Selective hydrogenation of nitroarenes to aminoarenes using a MoO:X-modified Ru/SiO2 catalyst under mild conditions

Article abstract of DOI:10.1039/c7cc00653e

Modification of Ru/SiO₂ with metal oxides (MoO_x, WO_x, and ReO_x) improved the activity and selectivity in the hydrogenation of 3-nitrostyrene to 3-aminostyrene under mild conditions such as 0.3 MPa H₂, 303 K, and no solvent. Ru-MoO_x/SiO₂(Mo/Ru = 1/2) catalyst was applicable to various substituted nitroarenes, providing the corresponding substituted aminoarenes in high yields (85-99%).

Full text of DOI:10.1039/c7cc00653e

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
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Selective hydrogenation of nitroarenes to aminoarenes using
MoOx modified Ru/SiO2 catalyst under mild conditions
Masazumi Tamura*, Naoto Yuasa, Yoshinao Nakagawa, Keiichi Tomishige*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
NH2
Modification of metal oxides (MoOx, WOx and ReOx) with Ru/SiO2
improved activity and selectivity in hydrogenation of 3-nitrostyrene
to 3-aminostyrene under mild conditions such as 0.3 MPa H2, 303 K
and no solvent. Ru-MoOx/SiO2(Mo/Ru=1/2) catalyst was applicable
to various substituted nitroarenes, providing the corresponding
substituted aminoarenes in high yields (85%-99%).
H2
H2
H2
H2
NH2
NO2
NO2
Scheme 1 Hydrogenation of nitrostyrenes
Development of highly selective and active catalysts hydrogenation of the produced aminoarenes also occurs, leading
contributes to energy saving, cost reduction, and waste reduction, to low selectivity to the aminoarenes (Scheme 1). Various
and supported metal catalysts will be ideal among various effective heterogeneous catalysts for selective hydrogenation of
catalysts in terms of its reusability, durability and easy separation nitrostyrene as a model reaction have been developed such as Pt-
of products and catalysts. However, for supported metal catalysts, based catalysts4, Au-based catalysts5 and Co-based catalysts6 and
control of selectivity is generally difficult because of the non- so on7. In particular, in spite that Pt metal originally shows higher
uniformity of the surface active sites, and hence effective activity to hydrogenation of alkenes than that of nitro groups,
methodologies to control selectivity and activity, particularly modification of Pt metal with other species4c,e-g or strong metal
selectivity, are quite necessary. Modification of active metal support interaction (SMSI) effect4a,b,d,h drastically changed the
species with inorganic or organic modifiers will be one of the activity of Pt metal, achieving high selectivity to the target
most promising approaches1, however, these systems often not amines. Other noble metal species such as Rh, Ru and Pd also
only require complex and tedious preparation but also decrease showed low selectivity4h, however, there are few reports on
the activity via coverage of the active sites by modifiers2. activity and selectivity control of these metal species.
Therefore, more facile, simple and effective catalyst systems
enabling both high selectivity and activity are desirable to be catalysts (noble metal: Ir, Rh and Ru; metal oxide: ReOx, MoOx,
developed from the viewpoint of green sustainable chemistry.
WOx) for hydrogenolysis of polyols or ethers8 and hydrogenation
To date, we have developed metal-oxide-modified noble metal
Selective hydrogenation of substrates having multiple different of carbonyl compounds such as carboxylic acids9, aldehydes10
functional groups are often used as a model reaction for and amides11. These studies showed that modification of noble
development of selective heterogeneous catalysts, and selective metals with metal oxides formed active sites at the interface of
hydrogenation of functionalized nitroarenes to the corresponding noble metals and metal oxides, leading to drastic improvement
aminoarenes is a useful organic reaction because the produced of the activity and selectivity. Herein, we applied the metal-
aminoarenes are important chemicals and intermediates for oxide-modified noble metal catalysts to selective hydrogenation
agrochemicals, pharmaceuticals polymers and pigments1a,3
.
of functionalized nitroarenes to the aminoarenes, showing that
However, for conventional hydrogenation catalysts such as noble MoOx-modified Ru/SiO2 was effective for the reaction, and that
metal supported catalysts, nonpolar functional groups such as modification of Ru metal with MoOx species improved both the
alkenes and alkynes are thermodynamically and kinetically more activity (about 5-fold) and selectivity (73%  99%).
subjective to hydrogenation than the nitro groups, and over-
At first, hydrogenation of 3-nitrostyrene as a model reaction
was conducted with various catalysts under mild reaction
conditions such as 303 K, 0.3 MPa H2 and no solvent (Table 1).
