We also found that regio-selectivities determined for the oxi-
dations of n-hexane and n-heptane (Table 1) are in accordance
with the proposed radical mechanism. Indeed, comparison with
2002, 179, 113–123; (af) M. Nowotny, L. N. Pedersen, U. Hanefeld
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3
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the same parameters obtained for certain other systems show
Ϫ
that the t-BuOOH–VO3 system is similar to the H O –n-
2
2
Bu NVO –PCA reagent which has been shown by us earlier to
4
3
6
operate via hydroxyl radicals.
Thus we can conclude that the system under discussion
Reviews: (a) A. Butler, M. J. Clague and G. E. Meister, Chem. Rev.,
(
like the “O –H O –V complex–PCA” reagent described by us
2
2
2
1
994, 94, 626–638; (b) V. Conte, F. Di Furia and G. Licini, Appl.
6
previously ) efficiently transforms alkanes to corresponding
alkyl hydroperoxides. In both catalytic systems molecular
oxygen from the atmosphere plays the role of “true” oxidant
whereas used in stoichiometric amounts peroxide (hydrogen
peroxide or t-butyl hydroperoxide) is a promoter of the process.
Catal. A, 1997, 157, 335–361; (c) A. E. Shilov and G. B. Shul’pin,
Activation and Catalytic Reactions of Saturated Hydrocarbons in the
Presence of Metal Complexes, Kluwer, Dordrecht/Boston/London,
2000, ch. 10 (Homogeneous catalytic oxidation of hydrocarbons by
peroxides and other oxygen atom donors).; (d ) A. E. Shilov and
G. B. Shul’pin, Chem. Rev., 1997, 97, 2879–2932.
5
(a) H. Mimoun, M. Mignard, P. Brechot and L. Saussine, J. Am.
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Acknowledgments
The authors thank the Russian Basic Research Foundation for
support.
(
2
d ) K. P. Bryliakov, E. P. Talsi, T. Kühn and C. Bolm, New. J. Chem.,
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