期刊
MACROMOLECULES
卷 53, 期 5, 页码 1809-1818出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.0c00092
关键词
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资金
- NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation [CHE-901635]
- NSF-MRI (University of Minnesota) [CHE-1229400]
- Washington University in St. Louis [1827756]
The solid state and fluxional behaviors in solution of complexes (LAlOBn)-Al-2 and (LAlOBn)-Al-7 (Bn = benzyl) supported by an analog of salen incorporating indolide arms connected via their 2- and 7-positions were defined by experiment and theory. The complexes catalyze the stereoselective conversion of rac-lactide (rac-LA) to isotactically enriched polylactide. A key aspect of the stereocontrol was examined through study of the initiation reactions via NMR spectroscopy, X-ray crystal structures of the ring-opened products, and theory. The results include the first unambiguous structural definition of stereocontrol in ring-opening of LA by a metal-alkoxide complex and the finding that definition of the stereochemistry of initiation by the studied system is governed thermodynamically rather than kinetically.
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