Catalytic activity of systems based on supported potassium salts of transition metal carbonyl hydrides in hydrogen-deuterium exchange of hydrocarbons

Article abstract of DOI:10.1007/s11172-013-0162-6

The deposition of K₂[Ru₄(CO)₁₃], K ₂[Os₃(CO)₁₁], K₂[Fe ₂(CO)₈], and K[Re(CO)₅] onto graphite-like carbon Sibunit followed by the thermal decomposition of the supported carbonylmetallate in a flow of dihydrogen or argon affords systems capable of activating C-H bonds of methane, ethylene, and acetylene and of introducing them into hydrogen-deuterium exchange reactions. In the case of ethylene and acetylene, the isotope exchange proceeds at room temperature, while in the case of methane reaction temperatures not lower than 150 C are needed.

Full text of DOI:10.1007/s11172-013-0162-6

Russian Chemical Bulletin, International Edition, Vol. 62, No. 5, pp. 1191—1194, May, 2013
1191
Catalytic activity of systems based on supported
potassium salts of transition metal carbonyl hydrides
in hydrogen—deuterium exchange of hydrocarbons
S. M. Yunusov,a S. Rummel,b M. Herrmann,b E. S. Kalyuzhnaya,a and V. B. Shura
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: vbshur@ineos.ac.ru
bLeibniz Institute of Surface Modification,
15 Permoserstrasse , Dꢀ04318 Leipzig, Germany*
The deposition of K2[Ru4(CO)13], K2[Os3(CO)11], K2[Fe2(CO)8], and K[Re(CO)5] onto
graphiteꢀlike carbon "Sibunit" followed by the thermal decomposition of the supported carbonꢀ
ylmetallate in a flow of dihydrogen or argon affords systems capable of activating C—H bonds
of methane, ethylene, and acetylene and of introducing them into hydrogen—deuterium exꢀ
change reactions. In the case of ethylene and acetylene, the isotope exchange proceeds at room
temperature, while in the case of methane reaction temperatures not lower than 150 С are
needed.
Key words: methane, ethylene, acetylene, iron, ruthenium, osmium, rhenium, potassium
carbonylmetallates, С—H bond activation, hydrogen—deuterium exchange, heterogeneous
catalysis.
In the course of studies on the development of cataꢀ
lysts for lowꢀtemperature synthesis of ammonia (see reꢀ
view1 and articles2—8) we proposed for the first time to use
supported potassium salts of transition metal carbonyl hyꢀ
drides (K2[Ru4(CO)13], K2[Ru(CO)4], K2[Os3(CO)11],
K2[Fe2(CO)8], and others) as precursors of catalytically
active species. It was assumed that the thermal decompoꢀ
sition of supported carbonylmetallates of this type with
the formation of CO would lead to the generation of negaꢀ
tively charged potassiumꢀcontaining transition metal parꢀ
ticles on the support surface, which would favor the effiꢀ
cient activation of dinitrogen. In fact, using this approach,
we succeeded to develop the first catalysts on a carbon
in hydrocarbons. The hydrogen—deuterium exchange was
chosen as a test reaction in this study. It could be expected
that the results obtained in the study of the H/D exchange
would be useful for the accomplishment of new catalytic
transformations of hydrocarbons under mild conditions.
Particularly interesting would be the involvement of moꢀ
lecular nitrogen in the interaction with hydrocarbons.
Here, we report results of determination of the catalytꢀ
ic activity of the systems based on K2[Ru4(CO)13],
K2[Os3(CO)11], K2[Fe2(CO)8], and K[Re(CO)5] in the
hydrogen—deuterium exchange in methane, ethylene, and
acetylene as well as between methane and D2. The hydroꢀ
gen—deuterium exchange of hydrocarbons over the tradiꢀ
tional heterogeneous catalysts (metallic films, metals on
supports) has been reported previously (see, e.g., Ref. 12).
support (graphiteꢀlike carbons "Sibunit" 9 and CFC10,11
)
capable of accomplishing synthesis of ammonia with sufꢀ
ficiently high rates even in the absence of a specially added
electron promoter.1—3,6 Among these new catalysts, the
rutheniumꢀcontaining systems exhibited the highest acꢀ
tivity. The replacement of the carbon support by highly
basic MgO also resulted in efficient catalysts for dinitroꢀ
gen hydrogenation.1,2,6
The purpose of the present work is to elucidate the
possibility of using the catalysts described above to actiꢀ
vate not only a dinitrogen molecule but also C—H bonds
Experimental
All operations on the synthesis of potassium carbonylmetalꢀ
lates and preparation of the catalysts were carried out under
argon or in vacuo with careful exclusion of air oxygen and moisture.
