Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

• Published in: Journal of molecular catalysis. A, Chemical Chemical, 2013-02, Vol.367, p.52-60
• Main Authors: Silva, Telma F.S., Leod, Tatiana C.O. Mac, Martins, Luísa M.D.R.S., Guedes da Silva, M. Fátima C., Schiavon, Marco A., Pombeiro, Armando J.L.
• Format: Article
• Language: English
• Subjects: C-scorpionates; Catalysis; Chemistry; Crystal structure; Cyclohexane; Exact sciences and technology; General and physical chemistry; Homogeneous catalysis; Oxidation; Supported catalysis; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Vanadium
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2012.10.024

[Display omitted] ► New oxo-vanadium(IV) complexes with pyrazole or tris(pyrazolyl)ethanol ligands. ► Immobilization of those V complexes on a polydimethylsiloxane membrane. ► Homogeneous or supported V complexes catalyze cyclohexane oxidation. The oxovanadium(IV) complexes [VO(acac)2(Hpz)]·HC(pz)31·HC(pz)3 (acac=acetylacetonate, Hpz=pyrazole, pz=pyrazolyl) and [VOCl2{HOCH2C(pz)3}] 2 were obtained from reaction of [VO(acac)2] with hydrotris(1-pyrazolyl)methane or of VCl3with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONs up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BPO as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems.