Disproportionation of cyclohexadienes and cyclohexene under the action of catalysts based on supported tetranuclear potassium carbonylruthenate K2[Ru4(CO)13]

Article abstract of DOI:10.1007/s11172-014-0519-5

The deposition of tetranuclear potassium carbonylruthenate K₂[Ru₄(CO)₁₃] onto carbon Sibunit, SiO₂, γ-Al₂O₃, and MgO followed by the thermal decomposition of the supported anionic cluster at 300°C in an H₂ or Ar flow leads to systems capable of catalyzing the disproportionation of cyclohexa-1,3-diene and cyclohexa-1,4-diene. The reactions proceed at room temperature to form mixtures of benzene and cyclohexene, benzene, cyclohexene, and cyclohexane, or benzene and cyclohexane. The catalytic systems developed are also active in cyclohexene disproportionation to benzene and cyclohexane at 100-130 °C.

Full text of DOI:10.1007/s11172-014-0519-5

Russian Chemical Bulletin, International Edition, Vol. 63, No. 4, pp. 843—847, April, 2014
843
Disproportionation of cyclohexadienes and cyclohexene
under the action of catalysts based on supported tetranuclear
potassium carbonylruthenate K2[Ru4(CO)13]*
S. M. Yunusov,a S. Rummel,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
bInstitut für Oberflächenmodifizierung e.V.,
Permoserstrasse 15, Dꢀ04303 Leipzig, Germany
The deposition of tetranuclear potassium carbonylruthenate K2[Ru4(CO)13] onto carbon
Sibunit, SiO2, ꢀAl2O3, and MgO followed by the thermal decomposition of the supported
anionic cluster at 300 C in an H2 or Ar flow leads to systems capable of catalyzing the
disproportionation of cyclohexaꢀ1,3ꢀdiene and cyclohexaꢀ1,4ꢀdiene. The reactions proceed at
room temperature to form mixtures of benzene and cyclohexene, benzene, cyclohexene, and
cyclohexane, or benzene and cyclohexane. The catalytic systems developed are also active in
cyclohexene disproportionation to benzene and cyclohexane at 100—130 C.
Key words: cyclohexadienes, cyclohexene, disproportionation, ruthenium, potassium carboꢀ
nylmetallates, clusters, С—H bond activation, supported catalysts, heterogeneous catalysis.
One of the promising trends in modern heterogeneous
catalysis is a wide use of concepts and methods of organoꢀ
metallic and coordination chemistry for the development
of efficient catalysts and catalytic processes. Among these
processes requiring nontraditional approaches are lowꢀ
temperature synthesis of ammonia from dinitrogen and
dihydrogen, catalytic conversions of alkanes and cycloalꢀ
kanes under mild conditions and others. Earlier, when deꢀ
veloping catalysts for lowꢀtemperature ammonia syntheꢀ
sis (see review1 and articles2—8), we have proposed for the
first time to use supported potassium salts of carbonylhyꢀ
drides of transition metals (K2[Ru4(CO)13], K2[Ru(CO)4],
K2[Os3(CO)11], K2[Fe2(CO)8], etc.) as precursors of catꢀ
alytically active particles. It was assumed that the thermal
decomposition of such carbonylmetallates (with the CO
formation) would result in the generation of negatively
charged potassiumꢀcontaining transition metal particles
on the support surface which should favor the efficient
dinitrogen activation. Fruitfulness of the proposed apꢀ
proach was demonstrated by the successful development
of the first catalysts on a carbon support (graphiteꢀlike
carbon Sibunit,9 catalytic filamentous carbon10,11) capaꢀ
ble of accomplishing the ammonia synthesis with sufꢀ
ficiently high rates even in the absence of a specially added
electron promoter.1—3,6 Rutheniumꢀcontaining systems
turned out to be most efficient among these new catalysts.
The replacement of the carbon support by highly basic
MgO still further increased the rate of the ammonia
synthesis.
We have recently reported the ability of the above sysꢀ
tems to activate also C—H bonds of hydrocarbons (methꢀ
ane, ethylene, acetylene) and involve them in the
hydrogen—deuterium exchange reactions.12 The catalysts
were obtained by the thermal decomposition of supportꢀ
ed K2[Ru4(CO)13], K2[Os3(CO)11], K2[Fe2(CO)8], and
K[Re(CO)5] on carbon Sibunit in an H2 or Ar flow.
