Comba, Peter, Nunn, George, Scherz, Frederik et al. (1 more author) (2022) Intermediate-spin iron(IV)-oxido species with record reactivity. FARADAY DISCUSSIONS. pp. 232-244. ISSN 1364-5498
Abstract
The nonheme iron(IV)-oxido complex trans-N3-[(L1)FeIVO(Cl)]+, where L1 is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, has an S = 1 electronic ground state and is the most reactive nonheme iron model system known so far, of a similar order of reactivity as nonheme iron enzymes (C-H abstraction of cyclohexane, -90 °C (propionitrile), t1/2 = 3.5 s). The reaction with cyclohexane selectively leads to chlorocyclohexane, but "cage escape" at the [(L1)FeIII(OH)(Cl)]+/cyclohexyl radical intermediate lowers the productivity. Ligand field theory is used herein to analyze the d-d transitions of [(L1)FeIVO(X)]n+ (X = Cl-, Br-, MeCN) in comparison with the thoroughly characterized ferryl complex of tetramethylcyclam (TMC = L2; [(L2)FeIVO(MeCN)]2+). The ligand field parameters and d-d transition energies are shown to provide important information on the triplet-quintet gap and its correlation with oxidation reactivity.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2022. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details |
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: | 23 Mar 2022 15:50 |
Last Modified: | 16 Oct 2024 18:14 |
Published Version: | https://doi.org/10.1039/d1fd00073j |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/d1fd00073j |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:185085 |
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Description: Intermediate-spin iron(IV)-oxido species with record reactivity