Cited by 226biodegradable polymer synthesis and propertiesAsymmetric Synthesis and CatalysisOrganometallic Complex Synthesis and Catalysis

Yttrium Phosphasalen Initiators for rac-Lactide Polymerization: Excellent Rates and High Iso-Selectivities

Bakewell, Clare, Cao, Thi-Phuong-Anh, Long, Nicholas, Le Goff, Xavier F., Auffrant, Audrey, Williams, Charlotte K.·2012·Journal of the American Chemical Society

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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Crossref · 10.1021/ja310003v

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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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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
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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