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Cited by 178biodegradable polymer synthesis and propertiesOrganometallic Complex Synthesis and CatalysisAdvanced Polymer Synthesis and Characterization

The DOI matches its Crossref record; 71 of the 72 references it cites were found in a registry or an index.

Metal‐Size Influence in Iso‐Selective Lactide Polymerization

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Bakewell, Clare, White, Andrew J. P., Long, Nicholas J., Williams, Charlotte K.·2014·Angewandte Chemie International Edition
DOI 10.1002/anie.201403643PMC PMC4499264
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Abstract

Iso‐selective initiators for the ring‐opening polymerization (ROP) of rac‐lactide are rare outside of Group 13. We describe the first examples of highly iso‐selective lutetium initiators. The phosphasalen lutetium ethoxide complex shows excellent iso‐selectivity, with a Pi value of 0.81–0.84 at 298 K, excellent rates, and high degrees of polymerization control. Conversely, the corresponding La derivative exhibits moderate heteroselectivity (Ps=0.74, 298 K). Thus, the choice of metal center is shown to be crucial in determining the level and mode of stereocontrol. The relative order of rates for the series of complexes is inversely related to metallic covalent radius: that is, La>Y>Lu.

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Figures

Figure 1 The structure of iso-selective yttrium phosphasalen complexes A and B[8c] and a homochiral lanthanide complex C, reported by Arnold et al.[8a]
Figure 1 The structure of iso-selective yttrium phosphasalen complexes A and B[8c] and a homochiral lanthanide complex C, reported by Arnold et al.[8a]CC BY · PubMed Central
Scheme 1 Synthesis and structure of initiators 1–3. a) Reaction conditions: 1) KN(SiMe3)2 (5 equiv), THF, 2 h, 298 K; 2) LuCl3 or LaCl3, THF, 4 h, 298 K; 3) KOR, THF, 4 h, 298 K.
Scheme 1 Synthesis and structure of initiators 1–3. a) Reaction conditions: 1) KN(SiMe3)2 (5 equiv), THF, 2 h, 298 K; 2) LuCl3 or LaCl3, THF, 4 h, 298 K; 3) KOR, THF, 4 h, 298 K.CC BY · PubMed Central
Figure 2 Schematic representation of the single-crystal X-ray structures of complex 1 (M=Lu, R=tBu), 2 (M=Lu, R=Et) and 3 (molecules A and B, M=La, R=tBu).
Figure 2 Schematic representation of the single-crystal X-ray structures of complex 1 (M=Lu, R=tBu), 2 (M=Lu, R=Et) and 3 (molecules A and B, M=La, R=tBu).CC BY · PubMed Central
Figure 3 Plot of kobs value versus [2]. Polymerization conditions: [LA]0=1 m, [2]=2–5 mm,THF, 298 K. Average errors: 1–8 %.
Figure 3 Plot of kobs value versus [2]. Polymerization conditions: [LA]0=1 m, [2]=2–5 mm,THF, 298 K. Average errors: 1–8 %.CC BY · PubMed Central

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Research works printed but not linked: 2

  1. 10.1021/ja012052 · DOI
  2. 10.1002/1521-3757(20021202)114:23<4692::AID-ANGE4692>3.0.CO;2-5 · DOI

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Metadata

Authors
Bakewell, C., White, A. J. P., Long, N. J., & Williams, C. K.
Affiliations
Imperial College London (GB)
Corresponding author
  • Long, Nicholas J.
  • Williams, Charlotte K.
ORCID
Venue
Angewandte Chemie International Edition
Publisher
Wiley
Published
2014-07-07
Volume
53
Issue
35
Pages
9226-9230
ISSN
  • 1433-7851 (ISSN-L)
  • 1521-3773
DOI
10.1002/anie.201403643
PMC
PMC4499264
OpenAlex
W2161922448
Cited by
178
References
72
Citations by year
2026: 3 · 2025: 2 · 2024: 4 · 2023: 4 · 2022: 10 · 2021: 9 · 2020: 16 · 2019: 21 · 2018: 23 · 2017: 31 · 2016: 27 · 2015: 23 · 2014: 4
FWCI
10.74
Type
journal article
Language
en
Open access
Licence
Locations
  • Angewandte Chemie International Edition (publishedVersion)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • Spiral (Imperial College London) (submittedVersion, other-oa)
Funders
Engineering and Physical Sciences Research Council (EP/C544838/1, EP/K035274/1, EP/C544846/1)
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Keywords
rac-lactide, stereocontrol, polymerization rate, degree of polymerization control

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