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Tuning the Thiolen: Al(III) and Fe(III) Thiolen Complexes for the Isoselective ROP of rac-Lactide

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    Article

    Tuning the Thiolen: Al(III) and Fe(III) Thiolen Complexes for the Isoselective ROP of rac-Lactide
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    • Jack A. Stewart
      Jack A. Stewart
      Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
      More by Jack A. Stewart
    • Paul McKeown
      Paul McKeown
      Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
      More by Paul McKeown
    • Oliver J. Driscoll
      Oliver J. Driscoll
      Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
      More by Oliver J. Driscoll
    • Mary F. Mahon
      Mary F. Mahon
      Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
      More by Mary F. Mahon
    • Benjamin D. Ward
      Benjamin D. Ward
      Department of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, U.K.
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      Orcidhttp://orcid.org/0000-0003-1406-5940
    • Matthew D. Jones*
      Matthew D. Jones
      Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
      *E-mail: [email protected]. Tel.: +44 (0) 122 538 4908. Fax: +44 (0) 122 538 6231.
      More by Matthew D. Jones
      Orcidhttp://orcid.org/0000-0001-5991-5617
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    Macromolecules

    Cite this: Macromolecules 2019, 52, 15, 5977–5984
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    https://doi.org/10.1021/acs.macromol.9b01205
    Published July 31, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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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 (Pm = 0.79–0.89) and well-defined melting temperatures (Tm = 154–181 °C). The polymers have been characterized by a combination of 1H{1H} NMR, 13C{1H} NMR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and powder X-ray diffraction. Fe(1)Cl has also been shown to activate CO2, 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 (Pm = 0.56–0.72), with polymerization outcome correlating with ligand substituents.

    Copyright © 2019 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.9b01205.

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    Macromolecules

    Cite this: Macromolecules 2019, 52, 15, 5977–5984
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b01205
    Published July 31, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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