Weiwei Zuo

Synthesis of Aluminum Complexes Bearing 8-Anilide-5,6,7-trihydroquinoline Ligands: Highly Active Catalyst Precursors for Ring-Opening Polymerization of Cyclic Esters

The stoichiometric reactions of 8-(2,6-R1-4-R2-anilide)-5,6,7-trihydroquinoline (LH) with AlR3 (R = Me or Et) afforded the aluminum complexes LAlR2 (Al1–Al5,Al1: R1 = iPr, R2 = H, R = Me; Al2: R1 = Me, R2 = H, R = Me; Al3: R1 = H, R2 = H, R = Me; Al4: R1 = Me, R2 = Me, R = Me; Al5: R1 = Me, R2 = Me, R = Et) in high yields. All aluminum complexes were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes Al4 and Al5 were determined by single-crystal X-ray diffractions and revealed a distorted tetrahedral geometry at aluminum. In the presence of BnOH, complexes Al1–Al5 efficiently initiated the ring-opening homopolymerization of ε-caprolactone (ε-CL) and rac-lactide (rac-LA), respectively, in a living/controlled manner.

Synthesis of dinuclear aluminum complexes bearing bis-phenolate ligand and application in ring-opening polymerization of ε-caprolactone

The stoichiometric reaction of bis-phenolate ligands with AlMe3 afforded zwitterionic aluminum complexes Al1-Al3, which were characterized by NMR spectroscopy and elemental analysis. The solid state structure of Al2 was determined by single-crystal X-ray diffraction, which revealed a dinuclear feature. Two Al centers were bridged by two ligands and thus formed an unusual large 24-membered-ring metallacycle. In the presence of BnOH, Al1-Al3 were efficient for the ring-opening polymerization of e-caprolactone in a controlled manner, and the efficiency was affected by substituents on the ligands. The polymerizations exhibited a feature of immortal catalysis with an excess of BnOH.

Bimetallic Aluminum Complexes Supported by Bis(salicylaldimine) Ligand:Synthesis, Characterization and Ring-Opening Polymerization of Lactide

Two types of bifunctional bis(salicylaldimine) ligands (syn-L and anti-L) were designed and synthesized to support bimetallic aluminum complexes. Owing to the rigid anthracene skeleton, syn-L and anti-L successfully locked two Al centers in close proximity (syn-Al2) and far apart (anti-Al2), respectively. The distance between two Al centers in syn-Al2 was defined by X-ray diffraction as 6.665 Å, which is far shorter than that in anti-Al2. In the presence of stoichiometrical BnOH, syn-Al2 and anti-Al2 were both efficient for ring-opening polymerization (ROP) of rac-LA with the former being more active. In the presence of excess BnOH, syn-Al2 showed an efficient and immortal feature, consistent with high conversions, matched Mns, narrow molecular weight distributions and end group fidelity, while anti-Al2 had a much lower activity or even became entirely inactive due to rapid decomposition, indicated by in situ1H-NMR experiments of Al complexes with BnOH.