Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core

Abstract

Di-iron systems that activate O2 to form high-valent, oxo-bridged FeIV2 or FeIIIFeIV products are of great interest to bio-inorganic chemists due to their relevance to the chemistry of soluble methane mono-oxygenase (sMMOH), which incorporates both atoms of O2 gas into a diiron(IV) complex with an Fe2O2 diamond core. In this study, the [FeIII2(Me3NTB)2(μ-O)(μ-O 2)]2+ adduct (Me3NTB = tris((1-methyl-1H-benzo[d]imidazole-2-yl)methyl)amine) reacts with two Sc3+ to break the O–O bond that in turn forms the target FeIV(μ-O)2FeIV product. This study provides the first evidence that a Lewis acid can interact directly with a diferric-peroxo complex to initiate O–O bond cleavage, as evidenced via vibrational and X-ray absorption spectroscopy.

Graphical abstract: Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core

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Article information

Article type
Edge Article
Submitted
28 Jul 2025
Accepted
27 Sep 2025
First published
03 Oct 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2025, Advance Article

Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core

P. M. Crossland, B. Chandra, S. Banerjee, C. S. Abelson, Y. Guo, M. Swart and L. Que, Chem. Sci., 2025, Advance Article , DOI: 10.1039/D5SC05667E

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