Block Copolymerization of Lactide and an Epoxide Facilitated by a Redox Switchable Iron‐Based Catalyst
Abstract
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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This allowed the formation of clean diblock copolymers.
“This allowed the formation of clean diblock copolymers.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [320]
Unlike the previous case, the two monomers exhibited orthogonal reactivity with one being completely inactive during the polymerization of the other.
“Unlike the previous case, the two monomers exhibited orthogonal reactivity with one being completely inactive during the polymerization of the other.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [320]
Byers developed a chemoselective copolymerization of LA and epoxides using a redox-switchable iron catalyst.
“In the similar vein, Byers developed a chemoselective copolymerization of LA and epoxides using a redox-switchable iron catalyst (Scheme 8B).320”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [320]
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Lastovickova, D. N., Teator, A. J., Shao, H., Liu, P., & Bielawski, C. W. (2017) · Inorganic Chemistry Frontiers · doi:10.1039/c7qi00018a · Cited by 21 · see citing works
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Zhao, B., & Wilson, P. (2023) · Polymer Chemistry · doi:10.1039/d3py00062a · Cited by 18 · see citing works
Multistimuli‐Responsive [3]Dioxaphosphaferrocenophanes with Orthogonal Switches
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- Authors
- Biernesser, A. B., Delle Chiaie, K. R., Curley, J. B., & Byers, J. A.
- Affiliations
- Boston College (US)
- Department of Chemistry Boston College Eugene F. Merkert Chemistry Center 2609 Beacon Street Chestnut Hill MA 02467 USA
- Corresponding author
- Byers, Jeffery A.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2016-03-17
- Volume
- 55
- Issue
- 17
- Pages
- 5251-5254
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2296815437
- Cited by
- 165
- References
- 15
- Citations by year
- 2026: 3 · 2025: 9 · 2024: 9 · 2023: 8 · 2022: 14 · 2021: 21 · 2020: 18 · 2019: 22 · 2018: 27 · 2017: 23 · 2016: 11
- FWCI
- 11.32
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (1454807)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- block copolymerization, lactide, epoxide polymerization, cyclohexene oxide, iron catalysts, iron(III) complexes, iron(II) complexes, cationic polymerization, catalyst oxidation state, selective polymerization, conducting polymers
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