Terminal C ≡ C triple bond hydrogenation using immobilized Wilkinson's catalyst

Article abstract of DOI:10.1007/s11164-010-0162-1

In this work, we try to hydrogenate selectively phenylacetylene to styrene and 3-phenylpropyne to allylbenzene using immobilized or pure Wilkinson's catalyst. The catalyst was immobilized using two approaches-immobilization using ionic exchange and immobilization using covalent bonding. In the first case, the smectite minerals (hectorite and montmorillonite) were used as the supports. In the second case, MCM-41 and SBA-15 were used as the supports. Both types of immobilization were successful and the solid products were characterized. For the covalent bond formation, it was necessary to first modify the surface of the silica material. The modification was carried out using two substances, one adding an amino group to the silica material, and the second adding a phenyl group to the material. The selectivity of hydrogenation of both substances was higher using heterogeneous catalyst in the case of phenylacetylene. In the case of phenylpropyne, no difference in selectivity using Wilkinson's catalyst in homogeneous or heterogeneous arrangement was observed. The type of immobilization has no influence on either activity or selectivity of catalyst. Springer Science+Business Media B.V. 2010.

Full text of DOI:10.1007/s11164-010-0162-1

Res Chem Intermed (2010) 36:511–522
DOI 10.1007/s11164-010-0162-1
Terminal C:C triple bond hydrogenation using
immobilized Wilkinson’s catalyst
•
Eliska Leitmannova Petr Jirasek Jakub Rak
•
•
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Lucie Potucka Petr Kacer Libor Cerveny
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•
•
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Received: 23 March 2010 / Accepted: 27 May 2010 / Published online: 7 September 2010
Ó Springer Science+Business Media B.V. 2010
Abstract In this work, we try to hydrogenate selectively phenylacetylene to sty-
rene and 3-phenylpropyne to allylbenzene using immobilized or pure Wilkinson’s
catalyst. The catalyst was immobilized using two approaches—immobilization
using ionic exchange and immobilization using covalent bonding. In the first case,
the smectite minerals (hectorite and montmorillonite) were used as the supports. In
the second case, MCM-41 and SBA-15 were used as the supports. Both types of
immobilization were successful and the solid products were characterized. For the
covalent bond formation, it was necessary to first modify the surface of the silica
material. The modification was carried out using two substances, one adding an
amino group to the silica material, and the second adding a phenyl group to the
material. The selectivity of hydrogenation of both substances was higher using
heterogeneous catalyst in the case of phenylacetylene. In the case of phenylpropyne,
no difference in selectivity using Wilkinson’s catalyst in homogeneous or hetero-
geneous arrangement was observed. The type of immobilization has no influence on
either activity or selectivity of catalyst.
Keywords Hydrogenation Á Immobilization Á Phenylacetylene Á
Wilkinson’s catalyst
ˇ
´
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E. Leitmannova Á P. Jirasek Á L. Potucka Á P. Kacer Á L. Cerveny (&)
Faculty of Chemical Technology, Department of Organic Technology, Institute of Chemical
´
Technology in Prague, Technicka 5, 166 28 Prague 6, Czech Republic
e-mail: libor.cerveny@vscht.cz
J. Rak
Faculty of Chemical Engineering, Department of Analytical Chemistry, Institute of Chemical
´
Technology in Prague, Technicka 5, 166 28 Prague, Czech Republic
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Introduction
Partial hydrogenation of a triple bond to a double bond is a very important synthetic
reaction with high utilization both in the laboratory and on the industrial scale. In spite
of the existence of a large number of systems with high selectivity to double bond
formation (Lindlar catalyst, palladium supported catalysts) there is still a large field
for exploring new accesses and catalytic systems using new methods in catalysis.
Rhodium complexes represent a promising class of robust hydrogenation catalysts
since, in addition to high catalytic activity, they also show high stability in air as well as
high tolerance to the reaction medium and functional groups of reactants [1, 2].
Besides hydrogenation, a particular Rh complex can usually catalyze a few types of
other reactions such as hydrocarbonylation, isomerization, hydrosilylation and
silylation [1–6], Kharash addition [7], methanation of carbon oxides [8], transforma-
tions of diazo compounds [9], and various kinds of polymerizations [2, 10–12].
