Aluminum methyl, alkoxide and α-alkoxy ester complexes supported by 6,6'-dimethylbiphenyl-bridged salen ligands: synthesis, characterization and catalysis for rac-lactide polymerization.

The synthesis and characterization of aluminum alkyl and alkoxide complexes bearing racemic 6,6'-dimethylbiphenyl-bridged salen-type ligands, and their catalysis in the ring-opening polymerization (ROP) of rac-lactide are reported. Reactions of AlMe3 with various amounts of the proligands (6,6'-[(6,6'-dimethyl-[1,1'-biphenyl]-2,2'-diyl)bis(nitrylomethilidyne)]-bis(2-R(1)-4-R(2)-phenol): , R(1) = R(2) = Me; , R(1) = (t)Bu, R(2) = Me; , R(1) = R(2) = cumyl; , R(1) = Br, R(2) = (t)Bu) afforded the corresponding mono- and dinuclear aluminum methyl complexes [AlMe (), Al2Me4 ()]. Aluminum alkoxide complexes AlO(i)Pr (), AlOBn (), and α-alkoxy ester complexes Al(OCMe2CO2Me) (), Al[(S)-OCHMeCO2Me] () were prepared via in situ alcoholysis of the parent aluminum methyl complex with the corresponding alcohols. The molecular structures of mononuclear complexes , dinuclear complex , alkoxide complexes and α-alkoxy ester complexes were established by single-crystal X-ray diffraction studies. Two broad resonances at about 69-70 ppm and 25-41 ppm were observed in the (27)Al NMR spectra of complexes and , indicating the existence of both four- and five-coordinate aluminum centers in solution, which results from the dissociation of one N donor of the salen ligand, accompanied by an association and dissociation equilibrium of the carbonyl group of the α-alkoxy ester ligand to the aluminum center. Complex is also a rare example of an O-lactate model complex that mimics the first insertion of l-LA. All complexes were investigated for the ROP of rac-LA at 110 °C in toluene. The polymerization initiated by complexes in the presence of (i)PrOH showed living features, affording PLAs with narrow molecular weight distributions (PDIs = 1.03-1.05) and 65-73% isotacticities. Particularly, complex showed an "immortal" behavior for the polymerization of rac-LA in the presence of excess alcohol. Compared with the mononuclear counterparts, the tetra-coordinate dinuclear aluminum complexes enabled a few fold boosts in activity, but gave atactic PLAs with broadened PDIs.