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Computational Insights of Selective Intramolecular O‐atom Transfer Mediated by Bioinspired Copper Complexes
Author(s) -
GamboaRamirez Stefani,
Faure Bruno,
Réglier Marius,
Simaan A. Jalila,
Orio Maylis
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202202206
Subject(s) - intramolecular force , copper , chemistry , atom (system on chip) , combinatorial chemistry , nanotechnology , materials science , stereochemistry , computer science , organic chemistry , embedded system
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 non‐activated ( 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.