It turned out that for ethylene and acetylene the isotope
exchange occurs with a high rate already at ~20 C, while in
the case of methane the isotope exchange occurs beginꢀ
ning from 150 C. It was also concluded that the activity
of the K2[Fe2(CO)8]ꢀbased systems in the H/D exchange
is due to the presence in the catalysts of ironꢀcontaining
amorphous alloys of an unknown nature which are formed
(according to the data of the ꢀresonance spectra) during
the thermal decomposition of the starting carbonylferrate.
Based on these results, we decided to find out whether
the aboveꢀconsidered systems can be used for the catalytic
hydrogenation of С=С double bonds by means of the
hydrogen transfer to them from the С—H bonds of hyꢀ
drocarbons under mild conditions (see, e.g., review13).
As model reactions of the hydrogenation of such a type,
we chose the reactions of disproportionation of cycloꢀ
hexadienes and cyclohexene that occur under the action
* Dedicated to the memory of Academician M. E. Vol´pin on
the occasion of his 90th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0843—0847, April, 2014.
1066ꢀ5285/14/6304ꢀ0843 © 2014 Springer Science+Business Media, Inc.

844
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
Yunusov et al.
a well developed mesoporous structure,9 which is substantial for
catalysis. Prior to K2[Ru4(CO)13] deposition, carbon Sibunit was
dried for 6 h by heating in vacuo at 130 С, MgO was dried for 2 h
at 200 C in vacuo, and SiO2 and ꢀAl2O3 were heated for 11 h at
400 C in an H2 flow and then for 1 h in vacuo at 300 C. The
deposition of K2[Ru4(CO)13] was carried out from a THF soluꢀ
tion (Ru/support = 9 wt.%). After deposition and drying, the
samples were thermally decomposed in a dihydrogen flow
(7.5 L h–1) at 300 С for 6 h to remove CO from the supported
carbonyl cluster. In the case of Sibunit, thermal decomposition
of the supported sample was also carried out in an argon flow
(10 L h–1). Thus prepared catalysts were further tested in the
disproportionation of cyclohexadienes and cyclohexene. Prior
to use commercial cyclohexaꢀ1,3ꢀdiene, cyclohexaꢀ1,4ꢀdiene, and
cyclohexene (Aldrich) were distilled trapꢀtoꢀtrap in vacuo. The
catalysts were tested in disproportionation by shaking the starting
reagents in sealed glass ampules in an Ar atmosphere. The reaction
conditions are presented in Tables 1—5. After the end of the exꢀ
periment, the resulting reaction mixture was separated from the
catalyst by trapꢀtoꢀtrap distillation in vacuo and analyzed by GLC
and GLC/MS. The GLC analyses were carried out under the
temperatureꢀprogrammed conditions (60 С, 2 min; 60—120 С,
5 С min–1; 120 С, 1 min; 120—250 С, 10 С min–1; 250 С,
5 min) on a Chrompack CP 9001 chromatograph equipped with
a flameꢀionization detector and the CPSil13CB capillary colꢀ
umn (50 m×0.32 mm) using dodecane as an internal standard.
of palladium catalysts and some other heterogeneous and
homogeneous catalytic systems (see, e.g., articles14—32).
In the course of the disproportionation, the intermolecuꢀ
lar hydrogen transfer proceeds from the CH2 groups of
the unsaturated compound to the double bond of its
other molecule, which makes it possible to consider this
process as a peculiar model for olefin hydrogenation by
natural gas.
In the present work, we report the results obtained on
the study of the catalytic activity of the systems based on
tetranuclear potassium carbonylruthenate K2[Ru4(CO)13]
on various supports in the disproportionation of cycloꢀ
hexaꢀ1,3ꢀdiene, cyclohexaꢀ1,4ꢀdiene, and cyclohexene.
Experimental
All procedures on catalyst preparation were carried out with
a thorough exclusion of air oxygen and moisture. The starting
K2[Ru4(CO)13] was prepared according to a described proceꢀ
dure.33 The following supports were used for the preparation of
the catalysts: ꢀAl2O3 (350 m2 g–1), SiO2 (300 m2 g–1), MgO
(200 m2 g–1), and graphiteꢀlike carbon Sibunit (440 m2 g–1, carbꢀ
on content 99.5%). A characteristic feature of Sibunit that disꢀ
tinguishes it from the most part of conventional active carbons is
Table 1. Disproportionation of cyclohexaꢀ1,4ꢀdiene under the action of the catalysts K2Ru4/H2
and K2Ru4/Ar on carbon Sibunit*
Catalyst
T/C
**/h
Conversion of cyclohexaꢀ
Ratio of products (mol.%)
1,4ꢀdiene to products (%)
K2Ru4/H2
K2Ru4/Ar
20
70
20
70
100
0.17
20
5
20
20
95
98
26
87
89
59.8
19.0
0
49.9
0
21.2
33.9
0
33.9
34.1
65.8
50.1
66.1
65.9
0
* Catalyst weight 0.16—0.19 g, molar ratio cyclohexaꢀ1,4ꢀdiene : Ru = (28—34) : 1.
