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Evolution of Ate- organoiron(II) species towards lower oxidation states: role of the steric and electronic factors

Abstract : Ate -iron(II) species such as [Ar 3 Fe II ] ─ (Ar = aryl) are key intermediates in Fe-catalyzed couplings between aryl nucleophiles and organic electrophiles. They can be active species in the catalytic cycle, or lead to Fe 0 and Fe I oxidation states, which can themselves be catalytically active or lead to unwished organic byproducts. Analysis of the reactivity of the intermediates obtained by step-by-step displacement of the mesityl groups in high-spin [Mes 3 Fe II ] ─ by less hindered phenyl ligands was performed, and enlightened the crucial role of both steric and electronic parameters in the formation of the Fe 0 and Fe I oxidation states. The formation of quaternized [Ar 4 Fe II MgBr(THF)] ─ intermediates allows to reduce the bielectronic reductive elimination energy required for the formation of Fe 0 . Similarly, a small steric pressure of the aryl groups in [Ar 3 Fe II ] ─ enables the formation of aryl-bridged [{Fe II (Ar) 2 } 2 (µ-Ar) 2 ] 2─ species, which afford the Fe I oxidation state by bimetallic reductive elimination. These results are supported by 1 H NMR, EPR and 57 Fe-Mössbauer spectroscopies, as well as by DFT calculations.
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https://hal-cea.archives-ouvertes.fr/cea-02378178
Contributor : Serge Palacin <>
Submitted on : Monday, November 25, 2019 - 8:29:23 AM
Last modification on : Wednesday, October 14, 2020 - 4:21:03 AM

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Lidie Rousseau, Christian Herrero, Martin Clémancey, Arnaud Imberdis, Geneviéve Blondin, et al.. Evolution of Ate- organoiron(II) species towards lower oxidation states: role of the steric and electronic factors. Chemistry - A European Journal, Wiley-VCH Verlag, 2020, 26, pp.2417-2428. ⟨10.1002/chem.201904228⟩. ⟨cea-02378178⟩

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