Rare-earth complexes supported by an ansa-bis(amidinate) ligand with a rigid o-phenylene linker: synthesis,...

A bis(amidinate) ligand with a rigid o-phenylene linker C₆H₄-1,2-[NC(^tBu)NH(C₆H₅)]₂ (1) was successfully employed for the syntheses of rare-earth amides 2-5 in good yields. The structures of the amides were established by X-ray diffraction analysis and revealed that the ligand framework coordinated to the lanthanide atoms in different fashions depending on the central ion size. Larger lanthanide metal ions La³⁺ and Nd³⁺ prefer to form dinuclear complexes with one linked bis(amidinate) ligand as a bridge, while the smaller sized Y³⁺ and Er³⁺ favor the formation of mononuclear complexes. These complexes exhibited good catalytic activity for ring-opening polymerization of ε-caprolactone and l-lactide and the mononuclear complexes display higher activity.