Indium Catalysts for Low-Pressure CO2 /Epoxide Ring-Opening Copolymerization: Evidence for a Mononuclear Mechanism?

Journal of the American Chemical Society
Arnaud ThevenonCharlotte K Williams

Abstract

The alternating copolymerization of CO2/epoxides is a useful means to incorporate high levels of carbon dioxide into polymers. The reaction is generally proposed to occur by bimetallic or bicomponent pathways. Here, the first indium catalysts are presented, which are proposed to operate by a distinct mononuclear pathway. The most active and selective catalysts are phosphasalen complexes, which feature ligands comprising two iminophosphoranes linked to sterically hindered ortho-phenolates. The catalysts are active at 1 bar pressure of carbon dioxide and are most effective without any cocatalyst. They show low-pressure activity (1 bar pressure) and yield polymer with high carbonate linkage selectivity (>99%) and isoselectivity ( Pm > 70%). Using these complexes, it is also possible to isolate and characterize key catalytic intermediates, including the propagating indium alkoxide and carbonate complexes that are rarely studied. The catalysts are mononuclear under polymerization conditions, and the key intermediates show different coordination geometries: the alkoxide complex is pentacoordinate, while the carbonate is hexacoordinate. Kinetic analyses reveal a first-order dependence on catalyst concentration and are zero-order in ca...Continue Reading

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Citations

Mar 22, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·James R PankhurstJason B Love
Jun 6, 2019·Chemical Communications : Chem Comm·Ralte LalrempuiaErwan Le Roux
Dec 10, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Arron C DeacyCharlotte K Williams
May 6, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Hart PlommerFrancesca M Kerton
Apr 22, 2020·Chemical Science·Chatura GoonesingheParisa Mehrkhodavandi
Dec 1, 2018·Inorganic Chemistry·Arron C DeacyCharlotte K Williams
Jun 17, 2020·Journal of the American Chemical Society·Guan-Wen YangGuang-Peng Wu
Nov 18, 2021·Biomaterials Science·Anjeza PetersenMark W Grinstaff
Dec 7, 2021·Inorganic Chemistry·Hassan A BaalbakiParisa Mehrkhodavandi

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