Catalytic Formation of Cyclic Carbonates using Gallium Aminotrisphenolate Compounds and Comparison to their Aluminium Congeners: A Combined Experimental and Computational Study

ÁLVAREZ‐MIGUEL, Lucía, BURGOA, Jesús Damián, MOSQUERA, Marta E. G., HAMILTON, Alex and WHITEOAK, Christopher J. (2021). Catalytic Formation of Cyclic Carbonates using Gallium Aminotrisphenolate Compounds and Comparison to their Aluminium Congeners: A Combined Experimental and Computational Study. ChemCatChem, 13.

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Link to published version:: https://doi.org/10.1002/cctc.202100910
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    Abstract

    Abstract: This work reports on the use of gallium aminotrisphenolate compounds as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The results show that they are highly active, and more so than the corresponding aluminium congeners. The catalyst system is applicable at low and elevated temperatures across a wide substrate scope including terminal, internal, multiple and fully deuterated epoxides. Applying low catalyst loadings has allowed for a TON of 344,000 to be obtained, highlighting their stability. A DFT investigation has confirmed that the gallium catalysts have lower energetic profiles compared to the aluminium congeners. Measurement of the Lewis acidity of both the gallium and aluminium aminotrisphenolate compounds using the Gutmann‐Beckett method provides the experimental proof that the gallium compounds are more Lewis acidic than their aluminium congeners. Finally, Ab‐Initio Molecular Dynamic (AIMD) simulations have investigated and quantified the dynamic behaviour of the catalytic systems, highlighting an important increase in fluxionality in some cases which helps to explain the increase in catalytic activity.

    Item Type: Article
    Additional Information: ** Article version: VoR ** From Wiley via Jisc Publications Router ** Licence for VoR version of this article: http://creativecommons.org/licenses/by-nc-nd/4.0/ **Journal IDs: issn 1867-3880; issn 1867-3899 **Article IDs: publisher-id: cctc202100910 **History: published 19-08-2021; rev-recd 01-08-2021; submitted 22-06-2021
    Uncontrolled Keywords: Full Paper, Full Papers, gallium, aminotrisphenolate ligands, carbon dioxide, cyclic carbonates, DFT study.
    Identification Number: https://doi.org/10.1002/cctc.202100910
    SWORD Depositor: Colin Knott
    Depositing User: Colin Knott
    Date Deposited: 20 Aug 2021 09:21
    Last Modified: 20 Aug 2021 09:30
    URI: http://shura.shu.ac.uk/id/eprint/28959

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