From the results of the carbon-supported noble metal catalysts
(M/C, M=Ru, Pd, Rh, Pt, entries 1-4), Ru/C provided high
a.Department of Applied Chemistry, Graduate School of Engineering, Tohoku
University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
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Table 1 Hydrogenation of 3-nitrostyrene using various catalysts
Journal Name
Time-courses of hydrogenation of 3-nitrostyrene over Ru-
View Article Online
DOI: 10.1039/C7CC00653E
NO2
NH2
NO2
NH2
MoOx/SiO2 and Ru/SiO2 are shown in Figure 1. The reaction
0.3 MPa H2
+
+
over Ru-MoOx/SiO2(Mo/Ru=1/2) proceeded smoothly with high
303 K
Catalyst
1
2
3
selectivity to reach almost 100% at 12 h, providing
yield (Figure 1a). On the other hand, although the reaction over
Ru/SiO2 proceeded smoothly, the selectivity to drastically
decreased after 100% conversion of 3-nitrostyrene. These results
1 in 97%
Selectivity (%)
Conversion
(%)
Entry
Catalyst
1
91.2
2
3
Others
0.5
0.5
1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Ru/C*
Pd/C*
Rh/C*
Pt/C*
Ru/SiO2
6.2
8.3 <0.1
<0.1 76.9 22.6
13.6 76.0
90.0
58.3
41.1
2.8
14.2
15.3
9.9
98.0
86.8
92.2
92.4
73.0
59.9
66.9
71.1
31.7
38.0
27.9
38.3
30.2
28.1
29.2
30.9
9.2
5.4
1.2
suggest that over-hydrogenation of
of MoOx species to Ru/SiO2.
1 was suppressed by addition
52.6
73.4
8.6
33.4
17.1
<0.1
0.5
1.2
0.4
3.6
2.2
9.4
<0.1
<0.1
0.1
0.1
8.8
4.8
4.3
13.0
8.6
9.5 <0.1
0.4
99.5 <0.1 <0.1
97.9 0.9 <0.1
The scope of nitroarenes was investigated by using Ru-
MoOx/SiO2(Mo/Ru=1/2) catalyst (Table 3). Various substituted
nitrobenzenes with unsaturated functional groups were
selectively converted to the corresponding anilines in high yields
(entries 1-4). In addition, chloronitrobenzenes were transferred
to the corresponding chloroanilines (CANs), which are typical
scaffold compounds for dyes, pharmaceuticals, and agricultural
chemicals1a (entries 5-7). Therefore, this catalyst will be
practically very useful for the synthesis of various substituted
anilines.
Ru-WOx/SiO2
Ru-MoOx/SiO2
Ru-ReOx/SiO2
Pd/SiO2
Pd-WOx/SiO2
Pd-MoOx/SiO2
Pd-ReOx/SiO2
Rh/SiO2
Rh-WOx/SiO2
Rh-MoOx/SiO2
Rh-ReOx/SiO2
Pt/SiO2
Pt-WOx/SiO2
Pt-MoOx/SiO2
Pt-ReOx/SiO2
Ir/SiO2
>99.9 <0.1
<0.1 70.9 28.7
<0.1 76.2 22.4
<0.1 77.9 22.1
<0.1 75.2 24.3
0.5 96.0
2.0 80.2 17.7
1.6 80.8 17.5
3.5
0.9 89.9
9.0
32.6 35.7 22.9
11.8 56.8 26.7
41.9 34.6 19.2
20.3 54.2 12.5
32.9 47.1 11.3
66.3 15.4 17.6
In order to clarify the catalyst structure of Ru-
MoOx/SiO2(Mo/Ru=1/2), the catalyst was characterized by
100
Ir-WOx/SiO2
Ir-MoOx/SiO2
Ir-ReOx/SiO2
0.8
1.7
9.3
100
(a)
(b)
83.2
6.6
8.5
80
60
40
20
0
36.2 40.0 14.5
80
60
40
20
0
Reaction conditions: 3-nitrostyrene 3 mmol, catalyst (M’/M=1/4, M=4
wt% (*M=5 wt%), M=Ru, Pd, Rh, Pt, Ir, M’=W, Mo, Re) 30 mg, 303 K,
H2 0.3 MPa, 2 h. Others: 3-nitrosostyrene and 3-ethyl-N-hydroxyaniline.
