期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 71, 页码 17183-17189出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202003616
关键词
isoselectivity; living polymerization; magnesium; poly(lactic acid); ring-opening polymerization
资金
- Israel Science Foundation [553/18]
- University Grant Commission of India
- grant project 2015CTEBBA of the MIUR-PRIN 2015
- Israel Sciene Foundation [2711/17]
- grant POR FESR 2014/2020
The coordination chemistry and the activities in the ring-opening polymerization catalysis of racemic lactide (LA) of magnesium complexes of a series of {ONNN}-type sequential monoanionic ligands are described. All ligands include pyridyl and substituted-phenolate as peripheral groups. The ligands bearing either chiral or meso-bipyrrolidine cores led to single diastereomeric complexes, whereas the ligands bearing a diaminoethane core led to diastereomer mixtures. All {ONNN}Mg-X complexes [X=Cl, HMDS (hexamethyldisilazide)] led to highly active and isoselective catalysts. The complexes bearing the chiral bipyrrolidine core exhibited the highest activities (full consumption of 5000 equiv. of rac-LA at RT within 5 min) and highest isoselectivities (P-m=0.91), as well as a living character. The complexes of the meso-bipyrrolidine based ligands were almost as active and slightly less stereoselective, while those of the diaminoethane based ligands exhibited reduced activities and isoselectivities.
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