Sustainable Oxidation of Cyclohexane and Toluene in the Presence of Affordable Catalysts: Impact of the Tandem of Promoter/Oxidant on Process Efficiency.

The oxygenation of cyclohexane and toluene by O and HO catalyzed by VO(acac) and Co(acac) was studied at 40-100 °C and 1-10 atm. Upon such conditions, the process can be remarkably (30× times) enhanced by the minute (6-15 mM) additives of oxalic acid (H) or -hydroxyphthalimide (NHPI). The revealed effect of H on HO-piloted oxidation is closely associated with the nature of the catalyst cation and boosted by VO(acac). Whereas the effectiveness of Co(acac)-based systems was curbed by the addition of OxalH and remained much below the one displayed with the previous system. The observed conspicuous difference in activity was attributed to the substantially higher solubility of in situ formed VO(IV)oxalate compared to that of Co(II)oxalate. The exploration of HO for the NHPI-promoted process leads to the decisively lower (5-7 times) yield in comparison to the O-driven reaction. Similarly, for the O-operated protocol, the yield cannot be improved by addition of OxalH either to VO(acac) + NHPI or to Co(acac) + NHPI mixture. By contrast, the combination of NHPI with VO(acac) or Co(acac) and particularly with the above two mixtures in O-piloted oxidation enhances the yield of the aimed products 3-6 times regardless of the substrate used. The revealed significant synergetic effect of the cobalt + vanadyl bicomponent catalyst was due to the participation of each of its moiety in the different stages of the process mechanism. Only benzyl alcohol and benzaldehyde were identified in VO(acac)- or Co(acac)-catalyzed toluene oxidation, while cyclohexane oxidation yields cyclohexylhydroperoxide in line with cyclohexanol and cyclohexanone. The putative mechanism of investigated processes is highlighted and discussed.