** Here and further  is the reaction time.
Table 2. Disproportionation and isomerization of cyclohexaꢀ1,3ꢀdiene under the action of the catalysts K2Ru4/H2
and K2Ru4/Ar on carbon Sibunit*
Catalyst
T/C
/h
Conversion of cyclohexaꢀ
1,3ꢀdiene to products (%)
Ratio of products (mol.%)
K2Ru4/H2
20
20
20
70
100
20
1.33
3
6
62
77
88
90
96
13
84
0.9
0.8
0
0
0
49.9
50.5
52.9
56.1
66.3
45.8
53.0
46.7
45.9
41.1
29.6
0
2.5
2.8
6.0
14.3
33.7
0
20
20
20
20
K2Ru4/Ar
9.5
0
44.7
39.8
100
7.2
* Catalyst weight 0.17—0.19 g, molar ratio cyclohexaꢀ1,3ꢀdiene : Ru = (26—32) : 1.

Cyclohexadiene and cyclohexene disproportionation Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
845
Table 3. Effect of the support nature on the disproportionation of cyclohexaꢀ1,4ꢀ
diene under the action of the catalyst K2Ru4/H2*
Support
Conversion of cyclohexaꢀ
1,4ꢀdiene to products (%)
Ratio of products (mol.%)
Sibunit
SiO2
ꢀAl2O3
MgO
95
97
95
35
59.8
19.0
31.4
34.9
50.9
21.2
56.0
54.7
49.1
12.6
10.4
0.
* T = 20 C,  = 10 min, catalyst weight 0.19—0.21 g, molar ratio cyclohexaꢀ1,4ꢀ
diene : Ru = 26 : 1.
Table 4. Effect of the support nature on the disproportionation and isomerization of cycloꢀ
hexaꢀ1,3ꢀdiene under the action of the catalyst K2Ru4/H2*
Support
Conversion of cyclohexaꢀ
1,3ꢀdiene to products (%)
Ratio of products (mol.%)
ꢀAl2O3
SiO2
Sibunit
MgO
97
69
62
13
0
53.7
49.7
50.0
43.2
36.4
48.0
46.7
41.2
9.9
1.1
2.4
0
1.2
0.9
15.6
* T = 20 C,  = 80 min, catalyst weight 0.17—0.20 g, molar ratio cyclohexaꢀ1,3ꢀdiene : Ru =
= (26—30) : 1.
Table 5. Effect of the support nature on the disproportionation
of cyclohexene under the action of the catalyst K2Ru4/H2*
the conversion of the cyclohexadiene to the disproporꢀ
tionation products at room temperature already in 10 min
achieves 95%. The reaction affords a mixture of benzꢀ
ene, cyclohexene, and cyclohexane in a molar ratio of
59.8 : 19.0 : 21.2, thus indicating that the disproportionꢀ
ation proceeds via two routes (Scheme 1). One route inꢀ
volves the transformation of the cyclohexadiene into an
equimolar mixture of benzene and cyclohexene (see
Scheme 1, reaction (1)). In another route (see Scheme 1,
Support
Conversion of
cyclohexene to
products (%)
Ratio of products (mol.%)
ꢀAl2O3
SiO2
Sibunit
MgO
86
84
68
27
32.3
34.0
32.5
32.4
67.7
66.0
67.5
67.6
Scheme 1
* T = 130 C,  = 0.5 h, catalyst weight 0.17—0.19 g, molar ratio
cyclohexene : Ru = (26—28) : 1.
The GLC/MS analyses were carried out on a Trio 1000, FISONS
instrument (70 eV). The catalysts used in the work are further
designated in the text and tables as K2Ru4/H2 and K2Ru4/Ar,
depending on whether the supported K2[Ru4(CO)13] was therꢀ
mally decomposed in a flow of dihydrogen or argon.