Therefore, they can be used for the activation of various organic compounds towards a
variety of chemical transformations under mild conditions (room or slightly elevated
temperature, in solvents from water to hydrocarbons, and in the presence of air), which
compensates for the high cost of these catalysts.
The most famous Rh complex is Wilkinson’s catalyst (RhCl(PPh3)3) that is
utilized [3, 13–15] in the industrial hydrocarbonylation of olefins and is also known
as an effective catalyst of the hydrogenation of unsaturated compounds including
the hydrogenation of the C:C triple bond to the double bond.
The Wilkinson’s catalyst was prepared in situ and used for selective hydroge-
nation of octynes to octenes and decynes to decenes [14]. As supports, smectites
clays were used [16–18] (hectorite and montmorillonite) for immobilization using
ionic exchange. Because the silica materials do not have the optimal group for
ligand exchange that is the basis for covalent bond formation, it is necessary to add
some ‘‘spacers’’ to the material. As a spacer, two different species can be used—
aminopropyltriethoxysilane [19], this has the amino group for ligand exchange, and
diphenylphosphinoethyltriethoxysilane [20–23], which has the phenyl group for
ligand exchange.
In this work, the activity and selectivity of the Wilkinson’s catalyst in pure and
immobilized forms for the hydrogenation of phenylacetylene to styrene and
phenylpropyne to allylbenzene were tested.
Experimental
Materials
Wilkinson’s catalyst (pure), phenylacetylene (98%), phenylpropyne (97%) and
montmorillonite-K10 were purchased from Aldrich. Aminopropyltriethoxysilane
(97%), diphenylphosphinoethyltriethoxysilane (97 %) and hectorite were purchased
from ABCR. Hexane, methanol, chloroform and diethylether were purchased from
Penta. Materials for immobilization, i.e. MCM-41 and SBA-15, were kindly
supplied by J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences,
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Terminal C:C triple bond hydrogenation
513
Czech Republic. Hexane, methanol and diethylether were distilled from sodium
under argon atmosphere; all other chemicals were used as obtained.
Preparation of heterogeneous catalysts
Catalyst anchored on smectite minerals
Smectite minerals are ionic clays with negative charge on the layers and positive
charge in the interlayers carried by alkali metal cations (sodium, potasium etc.). The
cationic part of the Wilkinson’s can be exchanged with these alkali metals. The
mineral (200 mg) was first dried under a nitrogen atmosphere at 300 °C for 6 h and
after cooling inserted into a Schlenk vessel under an argon atmosphere. Then, a
solution (20 mg in 20 mL) of [Rh(PPh3)3Cl] in solvent (methanol, diethylether,
hexane) was added with vigorous stirring. After 24 h of stirring, the catalyst was
formed. Rh-hectorite or Rh-MTM-K10 was isolated by decantation washed four
times with an appropriate solvent and dried under vacuum (4 h).
Catalyst anchored on mesoporous molecular sieve
Because Wilkinson’s catalyst only partly and weakly anchors on all-siliceous
molecular sieves, the sieve was first modified by reaction with 3-aminopropyl-
triethoxysilane, NH2(CH2)3Si(OEt)3, or 2-diphenylphosphinoethyltriethoxysilane
PPh2(CH2)2Si(OEt)3 to introduce anchoring amino or phosphino groups, respec-
tively, into MCM-41 pores using the procedure described earlier [24–26]. The sieve
(1,000 mg) was first dried under a nitrogen atmosphere at 300 °C for 6 h and after
cooling was suspended in CH2Cl2 (5 mL) in a Schlenk vessel under Ar atmosphere.
Then, a solution of NH2(CH2)3Si(OMe)3 (6.0 mmol) or PPh2(CH2)2Si(OEt)3
(6.0 mmol) in CHCl3 (15 mL) was added and the suspension was kept under
vigorous stirring at room temperature for 24 h. The white solid obtained, denoted as
MCM*NH2 or MCM*PPh2 or SBA*NH2 or SBA*PPh2, was separated by
decantation, washed four times with 15 mL of CHCl3 and dried under vacuum (4 h).
