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C-F bonds are one of the most inert functionalities. Nevertheless, some [Cu 2 O 2 ] 2+ species are able to defluorinate-hydroxylate ortho -fluorophenolates in a chemoselective manner over other ortho -halophenolates. Albeit it is known that such reactivity is promoted by an electrophilic attack of a [Cu 2 O 2 ] 2+ core over the arene ring, the crucial details of the mechanism that explain the chemo- and regioselectivity of the reaction remain unknown, and it has not being determined either if Cu II  2 (η 2 :η 2 -O 2 ) or Cu III  2 (μ-O) 2 species are responsible for the initial attack on the arene. Herein, we present a combined theoretical and experimental mechanistic study to unravel the origin of the chemoselectivity of the ortho-defluorination-hydroxylation of 2-halophenolates by the [Cu 2 (O) 2 (DBED) 2 ] 2+ complex (DBED = N , N '-di- er -butylethylenediamine). Our results show that the equilibria between (side-on)peroxo ( P ) and bis(μ-oxo) ( O ) isomers plays a key role in the mechanism, with the latter being the reactive species. Furthermore, on the basis of quantum-mechanical calculations, we were able to rationalize the chemoselective preference of the [Cu 2 (O) 2 (DBED) 2 ] 2+ catalyst for the C-F activation over C-Cl and C-H activations.

Mechanistic Insights into the ortho-Defluorination-Hydroxylation of 2-Halophenolates Promoted by a Bis(μ-oxo)dicopper(III) Complex