title: Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper(I) complex.
abstract: In this work we analyze the whole molecular mechanism for intramolecular aromatic hydroxylation through O2 activation by a Schiff hexaazamacrocyclic dicopper(I) complex, [Cu(I) 2(bsH2m)](2+). Assisted by DFT calculations, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, i.e., from the initial O2 reaction with the dicopper(I) species to first form a Cu(I)Cu(II)-superoxo species, the subsequent reaction with the second Cu(I) center to form a μ-η(2):η(2)-peroxo-Cu(II) 2 intermediate, the concerted peroxide O-O bond cleavage and C-O bond formation, followed finally by a proton transfer to an alpha aromatic carbon that immediately yields the product [Cu(II) 2(bsH2m-O)(μ-OH)](2+).
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, E-17071 Girona, Spain ; Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, E-17003 Girona, Spain.
authors.forename: Albert
authors.initials: A
authors.lastname: Poater
authors.forename: Miquel
authors.initials: M
authors.lastname: Solà
keywords: C–H bond activation; C–H functionalization; DFT calculations; Schiff base; aromatic hydroxylation; copper; mechanism