The starting K2[Ru4(CO)13], K2[Os3(CO)11], K2[Fe2(CO)8], and
K[Re(CO)5] were obtained using described procedures13—15 and
deposited from a THF solution onto graphiteꢀlike carbon "Siꢀ
bunit" (surface area 440 m2 g–1, carbon content 99.5%) preheatꢀ
ed for 6 h in vacuo at 130 С. A characteristic feature of "Siꢀ
bunit" 9 that distinguishes it from the most part of conventional
active carbons is a developed structure of mesopores. After carbꢀ
* LeibnizꢀInstitut für Oberflächenmodifizierung e.V., Permoserꢀ
strasse 15, Dꢀ04318 Leipzig, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1191—1194, May, 2013.
1066ꢀ5285/13/6205ꢀ1191 © 2013 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 5, May, 2013
Yunusov et al.
onylmetallate was deposited onto "Sibunit," the sample was heatꢀ
ed in a dihydrogen or argon flow for 6 h to remove CO from
the supported anionic carbonyl. The heating temperature was
300 С for K2[Ru4(CO)13], K2[Os3(CO)11], and K[Re(CO)5]
and 200 С for K2[Fe2(CO)8]. The Ru : carbon, Os : carbon,
Re : carbon, and Fe : carbon ratios in the samples were 9, 17.3,
16.8, and 9 wt.%, respectively. Thus obtained catalysts were
further tested in the hydrogen—deuterium exchange of hydroꢀ
carbons. Nonequilibrium mixtures of nonꢀdeuterated and deuꢀ
terated ethylene (d0 = 49.4%, d3 = 1.4%, d4 = 49.2%) and nonꢀ
deuterated and deuterated acetylene (d0 = 49.8%, d2 = 50.2%),
as well as trideuteromethane (d3 = 99.6%, d2 = 0.4%), and
a mixture (~1 : 1) of methaneꢀd0 with D2 (99.5 at.% D) were
introduced in hydrogenꢀ—deuterium exchange reactions.
Experiments on the hydrogen—deuterium exchange were conꢀ
ducted using the following procedure. The catalyst (0.16—0.20 g),
containing 0.14—0.16 mmole of a transition metal in the case
of the Ru, Os, and Re samples and 0.24—0.27 mmole in the case
of the Fe sample, was placed under argon in a 9—10ꢀmL glass
ampule. The ampule was evacuated and filled with the studied
gas or a mixture of gases to a pressure of 600 Torr. Then the
ampule was sealed off and, after keeping for a certain time at
room or higher temperature, the isotope composition of the gas
phase was analyzed by mass spectrometry. Analyses were perꢀ
formed on a MAT CHꢀ3 instrument at 13 eV. The determination
accuracy was 5 rel.%. Since it is known that the ionization cross
sections for nonꢀdeuterated and the corresponding deuterated
compounds are similar, the sensitivity of the mass spectrometer
to these compounds was accepted to be the same.
um exchange occurs in the system (Table 1). The rate of
the process depends on both the nature of transition metal in
the catalyst and the method of the sample preparation.
The ruthenium catalyst K2Ru4/H2 obtained by the deꢀ
composition of the starting carbonylruthenate in a dihyꢀ
drogen flow was found to be most active. When this cataꢀ
lyst is used, the isotope composition of ethylene by 82%
approaches the composition corresponding to the statistic
isotope equilibrium (based on ethyleneꢀd2) already in 9
min after the beginning of the reaction, while in 18 min
the hydrogen—deuterium exchange reaches the equilibriꢀ
um almost completely. A similar activity is exhibited by
the ruthenium catalyst K2Ru4/Ar, which was prepared
using argon instead of dihydrogen at the step of the
thermal decomposition of the supported carbonylmetalꢀ
late. However, in the case of the osmium, iron, and rhenium
catalysts, the replacement of dihydrogen by argon at this
step sharply decreases the H/D exchange rate (see Table 1).
This effect is especially pronounced on using the rhenium
samples. The iron catalyst K2Fe2/Ar shows the lowest acꢀ
tivity. In the presence of this catalyst the extent of adꢀ
vancement of the isotope exchange in ethylene to the statisꢀ
tic isotope equilibrium does not exceed 7% even after 48 h.
