{[Cu3Lu2(ODA)6(H2O)6]·10H2O}: N: The first heterometallic framework based on copper(II)/lutetium(III) for the catalytic oxidation of olefins and aromatic benzylic substrates

Article abstract of DOI:10.1039/c7cy01385j

The catalytic performance of the novel framework {[Cu₃Lu₂(ODA)₆(H₂O)₆]·10H₂O}_n was tested in the oxidation of alkenes and benzylic hydrocarbons, using tert-butyl hydroperoxide (TBHP) and molecular oxygen (O₂) as oxidants. Excellent conversions were obtained with O₂ under solvent-free conditions, in the absence of a co-catalyst, for cyclohexene (95%) and for cumene (91%).

Full text of DOI:10.1039/c7cy01385j

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ISSN 2044-4753
PAPER
Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
analysis of fluoroacetate dehalogenase
rsc.li/catalysis

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{
[Cu Lu (ODA) (H O) ]•10H O} . First heterometallic framework
3 2 6 2 6 2 n
based on copper(II)/lutetium(III) for the catalytic oxidation of
olefins and aromatic benzylic substrates.
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
b,c
d
d
d
a,b
DOI: 10.1039/x0xx00000x
P. Cancino , V. Paredes-García , J. Torres , S. Martínez , C. Kremer ,E. Spodine *.
www.rsc.org/
The catalytic performance of the novel framework or both [5-12]. For example, the review done by Kremer et al.
[Cu Lu (ODA) (H O) ]•10H O} was tested on the oxidation of [10], reports a series of compounds with lanthanide(III) ions,
alkenes and benzylic hydrocarbons, using
tert- and heterometallic combinations using transition metal ions
butylhydroperoxide (TBHP) and molecular oxygen (O
as and lanthanide ions. The authors analyze the thermodynamic
oxidants. Excellent conversions were obtained with O
in solvent properties, magnetism and thermal stability of these
free conditions, in the absence of co-catalyst, for cyclohexene
95%) and for cumene (91%).
{
3
2
6
2
6
2
n
2
)
2
compounds. However, this review does not mention homo or
heterometallic compounds of lutetium. In general, the
catalytic properties for lutetium based compounds have not
(
Heterogeneous catalysis was one of the earliest proposed been extensively studied, and are not well detailed in
literature. There are few examples about the catalytic
performance of lutetium. For example, the hydroformylation
applications for crystalline metal-organic frameworks (MOFs), and it
was also one of the early demonstrated applications. In 1994 the
cyanosylation of various aldehydes, using a cadmium-based MOF as
catalyst, was reported [1], and many more examples can be found
in the literature up to date [2,3]. MOFs provide powerful platforms
to immobilize multiple functional sites within a single crystal, and
this makes them potential materials to be probed as heterogeneous
catalysts. This fact can be amplified by using two different metal
ions to build MOFs catalysts. In spite of this, the application of
heterometallic MOFs as catalysts has been much less explored in
comparison to homometallic ones. With this in mind we started a
of 1-octene was studied using
LuCl/NaCo(CO) or (C Lu/0.5Co
a
mixture of
[13]. The
(C
2
H
2
)
2
4
2
H
2
)
3
2
(CO)
8
observed conversion was greater than 50 %, and the products
obtained were n-aldehydes and iso-aldehydes. More recent
studies have used lutetium(III) ions to change the catalytic site
in DNA and modify the sequence of the specific protein [14].
To the best of our knowledge, there are no studies that
demonstrate the catalytic properties of heterometallic MOFs
based on copper(II)/lutetium(III). Our group synthesized a new
heterometallic MOF based on the ODA ligand, copper(II) and
lutetium(III) ions, {[Cu Lu (ODA) (H O) ]•10H O} (CuLuMOF),
study on the catalytic properties of a series of MOFs with general
3
2
6
2
6
2
n
III
formula {[Cu Ln (ODA) (H O) ]⋅xH O}n (Ln = lanthanide ion, H ODA
3
2
6
2
6
2
2
and investigated the catalytic activity on alkene and aromatic
benzylic substrate oxidation. Thus, we herein report the
=
2,2’-oxydiacetic acid) [4].
