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Computational Insights of Selective Intramolecular O‐atom Transfer Mediated by Bioinspired Copper Complexes

Abstract : The stereoselective copper-mediated hydroxylation of intramolecular C H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated (L 1) or nonactivated (L 2) C H bonds. Configurational analysis allows rationalization of the experimentally observed regio-and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species (P) in equilibrium with the key intermediate bis-(μ-oxo) isomer (O) responsible for the C H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C H activation step, where the complex bearing the non-activated C H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions.
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https://hal-amu.archives-ouvertes.fr/hal-03789397
Contributor : Jalila SIMAAN Connect in order to contact the contributor
Submitted on : Tuesday, September 27, 2022 - 1:38:16 PM
Last modification on : Friday, December 2, 2022 - 12:33:05 PM

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Chemistry A European J - 2022 ...
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Stefani Gamboa-Ramírez, Bruno Faure, M. Réglier, A. Jalila Simaan, Maylis Orio. Computational Insights of Selective Intramolecular O‐atom Transfer Mediated by Bioinspired Copper Complexes. Chemistry - A European Journal, 2022, pp.e202202206. ⟨10.1002/chem.202202206⟩. ⟨hal-03789397⟩

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