Oxidation of cyclohexane catalyzed by bis-(2-pyridylmethyl)amine Cu(II) complexes

• Published in: Applied catalysis. A, General Vol. 317; no. 2; pp. 154 - 160
• Main Authors: Silva, Aires C., Fernández, Tatiana Lopez, Carvalho, Nakédia M.F., Herbst, Marcelo H., Bordinhão, Jairo, Jr, Adolfo Horn, Wardell, James L., Oestreicher, Enrique G., Antunes, O.A.C.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 07-02-2007; Elsevier
• Subjects: Adipic acid; Catalysis; Chemistry; Cu(II) complexes; Cu(II) enzymes; Cyclic voltammetry; Cyclohexanol; Cyclohexanone; Cyclohexyl hydroperoxide; EPR; Exact sciences and technology; General and physical chemistry; Hydrogen peroxide; Oxidation; pMMO; tert-Butyl hydroperoxide; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Cyclic voltammetry; Cu(II) complexes; Hydrogen peroxide; Cyclohexanone; Cyclohexyl hydroperoxide; EPR; Oxidation; Cu(II) enzymes; pMMO; Cyclohexanol; Adipic acid; tert-Butyl hydroperoxide; Catalytic reaction; Enzyme; EPR spectrometry; Hydroperoxide; Complexes; Heterogeneous catalysis; Amine; Cyclohexane
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2006.10.012

In this work, it is showed the cyclohexane oxidation catalyzed by the copper(II) complexes, [Cu(BMPA)Cl
2] (
1) and {[Cu(BMPA)Cl
2][Cu(BMPA)(H
2O)Cl] [Cu(BMPA)Cl][CuCl
4]} (
2), using hydrogen peroxide or
tert-butyl hydroperoxide as terminal oxidants and acetonitrile as solvent. Although the complexes were previously reported, in the present paper it is disclosed an alternative method for the synthesis of the complex 2, as well as additional characterization data on these complexes including EPR and cyclic voltammetry. The complexes were able to oxidize cyclohexane into cyclohexanol, cyclohexanone, cyclohexyl hydroperoxide and adipic acid, in mild conditions. Complex
2 exhibited the best results, reaching as high as 68.9% of total yield in 24
h with H
2O
2. In general, H
2O
2 showed better results than
tert-butyl hydroperoxide as terminal oxidant.
In this work, it is showed the cyclohexane oxidation catalyzed by the copper(II) complexes, [Cu(BMPA)Cl
2] and {[Cu(BMPA)Cl
2][Cu(BMPA)(H
2O)Cl] [Cu(BMPA)Cl][CuCl
4]} (
2), using hydrogen peroxide or
tert-butyl hydroperoxide as terminal oxidants and acetonitrile as solvent.
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