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Article Dans Une Revue Inorganic Chemistry Année : 2021

Relevance of single-transmetallated resting states in iron-mediated cross-couplings: unexpected role of σ-donating additives

Résumé

Control of the transmetalation degree of organoiron(II) species is a critical parameter in numerous Fe-catalyzed cross-couplings to ensure the success of the process. In this report, we however demonstrate that the selective formation of a monotransmetalated FeII species during the catalytic regime counterintuitively does not alone ensure an efficient suppression of the nucleophile homocoupling side reaction. It is conversely shown that a fine control of the transmetalation degree of the transient FeIII intermediates obtained after the activation of alkyl electrophiles by a single-electron transfer (SET), achievable using σ-donating additives, accounts for the selectivity of the cross-coupling pathway. This report shows for the first time that both coordination spheres of FeII resting states and FeIII short-lived intermediates must be efficiently tuned during the catalytic regime to ensure high coupling selectivities.

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hal-03417424 , version 1 (05-11-2021)

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Lidie Rousseau, Nadia Touati, Laurent Binet, Pierre Thuéry, Guillaume Lefèvre. Relevance of single-transmetallated resting states in iron-mediated cross-couplings: unexpected role of σ-donating additives. Inorganic Chemistry, 2021, 60 (11), pp.7991-7997. ⟨10.1021/acs.inorgchem.1c00518⟩. ⟨hal-03417424⟩
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