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, [CuI2 (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 CuICuII-superoxo species, the subsequent reaction with the second CuI center to form a μ-η2:η2+-peroxo-CuII2 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 [CuII2 (bsH2m-O)(μ-OH)] 2+. © 2013 Poater and Solà.