Tuning the thiolen: Al(III) and Fe(III) thiolen complexes for the isoselective ROP of rac-Lactide

Stewart, Jack A., McKeown, Paul, Driscoll, Oliver J., Mahon, Mary F., Ward, Benjamin D. ORCID: https://orcid.org/0000-0003-1406-5940 and Jones, Matthew D. 2019. Tuning the thiolen: Al(III) and Fe(III) thiolen complexes for the isoselective ROP of rac-Lactide. Macromolecules 52 (15) , pp. 5977-5984. 10.1021/acs.macromol.9b01205

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Abstract

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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0024-9297
Funders:	EPSRC
Date of First Compliant Deposit:	7 August 2019
Date of Acceptance:	18 July 2019
Last Modified:	22 Nov 2024 15:45
URI:	https://orca.cardiff.ac.uk/id/eprint/124762

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