Direct Benzene Hydroxylation with Dioxygen Induced by Copper Complexes: Uncovering the Active Species by DFT Calculations

[Image: see text] The direct oxidation of benzene into phenol using molecular oxygen at very mild temperatures can be promoted in the presence of the copper complex Tp(Br3)Cu(NCMe) in the homogeneous phase in the presence of ascorbic acid as the source of protons and electrons. The stoichiometric nature, relative to copper, of this transformation prompted a thorough DFT study in order to understand the reaction pathway. As a result, the dinuclear species Tp(Br3)Cu(II)(μ-O(•))(μ-OH)Cu(II)Tp(Br3) is proposed as the relevant structure which is responsible for activating the arene C–H bond leading to phenol formation.