Abstract
A series of enolic Schiff base aluminum(III) complexes LAlR (where L=NNOO‐tetradentate enolic Schiff base ligand) containing ligands that differ in their steric and electronic properties were synthesized. Their single crystals showed that these complexes are five‐coordinated around the aluminum center. Their coordination geometries are between square pyramidal and trigonal bipyramidal. Their catalytic properties in the solution polymerization of racemic lactide (rac‐LA) were examined. The modifications in the auxiliary ligand exhibited a dramatic influence on the catalytic performance. Lengthening the backbone from C~2~ alkylene to C~3~ alkylene resulted in remarkable enhancement of both the stereoselectivity and the polymerization rate because of the increasing flexibility of the diimine backbone. Electron‐withdrawing substituents in the diketone also highly improved the activity and the stereoselectivity. Among these complexes, 4 b had the highest activity and the stereoselectivity owing to the C~3~ alkylene backbone and the two gem‐methyl groups on the middle carbon atom. The value of the polymerization rate constant (k~p~) catalyzed by 4 b in 70 °C was 1.90 L mol^−1^ min^−1^, the activation energy of the polymerization (35.4 kJ mol^−1^) was calculated according to the Arrhenius equation. Other factors that influenced the polymerization, such as the polymerization time, the temperature, and the monomer concentration, are also discussed in detail.