Low-Symmetry β-Diketimine Aryloxide Rare-Earth Complexes: Flexible, Reactive, and Selective

We report the synthesis, characterization, and reactivity of a new low-symmetry β-diketimine featuring a pendant amino(methyl)phenol donor and its corresponding heteroleptic rare-earth (RE) complexes. This includes the first structurally characterized examples of alcoholysis and insertion from an isolated RE^III amide in a β-diketimine framework. The flexible methylene linkage leads to RE^III complexes with tunable dynamic solution behavior that defines their stoichiometric and catalytic reactivity. The addition of a strong neutral donor ligand, tricyclohexylphosphine oxide, suppresses a prevalent catalyst degradation pathway (base-promoted elimination) and dramatically enhances the catalyst performance in the stereospecific ring-opening polymerization of rac-β-butyrolactone. Our results further demonstrate the importance of ligand reorganization in the stoichiometric and catalytic activity of RE^III ions.