Unraveling cyclohexane peroxidation pathways over a pMMO-inspired Cu-N4 complex: combined experimental and computational study

• Cu– N 4 complexes mimicking the Cu B site of pMMO were evaluated as oxidation catalysts. • The catalytic activity depends on the copper initial oxidation state. • First-order kinetics with respect to H 2 O 2 and Cu concentrations were observed. • DFT calculations indicate a Fenton-type catalytic mechanism. • In situ spectroscopy confirms a Cu(I)/Cu(II) redox cycle during catalysis. • Catalyst decomposition occurs, yet precipitates retain catalytic activity. The reactivity of a Cu- N 4 complex with an imidazole-based ligand, inspired by the mono-Cu B site suggested for particulate methane monooxygenase (pMMO), has been studied by catalytic testing, UV–Vis and XAS spectroscopies and DFT methods. The Cu- N 4 complex was synthesized in Cu(I) and Cu(II) initial oxidation states, referred to as 1 and 2 , respectively. Both were tested for cyclohexane (CyH) oxidation in acetonitrile (MeCN) at 25 °C and ambient pressure, using H 2 O 2 as co-substrate. 1 showed higher activity in CyH oxidation than 2, with both forming cyclohexyl hydroperoxide (Cy–OOH) as the main product. In situ ultraviolet–visible (UV–Vis) and X-ray absorption (XAS) spectroscopies support a Cu(I)/Cu(II) redox cycle triggered by the excess amount of H 2 O 2 . Starting from 2 , a slow reduction to Cu(I) and distinct Cu(II) signals, compared to those observed with 1 , were detected using operando UV–Vis spectroscopy. Density functional theory (DFT) results suggest both Fenton- (via • OH and • OOH) and Cu(II)-oxyl-mediated reactions from 1 leading to C–H oxidation and H 2 O 2 disproportionation. Kinetic data at 30 min of reaction indicate a ∼ 1st order reactivity with respect to H 2 O 2 and Cu concentrations, and a fractional (∼0.5) order with respect to CyH, in line with the mechanism proposed by DFT calculations. These reaction orders change at 240 min of reaction, indicating catalyst decomposition by ligand oxidation, hydrolysis, or aggregation. This study highlights the importance of preventing the reaction of Cu(II)-oxyl with H 2 O 2 and Fenton-type chemistry for efficient and selective oxidation of C–H to alcohol, providing hints for further catalyst design.