The hydrogen—deuterium exchange in acetylene occurs
at room temperature with a considerably higher rate than in
ethylene (Table 2). In this case, the iron catalyst K2Fe2/Ar
exhibits the highest activity, while it showed the lowest
The efficiency of the isotope exchange in ethylene, acetylꢀ
ene, and trideuteromethane was characterized by the extent to
which the exchange process approaches the statistic isotope
equilibrium (). The extent of advancement of the reaction toꢀ
ward equilibrium for the aboveꢀmentioned hydrocarbons was
calculated using the general formula (1)
Table 1. Results of the hydrogen—deuterium exchange in the
ethyleneꢀd0—ethyleneꢀd4 systemа
 = ([dn]/[dn]e)•100%
(1)
Cataꢀ
lyst
t
Isotope composition of ethylene (%) fD

/hb
(at.%) (%)
d0
d1
d2
d3
d4
where [dn] is the content of ethyleneꢀd2, acetyleneꢀd1, and methꢀ
aneꢀd4 in ethylene, acetylene, and methane, respectively, at time
 (%); [dn]e is the calculated equilibrium contents of ethyleneꢀ
d2, acetyleneꢀd1, and methaneꢀd4 (%).
—
—
49.4
—
—
1.4 49.2 50.2
0
K2Ru4/H2 9c 11.8 23.0 30.7 21.9 12.6 50.1 82
18c
4.3 28.6 35.9 24.8
6.4 50.1 96
The equilibrium concentrations of ethyleneꢀd2, acetyleneꢀd1,
and methaneꢀd4 were calculated using the formulas of binomial
distribution based on the experimentally determined deuterium
contents (fD (at.%)) in the above hydrocarbons. During the time
of experiments, the isotope exchange in ethylene and acetylene
was not accompanied by the formation of hydrogenation products.
The catalysts used are further designated in the text and tables
as K2Ru4/H2, K2Os3/H2, K2Fe2/H2, KRe/H2 and K2Ru4/Ar,
K2Os3/Ar, K2Fe2/Ar, KRe/Ar, depending on whether the therꢀ
mal decomposition of the supported carbonylmetallate was carꢀ
ried out in a flow of dihydrogen or argon.
K2Ru4/Ar 8c 14.4 20.8 29.3 20.9 14.6 50.1 78
20c
1
4
1
4
24
1
4
6.8 25.3 36.4 24.8
13.7 22.9 24.3 25.5 13.6 50.6 65
6.7 26.3 36.1 24.1 6.8 49.5 96
31.6 12.5 8.8 14.3 32.8 51.0 24
6.7 49.8 97
K2Os3/H2
KRe/H2
10.5 23.8 31.0 25.4
5.3 24.5 36.7 26.4
9.3 49.8 83
7.1 51.4 98
K2Os3/Ar
33.0 13.3
28.5 16.1 10.8 19.0 25.6 49.3 29
5.1 25.2 35.5 26.5 7.7 51.6 95
33.6 11.0 7.0 15.0 33.4 50.9 19
20.4 19.0 17.3 23.9 19.4 50.7 46
5.8 14.4 33.5 50.5 16
24
K2Fe2/H2 20
48
KRe/Ar
Results and Discussion
24
49
42.5
4.9
2.7
5.8 44.1 51.0
7
9
4
7
37.0 10.2
3.4 11.7 37.7 50.7
K2Fe2/Ar 24
48
46.0
40.6
2.8
7.2
1.3
2.5
3.2 46.7 50.5
9.1 40.6 50.5
The exposure of the aboveꢀmentioned catalysts to an
equimolar mixture of ethyleneꢀd0 and ethyleneꢀd4 (conꢀ
taining traces of ethyleneꢀd3) at room temperature results
in the gradual formation of all five isotopic forms of ethylꢀ
ene (d0—d4), thus indicating that the hydrogen—deuteriꢀ
a At 20 С and 600 Torr.
b Reaction time.
c t/min.

