min at room temperature). Density functional theory calculations revealed a polymerization mechanism in which CL first approached the central Al atom and then moved to an external Al. The coordinated CL ring was opened because the repulsion of two tert-butyl groups on the ligands pushed an alkoxide initiator on an external Al to initiate CL. In these trinuclear Al catalysts, the central Al plays a role in monomer capture and then collaborates with the external Al to activate CL, accelerating polymerization.
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