Computational Insights of Selective Intramolecular O‐atom Transfer Mediated by Bioinspired Copper Complexes - Aix-Marseille Université Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2022

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

Résumé

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.
Fichier principal
Vignette du fichier
Chemistry A European J - 2022 - Gamboa%E2%80%90Ramirez - Computational Insights of Selective Intramolecular O%E2%80%90atom Transfer.pdf (3.31 Mo) Télécharger le fichier
Vignette du fichier
tocgraphic.jpg (642.23 Ko) Télécharger le fichier
Origine : Publication financée par une institution
Format : Figure, Image
Licence : CC BY NC - Paternité - Pas d'utilisation commerciale
Commentaire : illustration for the article; reactivity of binuclear copper(III) bis mu-oxo species for C-H hydroxylation

Dates et versions

hal-03789397 , version 1 (27-09-2022)

Licence

Paternité - Pas d'utilisation commerciale - Pas de modification

Identifiants

Citer

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⟩

Relations

67 Consultations
57 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More