Lanthanum complexes stabilized by a pentadentate Schiff-base ligand: synthesis, characterization, and reactivity in...

Developing catalysts that are capable of catalyzing the copolymerization of ε-caprolactone and l-lactide to give random CL/LA copolymers is of great importance. One-pot reaction of La[N(SiMe₃)₂]₃ with 1 equiv. of LH₂ (LH₂ = NH(CH₂CH₂N[double bond, length as m-dash]CHC₆H₂-3,5-^tBu₂-2-OH)₂) in THF at room temperature, followed by protolysis with one equivalent amount of ROH (R = C₆H₂-2,6-^tBu₂-4-CH₃, ^tBu, ⁱPr, Bn, and Et) at 60 °C gave the mono-Schiff-base-ligated lanthanum aryloxide complex LLa(OC₆H₂-2,6-^tBu₂-4-CH₃)(THF) (1), and lanthanum alkyloxide complexes LLaO^tBu(THF) (2), [LLaOⁱPr]₂ (3), [LLaOBn]₂ (4), and [LLaOEt]₂ (5) in 59-69% isolated yields. These lanthanum complexes were capable of initiating the homopolymerization of l-lactide and rac-lactide with extremely high activity, and the copolymerization of ε-caprolactone (ε-CL) and l-lactide (l-LA) to give statistical CL/LA copolymers via a transesterification reaction.