Tuning the H-Atom Transfer Reactivity of Iron(IV)-Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy

Guilherme L. Tripodi; Magda M.J. Dekker; Jana Roithová; Lawrence Que

doi:10.1002/anie.202016695

Tuning the H-Atom Transfer Reactivity of Iron(IV)-Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy

Guilherme L. Tripodi, Magda M.J. Dekker, Jana Roithová, Lawrence Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

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)
Pages (from-to)	7126-7131
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	13
DOIs	https://doi.org/10.1002/anie.202016695
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

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title = "Tuning the H-Atom Transfer Reactivity of Iron(IV)-Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy",

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.",

keywords = "C−H activation, ion spectroscopy, iron-oxo, mass spectrometry, reactivity screening",

author = "Tripodi, {Guilherme L.} and Dekker, {Magda M.J.} and Jana Roithov{\'a} and Lawrence Que",

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: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

year = "2021",

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doi = "10.1002/anie.202016695",

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T1 - Tuning the H-Atom Transfer Reactivity of Iron(IV)-Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy

AU - Tripodi, Guilherme L.

AU - Dekker, Magda M.J.

AU - Roithová, Jana

AU - Que, Lawrence

N1 - 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

PY - 2021/3/22

Y1 - 2021/3/22

N2 - 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.

AB - 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.

KW - C−H activation

KW - ion spectroscopy

KW - iron-oxo

KW - mass spectrometry

KW - reactivity screening

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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IS - 13

ER -

Tuning the H-Atom Transfer Reactivity of Iron(IV)-Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy

Abstract

Bibliographical note

Keywords

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