Hydrogen—deuterium exchange
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 5, May, 2013
1193
Table 2. Results of the hydrogen—deuterium exchange in the
Table 3. Redistribution of hydrogen isotopes in methaneꢀd3*
acetyleneꢀd0—acetyleneꢀd2 system*
Catalyst
T
/C
Isotope composition of methane (%) fD

(%)
(at.%)
Catalyst
Isotope composition of acetylene (%)
fD

d0
d1
d2
d3
d4
(at.%) (%)
d0
d1
d2
—
—
—
—
—
10.4 99.6
—
74.9
0
—
49.8
28.0
31.9
28.3
33.1
32.2
33.4
33.3
35.1
—
50.2
25.6
26.7
31.8
29.0
30.4
30.2
33.7
34.0
50.2
48.8
47.4
51.8
48.0
49.1
48.5
50.2
49.5
10
93
83
80
76
75
73
66
62
K2Ru4/H2 150
K2Ru4/H2 200
K2Os3/H2 200
11.9 12.1 82.2 13.8
72.0 14
67.7 98
65.5 54
K2Fe2/Ar
K2Os3/H2
KRe/H2
K2Ru4/H2
K2Os3/Ar
KRe/Ar
K2Ru4/Ar
K2Fe2/H2
46.4
41.4
39.9
37.9
37.3
36.6
33.0
30.9
0.2 11.1 27.0 41.1 20.6
0.3 15.4 16.4 57.9 10.0
* At 600 Torr, reaction time 20 h.
It should be noted that, if the ruthenium and osmium
catalysts are used, the deuterium content in methane after
carrying out the reaction is noticeably lower than that
in the initial methane, and these differences in the deuteꢀ
rium content increase with an increase in temperature (see
Table 3). Such a violation of the isotope balance indiꢀ
cates that the system contains an additional source of light
hydrogen capable of H/D exchange. Among such potenꢀ
tial sources are hydrogen chemisorbed on active sites of
the catalyst during the thermal decomposition of the corꢀ
responding carbonylmetallate in a flow of H2 as well as
hydrogen in the carbon support. Unlike the experiments
on the H/D exchange in trideuteromethane, the isotope
balance in the hydrogen—deuterium exchange reactions
in ethylene and acetylene (see Tables 1 and 2) is satisfacꢀ
torily obeyed, on the whole, within the accuracy of massꢀ
spectrometric analysis.
The hydrogen—deuterium exchange between methaneꢀ
d0 and D2, like the hydrogen isotope redistribution in triꢀ
deuteromethane, occurs with a noticeable rate only at
150 С (Table 4). However, not only K2Ru4/H2 but also
K2Ru4/Ar, K2Os3/H2, and K2Os3/Ar are active in this
reaction under such conditions. Interestingly, the highest
H/D exchange rate is observed here when using the rutheꢀ
nium catalyst K2Ru4/Ar, in the presence of which a mixꢀ
ture of five isotopic forms of methane (d0—d4) with the
* At 20 С and 600 Torr, reaction time 5 min.
efficiency in the H/D exchange in ethylene. When the
K2Fe2/Ar catalyst is used, the reaction of acetyleneꢀd0 with
acetyleneꢀd2 gives a mixture of all the three isotopic forms of
acetylene (d0—d2) already after 5 min. The composition
of this mixture (d0 = 28.0%, d1 = 46.4%, d2 = 25.6%)
corresponds to 93% ot the statistic isotope equilibrium
(based on acetyleneꢀd1). The K2Fe2/H2 catalyst is inferior
in activity not only to the K2Fe2/Ar catalyst but also to all
other catalysts tested in the work. When the H/D exchange
is carried out in the presence of K2Fe2/H2, the extent of
advancement of the exchange in acetylene toward equilibꢀ
rium within 5 min does not exceed 62%. In the case of the
rutheniumꢀ, osmiumꢀ, and rheniumꢀcontaining samples,
the replacement of dihydrogen by argon at the step of
decomposition of the supported carbonylmetallate deꢀ
creases the hydrogenꢀdeuterium exchange rate. When the
reaction time increases from 5 to 60 min, the isotope exꢀ
change over all catalysts virtually reaches the equilibrium.
Unlike the hydrogen—deuterium exchange in ethylene
and acetylene, the reaction of the hydrogen isotope redisꢀ
tribution in trideuteromethane begins to occur with a noꢀ
ticeable rate only at 150 С, and only the K2Ru4/H2 cataꢀ
lyst exhibits activity in the H/D exchange under such conꢀ
ditions. As can be seen from Table 3, the heating of methꢀ
aneꢀd3 containing 0.4% CH2D2 with this catalyst for 20 h
at 150 С affords a mixture of four isotopic forms of methane
(d1—d4), whose composition corresponds to 14% of the
equilibrium (based on methaneꢀd4). The reaction rate inꢀ
creases as the temperature increases to 200 С, and in 20 h
the isotope composition of a mixture of all five isotopic
forms of methane (d0—d4) produced at this temperature
corresponds to 98% of the statistic equilibrium. A similar
osmium sample K2Os3/H2 turned out to be also capable of
catalyzing the H/D exchange in methane at 200 С
but with a considerably lower rate than K2Ru4/H2 (see
Table 3). All other catalysts manifest only negligible activꢀ
ity in the isotope exchange even under such conditions or
are inactive at all.