selectivity (91.2%) to 3-aminostyrene (1), the target product,
although the conversion was low. In addition, metal-oxide-
modified noble metal catalysts (M-M’Ox/SiO2 (M’/M=1/4),
M=Ru, Pd, Rh, Pt, Ir, M’= W, Mo, Re) were also applied to the
reaction (entries 5-24). Modification of Ru with M’Ox improved
both the activity and selectivity to
modification of Ir with M’Ox improved only the selectivity to
(entries 21-24), while modification of Pd, Rh and Pt with M’Ox
showed no significant improvement of the selectivity and
activity (entries 9-20). Ru-M’Ox/SiO2 catalysts showed higher
0
20
40
Time / h
60
80
0
10
Time / h
20
Figure 1 Time-course of hydrogenation of 3-nitrostyrene over
Ru-MoOx/SiO2 (a) and Ru/SiO2 (b) ( : Conversion,
Selectivity to : selectivity to : selectivity to
●
○ :
1 (entries 5-8), and
1
,
◇
2
,
□
3)
1
Reaction conditions: 3-nitrostyrene 3 mmol, catalyst 100 mg, 303 K, H2
0.3 MPa.
Table 3 Scope of substrates in hydrogenation of nitroarenes over
Ru-MoOx/SiO2(Mo/Ru=1/2) catalyst
selectivity to
1 than Ir-M’Ox/SiO2 catalysts. Therefore, Ru is a
t
Conv. Select.
Entry
Substrate
Product
preferable noble metal for the reaction, and modification of Ru
with metal oxides improved both the selectivity and activity.
In order to determine the optimal molar ratio of M’/Ru in Ru-
M’Ox/SiO2 (M’=W, Mo, Re) catalysts, hydrogenation of 3-
nitrostyrene was conducted by using Ru-M’Ox/SiO2 catalysts
with various M’/Ru molar ratios (Table S1). The conversion
showed volcano pattern to the M’/Ru molar ratio in all series of
Ru-M’Ox/SiO2 catalysts, and the highest conversion was
obtained at M’/Ru molar ratio of 1/8. On the other hand,
(h)
(%)
(%)
NO2
NO2
NH2
NH2
1
8
24
36
97
98
2
3
96
88
97
NO2
NO2
NH2
NH2
>99
NC
NC
4
5
6
7
17
4
>99
96
99
selectivity to
1 gradually increased with increasing the M’/Ru
O
O
molar ratio. Ru-MoOx/SiO2(Mo/Ru=1/2), which showed high
selectivity (99.5%) and about 5-fold higher activity than that of
Ru/SiO2, was selected in terms of conversion and selectivity. Ru-
MoOx/SiO2(Mo/Ru=1/2) was reusable without loss of its
catalytic performance (Table S2), and the XRD patterns and
XAFS spectra were not changed after the reaction (shown later).
Various solvents were applied to the reaction using Ru-
MoOx/SiO2(Mo/Ru=1/2) (Table S3). Water and toluene showed
similar performance to that at neat condition.
NO2
NH2
>99
>99
>99
Cl
Cl
NO2
NH2
4
95
Cl
Cl
NO2
Cl
NH2
Cl
6
96
Reaction conditions: nitroarenes 3 mmol, Ru-MoOx/SiO2(Mo/Ru=1/2) 100
mg, toluene 3 g, 303 K, H2 0.3 MPa.
