Enhanced Catalytic Activity of Aluminum Complexes for the Ring-Opening Polymerization of ε-Caprolactone

A series of dinuclear aluminum (Al2Pyr2) complexes bridged by two pyrazole ligands were synthesized, and their catalytic activity toward ring-opening polymerization of e-caprolactone (CL) was investigated. Different types of the Al–N–N–Al–N–N skeletal ring were found among these Al2Pyr2 complexes. The butterfly form, LThio2Al2Me4, exerted the highest catalytic activity for CL polymerization. κ2-CL coordination with both Al centers within the butterfly form LThio2Al2Me4 facilitates the initiation process. Generally speaking, the Al2Pyr2 complexes exhibited substantially higher catalytic activity for CL polymerization than literature examples such as β-diketiminate- or traiaza-bearing aluminum complexes. In fact, the Al2Pyr2 complexes can even carry out CL polymerization at room temperature.