The chemistry of compounds based on the 2,2´-oxydiacetic catalytic study related to this novel heterometallic framework.
acid ligand is currently well documented. The coordination
The synthesis of {[Cu Lu (ODA) (H O) ]•10H O}
n
3
2
6
2
6
2
modes of this ligand have permitted to obtain a large variety of (CuLuMOF) was done starting from ODA in the acidic form and
compounds derived from transition metal ions, lanthanide ions the metal chloride at a controlled pH value (see supplementary
information for details). After 48 hours light blue crystals were
obtained, suitable for single crystal X-ray diffraction. The
a
CuLuMOF framework crystallizes in the P6/mcc space group.
III
The molecular structure contains Lu ions tridentate
Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile
espodine@ciq.uchile.cl
b
Centro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Santiago,
coordinated by three ODA ligands, forming the building block
3-
Lu(ODA) ] . The central atom is surrounded by nine oxygen
Chile
c
[
3
Departamento de Ciencias Exactas, Universidad Andrés Bello, Santiago, Chile.
d
atoms, its coordination geometry being better described as a
distorted tricapped trigonal prism. The six carboxylate oxygen
atoms form a trigonal prism (Lu-O2 at 2.336Å), with three
ether
Departamento Estrella Campos, Facultad de Química, Universidad de la República,
Montevideo, Uruguay.
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amount of copper(II) was less than 0.01% in the filtered reaction
solution of
Table 1. Oxidation of cyclohexene and styrene using CuLuMOF as catalyst.
Conversion
%)
Solvent
TON/
TOF(h )
Main reaction
products
Selec
(%)
-
1
(
Cyclohexene
Cyclohexene
Styrene
60
69
75
88
1,2-DEC
10827/
Cyclohexenone
Cyclohexenol
Cyclohexene
oxide
57
30
5
4
51
n-
decane
12451/
519
Cyclohexenone
Cyclohexenol
Cyclohexene
oxide
55
28
6
1,2-DCE
13534/
Styrene oxide
Benzaldehyde
Phenylacetalde
hyde
31
24
45
5
64
3 2 6 2 6 2 n
Figure 1. (a) View of plane ab of {[Cu Lu (ODA) (H O) ]•10H O}
Styrene
n-
decane
15880/
662
Styrene oxide
Benzaldehyde
Phenylacetalde
hyde
12
30
43
(
(
CuLuMOF) (blue (copper), green (lutetium), red (oxygen), grey
carbon), white (hydrogen)). (b) ORTEP view and labeling scheme
Lu (ODA) (H O) ] •10H O}
for [Cu
3
2
6
2
6
2
n
.
oxygen atoms as capping ones at a longer distance (Lu-O1 at
Reaction conditions: Catalyst (0.0165 mmol), substrate (40 mmol), TBHP (40 mmol),
75 ºCand 24 h of reaction time. Ratio S/C = 2400/1 or 0.001mol% of copper per mole
3
-
II
2
.415Å). Each [Lu(ODA)
3
]
unit is connected to six Cu atoms via
II
of substrate. TON is calculated as moles of products per mole of active site (Cu
single syn-anti
ꢀ
-carboxylato-O-O’ bridges; copper(II) ions are six
II
ions); TOF is calculated as moles of products per mole of active site (Cu ions) per
coordinated. They are surrounded by four carboxylate oxygen
atoms (Cu-O average distance 1.953Å), which define the equatorial
plane, and two water molecules at longer distances (2.457Å). Thus,
hour (TOF was calculated using the time reported in the table).
