CABRERA, Diego Jaraba, LEWIS, Ryan, DÍEZ-POZA, Carlos, ÁLVAREZ-MIGUEL, Lucía, MOSQUERA, Marta E. G., HAMILTON, Alex and WHITEOAK, Christopher J. (2023). Group 13 salphen compounds (In, Ga and Al): a comparison of their structural features and activities as catalysts for cyclic carbonate synthesis †. Dalton Transactions.
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Abstract
Many complexes based on group 13 elements have been successfully applied as catalysts for the synthesis of cyclic carbonates from epoxides and CO2 and to date these have provided some of the most active catalysts developed. It is notable that most reports have focused on the use of aluminium-based compounds likely because of the well-established Lewis acidity of this element and its cost. In comparison, relatively little attention has been paid to the development of catalysts based on the heavier group 13 elements, despite their known Lewis acidic properties. This study describes the synthesis of aluminium, gallium and indium compounds supported by a readily prepared salphen ligand and explores both their comparative structures and also their potential as catalysts for the synthesis of cyclic carbonates. In addition, the halide ligand which forms a key part of the compound has been systematically varied and the effect of this change on the structure and catalytic activity is also discussed. It is demonstrated that the indium compounds are actually, and unexpectedly, the most active for cyclic carbonate synthesis, despite their lower Lewis acidity when compared to their aluminium congeners. The experimental observations from this work are fully supported by a Density Functional Theory (DFT) study, which provides important insights into the reasons as to why the indium catalyst with bromide, [InBr(salphen)], is most active.
Item Type: | Article |
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Additional Information: | ** Embargo end date: 22-02-2023 ** From Royal Society of Chemistry via Jisc Publications Router ** Licence for this article starting on 22-02-2023: http://creativecommons.org/licenses/by/3.0/ ** Acknowledgements: CW would like to thank the Comunidad de Madrid (Spain) for funding (Programa de Atracción de Talento 2019: Modalidad 1; Award number 2019-T1/AMB-13037, and CM/JIN/2021-018). All authors would like to acknowledge funding from the Spanish Government (RTI2018-094840-BC31 and PID2020-113046RA-I00/AEI/10.13039/501100011033) and the Universidad de Alcalá (UAH-AE-2017-2). DJC thanks the Comunidad de Madrid (Spain) and European Union for funding a contract under the Programa INVESTIGO (47-UAH-INV). AH and RL would like to thank Sheffield Hallam University and the Biomolecular Sciences Research Centre for funding and computational resource access. **Journal IDs: pissn 1477-9226; eissn 1477-9234 **Article IDs: publisher-id: d3dt00089c **History: published 22-02-2023; accepted 21-02-2023; submitted 10-01-2023 |
Identification Number: | https://doi.org/10.1039/D3DT00089C |
SWORD Depositor: | Colin Knott |
Depositing User: | Colin Knott |
Date Deposited: | 02 Mar 2023 15:36 |
Last Modified: | 02 Mar 2023 15:36 |
URI: | https://shura.shu.ac.uk/id/eprint/31601 |
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