The ring-opening polymerisation of lactide is a useful means to prepare biodegradable materials with well controlled polymer architectures and bespoke material properties. While homogeneous ligand-Al-OR complexes have shown great success in this field, initiation from ligand-AlCl complexes has lagged behind. Here, we report four new salen-AlCl complexes featuring NEt2-substituents, which display high catalyst activities towards rac-lactide ring-opening polymerisation (kobs < 1.9 x 10 -3 s -1 ) via in situ activation with a single equivalent of propylene oxide. Incorporating Lewis basic NEt2 groups into the ligand scaffold not only improves the initiation efficiency but also avoids the need for a Lewis basic co-catalyst and excess epoxide. Notably, studies of our amino-substituted catalysts reveal that the formation of a hexacoordinate aluminate species may hinder rather than enhance catalytic activity.

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.

No abstract

No abstract