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The analysis of the amount of 2 at the end of the oxida-
tion showed that this additive is partially consumed (30–40%). In
and oxalic acid have been detected.
[1] H. Arakawa, M. Aresta, J.N. Armor, M.A. Barteau, E.J. Beckman, A.T. Bell, J.E.
Bercaw, C. Creutz, E. Dinjus, D.A. Dixon, K. Domen, D.L. DuBois, J. Eckert, E. Fujita,
D.H. Gibson, W.A. Goddard, D.W. Goodman, J. Keller, G.J. Kubas, H.H. Kung, J.E.
Lyons, L.E. Manzer, T.J. Marks, K. Morokuma, K.M. Nicholas, R. Periana, L. Que, J.
Rostrup-Nielson, W.M.H. Sachtler, L.D. Schmidt, A. Sen, G.A. Somorjai, P.C. Stair,
B.P. Stults, W. Tumas, Chem. Rev. 101 (2001) 953–996.
[2] J. Metzger, M. Eissen, C. R. Chim. 7 (2004) 569–581.
[3] M. Eissen, J. Metzger, E. Schmidt, U. Schneidewind, Angew. Chem. Int. Ed. Engl.
41 (2002) 414–436.
Taking into account the above experimental data, we sug-
gest a mechanism involving the key steps depicted by Scheme 1.
The process would occur via a radical pathway represented
by A → B → C → D → E → A [12,19,24,27], and a non-radical one
illustrated by A → B → C → F → E → A. The F → E transformation
would involve interactions of cyclohexane at the second sphere
coordination of F. Under our oxidation conditions, cyclohexanol,
cyclohexanone and cyclohexyl hydroperoxide would be generated
simultaneously, with different rates, from the beginning of the oxi-
dation process.
[4] K.U. Ingold, Aldrichim. Acta 22 (1989) 69–73.
[5] G. Strukul (Ed.), Catalytic Oxidations with Hydrogen Peroxide as Oxidant,
Kluwer Academic Publishers, Dordrecht, The Netherlands, 1992.
[6] G.W. Parshall, S.D. Ittel, Homogeneous Catalysis, Wiley, New York, 1992.
[7] G.S. Mishra, E.C.B. Alegria, L.M.D.R.S. Martins, J.J.R. Frausto da Silva, A.J.L.
Pombeiro, J. Mol. Catal. A: Chem. 285 (2008) 92–100.
[8] L. Que, W. Tolman, Nature 455 (2008) 333–340.
[9] L.D. Wang, E.R. Farquhar, A. Stubna, E. Münck, L. Que Jr., Nature 1 (2009)
145–150.
4. Conclusion
[10] C.D. Nicola, F. Garau, Y.Y. Karabach, L.M.D.R.S. Martins, M. Monari, L. Pandolfo,
C. Pettinari, A.J.L. Pombeiro, Eur. J. Inorg. Chem. (2009) 666–676.
[11] A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, E.Yu. Karabach, M. Haukka, M.F.C.
Guedes da Silva, A.J.L. Pombeiro, Adv. Synth. Cat. 348 (2006) 159–174.
[12] M.V. Kirillova, Y.N. Kozlov, L.S. Shul’pina, O.Y. Lyakin, A.M. Kirillov, E.P. Talsi,
A.J.L. Pombeiro, G.B. Shul’pin, J. Catal. 268 (2009) 26–38.
[13] L.S. Shul’pina, M.V. Kirillova, A.J.L. Pombeiro, G.B. Shul’pin, Tetrahedron 65
[14] U.R. Pillai, E. Sahle-Demessie, Chem. Commun. (2002) 2142–2143.
[15] I.V. Berezin, E.T. Denisov, N.M. Emanuel, Oxidation of Cyclohexane, Pergamon
Press, New York, 1966.
[16] A. Pokutsa, J. Le Bras, J. Muzart, Kinet. Catal. (Engl. Transl.) 48 (2007) 26–31.
[17] G.B. Shul’pin, Y.N. Kozlov, L.S. Shul’pina, P.V. Petrovskiy, Appl. Organomet.
Chem. 24 (2010) 464–472.
[18] D.C. Harris, Quantitative Chemical Analysis, 6th ed., Freeman, New York, 2003.
[19] G. Shulpin, Yu. Kozlov, G. Nizova, G. Suss-Fink, S. Stanislas, A. Kitaygorodskiy,
V. Kulikova, J. Chem. Soc. Perkin Trans. 2 (2001) 1351–1371.
[20] R. Khaliullin, A. Bell, M. Head-Gordon, J. Phys. Chem. B 109 (2005) 17984–17992.
[21] C. Walling, Acc. Chem. Res. 8 (1975) 125–131.
Given the above experimental data, it appears that the tra-
ditional free radical chain scheme of hydrocarbons oxidation
(C6H12 → C6H11OOH → C6H11OH + C6H10O) has to be comple-
mented with a non-radical pathway. The practical interest of the
above protocol lies in the use of commercially available rela-
tively cheap low toxic reagents leading to an effective oxidation
of cyclohexane with hydrogen peroxide at 40 ◦C under atmo-
spheric pressure. The application of the acquired knowledge to
the oxidation of others substrates, such as linear alkanes [27] is
underway.
Acknowledgments
This work has been supported by NATO CLG No. 982510. Authors
are indebted to Dr. R. Fl’unt and Dr. E. Karpenko for the catalase
delivering.
[22] N. Greenwood, A. Earnshaw, Chemistry of the Elements, Pergamon, Oxford,
1984.
[23] A. Cotton, G. Wilkinson, C. Murillo, M. Bochmann, Advanced Inorganic Chem-
istry, 6th ed., Wiley, New York, 1999.
[24] Y.N. Kozlov, V.B. Romakh, A. Kitaygorodskiy, P. Buglyo, G. Süss-Fink, G.B.
Shul’pin, J. Phys. Chem. A 111 (2007) 7736–7752.
[25] V. Srinivasan, J. Rocek, J. Am. Chem. Soc. 96 (1974) 127–133.
[26] G.B. Shul’pin, Y.N. Kozlov, L.S. Shul’pina, T.V. Strelkova, D. Mandelli, Catal. Lett.
138 (2010) 193–204.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
[27] G.B. Shul’pin, Mini Rev. Org. Chem. 6 (2009) 95–104.