Influence of a 2nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H2O2

Amanda Lyn Robinson; Eva Bannerman; Marika Di Berto Mancini; Wesley R. Browne; Régis Guillot; Christian Herrero; Tanya Inceoglu; Hélène Maisonneuve; Frédéric Banse; Jean Noël Rebilly

doi:10.1002/chem.202404668

Influence of a 2^nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H₂O₂

Amanda Lyn Robinson, Eva Bannerman, Marika Di Berto Mancini, Wesley R. Browne, Régis Guillot, Christian Herrero, Tanya Inceoglu, Hélène Maisonneuve, Frédéric Banse^*, Jean Noël Rebilly^*

^*Corresponding author for this work

Molecular Inorganic Chemistry

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Abstract

Two iron(II) complexes of the pentadentate aminopyridine ligand L₅^2(OH), bearing a 2^nd sphere OH group in ortho position of one pyridine, were studied in the oxidation of various substrates using H₂O₂. While the addition of the OH group lowers the yields of alkane and aromatic oxidation, it improves the yield in alkene epoxidation. Spectroscopic analyses suggest that the pyridine-OH group stabilizes an Fe(III)OOH intermediate by hydrogen-bonding with the proximal O atom of hydroperoxo, but also eventually drives the system towards a dimeric structure, which competes with the oxidation process. The improvement in epoxidation yields is proposed to result from the fast reaction of cyclooctene with the active species, together with an enhanced oxidizing power induced by the hydrogen-bonding pattern.

Original language	English
Article number	e202404668
Number of pages	13
Journal	Chemistry - A European Journal
Volume	31
Issue number	23
Early online date	24-Mar-2025
DOIs	https://doi.org/10.1002/chem.202404668
Publication status	Published - 22-Apr-2025

Keywords

non-heme
iron
second coordination sphere
hydrogen peroxide
hydrogen bond

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Influence of a 2nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H2O2Proof, 4.54 MBLicence: CC BY-NC-ND

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Robinson, A. L., Bannerman, E., Di Berto Mancini, M., Browne, W. R., Guillot, R., Herrero, C., Inceoglu, T., Maisonneuve, H., Banse, F., & Rebilly, J. N. (2025). Influence of a 2^nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H₂O₂. Chemistry - A European Journal, 31(23), Article e202404668. https://doi.org/10.1002/chem.202404668

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title = "Influence of a 2nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H2O2",

abstract = "Two iron(II) complexes of the pentadentate aminopyridine ligand L52(OH), bearing a 2nd sphere OH group in ortho position of one pyridine, were studied in the oxidation of various substrates using H2O2. While the addition of the OH group lowers the yields of alkane and aromatic oxidation, it improves the yield in alkene epoxidation. Spectroscopic analyses suggest that the pyridine-OH group stabilizes an Fe(III)OOH intermediate by hydrogen-bonding with the proximal O atom of hydroperoxo, but also eventually drives the system towards a dimeric structure, which competes with the oxidation process. The improvement in epoxidation yields is proposed to result from the fast reaction of cyclooctene with the active species, together with an enhanced oxidizing power induced by the hydrogen-bonding pattern.",

keywords = "non-heme, iron, second coordination sphere, hydrogen peroxide, hydrogen bond",

author = "Robinson, {Amanda Lyn} and Eva Bannerman and {Di Berto Mancini}, Marika and Browne, {Wesley R.} and R{\'e}gis Guillot and Christian Herrero and Tanya Inceoglu and H{\'e}l{\`e}ne Maisonneuve and Fr{\'e}d{\'e}ric Banse and Rebilly, {Jean No{\"e}l}",

note = "Publisher Copyright: {\textcopyright} 2025 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2025",

month = apr,

day = "22",

doi = "10.1002/chem.202404668",

language = "English",

volume = "31",

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Robinson, AL, Bannerman, E, Di Berto Mancini, M , Browne, WR, Guillot, R, Herrero, C, Inceoglu, T, Maisonneuve, H, Banse, F & Rebilly, JN 2025, 'Influence of a 2^nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H₂O₂', Chemistry - A European Journal, vol. 31, no. 23, e202404668. https://doi.org/10.1002/chem.202404668

Influence of a 2^nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H₂O₂. / Robinson, Amanda Lyn; Bannerman, Eva; Di Berto Mancini, Marika et al.
In: Chemistry - A European Journal, Vol. 31, No. 23, e202404668, 22.04.2025.

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

TY - JOUR

T1 - Influence of a 2nd Sphere Hydrogen-Bond Donor on the Reactivity of Non-heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H2O2

AU - Robinson, Amanda Lyn

AU - Bannerman, Eva

AU - Di Berto Mancini, Marika

AU - Browne, Wesley R.

AU - Guillot, Régis

AU - Herrero, Christian

AU - Inceoglu, Tanya

AU - Maisonneuve, Hélène

AU - Banse, Frédéric

AU - Rebilly, Jean Noël

PY - 2025/4/22

Y1 - 2025/4/22

N2 - Two iron(II) complexes of the pentadentate aminopyridine ligand L52(OH), bearing a 2nd sphere OH group in ortho position of one pyridine, were studied in the oxidation of various substrates using H2O2. While the addition of the OH group lowers the yields of alkane and aromatic oxidation, it improves the yield in alkene epoxidation. Spectroscopic analyses suggest that the pyridine-OH group stabilizes an Fe(III)OOH intermediate by hydrogen-bonding with the proximal O atom of hydroperoxo, but also eventually drives the system towards a dimeric structure, which competes with the oxidation process. The improvement in epoxidation yields is proposed to result from the fast reaction of cyclooctene with the active species, together with an enhanced oxidizing power induced by the hydrogen-bonding pattern.

AB - Two iron(II) complexes of the pentadentate aminopyridine ligand L52(OH), bearing a 2nd sphere OH group in ortho position of one pyridine, were studied in the oxidation of various substrates using H2O2. While the addition of the OH group lowers the yields of alkane and aromatic oxidation, it improves the yield in alkene epoxidation. Spectroscopic analyses suggest that the pyridine-OH group stabilizes an Fe(III)OOH intermediate by hydrogen-bonding with the proximal O atom of hydroperoxo, but also eventually drives the system towards a dimeric structure, which competes with the oxidation process. The improvement in epoxidation yields is proposed to result from the fast reaction of cyclooctene with the active species, together with an enhanced oxidizing power induced by the hydrogen-bonding pattern.

KW - non-heme

KW - iron

KW - second coordination sphere

KW - hydrogen peroxide

KW - hydrogen bond

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DO - 10.1002/chem.202404668

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