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 voor dit werk

Moleculaire Anorganische Chemie

Onderzoeksoutput: Article › Academic › peer review

8 Downloads (Pure)

Samenvatting

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.

Originele taal-2	English
Artikelnummer	e202404668
Aantal pagina's	13
Tijdschrift	Chemistry - A European Journal
Volume	31
Nummer van het tijdschrift	23
Vroegere onlinedatum	24-mrt.-2025
DOI's	https://doi.org/10.1002/chem.202404668
Status	Published - 22-apr.-2025

Toegang tot document

10.1002/chem.202404668Licentie: CC BY-NC-ND

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 MBLicentie: CC BY-NC-ND

Handle.net

Permanente koppeling

Andere bestanden en links

Link naar publicatie in Scopus

Citeer dit

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), Artikel e202404668. https://doi.org/10.1002/chem.202404668

@article{a651045b78cb46e68b1d34674960bf55,

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",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag GmbH \& Co. KGaA",

number = "23",

}

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, nr. 23, e202404668. https://doi.org/10.1002/chem.202404668

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

UR - http://www.scopus.com/inward/record.url?scp=105000813629&partnerID=8YFLogxK

U2 - 10.1002/chem.202404668

DO - 10.1002/chem.202404668

M3 - Article

AN - SCOPUS:105000813629

SN - 0947-6539

VL - 31

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 23

M1 - e202404668

ER -