Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 17, Pages 5251-5254Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201511793
Keywords
block copolymers; iron; redox chemistry; redox-switch; ring-opening polymerization
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Funding
- NSF-CAREER [1454807]
- NSF-GRF
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1454807] Funding Source: National Science Foundation
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A cationic iron(III) complex was active for the polymerization of various epoxides, whereas the analogous neutral iron(II) complex was inactive. Cyclohexene oxide polymerization could be switched off upon in situ reduction of the iron(III) catalyst and switched on upon in situ oxidation, which is orthogonal to what was observed previously for lactide polymerization. Conducting copolymerization reactions in the presence of both monomers resulted in block copolymers whose identity can be controlled by the oxidation state of the catalyst: selective lactide polymerization was observed in the iron(II) oxidation state and selective epoxide polymerization was observed in the iron(III) oxidation state. Evidence for the formation of block copolymers was obtained from solubility differences, GPC, and DOSY-NMR studies.
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