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Bioinspired semi-hemic iron(III) complex for chemical and photochemical oxygen atom transfer reactions

Abstract : Hydrocarbon oxidation is a real challenging chemical transformation both in biology and chemistry. Highly oxidized metal-oxo species are the active intermediates to perform these transformations. In this manuscript we report the synthesis and characterization of an iron(III) complex supported by a non-innocent hemi-porphyrinic ligand, constructed with a dipyrrin fragment and two pyridine functions. The iron(III) complexes have been prepared and characterized, with a focus on their electrochemical behavior and their potential use as catalysts in the activation of green oxygen source such as dioxygen and water for hydrocarbon oxidation. We found that these complexes can catalyze the oxidation of a fair variety of substrates using oxidant agent such as iodosylbenzene. Intriguingly, our gathered results point to a reactivity pattern that stems from a low-oxidation state iron species. Electron Paramagnetic Resonance and Mössbauer analyses support a high spin iron(III) reactive species. Furthermore, data from mass spectrometry and Infra-red spectroscopy supported by DFT calculations helped us to propose the chemical formulation of this chemically generated intermediate where the ligand has been reversibly oxidized. Additionally, these complexes were used as catalysts in a photocatalytic system using a reversible electron acceptor to preclude the “evil necessity” of a sacrificial electron donor. Our study provides a new paradigm to perform photoinduced oxygen atom transfer reactions with solely light as energy input and O₂ as oxygen atom source in aqueous solution.
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  • HAL Id : tel-02615260, version 1

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Nhat Tam Vo. Bioinspired semi-hemic iron(III) complex for chemical and photochemical oxygen atom transfer reactions. Catalysis. Université Paris-Saclay, 2019. English. ⟨NNT : 2019SACLS319⟩. ⟨tel-02615260⟩

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