Vanadium(V) complexes supported on porous MIL-100(Fe) as catalysts for the selective oxidation of toluene

The vanadium(V) complexes bearing the aroylhydrazone Schiff base 2-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide ligand [VO(OMe)L] (1) and [Et3NH][VO2L] (2) were synthesized, characterized and supported on porous MIL-100(Fe) forming the 1@MIL-100(Fe) and 2@MIL-100(Fe) composites. The outcome of such immobilizations was assessed by several characterization techniques, namely powder X-ray diffraction, UV/Vis, FTIR, SEM-EDS, ICP and BET surface area analysis, confirming the successful heterogenization of both vanadium complexes. They were screened as catalysts towards the oxidation of toluene, under homogenous (1 and 2) and heterogeneous (1@MIL-100 and 2@MIL-100) conditions. The influence of several parameters, namely the type and amount of catalyst or oxidant, reaction time, temperature, and radical trapping, was studied. The main products obtained were benzaldehyde, benzyl alcohol and benzoic acid. Under the optimized conditions, using 1 and 2 as homogeneous catalysts, total yields of 19 and 23%, respectively, were achieved at 80 °C after 6 h. Using 1@MIL100(Fe) and 2@MIL100(Fe) composites under heterogeneous conditions, total yields up to 11% after 24 h, were achieved. © 2022 Elsevier Inc.