Ionic liquid-stabilized vanadium oxo-clusters catalyzing alkane oxidation by regulating oligovanadates

Abstract

Alkane oxidation under mild conditions occupies an important position in the chemical industry. Herein, we have designed a novel class of ionic liquid ([TBA][Pic])-stabilized vanadium oxo-clusters (TBA = tetrabutylammonium; Pic = picolinate ions), in which the molar ratio of the IL to V atoms can be tuned facilely to obtain V-OC@IL-0.5, V-OC@IL-1 and V-OC@IL-2, respectively. The as-synthesized vanadium oxo-clusters have been characterized by elemental analysis, FT-IR, UV-vis, XRD, TGA, EPR, NMR and MS. These vanadium oxo-clusters were catalytically active for catalyzing the oxidation of cyclohexane with H₂O₂ as an oxidant. In particular, the oxo-cluster V-OC@IL-1 (where IL/V is 1.0) can provide an approximately 30% total yield of KA oil (cyclohexanol and cyclohexanone) without adding any co-catalyst at 50 °C within 1.0 h. Moreover, the present vanadium oxo-cluster was recyclable owing to the modification of the IL and it can also be extended to the oxidation of the sp² hybrid aromatic ring. The further characterization results demonstrated that the oligovanadate anions were strongly dependent on the molar ratio of the IL to V atoms. The vanadium oxo-clusters with the appropriate molar ratio of IL/V could exist in the form of a trimer and a dimer due to the presence of the TBA cation and the coordination of picolinate. Notably, the oligovanadate anions are highly active species for the C–H oxidation but the mononuclear vanadate afforded a very poor activity according to the activity assessment and the identification of vanadium species from the ⁵¹V NMR spectra and MS spectra. The annihilation reaction of free radicals and EPR characterization suggested that the vanadium oxo-clusters operated via a mechanism of the HO˙ radical in the oxidation reaction.