Anchoring of [Rh(PPh3)3Cl] complex was achieved by its direct immobilization
on the modified molecular sieve. MCM*NH2, MCM*PPh2, SBA*NH2 or
SBA*PPh2 (200 mg) was inserted into the Schlenk vessel and an orange solution
of [Rh(PPh3)3Cl] (20 mg) in CHCl3 (20 mL) was added under vigorous stirring. The
sieves turned pale orange while the CHCl3 phase became colorless. After 24 h of
stirring, a catalyst formed, Rh/MCM*NH2, Rh/MCM*PPh2, Rh/SBA*NH2 or
Rh/SBA*PPh2 was isolated by decantation, washed four times with 15 mL CHCl3
and dried under vacuum (4 h).
Hydrogenation experiments
Hydrogenations were carried out in a stainless steel autoclave Parr. Typical reaction
conditions were 2 MPa, laboratory temperature and 2.5% of catalyst calculated on
active complex. The samples were analyzed on GC Varian 3800 with FID on
column VA-1. Nonane was used as internal standard.
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Techniques
GC
Varian 3800 instrument was used for GC analysis with FID detector and VA-1
column (60 m, 0.25 mm, 0.25 lm). Nitrogen was used as the carrier gas.
UV/VIS
For the detection of complexes in solvent after immobilization and after the
hydrogenation experiments, PE Systems Lambda 35 UV/VIS instrumentation was
used. Detection of released amount of catalyst (during immobilization experiments
as the same as after hydrogenation experiments) was performed at wavelength
265 nm. Shape of spectrum of Rh specie is visible in Fig. 1.
AAS
For the detection of Rh in solvent after the hydrogenation experiments, a Varian
Spectra AA880 instrument was used.
XRD
X-ray powder diffraction data were collected at room temperature with an X’Pert
PRO h–h powder diffractometer with parafocusing Bragg–Brentano geometry using
˚
CuKa radiation (k = 1.5418 A, U = 40 kV, I = 30 mA). Data were scanned with
an ultrafast detector X’Celerator (or with a scintilator detector equipped with a
secondary curved monochromator) over the angular range 5–60° (2h) with a step
size of 0.02° (2h) and a counting time of 0.3 s step-1. Data evaluation was
performed in the software package HighScore Plus.
Fig. 1 UV/Vis spectra of
Wilkinson’s catalyst
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Terminal C:C triple bond hydrogenation
515
Table 1 Characteristics of
Sieves
SBET (m2 g-1
)
Vme (cm3 g-1
)
Dme (nm)
parent and modified mesoporous
molecular sieves used as
catalysts support
MCM-41
1,140
807
769
720
403
385
0.86
0.53
0.44
0.88
0.60
0.48
3.5
3.0
2.9
7.7
7.0
6.9
MCM*NH2
MCM*PH2
SBA-15
SBET BET surface area, Vme
mesopore volume, Dme mean
mesopore diameter
SBA*NH2
SBA*PH2
Adsorption isotherm of nitrogen
Adsorption isotherm of nitrogen at 77.35 K was measured using Micromeritics
ASAP 2010 instrument. Data collected from measurement of supports and modified
supports are given at Table 1.
MAS-NMR
Data were collected using Varian Mercury Plus 300 instrument equipped with CP/
MAS probe with 5-mm rotors. The 31P spectra were performed at frequency
121.44 MHz.
Results and discussion
The Wilkinson’s catalyst was immobilized using two methods—by covalent
bonding on a silica mesoporous molecular sieve, and on smectite clay minerals by
ionic bonding.
Immobilization using ionic exchange
At first, the dependence of immobilized amount on time was tested. In the literature
[14, 16–18], times between 4 and 30 h were used. The Wilkinson’s catalyst was
immobilized on hectorite using hexane as the solvent, and each hour a sample of the
mother liquor was tested using UV to determine the amount of immobilized
complex. After 4 h, 96% of the complex was immobilized (only 4% was eluted in
the mother liquor), after 5 h, 98% of the complex was immobilized. After 24 h, the
amount of the immobilized complex remained the same (98%) indicating that
equilibrium of the reaction had been reached. The optimal time for immobilization
was 5 h and 19 mg of complex was attached to 200 mg of the hectorite support.
The most important property of the smectite clay minerals is their ability to
expand over their monomolecular intercalant dimension. The limit of the interlayer
swelling depends on the swelling solvent, exchangeable cation, interlayer charge
and the location of the charge. For inorganic systems, water is often used as the
solvent, and methanol, ethanol, propan-2-ol and dichloromethane are used for
organic systems. In our case, methanol was chosen as the swelling solvent, hexane
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as a non-polar solvent, and in addition the hydrogenations take place in hexane, and
diethylether as the last solvent. Depending on the solvent and minerals (hectorite
and montmorillonite K10) used, the amount of immobilized Rh complex was
compared.
In chosen minerals, the following exchangeable hydrated cations were detected:
˚
Na—interlayer distance 9.9 A; K—interlayer distance 14 A; and Ca—interlayer
˚
˚
distance 27 A.
The ionic exchange itself takes place in the movement of the cationic part of the
complex to the interlayers, forming the immobilized complex while the anionic
counter ion forms a salt with former interlayer cation; in this case, NaCl, KCl or
CaCl2 are formed.
The amount of immobilized complex can be detected by several methods. The
change in interlayer distance can be detected using XRD [16–18], but the complex
must be larger than the hydrated ions and the complex must be inserted into the
layers and not simply attached to the mineral surface by nonbonding interactions.
The amount of complex on the support can also be quantified using AAS. The
amount of metals in the mother liquor after immobilization can also be determined,
but there are several limitations in detection of Rh metals from complex substances.
The amount of released alkali metals can also be determined, but usually large
amounts of alkali metals are presented in the available solvents. Another method to
determine the quantity of immobilized complex is the use of UV/VIS spectropho-
tometry. The amount of the complex in the mother liquor after immobilization is
determined in these cases. UV detection, XRD and AAS were used to quantify the
amount of metal released.
Solvent effect was examined using both the supports and three solvents described
above. From the amount of the Rh complex present in the solvent, the amount of the
catalyst immobilized was calculated and is shown in Table 2.
XRD analysis was carried out to determine the real interlayer distance after
immobilization. There was only weak intensity peak corresponding to the interlayer
distance of the immobilized complex or its crystal structure. Using only hectorite in
methanol as a solvent, the structure of Wilkinson’s catalyst and the shift of
interlayer peak were visible (Fig. 2).
˚
In other solvents, the interlayer distance decreased from 14 A (hydrated
˚
potassium ions) to 9 A (hydrated sodium ions), this could be explained by the high
level of sodium cations in the solvents. We have obtained only a little information
about the amount immobilized using XRD, probably due to the attachment of the
Wilkinson’s catalyst to the surface of the support. The amount of alkali metal in the
mother liquor was determined using AAS. It was found that the exchanged amount
of alkali metals (Na and K) was distinctively higher using hectorite as a support than
in the case of montmorillonite. Use of methanol as the solvent offered the best
possibility for ionic exchange as predicted. The results obtained using the detection
of released ions (AAS detection, Table 3) were the opposite of the results obtained
by detection of immobilized catalyst amount (UV/VIS, Table 2, and AAS
detection).
The opposite results can be explained by the ionic exchange taking place in
methanol, and in the other solvents, the complex is more attached to the surface. In
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Terminal C:C triple bond hydrogenation
517
Structure of Wilkinson’s catalyst
5
10
15
20
25
30
2θ
Fig. 2 XRD pattern of immobilized Wilkinson’s catalyst on hectorite using methanol as a solvent
Table 2 Immobilized amount of catalyst (%) with respect to supports and solvents used, quantified by
UV/VIS spectrometry
Solvent
Supporta
Hectorite
MTM-K10
Methanol
Diethylether
Hexane
a
91
99
99
90
98
98
100% of immobilized catalyst = 20 mg/200 mg of the support
spite of this, these interactions are strong enough to hold the complex onto the
support under the hydrogenation conditions (see later). Immobilization of the
Wilkinson’s catalyst was confirmed by 13P MAS-NMR (pure Wilkinson catalyst,
see [20]; in the case of immobilized complex, the signals overlap more, but the
structure of complex is still visible [17]).
From the results, it is obvious that hectorite is the optimal support for the
immobilization of Wilkinson’s catalyst with 19 mg of the catalyst immobilized on
200 mg of the support.
Immobilization using covalent bonding
As mentioned above a direct bond between the silica material and Wilkinson’s
catalyst does not exist. It is necessary to modify the surface of the support using a
molecule that can form a covalent bond with the chosen catalyst. Two commonly
used silanes, aminopropyltriethoxysilane and diphenylphosphinotriethoxysilane,
were chosen as ‘‘spacers.’’ These substances have ligands that are able to exchange
with triphenylphosphine ligands of Wilkinson’s catalyst. Two different supports
were chosen: SBA-15 and MCM-41.
