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Mechanistic Insights into the ortho-Defluorination-Hydroxylation of 2‑Halophenolates Promoted by a Bis(μ-oxo)dicopper(III) Complex Besalú Sala, Pau Magallón, Carla Costas Salgueiro, Miquel Company Casadevall, Anna Luis Luis, Josep Maria Agencia Estatal de Investigación Quàntums, Teoria dels Quantum theory Química quàntica Quantum chemistry C-F bonds are one of the most inert functionalities. Nevertheless, some [Cu_2O_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_2O_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-tert-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. This work was supported with funds from the Spanish government MICINN (PGC2018-098212-B-C22 to JML, PGC2018-101737-BI00 to M.C., CTQ2016-77989-P to A.C.), and the Generalitat de Catalunya (2017SGR39 to J.M.L, 2017 SGR 00264 and ICREA Academia to M.C. and A.C.). We thank the Spanish government for the predoctoral grant to P.B.-S. (FPU17/02058) info:eu-repo/date/embargoEnd/2021-11-06 2020-11-06 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion peer-reviewed http://hdl.handle.net/10256/19065 http://hdl.handle.net/10256/19065 eng info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.0c02246 info:eu-repo/semantics/altIdentifier/issn/0020-1669 info:eu-repo/semantics/altIdentifier/eissn/1520-510X info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22/ES/DESCOMPOSICION EN EL ESPACIO REAL DE PROPIEDADES OPTICAS NO LINEALES PARA EL DISEÑO RACIONAL DE MATERIALES OPTOELECTRONICOS/ MINECO/PE 2016-2018/CTQ2016-77989-P info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-101737-B-I00/ES/CATALISIS DE OXIDACION BIOINSPIRADA MEDIANTE DISEÑO RACIONAL DE CATALIZADORES/ Tots els drets reservats info:eu-repo/semantics/openAccess 10 p. application/pdf American Chemical Society (ACS) © Inorganic Chemistry, 2020, vol. 59, núm. 23, p. 17018-17027 Articles publicats (D-Q) Besalú Sala, Pau Magallón, Carla Costas Salgueiro, Miquel Company Casadevall, Anna Luis Luis, Josep Maria 2020 Mechanistic Insights into the ortho-Defluorination-Hydroxylation of 2‑Halophenolates Promoted by a Bis(μ-oxo)dicopper(III) Complex Inorganic Chemistry 59 23 17018 17027