Generation and Reactivity of μ-1,2-Peroxo CuIICuII and Bis-μ-oxo CuIIICuIII Species and Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide.

Tetradentate-N4 ligands stabilize dinuclear {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} species, and CuII complexes of these ligands were reported to catalyze the oxidation of benzene with H2O2. Here, we report {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} intermediates of dinucleating bis(tetradentate-N4) ligands depending on the absence or presence of 6-methyl substituents on the terminal pyridine donors, respectively, generated either from {CuICuI} precursors with O2 or from {CuIICuII} precursors with H2O2 and NEt3. Both intermediates are not stable even at low temperatures, but they show no electrophilic HAT reactivity with DHA. Catalytic investigations on the hydroxylation of benzene with excess H2O2 between 30 and 50 °C indicate that both radical-based and {Cu2On}-based mechanisms depend strongly on the catalytic conditions. In the presence of a radical scavenger, TONs of ∼920/∼720 have been achieved without/with the 6-methyl group of the ligand. Although {CuII(μ-OH)CuII} reacts with excess H2O2 at -40 °C to {CuII(OOH)}2 species, these are only stable for seconds at 20 °C and cannot account for catalytic oxidations over a period of 24 h at 30-50 °C.