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Table 3 Amount (%) of
released ions (K or Na) from
mother liquor after
Solvent
Support
Hectorite
MTM-K10
immobilization (calculated from
AAS)
Methanol
Diethylether
Hexane
65
40
42
46
30
33
The complex was immobilized using the procedure described in the experimental
section. The amount of complex immobilized was strongly dependent on the type of
spacer used (see Table 4).
The total quantity of the immobilized complex was 19 mg on 200 mg of the
support *PPh2 and 15 mg of the complex on 200 mg of the support *NH2.
Immobilization of the Wilkinson’s catalyst by the ligand exchange using
MCM*PPh2 as the support was confirmed by 13P MAS-NMR (see [20]). In
contrast to this study, we have found a different intensity of the signals at 25 and
39 ppm; this is solely due to the difference in the immobilization, as the author used
two spacers and we only used one. So the shift at 25 corresponds to the attached
phosphino group and at 39 to the free group. In any case, the oxidized form of
spacer was not confirmed (EA and MAS-NMR [21]).
As shown in Table 4, the amount of the complex immobilized depended only on
the type of the spacer employed. Using *NH2 as the spacer, the immobilized
amount was around 75% irrespective of the support [SBA (larger pores) or MCM
(smaller pores)]. Using *PPh2 as a spacer, the amount of catalyst immobilized was
significantly higher, about 97% in both cases—using SBA as well as MCM. The
higher immobilized amount using the *PPh2 spacer can be explained by a higher
affinity of PPh2 groups to the Rh center of the complex [the PPh3 group of the
complex is exchanged with PPh2(CH2)2Si– group, the type of the groups is similar].
In contrast, using the *NH2 spacer, the affinity of Rh center is lower [PPh3 group of
the complex is exchanged with NH2(CH2)3Si– group, the type of the group is
different].
XRD was used for characterization of prepared material. The shift of the typical
band of MCM to higher degrees (lower pore size) is visible. The lower intensities of
the bands indicate that the rearrangement of the material caused some of the
material to become amorphous (Fig. 3).
The dependence of the immobilization using covalent bonding on time was
tested. We adopted the same procedure as was used for the immobilization using
ionic exchange. Surprisingly, after the first hour of the immobilization, the
maximum immobilized amount was achieved, i.e. 75% in the case of Rh/support
*NH2 and 96% in the case of the other Rh/support, *PPh2. The anchored amount
was unchanged 24 h after immobilization, indicating that 1 h is sufficient time for
immobilization using covalent bonding.
A molecular sieve (MCM-41 or SBA-15) with *PPh2 as a spacer for treatment
of the surface is optimal for immobilization using covalent bonding.
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Terminal C:C triple bond hydrogenation
519
MCM-41
Rh/MCM~NH2
4
6
8
10
2 θ
Fig. 3 Representative XRD patterns of immobilized Wilkinson’s catalyst using covalent bond
Hydrogenation experiments
Phenylacetylene and 3-phenylprop-1-yne hydrogenation were chosen as model
reactions for activity and selectivity tests of the prepared immobilized catalysts. The
concentration courses are shown in Figs. 4 and 5. In both cases, the unsaturated
compound (styrene or allylbenzene, respectively) is the desired product but is
converted to the saturated one (ethylbenzene or propylbenzene). The hydrogenation
of phenylacetylene is more selective and faster.
The catalysts prepared by immobilization on the different supports were tested
for selective hydrogenation of these two substances and the results were compared
with those obtained using the Wilkinson’s catalyst in a homogeneous arrangement.
From Table 5, it can be seen that either reaction rates (TOF) or selectivities are
very similar to the measurement error is up to 5%. It is probable that the catalytic
species still has the structure of Wilkinson’s catalyst and no changes occur in the
structure of cationic part during the immobilization process either by ionic exchange
or by ligand exchange.
When comparing the immobilized catalyst with the catalyst in the homogeneous
hydrogenation, surprising results were found. The reaction rate in the heterogeneous
conditions was lower, as was expected, but the selectivity in the homogeneous
arrangement was over 10% lower than in the heterogeneous one.
The reaction rate in the case of homogeneous hydrogenation of phenylpropyne
was 341 h-1 with a selectivity of up to 60%. Using immobilized catalyst (Rh/
MCM*PPh2 was chosen as an example), the reaction rate decreased as was
expected and the selectivity to allylbenzene remained the same (approximately
60%).
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100
80
60
40
20
0
0
50
100
150
200
250
300
350
Time [min]
Phenylacetylene
Styrene
Ethylbenzene
Fig. 4 The concentration course in phenylacetylene hydrogenation (200 mg phenylacetylene, 20 mg
Rh-MTM-K10, 100 mg of nonane and 28 mL of hexane)
100
80
60
40
20
0
0
50
100
150
200
250
300
Time [min]
Phenylpropyne Propylbenzene
Allylbenzene
Fig. 5 The concentration course in 3-phenylprop-1-yne hydrogenation (200 mg 3-phenylprop-1-yne,
20 mg Rh-hectorite, 100 mg of nonane and 28 mL of hexane)
Table 4 Immobilized amount (%) of the Wilkinson’s catalyst using immobilization by means of
covalent bond (UV/VIS)
Support with spacer
SBA*NH2
MCM*NH2
SBA*PPh2
MCM*PPh2
Immobilized amount (%)a
75
74
96
97
a
100% immobilized amount is 20 mg of the complex on 200 mg of the support (silica material with the
spacer)
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Terminal C:C triple bond hydrogenation
521
Table 5 Comparison of TOF and selectivity using the heterogenized catalyst prepared by the different
approaches and with the catalysis in the homogeneous arrangement
Support
Solvent used for
catalyst
immobilization
TOFinitial
(h-1
Selectivity toward
ST at conversion
50% (%)
)
Ionic exhange
Hectorite
Methanol
Diethylether
Hexane
546
428
420
441
520
456
452
403
443
410
997
72
68
68
72
74
75
77
68
77
73
63
Montmorillonite
Methanol
Diethylether
Hexane
Covalent bond
MCM*PPh2
MCM*NH2
SBA*PPh2
SBA*NH2
Chloroform
Homogeneous arrangement
After hydrogenations, the extent of eventual Rh leaching from the support into
the liquid part of the reaction system was studied. The liquid resulting after the
reaction was concentrated by evaporation and analyzed by AAS. No Rh was
detected by this method (limit of AAS detection = 0.1 mg/mL; concentration of Rh
corresponding to the total leaching = 2 mg/mL). It can be thus concluded, that no
or only marginal Rh leaching occurs during followed hydrogenation. This finding
was in agreement with no catalytic activity being observed in the liquid phase
isolated after finishing the hydrogenation cycle.
Conclusions
The Wilkinson’s catalyst [Rh(PPh3)3Cl] was immobilized by two approaches—
ionic exchange and covalent bonding. The ionic exchange was performed using two
different supports—hectorite and montmorillonite K10. The selection of a solvent
for the immobilization is an important parameter of this process due to possible
nonbonding interactions of the catalytic complex and the support (the complex is
immobilized to the surface or to the interlayers). The immobilized amount using this
approach was 19 mg of the complex on 200 mg of the support. Immobilization
using covalent bonding was performed using pretreated silica mesoporous
molecular sieves—MCM*PPh2, MCM*NH2, SBA*PPh2 and SBA*NH2.
Treatment with the *PPh2 spacer was more successful due to the higher
immobilized amount of the complex—19 mg on 200 mg of the support; in the
other cases, the immobilized amount of complex was lower than 15 mg of complex
on 200 mg of the support. A comparison of the two immobilization types was
performed and the amount immobilized was the same in both cases, but the
immobilization times were different—5 h in the case of ionic exchange and 1 h in
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the case of ligand exchange. The heterogeneous catalysts were compared in
phenylacetylene and phenylpropyne hydrogenations with the Wilkinson’s catalyst in
the homogeneous arrangement. The significant increase in selectivity in the case of
phenylacetylene was observed using heterogenized catalysts, which is caused by the
presence of only monomeric species. No change in the coordination of the complex
was observed in either of the immobilization types.
Acknowledgments Financial support of the Ministry of Education of the Czech Republic no.:
MSM6056137301 and Grant Agency of Czech Republic Grants No: 104/07/1239 and 203/08/H032-1.
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