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Two tetranuclear and two mononuclear Cu(II) complexes with arylhydrazones of malononitrile derived ligands (compounds 1–2 and 3–4, respectively), one trinuclear Co(II/III) complex with an arylhydrazone of acetoacetanilide (5) and one tetranuclear Zn(II) complex of 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (6) were screened as potential catalysts in the peroxidative oxidation of cyclohexane by aqueous H2O2 in acetonitrile. The best results were attained in the presence of pyrazine-2-carboxylic acid (PCA) with 1 (26% yield, TON = 52.0) and with 2 (24%, TON = 48.0) after 4 h at 40 °C. In the presence of complexes 5 and 6, no oxygenated products were detected in the studied conditions. The employment of non-conventional conditions like supercritical carbon dioxide (scCO2) as reaction medium or microwave (MW) irradiation was assessed for complexes 1 and 2. After 6 h in acetonitrile–scCO2, at 50 °C and with HNO3 as promoter, only 17% yield was achieved using 1 as catalyst, and 21% using 2. Total yields of oxygenates up to 14 (with 1) and 13% (2) and TOFs of 56.0 and 52.0 h−1, respectively, were obtained working under MW irradiation at 70 °C and for the much shorter time of 0.5 h. [ABSTRACT FROM AUTHOR]