Table 4. Isotope composition of methane after the reaction with D2*
Catalyst
T
Isotope composition of methane (%)
fD
/C
(at.%)
d0
d1
d2
d3
d4
K2Ru4/Ar 150
K2Ru4/H2 150
K2Os3/H2 150
K2Os3/Ar 150
K2Os3/H2 200
K2Ru4/Ar 200
K2Ru4/H2 200
K2Os3/Ar 200
78.2
87.1
92.6
95.6
2.9
4.4
2.1
0.6
5.8
3.3
1.7
0.1
7.5
3.6
2.3
0.9
7.3
5.6
1.6
1.3
2.8
1.6
4.5
1.0
5.1
4.3
1.2
14.9
7.1
4.4
3.7
27.3 40.7 23.1
28.8
26.9
25.8
18.2
6.6
42.4 26.6 16.5 10.0
32.4 39.3 21.9 5.4
8.1 10.0
70.8
91.9
97.2
6.0
0.9
0.7
KRe/Ar
200
0.4
0.2
2.5
0.7
K2Fe2/Ar 200
2.0
* At 600 Torr, D2 : CH4 ~ 1 : 1, reaction time 20 h.

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 5, May, 2013
Yunusov et al.
deuterium content 14.9 at.% is formed from methaneꢀd0
and D2 in 20 h. The K2Ru4/H2 catalyst is substantially
more active than K2Os3/H2 and K2Os3/Ar but is inferior
in activity to the K2Ru4/Ar catalyst.
Thus, as a result of our work it has been shown for the
first time that the systems based on supported potassium
salts of transition metal carbonyl hydrides are capable of
activating C—H bonds of hydrocarbons and introducing
them into hydrogen—deuterium exchange reactions.
On an increase in temperature to 200 С, the rhenium
and iron samples, KRe/Ar and K2Fe2/Ar, start also to catꢀ
alyze the H/D exchange between methaneꢀd0 and D2,
although with a lower rate. The highest activity at this temꢀ
perature is manifested by the osmium and ruthenium catꢀ
alysts K2Os3/H2, K2Ru4/Ar, and K2Ru4/H2, in the presꢀ
ence of which the deuterium content in methane reaches
26—29 at.% in 20 h. The K2Os3/Ar catalyst is less active.
The deuteration of methane during its interaction with
D2 is accompanied by the formation of HD and H2 and, as
a consequence, by a decrease in the deuterium content in
the starting D2. To reveal whether the hydrogen atoms of
the "Sibunit" carbon are involved in this process along with
methane, the K2Os3/Ar catalyst (0.19 g) was heated with
D2 for 20 h in the absence of methane at 150 С. The
results of the experiment showed that the deuterium conꢀ
tent in D2 also decreases (from 99.5 to 88.1 at.%) under
such conditions due to the formation of a mixture of D2,
HD, and H2 in a ratio of 78.1 : 19.9 : 2.0. In a similar
experiment but in the presence of methane, the
D2 : HD : H2 ratio is 70 : 20 : 10 and the deuterium content
is 80 at.%. Thus, the hydrogen atoms of "Sibunit" can also
be involved, along with methane, in the hydrogen—deuteꢀ
rium exchange with D2. It can be thus inferred that the
aboveꢀmentioned violations of the isotope balance in the
experiments on the H/D exchange in trideuteromethane
can be due, at least partially, to the participation of the hyꢀ
drogen atoms of the carbon support in the isotope exchange.
The nature of active particles responsible for the ocꢀ
currence of the aboveꢀconsidered H/D exchange reactions
remains yet unclear. It has previously been shown16 by the
ꢀresonance spectroscopy that the thermal decomposition
of K2[Fe2(CO)8] on the SKT carbon or of K2[Fe2(CO)8]
without a support in an H2 flow at 200 С for 6 h results in
the formation of two ironꢀcontaining amorphous alloys
characterized by a diffuse hyperfine structure in the
ꢀresonance spectra and differed from each other by spectral
characteristics. If the thermal decomposition of the supꢀ
ported K2[Fe2(CO)8] is carried out under the same condiꢀ
tions but in a flow of Ar, only one of these alloys is formed.