II
cyclohexene, and less than 0.05% in the filtered reaction solution of
styrene. These data permit to assess that the catalyst is robust and
leaching is insignificant. These catalytic results were compared
with those previously reported, using isostructural MOFs as
Cu exhibits an elongated octahedral geometry. As a result of this
connectivity, a 2D honeycomb pattern is formed in the (001) plane
(
Fig. 1a and 1b). Columnar hexagonal channels are then formed
along z direction. Detailed crystallographic data are given in
Tables 1S (A-D). Besides, CuLuMOF was characterized by
elemental and thermogravimetric analyses (supplementary
material).
III
III
III
catalysts, {[Cu
3 2 6 2 6 2 n
Ln (ODA) (H O) ]•10H O} (Ln = La , Gd or Yb )
(
Fig. 5S) [4]. As compared to the reported catalysts, CuLuMOF was
the most active of the series in the oxidation of olefins (Fig. 2). The
results reported in this study are in agreement with those obtained
by DFT calculations for CuLuMOF, in relation to the catalytic
performance of this family of frameworks. Thus, the conversion
increases as the lanthanide series progresses from lanthanum(III) to
lutetium(III), favoring the catalytic cycle as has been explained in
our previous work [4]. The catalytic performance of the
heterometallic CuLnODA catalysts, including the lutetium based
catalyst, was shown to be better than that of the homometallic
copper(II) catalyst CuMOF [4].
The initial catalytic reactions were done following the
conditions described by our group in previews reports [4,15].
3 2 6 2 6 2
{[Cu Lu (ODA) (H O) ]•10H O}n. resulted an active catalyst in the
oxidation of styrene and cyclohexene with TBHP, both in 1,2-
dichloroethane (DCE) and n-decane media. The oxidation of
cyclohexene produced cyclohexene oxide (A), 2-cyclohexenol (B), 2-
cyclohexenone (C) and 1,2-cyclohexenediol (D). (Scheme 1S). When
the reaction was done using DCE as solvent, the conversion after 24
h was 60%, and the main product was 2-cyclohexenone (57%). The
oxidation of styrene under the same experimental conditions,
Molecular oxygen is an ideal reagent as it is a naturally
occurring oxidant, which does not give any unwanted reduced
products, thus simplifying purification of products [16].
produced
phenylacetaldehyde (c) and 1,2- phenylethanediol (d) as products
Scheme 1S). The conversion was 75%, and the main product was 1-
styrene
oxide
(a),
benzaldehyde
(b),
1-
(
phenylacetaldehyde (45%). The corresponding yields for both
substrates are given in Table 1. The effect of the solvent was
studied changing the reaction medium from DCE to n-decane; an
increase in the conversion of approximately 10% was observed for
both substrates (Fig. 2S). It is important to mention that the main
products in both oxidation reactions remained the same. The
catalyst was analyzed by X-ray powder diffraction after the catalytic
reaction; the crystallinity of the catalyst remained unchanged, as
Figure 2. (I) Conversion of cyclohexene after 24 h of reaction; (II)
observed in figures 3S and 4S. The ICP results indicated that the conversion of styrene after 24 h of reaction in the presence of the
2
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bar), 120 °C and reaction time depending on the substrate in order to achieve the
indicated conversion. Ratio S/C = 2400/1 or 0.001mol% of copper per mole of
substrate. *Complete consumption of oxygen occurs at this reaction time. TON is
different catalysts. Reaction conditions: 1,2-dichloroethane as
solvent, TBHP (70% in water) as oxidant, 75°C, ratio S/C = 2400/1 or
II
0.001mol% of copper per mole of substrate.
calculated as moles of products per mole of active site (Cu ions); TOF is calculated as
II
Therefore, the performance of the CuLuMOF catalyst was moles of products per mole of active site (Cu ions) per hour (TOF was calculated using
the time reported in the table).
