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*

*Corresponding author for this work

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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.

Original languageEnglish
Article numbere202404668
Number of pages13
JournalChemistry - A European Journal
Volume31
Issue number23
Early online date24-Mar-2025
DOIs
Publication statusPublished - 22-Apr-2025

Keywords

  • non-heme
  • iron
  • second coordination sphere
  • hydrogen peroxide
  • hydrogen bond

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