Focus Article, Mendeleev Commun., 2009, 19, 175–181
– 175 –
© 2009 Mendeleev Communications. All rights reserved.
in the V
Alexander A. Markov, Sergei P. Dolin, Natalia I. Moiseeva,
Alexander E. Gekhman and Ilya I. Moiseev*
N. S. Kurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 495 952 1279; e-mail: email@example.com
In order to reveal the nature of intermediates of peroxide oxidation catalysed by vanadium compounds, the inner-sphere
transformations of vanadium(
) peroxo complexes with the general formula [VO
has been studied in approximations of the
density functional theory (B3LYP/6-31G**) and Møller–Plesset perturbation theory (MP2/6-31G**). It has been found that
the triperoxo complex [V(η-O
undergoes isomerization to a complex that is unexpectedly more stable, [V(=O)(η-O
which incorporates an O
group as a bidentate ligand. This reaction was found to occur via two intermediate complexes that can
transfer both singlet dioxygen and an oxygen atom to a substrate molecule. The reaction scheme proposed on the basis of
calculations is in qualitative agreement with the previously obtained kinetic regularities of ozone formation and oxidation of
alkanes, alkenes, arenes and singlet dioxygen acceptors in the V
/RCOOH catalytic system.
Hydroperoxide oxidation is a traditional method in synthetic
Fenton, Haber and Weiss, Baeyer and Villiger,
Prilezhaev, Pisarzhevskii, Shpital’skii, Udris and Hock who made
the most significant contribution to the chemistry of hydrogen
peroxide and its derivatives are among the most prominent
researchers in the history of science. Reactions catalysed by
compounds have found industrial
application. The kinetics and mechanism of propylene epoxida-
tion with α-phenylethylhydroperoxide in the presence of molyb-
denum complexes have been studied by Gavrilenko et al.
It is generally accepted that peroxo complexes of transition
metals are catalysts or active intermediates in hydroperoxide
The composition of the coordination sphere
and the type of coordination of the peroxo ligand depend on the
nature of the central atom and on the composition of the reaction
medium, and they are a matter of discussion in most cases.
The capability of vanadium(
) compounds to catalyse the
oxidation of hydrocarbons has been known since the classical
study by Milas and Sussman,
who have found that V
oxides of some other transition metals catalyse the hydroxyla-
tion of alkenes with hydrogen peroxide.
In this work, we summarise the results of studies on the
/RCOOH system. Our experiments have shown that
this system can cleave C–C and C–H bonds in alkanes,
C=C bond in alkenes,
transfer a singlet dioxygen molecule to
substrates capable of diene synthesis
and oxidise molecular
are generated in
the system (Scheme 1).
RHC CHR' + H
Left to right: Alexander A. Markov, junior scientist of Laboratory of
Metal-complex Catalysis of the N. S. Kurnakov Institute of General and
Inorganic Chemistry of the Russian Academy of Sciences (IGIC RAS),
graduated from Voronezh State University (2005); Sergei P. Dolin,
graduated from M. V. Lomonosov Moscow State University (1966),
Ph.D. in chemistry (1973), head of Laboratory of Quantum Chemistry of
the IGIC RAS; Natalia I. Moiseeva, graduated from M. V. Lomonosov
Moscow Institute of Fine Chemical Technology (MIFCT) (1974), Ph.D.
in chemistry (1993), Senior scientist at the Laboratory of Metal-
complex Catalysis of the IGIC RAS; Academician Ilya I. Moiseev,
graduated from MIFCT (1952), full member of the RAS (1992), full member of Academia Europaea (London, 1994), full member
of Academia Scientiarum et Artium Europaea (Vienna, 1996), Vice-President of D. I. Mendeleev Russian Chemical Society
(2000), full member of the Academy of Sciences, Arts and Literature (Paris, 2002), winner of A. P. Karpinsky Prize (1999),
Triumph Prize (2002), RF State Prize (2003); awarded the Silver medal and delivered a series of lectures (Centenary Lecture) at the
Royal Society of Chemistry, UK (2007), the supervisor of RAS research directions ‘Metal Complex Catalysis’ and ‘Coordination
Chemistry’, Chief researcher at the Laboratory of Metal-complex Catalysis of the IGIC RAS, Professor at I. M. Gubkin Russian
State University of Oil and Gas; Professor Alexander E. Gekhman, graduated from MIFCT (1972), Corresponding member of
the RAS (2000), head of Laboratory of Metal-complex Catalysis of the IGIC RAS. In the picture one can see a portrait of
Academician Yakov K. Syrkin (1894–1974), an authors’ predecessor and teacher.
Dedicated to Professor Roger A. Sheldon in the recognition of his outstanding contribution in oxidation catalysis.