2 | J. Name., 2012, 00, 1-3
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various characterization methods such as XRD, TEM, TEM- valence is about +5. The Mo species are highly dispersed and
View Article Online
DOI: 10.1039/C7CC00653E
DEX, TPR, XAS and CO adsorption. XRD profiles (Figure S1) partially cover Ru metal surface.
showed signals due to Ru metal in addition to those due to SiO2,
and the particle size of Ru metal was calculated to be about 5 nm of 3-nitrostyrene, the reactivities of various model substrates
on all the catalysts (Table S4). No signal due to MoOx species were compared by using Ru/SiO2 and Ru-
In order to elucidate the role of MoOx species in hydrogenation
was observed, implying that MoOx species were highly dispersed MoOx/SiO2(Mo/Ru=1/2), and the results and TOF per surface Ru
or amorphous. From TEM images (Figure S2) of Ru/SiO2 and (TOFsRu) were shown in Scheme 2. The results of nitrobenzene
Ru-MoOx/SiO2(Mo/Ru=1/2), the particles sizes of Ru metal over hydrogenation showed that addition of MoOx species increased
Ru/SiO2 and Ru-MoOx/SiO2(Mo/Ru=1/2) were estimated to be the activity of hydrogenation of the nitro group by a factor of 15,
5.1 nm and 5.0 nm, respectively (Table S4), which agreed with in contrast, those of styrene hydrogenation showed that addition
the results of XRD. In addition, mapping analysis of metal of MoOx species has little influence on the activity to
species over Ru-MoOx/SiO2(Mo/Ru=1/2) was carried out by hydrogenation of the olefin group. Hydrogenation of styrene in
TEM-EDX (Figure S3). MoOx species were dispersed on the the presence of the same molar amount of nitrobenzene was
surface of the catalyst, particularly around Ru species, carried out over Ru-MoOx/SiO2, showing that nitrobenzene was
suggesting that Ru metals can interact with MoOx species. TPR hydrogenated at a similar rate of hydrogenation of only
profiles of Ru/SiO2, Ru-MoOx/SiO2(Mo/Ru=1/8) and Ru- nitrobenzene, but styrene was hardly done. This suppression of
MoOx/SiO2(Mo/Ru=1/2) provided one main signal between 373 olefin hydrogenation by nitro compound can explain the high
and 500 K, and the signal was shifted to higher temperature with selectivity to
1 in hydrogenation of 3-nitrostyrene over Ru-
increasing Mo/Ru molar ratio (Figure S4). No signal assignable MoOx/SiO2. In the case of Ru/SiO2, nitrobenzene and styrene
to MoOx species on SiO2 support was observed. These results were hydrogenated at similar rates, which agreed with the low
imply that Ru metal and MoOx species interact with each other. selectivity (~70%) in hydrogenation of 3-nitrostyrene over
From the signal intensity, the valence of Mo species over Ru- Ru/SiO2. In addition, hydrogenation of styrene in the presence of
MoOx/SiO2 catalysts was calculated to be about +5 (Table S4), the same molar amount of aniline was conducted, presenting that
which is in good accordance with our previous results of Ru- the activity for styrene hydrogenation over Ru-MoOx/SiO2 was
MoOx/SiO2 in hydrogenation of lactic acid9c. XAS analyses of significantly decreased by addition of aniline, and the activity
Ru-MoOx/SiO2(Ru/Mo=1/2) after reaction and reduction were was lower than that over Ru/SiO2, which can explain the high
conducted (Table S5 and Figures S5-7). From the curve fitting selectivity at high conversion level over Ru-MoOx/SiO2.
results of Ru K-edge XAFS (Table S5), the Ru-Ru (or -Mo) bond
Kinetic parameters such as substrate concentration and H2
was present with the length (R) of 0.267 nm and the CN was pressure were investigated in hydrogenation of 3-nitrostyrene
about 11.6 for Ru-MoOx/SiO2 after the reduction and reaction. using Ru/SiO2 and Ru-MoOx/SiO2. The reaction orders with
Ru-O and Ru-O-Ru bonds were not detected. From the Ru K- respect to 3-nitrostyrene concentration over Ru/SiO2 and Ru-
edge XANES results (Figure S6), the spectra of Ru-MoOx/SiO2 MoOx/SiO2 were calculated to be 0.8 and 0.1, respectively
were similar to that of Ru powder. These results suggest that Ru (Figure S8a). Addition of MoOx species to Ru/SiO2 decreased
species was in the metallic state, and the reduced Ru metal was the reaction order, which can be interpreted by strong adsorption
maintained after the reaction, which is in agreement with the of 3-nitrostyrene on MoOx species. The reaction orders with
results of XRD analyses. From the Mo K-edge XANES results respect to H2 pressure over Ru/SiO2 and Ru-MoOx/SiO2 were
(Figure S7), the pre-edge signal due to MoOx species with the estimated to be 0.6 and 0.9, respectively (Figure S8b). Addition
most oxidized state (+6) was barely observed over Ru- of MoOx species to Ru/SiO2 decreased
MoOx/SiO2, suggesting that the MoOx species on Ru-MoOx/SiO2
was reduced to some extent, and the state of MoOx species was
maintained during the reaction. This result also agrees with the
results of TPR analyses. In order to estimate the surface Ru metal
amount over the catalysts, CO adsorption was carried out with
Ru/SiO2 and Ru-MoOx/SiO2(Mo/Ru=1/32-1/2) (Table S4). The
ratio of surface Ru metal amount to total Ru amount (CO/Ru)
over Ru/SiO2 was calculated to 0.14, and the ratios of CO/Ru
Ru/SiO2
Conv. 2.0% Conv.