Results and Discussion
The data on cyclohexaꢀ1,4ꢀdiene disproportionation
under the action of the catalysts K2Ru4/H2 and K2Ru4/Ar on
carbon Sibunit are presented in Table 1. The K2Ru4/H2
catalyst is most active: in the presence of this catalyst

846
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
Yunusov et al.
reaction (2)) the starting cyclohexadiene forms benzene
and cyclohexane in a molar ratio of 2 : 1. It follows from
the aforementioned benzene : cyclohexene : cyclohexane
ratio that the amount of benzene formed via route (2) is
~2 times higher indeed (59.8 – 19 = 40.8%) than the
amount of cyclohexane (21.2%).
As the temperature and reaction time increase to 70 С
and 20 h, respectively, the cyclohexene content in the
disproportionation products decreases to zero and the proꢀ
cess proceeds, under these conditions, according to Eq. (2),
i.e., with the formation of benzene and cyclohexane in
a molar ratio close to 2 : 1 (see Table 1).
The replacement of Sibunit by SiO2 and ꢀAl2O3 in the
K2Ru4/H2 catalyst exerts almost no effect on the converꢀ
sion of cyclohexaꢀ1,4ꢀdiene attaining 95—97% after
10 min at ~20 C (see Table 3). However, when using MgO
as a support, the conversion of cyclohexaꢀ1,4ꢀdiene deꢀ
creases to 35% under the same conditions. On going from
Sibunit to SiO2 and then to ꢀAl2O3 and MgO, the relative
content of cyclohexene in the reaction products increases
and the contents of benzene and cyclohexane decrease. In
the case of the K2Ru4/H2 catalyst on MgO, only benzene
and cyclohexene are formed in a molar ratio close to 1 : 1
due to the disproportionation via route (1) only.
The K2Ru4/Ar catalyst on Sibunit is considerably less
active in the cyclohexaꢀ1,4ꢀdiene disproportionation than
K2Ru4/H2 on the same support (see Table 1). When
K2Ru4/Ar is used, an equimolar mixture of benzene and
cyclohexene is formed at ~20 C from cyclohexaꢀ1,4ꢀdiꢀ
ene due to reaction (1). The conversion of the starting
diene to the disproportionation products at 20 C does not
exceed 26% even in 5 h. With an increase in temperature
to 70—100 C and in the reaction time to 20 h, the converꢀ
sion of cyclohexaꢀ1,4ꢀdiene increases to 87—89%. Cycloꢀ
hexene is not formed again under these conditions and
a mixture of benzene and cyclohexane is produced.
The disproportionation of cyclohexaꢀ1,3ꢀdiene under
the action of the K2Ru4/H2 and K2Ru4/Ar catalysts on
Sibunit also occurs at ~20 C but with a lower rate (see
Table 2). When the K2Ru4/H2 catalyst is used, benzene,
cyclohexene, and small amounts of cyclohexane appear in
80 min in the reaction mixture. The products also contain
trace amounts of cyclohexaꢀ1,4ꢀdiene, which are formed
due to the isomerization of cyclohexaꢀ1,3ꢀdiene. Howevꢀ
er, the conversion of the starting diene is only 62% under
the conditions indicated above. With an increase in the
reaction time and temperature, the amount of cyclohexꢀ
ene gradually decreases and the amounts of benzene and
cyclohexane, as well as conversion, increase. An analysis
of the products obtained in 20 h on carrying out the reacꢀ
tion at 100 C showed the complete absence of cyclohexꢀ
ene in the mixture and the presence of benzene and cycloꢀ
hexane formed due to the disproportionation via route (2).
The conversion of cyclohexaꢀ1,3ꢀdiene to the reaction
products reaches 96%.
The K2Ru4/H2 catalyst on ꢀAl2O3 is most active in
the disproportionation of cyclohexaꢀ1,3ꢀdiene. When this
catalyst is used, the conversion of cyclohexaꢀ1,3ꢀdiene to
a mixture of benzene, cyclohexene, and cyclohexane in
80 min at ~20 C attains 97% (see Table 4). The K2Ru4/H2
catalysts on SiO2 and Sibunit are less active and transform
cyclohexaꢀ1,3ꢀdiene (with 62—69% conversion) into
a mixture of benzene and cyclohexene containing also
trace amounts of cyclohexane and cyclohexaꢀ1,4ꢀdiene.