also studied by changing the reaction conditions to a solventless
medium and using molecular oxygen as oxidant, in order to obtain
more friendly environmental conditions. In a typical experiment the
substrate and catalyst were added to the reactor (0.001mol% of Cu
per mole of substrate). The reactions were carried out in solvent
free conditions in absence of a co-catalyst, and the temperature of
reaction was 120°C with an oxygen pressure of 5 bar, using a batch
reactor. After the reactor was charged with the 5 bar of oxygen, the
reactor was sealed, placed in a silicone oil bath and left to react at
of epoxide increasing as the number of carbons increased from C6
to C8. The stabilization of the double bond has an important role in
the formation of the products, being the alkene position most
active for the cyclooctene, and the allylic position most active for
cyclohexene (Table 2) [18, 19].
The previously reported catalyst CuLaMOF presents similar
results for the aerobic oxidation of cyclohexene [20]. However, a
7
5% of conversion was obtained after only 6h of reaction, while by
using CuLuMOF with identical reaction conditions this same
conversion was reached in 2h. These results can be compared with
those reported by Parra da Silva et al. [21], who used as catalyst 3
nm average diameter calcinated CuO NPs in the aerobic oxidation
120°C. After the reactor was cooled, the remaining oxygen was
released and the catalyst recovered by filtration. Excellent results
were obtained modifying the reactions conditions; the conversion
of the oxidation of cyclohexene increased from 60% for a time
interval of 24h (TBHP/DCE) to 95% for 4h of reaction
2
of cyclohexene, at 100°C and 4 bar of O . The results for a reaction
interval of 2h were 65% of conversion and 45% in the selectivity to
ketone, lower than those obtained using CuLuMOF.
2
time(O /solventless). The main product for both reactions remained
2-cyclohexene, with a selectivity close to 55%. Good results at
The activation of oxygen probably begins by the formation of
radical species, as suggested by Santiago-Portillo et al.[22]. The
origin of the radicals can be considered as the result of the
interaction of the molecular oxygen with the free positions on the
copper(II) ions, which are generated by the removal of ligand water
molecules from the first coordination sphere, as indicated by the
TGA analysis (supplementary material). The presence of radical
species was verified by incorporating into the reaction mixture 5
mol% of anthraquinone as a radical trap, since it is known to inhibit
the action of radical species [22], and observing under these
experimental conditions a null conversion of cyclohexene to the
corresponding cyclohexenone. On the other hand, the conversion
of cyclohexene was not altered by the addition to the reaction
mixture of DMSO, which is known to be reactive with the hydroxyl
radical. Thus it was possible to infer that the hydroxyl radical was
not playing an important role in the formation of the ol/one
products [23-25].
shorter times of reaction were also observed for the rest of the
studied cycloalkenes (Table 2) (Scheme 2S). It is important to
remark that the reactions done at 120°C imply the removal of the
coordinated water molecules bonded to copper(II) (Fig 1b and Fig.
1S), thus making this Lewis acid center accessible to molecular
oxygen [17]. Different conversions were observed depending on
the number of carbon atoms in the ring, being the cyclohexene the
substrate with the major conversion among the studied
cycloalkenes (95%). The selectivity also changed with the nature of
the cycloalkane, being the main product the conjugated ketone for
C6 and C7, and the epoxide for C8; the yield
Table 2. Aerobic oxidation of cycloalkenes and aromatic benzylic hydrocarbons using
CuLuMOF as catalyst.
