Fish, Heather, Hart, Sam, Lamb, Katie J. orcid.org/0000-0002-5244-5015 et al. (5 more authors) (2021) Structural analysis of five-coordinate aluminium(salen) complexes and its relationship to their catalytic activity. Dalton Transactions. pp. 587-598. ISSN 1477-9234
Abstract
The crystal structure of [Al(tBu-salen)]2O·HCl shows major changes compared to that of [Al(tBu-salen)]2O. The additional proton is localized on the bridging oxygen atom, making the aluminium atoms more electron deficient. As a result, a water molecule coordinates to one of the aluminium atoms, which becomes six-coordinate. This pushes the salen ligand associated with the six-coordinate aluminium ion closer to the other salen ligand and results in the geometry around the five-coordinate aluminium atom becoming more trigonal bipyramidal. These results experimentally mirror the predications of DFT calculations on the interaction of [Al(tBu-salen)]2O and related complexes with carbon dioxide. Variable temperature NMR studies of protonated [Al(tBu-salen)]2O complexes revealed that the structures were dynamic and could be explained on the basis of an intramolecular rearrangement in which the non-salen substituent of a five-coordinate aluminium(tBu-salen) unit migrates from one face of a square based pyramidal structure to the other via the formation of structures with trigonal bipyramidal geometries. Protonated [Al(tBu-salen)]2O complexes were shown to have enhanced Lewis acidity relative to [Al(tBu-salen)]2O, coordinating to water, dioxane and 1,2-epoxyhexane. Coordinated epoxyhexane was activated towards ring-opening, to give various species which remained coordinated to the aluminium centers. The protonated [Al(tBu-salen)]2O complexes catalysed the synthesis of cyclic carbonates from epoxides and carbon dioxide both in the presence and absence of tetrabutylammonium bromide as a nucleophilic cocatalyst. The catalytic activity was principally determined by the nature of the nucleophilic species within the catalyst structure rather than by changes to the Lewis acidity of the metal centers.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2021 |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 16 Dec 2020 11:10 |
Last Modified: | 21 Dec 2024 00:21 |
Published Version: | https://doi.org/10.1039/D0DT03598J |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/D0DT03598J |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:169071 |
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Description: Structural analysis of five-coordinate aluminium (salen) complexes and its relationship to their catalytic activity
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