The K2Ru4/H2 catalyst on MgO is again least active: apꢀ
proximately equal amounts of benzene and cyclohexene
are formed along with cyclohexaꢀ1,4ꢀdiene from cycloꢀ
hexaꢀ1,3ꢀdiene in the presence of this catalyst. The conꢀ
version of cyclohexaꢀ1,3ꢀdiene does not exceed 13%.
The driving force of the cyclohexaꢀ1,3ꢀdiene isomerizaꢀ
tion to cyclohexaꢀ1,4ꢀdiene is a close thermodynamic
stability of unconjugated cyclohexaꢀ1,4ꢀdiene and formally
conjugated cyclohexaꢀ1,3ꢀdiene having a nonplanar strainꢀ
ed structure.34,35 As is known, conjugated dienes usually
considerably excel unconjugated dienes in thermodynamꢀ
ic stability.
The experiments on the catalytic disproportionation
of cyclohexene were carried out at 100—130 C. The
K2Ru4/H2 samples on the aboveꢀindicated supports were
tested as catalysts. It turned out that in all cases the disꢀ
proportionation of cyclohexene proceeds according to
stoichiometric Eq. (3) and affords benzene and cyclohexꢀ
ane in a molar ratio of ~1 : 2.
The K2Ru4/Ar catalyst is also considerably less active
than K2Ru4/H2 in the disproportionation of cyclohexaꢀ
1,3ꢀdiene and (see Table 2). When the reaction is carried
out at ~20 C in the presence of K2Ru4/Ar, the starting
cyclohexaꢀ1,3ꢀdiene in 20 h gives an equimolar mixture of
benzene and cyclohexene as well as noticeable amounts of
cyclohexaꢀ1,4ꢀdiene but the conversion is only 13% under
these conditions. An increase in temperature to 100 C
results in an increase in the conversion in 20 h to 84%. In
this case, cyclohexaꢀ1,4ꢀdiene is not formed and the reacꢀ
tion products contain small amounts of cyclohexane along
with benzene and cyclohexene.
The highest activity is displayed by the catalysts on
ꢀAl2O3 and SiO2, on the use of which the cyclohexene
conversion to the disproportionation products at 130 С in
0.5 h reaches 84—86%. The lowest activity, as in the cycloꢀ
hexaꢀ1,3ꢀdiene and cyclohexaꢀ1,4ꢀdiene disproportionꢀ
ation, is exhibited by the sample on MgO, in the presence
of which the conversion of cyclohexene is only 27% under
the same conditions.
Thus, as a result of our study, the ability of the cataꢀ
lysts based on supported potassium salt of transition metal
carbonylhydride to perform the disproportionation of

Cyclohexadiene and cyclohexene disproportionation Russ.Chem.Bull., Int.Ed., Vol. 63, No. 4, April, 2014
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ene was demonstrated for the first time. The catalysts are
obtained by depositing tetranuclear potassium carbonꢀ
ylruthenate K2[Ru4(CO)13] on carbon Sibunit, SiO2,
ꢀAl2O3, or MgO followed by the thermal decomposition
of the supported cluster at 300 С in an H2 or Ar flow. In
the case of cyclohexaꢀ1,3ꢀdiene and cyclohexaꢀ1,4ꢀdiene,
the process of the disproportionation can proceed via two
routes: with the formation of an equimolar mixture of
benzene and cyclohexene (route 1) or/and a mixture of
benzene and cyclohexane in a molar ratio of 2 : 1 (route 2).
The contribution of route 2 to the overall course of the
disproportionation process increases with an increase in
the reaction temperature and time. The catalysts prepared
by the thermal decomposition of the supported carbonylꢀ
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and ꢀAl2O3 are used, the disproportionation of cycloꢀ
hexaꢀ1,4ꢀdiene occurs nearly quantitatively with a high
rate already at ~20 C. The disproportionation of cycloꢀ
hexaꢀ1,3ꢀdiene is also observed at ~20 C but the process
rate is substantially lower in this case. In a series of the
tested supports, the best results were obtained using
ꢀAl2O3 and SiO2, whereas MgO showed the lowest activꢀ
ity. The systems found can also catalyze the disproporꢀ
tionation of cyclohexene at 100—130 С to form benzene
and cyclohexane in a molar ratio of 1 : 2. The obtained
results indicate the possibility of using the systems based
on supported potassium salts of transition metal carbonylꢀ
hydrides for the processes of hydrogen transfer from C—H
bonds of hydrocarbons to С=С double bonds.
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Received September 17, 2013;
in revised form January 28, 2014