Yttrium Phosphasalen Initiators for rac-Lactide Polymerization: Excellent Rates and High Iso-Selectivities
Abstract
Highly active yttrium phosphasalen initiators for the stereocontrolled ring-opening polymerization of rac-lactide are reported. The initiators are coordinated by a new class of ancillary ligand: an iminophosphorane derivative of the popular "salen" ligand, termed "phosphasalen". Changing the phosphasalen structure enables access to high iso-selectivities (P(i) = 0.84) or hetero-selectivities (P(s) = 0.87). The initiators also show very high rates, excellent polymerization control, and tolerance to low loadings; furthermore, no chiral auxiliaries/ligands are needed for the stereocontrol. The combination of such high rates with high iso-selectivities is very unusual.
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Rare-earth metal catalysts supported by phosphasalen ligands displayed both high reactivity and stereoselectivity (Pi up to 0.84 at 25 °C) with the ability to produce high molecular weight isotactic PLAs (Mn > 100 kDa) with extremely narrow polydispersities (Ð < 1.1).
“Rare-earth metal catalysts supported by phosphasalen ligands (such as Ln-phosSALEN in Figure 8) displayed both high reactivity and stereoselectivity (Pi up to 0.84 at 25°C) with the ability to produce high molecular weight isotactic PLAs (Mn > 100 kDa) with extremely narrow polydispersities (Ð <1.1).310,311”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [310]
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Self-citation
- Authors
- Bakewell, C., Cao, T.-P.-A., Long, N., Le Goff, X. F., Auffrant, A., & Williams, C. K.
- Affiliations
- Imperial College London (GB)
- Centre National de la Recherche Scientifique (FR)
- Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, 9118 Palaiseau, France
- Corresponding author
- Auffrant, Audrey
- Williams, Charlotte K.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-12-11
- Volume
- 134
- Issue
- 51
- Pages
- 20577-20580
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2058599232
- Cited by
- 226
- References
- 48
- Citations by year
- 2026: 4 · 2025: 4 · 2024: 12 · 2023: 8 · 2022: 6 · 2021: 13 · 2020: 11 · 2019: 14 · 2018: 25 · 2017: 33 · 2016: 22 · 2015: 29 · 2014: 28 · 2013: 17
- FWCI
- 9.60
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- HAL (submittedVersion)
- Funders
- Engineering and Physical Sciences Research Council (EP/C544838/1)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- ring-opening polymerization, stereospecific polymerization, salen ligands, polymerization initiators, polymerization rate, chiral auxiliaries
- MeSH terms
- Dioxanes, Ethylenediamines, Ligands, Models, Molecular, Polyesters, Stereoisomerism, Yttrium, Polymerization
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