Journal of Molecular Catalysis A-Chemical, Vol.393, 175-181, 2014
Zinc/magnesium-sodium/lithium heterobimetallic triphenolates: Synthesis, characterization, and application as catalysts in the ring-opening polymerization of L-lactide and CO2/epoxide coupling
A series of heterobimetallic complexes supported by a bulky trisphenol ligand were synthesized and characterized. Treatment of 2,6-bis(3,5-bis-t-butyl-2-hydroxybenzyl)-4-t-butyl phenol with 1 equivalent sodium/(BuLi)-Bu-n and 1 equiv. Zn(Et)(2) in THF solution afforded complex 1 or 2; metal complexes 3 and 4 were obtained in quantitative yields by alternating Zn(Et)(2) to Mg(Bu-n)(2). The X-ray structures of 2 and 3 indicated that four metal atoms in the complexes are nearly collinear. Catalysis employing complexes 1-3 for L-lactide (L-LA) was systematically studied, and experimental results showed that 1 and 2 can catalyze the ring-opening polymerization of L-LA in a controlled fashion; what is more, both of these two complexes could catalyze L-LA with high conversion even in an air atmosphere. Complexes 1 and 2 also can effectively catalyze the coupling reaction of carbon dioxide with cyclohexene oxide using n-Bu4NBr/n-Bu4NCl as co-catalysts. (C) 2014 Elsevier B.V. All rights reserved.
Keywords:Polylactide;Cyclohexene oxide;Ring-opening polymerization;Catalyst;Heterobimetallic complex