NH2
Ru-MoOx/SiO2
8.3%
NO2
Select. >99.9% Select. >99.9%
TOFsRu 33 h-1 TOFsRu 530 h-1
3 mmol
Conv.
100% Conv. 46.7%
94% Select. >99.9%
Select.
TOFsRu(1800 h-1) TOFsRu(3000 h-1
)
3 mmol
Conv.
0.9%
Conv.
0.1%
Select. >99.9% Select. >99.9%
TOFsRu 15 h-1 TOFsRu 7 h-1
3 mmol
NO2
over
Ru-MoOx/SiO2(Mo/Ru=1/32-1/2)
decreased
with
+
+
NH2 Conv.
1.1%
Conv.
9.0%
increasing the Mo/Ru molar ratio. This result can be interpreted
by covering surface Ru metal with MoOx species, which was not
inconsistent with the results of TEM-EDX and TPR. Considering
that the sizes of Ru metal particles were almost the same at all
the catalysts, the decrease of CO/Ru from 0.14 over Ru/SiO2 to
0.04 over Ru-MoOx/SiO2(Mo/Ru=1/2) means that about 70% of
surface Ru metal was covered by MoOx species.
As above, the structure of Ru-MoOx/SiO2(Mo/Ru=1/2) is as
follows: Ru species are in the metallic state, and the particle size
of Ru is about 5 nm. Mo species is in the oxidized state, and the
Select. >99.9% Select. >99.9%
TOFsRu 19 h-1 TOFsRu 550 h-1
Conv. 60.7% Conv. 11.3%
Select. >99.9% Select. >99.9%
TOFsRu(1100 h-1) TOFsRu 680 h-1
3 mmol
NH2
3 mmol
3 mmol
Scheme 2 Comparison of the reactivities of various substrates
over Ru/SiO2 and Ru-MoOx/SiO2(Mo/Ru=1/2).
Reaction conditions: substrate
3
mmol, Ru/SiO2 or Ru-
MoOx/SiO2(Mo/Ru=1/2) 30 mg, 303 K, H2 0.3 MPa, 1 h.
the reaction order, indicating that MoOx changed the manner of
H2 activation. According to our previous works on metal-oxide-
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5, 431; (f) M. Makosch, W.-I. Lin, V.
ChemCatChem, 2013,
modified noble metal catalysts in hydrogenation and
hydrogenolysis reactions9c,12, the first order with respect to H2
pressure suggests that H2 was heterolytically dissociated to
produce active hydride (H-) and proton (H+) and nucleophilic
attack of the produced hydride species to the nitro group was the
rate-determining step.
Bumbálek, J. Sá, J. W. Medlin, K. HungerbühlerVaienwdArJt.iclAe.Ovnlainne
Bokhoven, ACS Catal., 2012,
2
, 2079D; O(gI:)10M.1.03J9. /BCe7CieCr0, 0J6.-5M3E.
Andanson and A. Baiker, ACS Catal., 2012, 2, 2587; (h) A.
Corma, P. Serna, P. Concepción and J. J. Calvino, J. Am. Chem.
Soc., 2008, 130, 8748.
(a) L. Wang, J. Zhang, H. Wang, Y. Shao, X. Liu, Y.-Q. Wang, J.
