Abstract
Molybdenum(VI) catalysts were obtained from methanol or acetonitrile by the reaction of [MoO2(C5H7O2)2] and isonicotinoyl- or nicotinoyl-based aroylhydrazones. Reactions in methanol resulted in the formation of the mononuclear complexes [MoO2(L1–4)(MeOH)] (1a–4a), while the ones in acetonitrile provided polynuclear complexes [MoO2(L1–4)]n (1–4). Crystals of polynuclear compound, [MoO2(L3)]n∙H2O (3∙H2O), suitable for X-ray diffraction analysis were obtained by the solvothermal procedure at 110 °C. Complexes were characterized by infrared spectroscopy (IR-ATR), nuclear magnetic resonance (NMR), elemental analysis (EA), and thermogravimetric analysis (TGA). The prepared catalysts were tested in alcohol oxidation reactions. Carveol, cyclohexanol, and butan-2-ol were investigated substrates. Because the alcohol oxidations are very challenging due to various possible pathways, the idea was to test different oxidants, H2O2, TBHP in water and decane, to optimize the researched catalytic system.
Highlights
Catalytic oxidations of alcohols to corresponding aldehydes and ketones are of great importance and interest [1,2]
All the complexes were insoluble in acetonitrile at room temperature but dissolved after 150 min in the carveol reaction mixture or after 20 min in the cyclohexanol reaction mixture at 80 ◦ C
Carvone yield was better with H2 O2 and can be compared to the previously reported results
Summary
Catalytic oxidations of alcohols to corresponding aldehydes and ketones are of great importance and interest [1,2]. Since the usual oxidation processes imply the use of KMnO4 , CrO3 , and halogenated solvents, which are often environmentally harmful, there is a definite need for developing more eco-friendlier and economically affordable catalytic procedures [3]. H2 O2 , is often recommended oxidizing agent in that regard. Another option is tert-butyl hydroperoxide (THBP) due to its solubility and stability in organic solvents [4]. The by-product of the reaction, tert-butanol can be separated by distillation, converted into methyl tert-butyl ether, and employed as a gasoline additive
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