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
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