P. Lewis and F.-S. Xiao, ACS Catal., 2016, 6, 4110; (b) A. L.
5
As above, the reaction proceeds via nucleophilic attack of the
produced hydride species to the nitro group of adsorbed
nitroarenes on MoOx species, and the improvement of activity
and selectivity can be due to strong adsorption of nitroarenes on
MoOx species and formation of hydride species at the active sites,
the interface between Ru metal and MoOx species. The hydride
species are generally active for nucleophilic addition due to the
anionic nature of the hydride, and also it is well-known that
hydride species are effective for the hydrogenation of polarized
functional groups such as carbonyl groups [13]. Therefore, the
formation of the hydride species will contribute to the high
activity and selectivity. Since the hydride species are considered
to be formed at the interface between Ru metals and MoOx
species, the structure of MoOx-covered Ru metals over Ru-
MoOx/SiO2 catalyst plays an important role on the formation of
the reactive hydride species. In addition, the structure of Ru-
MoOx/SiO2 catalyst will enhance the supply of the substrate to
the active site, leading to the high activity as well as the low
reaction order with respect to the substrate concentration.
Moreover, the structure of Ru-MoOx/SiO2 will decrease
adsorption of the substrate on bare Ru metals and suppress the
hydrogenation of the olefin group in the substrate, resulting in
high selectivity.
Nuzhdin, B. L. Moroz, G. A. Bukhtiyarova, S. I. Reshetnikov, P.
A. Pyrjaev, P. V. Aleksandrov and V. I. Bukhtiyarov,
ChemPlusChem, 2015, 80, 1741; (c) Y. Matsushima, R.
Nishiyabu, N. Takanashi, M. Haruta, H. Kimura and Y. Kubo, J.
Mater. Chem., 2012, 22, 24124; (d) K.-i. Shimizu, Y. Miyamoto,
T. Kawasaki, T. Tanji, Y. Tai and A. Satsuma, J. Phys. Chem. C,
2009, 113, 17803; (e) A. Corma and P. Serna, Science, 2006,
313, 332.
6
7
8
(a) L. Liu, P. Concepción, A. Corma, J. Catal., 2016, 340, 1; (b)
B. Chen, F. Li, Z. Huang and G. Yuan, ChemCatChem, 2016, 8,
1132; (c) X. Wang and Y. Li, J. Mol. Catal. A, 2016, 420, 56; (d)
Z. Wei, J. Wang, S. Mao, D. Su, H. Jin, Y. Wang, F. Xu, H. Li and
Y. Wang, ACS Catal., 2015, 5, 4783; (e) F. A. Westerhaus, R. V.
Jagadeesh, G. Wienhöfer, M.-M. Pohl, J. Radnik, A.-E. Surkus,
J. Rabeah, K. Junge, H. Junge, M. Nielsen, A. Brückner and M.
Beller, Nat. Chem., 2013,
(a) S. Furukawa, K. Takahashi and T. Komatsu, Chem. Sci., 2016,
, 4476; (b) R. V. Jagadeesh, A.-E. Surkus, H. Junge, M.-M. Pohl,
5, 537.
7
J. Radnik, J. Rabeah, H. Huan, V. Schünemann, A. Brückner,
and M. Beller, Science, 2013, 342, 1073; (c) T. Mitsudome, Y.
Mikami, M. Matoba, T. Mizugaki, K. Jitsukawa and K. Kaneda,
Angew. Chem. Int. Ed., 2012, 51, 136; (d) Y. Zhang, F. Hou and
Y. Tan, Chem. Commun., 2012, 48, 2391; (e) K.-i. Shimizu, Y.
Miyamoto and A. Satsuma, J. Catal., 2010, 270, 86.
(a) S. Liu, M. Tamura, Y. Nakagawa and K. Tomishige, ACS
Sustainable Chem. Eng., 2014, 2, 1819; (b) S. Liu, Y. Amada, M.
Tamura, Y. Nakagawa and K. Tomishige, Green Chem., 2014,
16, 617; (c) K. Chen, M. Tamura, Z. Yuan, Y. Nakagawa and K.
In conclusion, Ru-MoOx/SiO2 catalyst acted as an effective
heterogeneous catalyst for selective hydrogenation of the nitro
group in functionalized nitroarenes, providing the corresponding
amines in high yields (85-99%). Addition of MoOx species to
Ru/SiO2 formed the active site at the interface between Ru metal
and MoOx species, where the substrate was strongly adsorbed on
MoOx species and active hydride species were formed on Ru
metal, leading to the drastic improvement of both the activity and
selectivity.
