A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane (6-hpa), [Cu (μ-OH)(6-hpa)] , was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H O , thus attaining large turnover numbers (TONs) and high H O efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 °C under N , the highest value reported for benzene hydroxylation with H O catalyzed by homogeneous complexes. At 22 % benzene conversion, phenol (95.2 %) and p-benzoquinone (4.8 %) were produced. The mechanism of H O activation and benzene hydroxylation is proposed.

Ad icopper(II) complex, stabilized by the bis(tpa) ligand 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane (6-hpa), [Cu 2 (m-OH)(6-hpa)] 3+ ,w as synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H 2 O 2 ,t hus attaining large turnover numbers (TONs) and high H 2 O 2 efficiency.T he TONa fter 40 hours for the phenol production exceeded 12000 in MeCN at 50 8 8Cu nder N 2 ,t he highest value reported for benzene hydroxylation with H 2 O 2 catalyzedb y homogeneous complexes.At22% benzene conversion, phenol (95.2 %) and p-benzoquinone (4.8 %) were produced. The mechanism of H 2 O 2 activation and benzeneh ydroxylation is proposed.

Recently, it was shown that μ‐oxo‐μ‐peroxodiiron(III) is converted to high‐spin μ‐oxodioxodiiron(IV) through O−O bond scission. Herein, the formation and high reactivity of the anti‐dioxo form of high‐spin μ‐oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic‐absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ‐oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluene

A dicopper(II) complex, [Cu(μ-OH)(6-hpa)], where 6-hpa is 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane, generates an oxyl radical of CuO and catalyzes the selective hydroxylation of benzene to phenol. From the structural similarity to methane activation catalysts (e.g., bare CuO ion, Cu-ZSM-5, and particulate methane monooxygenase), it is expected to catalyze methane hydroxylation. The catalytic performance for the hydroxylation of methane to methanol by this dicopper complex is investigated by using density functional theory (DFT) calculations. The whole reaction of the methane conversion involves two steps without radical species: (1) C-H bond dissociation of methane by the CuO moiety and (2) C-O bond formation with methyl migration. In the first step, the activation barrier is calculated to be 10.2 kcal/mol, which is low enough for reactions taking place under normal conditions. The activation barrier by the other CuO moiety is higher than that by the CuO moiety, which should work to turn the next catalytic cycle. DFT calculations show that the dicopper complex has a precondition to hydroxylate methane to methanol. Experimental verification is required to look in detail at the reactivity of this dicopper complex.

Carboxylate donor stabilizes the peroxo state in dioxygen activation via reversible O–O bond scission of peroxodi-iron(iii) to high spin oxodi-iron(iv).