Well-Designed Unsymmetrical Salphen-Al Complexes: Synthesis, Characterization, and Ring-Opening Polymerization Catalysis

The unsymmetrical salphen ligand (3,5-tBu-1-OH-C6H2)CH═N-C6H4-N═CH(3-Ph-1-OH-C6H3) (tBu-PhLH2) was designed and synthesized to support aluminum complexes. Its symmetric analogues, (3,5-tBu-1-OH-C6H2)CH═N-C6H4-N═CH(3,5-tBu-1-OH-C6H2) (tBuLH2) and (3-Ph-1-OH-C6H3)CH═N-C6H4-N═CH(3-Ph-1-OH-C6H3) (PhLH2), were also explored and compared. The methane elimination reactions between ligands and AlMe3 resulted in formation of tBu-PhLAlMe (1), tBuLAlMe (2), and PhLAlMe (3) in high yields, which were characterized by elemental analysis, 1H and 13C NMR. The coordination geometries of unsymmetrical and symmetric ligands in 1 and 2 were studied by X-ray diffractions, which revealed a five-coordinated distorted square-pyramidal geometry around Al centers. The aluminum methyl compounds 1–3 reacted with BnOH at 70 °C to give tBu-PhLAlOBn (4), tBuLAlOBn (5), and PhLAlOBn (6), respectively, which existed as monometallic species in solution as indicated by NMR studies. However, the aluminum isopropoxide prepared by the reacti...

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