Tomishige, ChemSusChem, 2013,
6
, 613; (d) Y. Amada, S. Koso,
, 728;
Y. Nakagawa and K. Tomishige, ChemSusChem, 2010,
3
(e) Y. Nakagawa, Y. Shinmi, S. Koso and K. Tomishige, J. Catal.,
2010, 272, 191; (f) S. Koso, N. Ueda, Y. Shinmi, K. Okumura, T.
Kizuka and K. Tomishige, J. Catal., 2009, 267, 89; (g) S. Koso, I.
Furikado, A. Shimao, T. Miyazawa, K. Kunimori and K.
Tomishige, Chem. Commun., 2009, 2035.
(a) Y. Takeda, M. Tamura, Y. Nakagawa, K. Okumura, K.
Tomishige, Catal. Sci. Technol., 2016, 6, 5668; (b) Y. Takeda,
9
M. Tamura, Y. Nakagawa, K. Okumura, K. Tomishige, ACS
Catal., 2015, , 7034; (c) Y. Takeda, T. Shoji, H. Watanabe, M.
Tamura, Y. Nakagawa, K. Okumura, K. Tomishige,
ChemSusChem, 2015, , 1170; (d) Y. Takeda, Y. Nakagawa, K.
Tomishige, Catal. Sci. Technol., 2012, , 2221.
5
Notes and references
8
2
1
(a) H.-U. Blaser, H. Steiner and M. Studer, ChemCatChem,
2009, , 210; (b) G. A. Somorjai and J. Y. Park, Angew. Chem.
Int. Ed., 2008, 47, 9212; (c) S. Nishimura and K. Ebitani,
ChemCatChem, 2016, , 2303.
(a) P. Claus, Top. Catal., 1998,
Armbrüster, K. Kovnir, M. S. Tikhov, R. M. Lambert, J. Catal.,
2009, 261, 60.
(a) R. S. Downing, P. J. Kunkeler and H. Van Bekkum, Catal.
Today., 1997, 37, 121; (b) M. Pietrowski, Curr. Org. Synth.,
2012, 9, 470.
(a) C. Berguerand, A. Yarulin, F. Cárdenas-Lizana, J. Wärnå, E.
Sulman, D. Y. Murzin and L. Kiwi-Minsker, Ind. Eng. Chem. Res.,
2015, 54, 8659; (b) H. Yoshida, N. Igarashi, S.-i. Fujita, J.
Panpranot and M. Arai, Catal. Lett., 2015, 145, 606; (c) A.
Yarulin, C. Berguerand, I. Yuranov, F. Cárdenas-Lizana, I.
Prokopyeva and L. Kiwi-Minsker, J. Catal., 2015, 321, 7; (d) H.
Wei, X. Liu, A. Wang, L. Zhang, B. Qiao, X. Yang, Y. Huang, S.
10 (a) M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, Chem.
Commun., 2013, 49, 7034; (b) M. Tamura, K. Tokonami, Y.
1
Nakagawa, K. Tomishige, ACS Catal., 2016, 6, 3600.
8
11 (a) M. Tamura, R. Tamura, Y. Takeda, Y. Nakagawa, K.
Tomishige, Chem. Eur. J., 2015, 21, 3097; (b) M. Tamura, R.
Tamura, Y. Takeda, Y. Nakagawa, K. Tomishige, Chem.
Commun., 2014, 50, 6656.
2
3
4
5, 51; (b) E. Galloway, M.
12 (a) S. Koso, H. Watanabe, K. Okumura, Y. Nakagawa, K.
Tomishige, Appl. Catal. B, 2012, 111-112, 27; (b) Y. Amada, Y.
Shinmi, S. Koso, T. Kubota, Y. Nakagawa and K. Tomishige,
Appl. Catal. B, 2011, 105, 117.
13 (a) R. M. Bullock, Chem. Eur. J., 2004, 10, 2366; (b) R. Noyori,
Angew. Chem. Int. Ed., 2002, 41, 2008.
Miao, J. Liu and T. Zhang, Nat. Commun., 2014,
5, 5634; (e) E.
Boymans, S. Boland, P. T. Witte, C. Müller and D. Vogt,
4 | J. Name., 2012, 00, 1-3
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