Aluminum Initiators Supported by Asymmetric [ONNO′]‐Type Salan Ligands for the Ring‐Opening Polymerization of rac‐Lactide

A novel series of aluminum complexes supported by asymmetric [ONNO′]‐type Salan ligands ( 1–4 ) is successfully synthesized. Polylactides (PLAs) with molecular weights close to the theoretical values and narrow polydispersity indices (PDIs) can be obtained. Kinetic studies reveal first‐order polymerization kinetics and a linear relationship between the molecular weight and the percentage conversion. Complexes 1–4 display heteroselective polymerization to give heterotactic‐enriched PLAs with P r values ranging from 0.64 to 0.74. The character of the ligand substituents from the two different phenolic rings and the complex fluxionality arising from the ligand interconversion are suggested to be responsible for the different levels of stereoselectivity and activity. magnified image