Aluminium complexes containing salicylbenzothiazole ligands and their application in the ring-opening polymerisation of rac-lactide and epsilon-caprolactone

作者：Nakonkhet Chutikan; Nanok Tanin; Wattanathana Worawat; Chuawong Pitak; Hormnirun Pimpa^*

来源：Dalton Transactions, 2017, 46(33): 11013-11030.

DOI：10.1039/c7dt02435e

Two series of aluminium complexes bearing salicylbenzothiazole ligands, namely four-coordinate aluminium complexes (1a-7a) and five-coordinate aluminium complexes (1b-7b), were synthesized and characterized by NMR spectroscopy, elemental analysis and X-ray diffraction crystallography (for 5a and 1b). Their application in the ring-opening polymerisation of rac-lactide and e-caprolactone was studied with the aim of drawing comparisons to closely related aluminium salicylbenzoxazole complexes investigated previously. In the presence of benzyl alcohol, all complexes were active initiators and polymerisations were all well controlled and living. Kinetic studies revealed first-order kinetics in the monomer. In contrast, the catalytic activity of aluminium salicylbenzothiazole complexes was lower than that of aluminium salicylbenzoxazole counterparts. Detailed DFT calculations were performed and indicated that the observed lower catalytic activity of aluminium salicylbenzothiazole complexes agreed well with the observed higher Gibbs free energy at the ring-opening transition state.

• 出版日期2017-9-7