Influence of a 2<sup>nd</sup> Sphere Hydrogen‐Bond Donor on the Reactivity of Non‐heme Fe(II) Complexes in Alkane, Alkene and Aromatic Oxidation with H<sub>2</sub>O<sub>2</sub>
Two iron(II) complexes of the pentadentate aminopyridine ligand L<sub>5</sub> <sup>2(OH)</sup>, bearing a 2<sup>nd</sup> sphere OH group in ortho position of one pyridine, were studied in the oxidation of various substrates using H<sub>2</sub>O<sub>2</sub>. 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.
Authors
- Amanda Lyn Robinson
- Frédéric Banse (ORCID: https://orcid.org/0000-0001-8289-4965)
- Tanya Inceoglu
- Marika Di Berto Mancini (ORCID: https://orcid.org/0000-0001-8787-0241)
- Wesley R. Browne (ORCID: https://orcid.org/0000-0001-5063-6961)
- Hélène Maisonneuve
- Christian Herrero (ORCID: https://orcid.org/0000-0003-2113-4625)
- Jean‐Noël Rebilly (ORCID: https://orcid.org/0000-0003-1379-0913)
- Régis Guillot (ORCID: https://orcid.org/0000-0002-9003-0670)
- Eva Bannerman
Institutions
- Centre National de la Recherche Scientifique (FR)
- University of Groningen (NL)
- Université Paris-Saclay (FR)
- Institut de Chimie Moléculaire et des Matériaux d'Orsay (FR)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-03-11
- DOI
- https://doi.org/10.1002/chem.202404668
- Citations
- 2
- Primary Topic
- Metal-Catalyzed Oxygenation Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 1.07