Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization
Abstract
Here, a library of new dinuclear CeIV complexes of the type [NEt4]2[Ce2X6(TP)(sol)2] (X = Cl, ODipp, OSiMe3; sol = py, THF), where TP represents a family of tetraphenolate ligands that control intermetallic distance, are readily made in good yields. The ligands strongly stabilize the cerium +4 oxidation state and allow the incorporation of alkylammonium cocations in an "ate"complex formulation that enables them to be used as soluble, single-component catalysts for the ring-opening copolymerization (ROCOP) of a variety of anhydrides and epoxides. High turnover frequencies (TOFs) are achieved with high ester linkage selectivity, low dispersities, and rates that are highly tunable by the intermetallic distance enforced by the TP ligand, demonstrating that a closely coupled di-CeIV unit provides excellent rates of ROCOP catalysis and that, more generally, rare-earth complexes deserve further attention as ROCOP initiators.
- Authors:
-
[1];
[2]
- Univ. of Edinburgh, Scotland (United Kingdom)
- Univ. of Edinburgh, Scotland (United Kingdom); Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC); British Ramsay Memorial Trust
- OSTI Identifier:
- 1822868
- Grant/Contract Number:
- AC02-05CH11231; EP/L016419/1; EP/K014714/1; RSG\R1\180101
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 40; Journal Issue: 7; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cerium; rare-earth elements; dinuclear complexes; bimetallic catalysis; ringopening copolymerization (ROCOP)
Citation Formats
Gray, Steven J., Brown, Karen, Lam, Francis Y. T., Garden, Jennifer A., and Arnold, Polly L. Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization. United States: N. p., 2021.
Web. doi:10.1021/acs.organomet.1c00055.
Gray, Steven J., Brown, Karen, Lam, Francis Y. T., Garden, Jennifer A., & Arnold, Polly L. Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization. United States. https://doi.org/10.1021/acs.organomet.1c00055
Gray, Steven J., Brown, Karen, Lam, Francis Y. T., Garden, Jennifer A., and Arnold, Polly L. Thu .
"Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization". United States. https://doi.org/10.1021/acs.organomet.1c00055. https://www.osti.gov/servlets/purl/1822868.
@article{osti_1822868,
title = {Dinuclear Ce(IV) Aryloxides: Highly Active Catalysts for Anhydride/Epoxide Ring-Opening Copolymerization},
author = {Gray, Steven J. and Brown, Karen and Lam, Francis Y. T. and Garden, Jennifer A. and Arnold, Polly L.},
abstractNote = {Here, a library of new dinuclear CeIV complexes of the type [NEt4]2[Ce2X6(TP)(sol)2] (X = Cl, ODipp, OSiMe3; sol = py, THF), where TP represents a family of tetraphenolate ligands that control intermetallic distance, are readily made in good yields. The ligands strongly stabilize the cerium +4 oxidation state and allow the incorporation of alkylammonium cocations in an "ate"complex formulation that enables them to be used as soluble, single-component catalysts for the ring-opening copolymerization (ROCOP) of a variety of anhydrides and epoxides. High turnover frequencies (TOFs) are achieved with high ester linkage selectivity, low dispersities, and rates that are highly tunable by the intermetallic distance enforced by the TP ligand, demonstrating that a closely coupled di-CeIV unit provides excellent rates of ROCOP catalysis and that, more generally, rare-earth complexes deserve further attention as ROCOP initiators.},
doi = {10.1021/acs.organomet.1c00055},
journal = {Organometallics},
number = 7,
volume = 40,
place = {United States},
year = {Thu Mar 25 00:00:00 EDT 2021},
month = {Thu Mar 25 00:00:00 EDT 2021}
}
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