Cooperative Heterometallic Catalysts for Lactide Ring-Opening Polymerization: Combining Aluminum with Divalent Metals

While homometallic (salen)Al catalysts display excellent performance in lactide ring-opening polymerization (ROP), heterometallic (salen)Al complexes have yet to be reported. Herein, we describe four heterobimetallic (salen)Al catalysts and show that the choice of the heterometal is key. Cooperative Al/Mg and Al/Zn combinations improved the catalyst activity by a factor of up to 11 compared to the mono-Al analogue, whereas the mono-Mg and mono-Zn analogues were completely inactive. In contrast, Al/Li and Al/Ca heterocombinations stunted the polymerization rate. Kinetic and computational studies suggest that Al/Mg and Al/Zn cooperativity arises from the close intermetallic proximity facilitating chloride bridging (thus enhancing initiation), which promotes a rigid square pyramidal geometry around the Al center and further increases the available monomer coordination sites. This work also translates the use of ab initio molecular dynamics calculations to ROP, introducing a useful method of investigating catalyst flexibility and revealing that ligand strain and molecular rigidity can enhance heterometallic catalyst performance.