It is important that on using argon at the step of the deꢀ
composition of the carbonylferrate only trace amounts of
ꢀiron are present in the thermolysis products, while no
ꢀiron is formed when H2 is used. Based on these data, it can
be assumed that similar amorphous alloys are those partiꢀ
cles that are responsible for the activity of the K2Fe2/H2
and K2Fe2/Ar catalysts in the isotope exchange of hydroꢀ
carbons. Further studies are necessary to establish the comꢀ
position and structure of these amorphous alloys.
References
1. V. B. Shur, S. M. Yunusov, Russ. Chem. Bull. (Engl. Transl.),
1998, 47, 765 [Izv. Akad. Nauk, Ser. Khim., 1998, 796].
2. S. M. Yunusov, B. L. Moroz, A. S. Ivanova, V. A. Likholobov,
V. B. Shur, J. Mol. Catal. A: Chem., 1998, 132, 263.
3. S. M. Yunusov, E. S. Kalyuzhnaya, H. Mahapatra, V. K.
Puri, V. A. Likholobov, V. B. Shur, J. Mol. Catal. A: Chem.,
1999, 139, 219.
4. S. M. Yunusov, E. S. Kalyuzhnaya, B. L. Moroz, S. N.
Agafonova, V. A. Likholobov, V. B. Shur, J. Mol. Catal. A:
Chem., 2001, 165, 141.
5. S. M. Yunusov, E. S. Kalyuzhnaya, B. L. Moroz, S. N.
Agafonova, V. A. Likholobov, V. B. Shur, Appl. Cat. A: Genꢀ
eral, 2001, 218, 25.
6. S. M. Yunusov, E. S. Kalyuzhnaya, B. L. Moroz, A. S. Ivanoꢀ
va, T. V. Reshetenko, L. B. Avdeeva, V. A. Likholobov, V. B.
Shur, J. Mol. Catal. A: Chem., 2004, 219, 149.
7. A. S. Ivanova, E. S. Kalyuzhnaya, G. S. Litvak, E. M. Moroz,
S. M. Yunusov, V. S. Lenenko, B. L. Moroz, V. B. Shur,
V. A. Likholobov, Kinet. Katal., 2004, 45, 574 [Kinet. Catal.
(Engl. Transl.), 2004, 45, 541].
8. S. M. Yunusov, E. S. Kalyuzhnaya, B. L. Moroz, A. S. Ivanoꢀ
va, V. B. Shur, Russ. Chem. Bull., Int. Ed., 2011, 60, 1842
[Izv. Akad. Nauk, Ser. Khim., 2011, 1811].
9. Yu. I. Ermakov, V. F. Surovikin, G. V. Plaksin, V. A. Semiꢀ
kolenov, V. A. Likholobov, L. V. Chuvilin, S. V. Bogdanov,
React. Kinet. Catal. Lett., 1987, 32, 435.
10. V. B. Fenelonov, A. Yu. Derevyankin, L. G. Okkel, L. B.
Avdeeva, V. I. Zaikovskii, E. M. Moroz, A. N. Salanov, N.
A. Rudina, V. A. Likholobov, Sh. K. Shaikhutdinov, Carbon,
1997, 35, 1129.
11. T. V. Reshetenko, L. B. Avdeeva, Z. R. Ismagilov, V. V.
Pushkarev, S. V. Cherepanova, A. L. Chuvilin, V. A. Likhoꢀ
lobov, Carbon, 2003, 41, 1605.
12. G. C. Bond, Catalysis by Metals, Academic Press, Lonꢀ
don—New York, 1962.
13. A. A. Bhattacharyya, C. C. Nagel, S. G. Shore, Organoꢀ
metallics, 1983, 2, 1187.
14. C. C. Nagel, J. C. Bricker, D. G. Alway, S. G. Shore, J.
Organomet. Chem., 1981, 219, С. 9.
15. C. Ungurenasu, M. Palie, J. Chem. Soc., Chem. Commun.,
1975, 388.
16. I. L. Arkhipov, Author´s Abstract, Ph. D. (Chem.) Thesis,
Institute of Chemical Physics, Academy of Sciences of the
USSR, Moscow, 1987 (in Russian).
Received March 1, 2013;
in revised form April 4, 2013