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

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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 (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 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 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 (A = 1.04-1.12) and moderate isotactic preference (P m = 0.56-0.72), with polymerization outcome correlating with ligand substituents.

Original languageEnglish
Pages (from-to)5977-5984
Number of pages8
JournalMacromolecules
Volume52
Issue number15
Early online date31 Jul 2019
DOIs
Publication statusPublished - 13 Aug 2019

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Tuning the thiolen: Al(III) and Fe(III) thiolen complexes for the isoselective ROP of rac-lactide",
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 (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 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 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 (A = 1.04-1.12) and moderate isotactic preference (P m = 0.56-0.72), with polymerization outcome correlating with ligand substituents.",
author = "Jack Stewart and Paul McKeown and Oliver Driscoll and Mary Mahon and Benjamin Ward and Matthew Jones",
year = "2019",
month = "8",
day = "13",
doi = "10.1021/acs.macromol.9b01205",
language = "English",
volume = "52",
pages = "5977--5984",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "15",

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TY - JOUR

T1 - Tuning the thiolen: Al(III) and Fe(III) thiolen complexes for the isoselective ROP of rac-lactide

AU - Stewart, Jack

AU - McKeown, Paul

AU - Driscoll, Oliver

AU - Mahon, Mary

AU - Ward, Benjamin

AU - Jones, Matthew

PY - 2019/8/13

Y1 - 2019/8/13

N2 - 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 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 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 (A = 1.04-1.12) and moderate isotactic preference (P m = 0.56-0.72), with polymerization outcome correlating with ligand substituents.

AB - 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 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 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 (A = 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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U2 - 10.1021/acs.macromol.9b01205

DO - 10.1021/acs.macromol.9b01205

M3 - Article

VL - 52

SP - 5977

EP - 5984

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 15

ER -