The synthesis, characterisation and application of iron(III)-acetate complexes for cyclic carbonate formation and the polymerisation of lactide

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Abstract

Herein, we report the preparation, characterisation and catalytic applications of air-stable Fe(III)-acetate complexes consisting of salan, salen and salalen ligand frameworks. Owing to the simple synthetic protocol employed, a wide range of complexes have been prepared and structure-activity-relationships investigated. X-ray diffraction confirmed the solid-state structures for eight of the complexes. These represent the first Fe(III)-acetate complexes applied for the selective coupling of CO2 / epoxide and lactide polymerisation. The coupling of CO2 and challenging cyclohexene oxide substrate was performed under mild, solvent-free conditions (80 °C, 10 bar CO2) to selectively form the cis-cyclohexene carbonate as the exclusive product (selectivity >99%) with a metal loading of 0.08 mol%. A reduced aminopiperidine ligand backbone was found as the most active catalyst, and after investigating four co-catalysts, showed high functional group tolerance and robustness when applied to a broad, commercially available, terminal epoxide substrate scope with high conversions observed. The ring-opening polymerisation of rac-lactide was achieved using the Fe(III)OAc complexes using triethylamine and benzyl alcohol for initiation, interestingly isoselectivity was observed in some cases
Original languageEnglish
JournalDalton Transactions
DOIs
Publication statusPublished - 6 Sep 2019

Cite this

@article{56478b0f36b54947bd41ca4f074ed243,
title = "The synthesis, characterisation and application of iron(III)-acetate complexes for cyclic carbonate formation and the polymerisation of lactide",
abstract = "Herein, we report the preparation, characterisation and catalytic applications of air-stable Fe(III)-acetate complexes consisting of salan, salen and salalen ligand frameworks. Owing to the simple synthetic protocol employed, a wide range of complexes have been prepared and structure-activity-relationships investigated. X-ray diffraction confirmed the solid-state structures for eight of the complexes. These represent the first Fe(III)-acetate complexes applied for the selective coupling of CO2 / epoxide and lactide polymerisation. The coupling of CO2 and challenging cyclohexene oxide substrate was performed under mild, solvent-free conditions (80 °C, 10 bar CO2) to selectively form the cis-cyclohexene carbonate as the exclusive product (selectivity >99{\%}) with a metal loading of 0.08 mol{\%}. A reduced aminopiperidine ligand backbone was found as the most active catalyst, and after investigating four co-catalysts, showed high functional group tolerance and robustness when applied to a broad, commercially available, terminal epoxide substrate scope with high conversions observed. The ring-opening polymerisation of rac-lactide was achieved using the Fe(III)OAc complexes using triethylamine and benzyl alcohol for initiation, interestingly isoselectivity was observed in some cases",
author = "Oli Driscoll and Claudia Hafford-Tear and Paul McKeown and Jack Stewart and Gabriele Kociok-Kohn and Mary Mahon and Matthew Jones",
year = "2019",
month = "9",
day = "6",
doi = "10.1039/C9DT03327K",
language = "English",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - The synthesis, characterisation and application of iron(III)-acetate complexes for cyclic carbonate formation and the polymerisation of lactide

AU - Driscoll, Oli

AU - Hafford-Tear, Claudia

AU - McKeown, Paul

AU - Stewart, Jack

AU - Kociok-Kohn, Gabriele

AU - Mahon, Mary

AU - Jones, Matthew

PY - 2019/9/6

Y1 - 2019/9/6

N2 - Herein, we report the preparation, characterisation and catalytic applications of air-stable Fe(III)-acetate complexes consisting of salan, salen and salalen ligand frameworks. Owing to the simple synthetic protocol employed, a wide range of complexes have been prepared and structure-activity-relationships investigated. X-ray diffraction confirmed the solid-state structures for eight of the complexes. These represent the first Fe(III)-acetate complexes applied for the selective coupling of CO2 / epoxide and lactide polymerisation. The coupling of CO2 and challenging cyclohexene oxide substrate was performed under mild, solvent-free conditions (80 °C, 10 bar CO2) to selectively form the cis-cyclohexene carbonate as the exclusive product (selectivity >99%) with a metal loading of 0.08 mol%. A reduced aminopiperidine ligand backbone was found as the most active catalyst, and after investigating four co-catalysts, showed high functional group tolerance and robustness when applied to a broad, commercially available, terminal epoxide substrate scope with high conversions observed. The ring-opening polymerisation of rac-lactide was achieved using the Fe(III)OAc complexes using triethylamine and benzyl alcohol for initiation, interestingly isoselectivity was observed in some cases

AB - Herein, we report the preparation, characterisation and catalytic applications of air-stable Fe(III)-acetate complexes consisting of salan, salen and salalen ligand frameworks. Owing to the simple synthetic protocol employed, a wide range of complexes have been prepared and structure-activity-relationships investigated. X-ray diffraction confirmed the solid-state structures for eight of the complexes. These represent the first Fe(III)-acetate complexes applied for the selective coupling of CO2 / epoxide and lactide polymerisation. The coupling of CO2 and challenging cyclohexene oxide substrate was performed under mild, solvent-free conditions (80 °C, 10 bar CO2) to selectively form the cis-cyclohexene carbonate as the exclusive product (selectivity >99%) with a metal loading of 0.08 mol%. A reduced aminopiperidine ligand backbone was found as the most active catalyst, and after investigating four co-catalysts, showed high functional group tolerance and robustness when applied to a broad, commercially available, terminal epoxide substrate scope with high conversions observed. The ring-opening polymerisation of rac-lactide was achieved using the Fe(III)OAc complexes using triethylamine and benzyl alcohol for initiation, interestingly isoselectivity was observed in some cases

U2 - 10.1039/C9DT03327K

DO - 10.1039/C9DT03327K

M3 - Article

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -