Tuning the Thiolen: Al(III) and Fe(III) Thiolen Complexes for the Isoselective ROP of rac-Lactide
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A series of five iron and aluminum complexes bearing {ONSO} imine thiobis(phenolate) ligands have been prepared and applied to the ring-opening polymerization (ROP) of rac -lactide. Fe( 1 )Cl produced polylactide with a very strong isotactic bias ( P m = 0.79–0.89) and well-defined melting temperatures ( T m = 154–181 °C). The polymers have been characterized by a combination of 1 H{ 1 H} NMR, 13 C{ 1 H} NMR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and powder X-ray diffraction. Fe( 1 )Cl has also been shown to activate CO 2, at atmospheric pressure and concentrations, to form a carbonato-bridged dimer. Fe( 2 – 5 )Cl and Al( 1 – 5 )Me were also active for lactide ROP demonstrating good-molecular-weight control ( Đ = 1.04–1.12) and moderate isotactic preference ( P m = 0.56–0.72), with polymerization outcome correlating with ligand substituents.
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Comparatively little research has been directed at using inexpensive iron catalysts for effective ROP reactions.
“Still, comparatively little research has been directed at using inexpensive iron catalysts for effective ROP reactions.”
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- Authors
- Stewart, J. A., McKeown, P., Driscoll, O. J., Mahon, M. F., Ward, B. D., & Jones, M. D.
- Affiliations
- University of Bath (GB)
- Cardiff University (GB)
- Corresponding author
- Jones, Matthew D.
- ORCID
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-07-31
- Volume
- 52
- Issue
- 15
- Pages
- 5977-5984
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2965222898
- Cited by
- 40
- References
- 80
- Citations by year
- 2026: 4 · 2025: 6 · 2024: 5 · 2023: 7 · 2022: 9 · 2021: 4 · 2020: 2 · 2019: 3
- FWCI
- 1.28
- Type
- journal article
- Language
- en
- Open access
- Licence
- Locations
- Macromolecules (publishedVersion)
- ORCA Online Research @Cardiff (Cardiff University) (acceptedVersion)
- ORCA Online Research @Cardiff (Cardiff University) (submittedVersion)
- Pure (University of Bath) (submittedVersion, other-oa)
- Funders
- Engineering and Physical Sciences Research Council (EP/P016405/1, EP/L016443/1)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- ring-opening polymerization, rac-lactide, polylactic acid, iron(III) complexes, aluminum(III) complexes, isotacticity, ligand substituent effects, CO2 activation, molecular weight control, stereoselective polymerization
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