Abstract
Reactivities of non-heme iron(IV)-oxo complexes are mostly controlled by the ligands. Complexes with tetradentate ligands such as [(TPA)FeO]2+ (TPA=tris(2-pyridylmethyl)amine) belong to the most reactive ones. Here, we show a fine-tuning of the reactivity of [(TPA)FeO]2+ by an additional ligand X (X=CH3CN, CF3SO3−, ArI, and ArIO; ArI=2-(tBuSO2)C6H4I) attached in solution and reveal a thus far unknown role of the ArIO oxidant. The HAT reactivity of [(TPA)FeO(X)]+/2+ decreases in the order of X: ArIO > MeCN > ArI ≈ TfO−. Hence, ArIO is not just a mere oxidant of the iron(II) complex, but it can also increase the reactivity of the iron(IV)-oxo complex as a labile ligand. The detected HAT reactivities of the [(TPA)FeO(X)]+/2+ complexes correlate with the Fe=O and FeO−H stretching vibrations of the reactants and the respective products as determined by infrared photodissociation spectroscopy. Hence, the most reactive [(TPA)FeO(ArIO)]2+ adduct in the series has the weakest Fe=O bond and forms the strongest FeO−H bond in the HAT reaction.
Original language | English (US) |
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Pages (from-to) | 7126-7131 |
Number of pages | 6 |
Journal | Angewandte Chemie - International Edition |
Volume | 60 |
Issue number | 13 |
DOIs | |
State | Published - Mar 22 2021 |
Bibliographical note
Funding Information:The project was supported by the European Research Council (ERC CoG No. 682275) and the United States National Science Foundation (CHE‐1665391). G.L.T. thanks Dr. Erik Andris for his help during the initial experiments.
Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
Keywords
- C−H activation
- ion spectroscopy
- iron-oxo
- mass spectrometry
- reactivity screening
PubMed: MeSH publication types
- Journal Article
- Research Support, Non-U.S. Gov't