Conversion
%)
Time
(h)
TON/
TOF(h )
Main reaction
products
Selec
(%)
-
1
(
Cyclohexene
75
2*
13534/
Cyclohexenone
Cyclohexenol
Cyclohexene
oxide
55
25
9
The performance of CuLuMOF as catalyst was also studied
using aromatic benzylic hydrocarbon compounds (cumene and
indan) (Schemes 3S, 4S). The conversion after 4h of reaction was
6
767
9
1% for cumene and 60% for indan; the respective ketone being the
Cyclohexene
Cycloheptene
95
58
4
4
17143/
286
Cyclohexenone
Cyclohexenol
Cyclohexene
oxide
Cycloheptenone
Cycloheptenol
Cycloheptene
oxide
60
20
4
4
main product in both cases (74% for acetophenone and 49% for
indanone) (Table 2). These results are very interesting, due to the
fact that the performance of catalysts based on copper(II) or
lutetium(III) in oxidation reactions of benzylic compounds has not
been extensively studied. One of the examples that can be cited of
an heterogeneous copper(II) catalyst is the oxidation of cumene
using CuO at 100°C with 1 atm of molecular oxygen; the reported
conversion of cumene was 56% after 7 h of reaction with a
selectivity of 69% for cumyl hydroperoxide. Such a high selectivity in
hydroperoxide cannot be considered as positive, since these species
are considered hazardous [26, 27]. Moreover, the use of copper(II)
10466/
617
45
15
35
2
Cyclooctene
Cumene
Indan
35
91
60
4
4
4
6316/
579
Cyclooctenone
Cyclooctene oxide
10
1
9
0
16421/
105
Acetophenone
Cumyl
hydroperoxide
74
23
4
10827/
707
Indanone
Indanol
49
31
2 2 2
salts such as CuCl •2H O and Cu(acac) needs an activator or co-
2
catalyst to proceed with the oxidation of cumene at 90°C and
molecular oxygen as oxidant. The conversion for both salts is only
Reaction conditions: Catalyst (0.0041 mmol), substrate (10 mmol), O
2
atmosphere (5
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2
9% with a selectivity of 58% for acetophenone [29]. The use of
Cu(pymo) ]MOF (pymo: 2-hydroxypyrimidinolate) and
Cu(im) ]MOF (im: imidazole) for the aerobic oxidation of cumene
1
2
3
M. Fujita, Y.J. Known, S. Washizu, K. Ogura, J. Am. Chem. Soc.
1994, 116, 1151.
[
[
2
2
J. Y. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen, J. T.
Hupp, Chem. Soc. Rev., 2009, 38, 1450.
permitted to obtain a better catalytic performance for the second
MOF catalyst. For 4 h of reaction, ca. 57 and 71% of conversion
were obtained, respectively. For these two catalysts the results
B. Li, M. Chrzanowski, Y. Zhang, S. Ma, Coord. Chem. Rev., 2016,
307, 106.
indicated that the yield of products shows dependence with the 4 P. Cancino, V. Paredes-Garcia, C. Aliaga, P. Aguirre, D. Aravena, E.
geometry of the copper center, which was determined by the
nature of the ligands. [Cu(pymo) ]MOF has also been reported as
Spodine, Catal. Sci. Technol., 2017, 7, 231.
2
5
6
J. G. Hao, L. Song, J. S. Huang, Chin. J. Struct. Chem. (Jiegou
Huaxue), 1997, 16, 228.
catalyst for the aerobic oxidation of another benzylic substrate,
tetralin, with a conversion 51.5%. This copper(II) based catalytic
system produces hydroperoxyde as the main product with less than
J. G. Mao, L. Song, X. Y. Huang, J. S. Yuang, Polyhedron, 1997,
16, 963.
1
0% of tetralone after 15 h of reaction [29]. The oxidation of indan
7
8
J. G. Mao, J. S. Huang, Transition Met. Chem., 1997, 22, 277.
J. Torres, F. Peluffo, S. Domínguez, A. Mederos, J. M. Arrieta, J.
Castiglioni, F. Lloret, C. Kremer, J. Mol. Struct., 2006, 825, 60.
Q. D. Liu, J. R. Li, S. Gao, B. Q. Ma, F. H. Liao, Q. Z. Zhou, K. B. Yu,
Inorg. Chem. Commun., 2001, 4, 301.
was reported using Cu(OH) CuCl or Cu(TPIP) (TPIP:
2
,
2
2
tetraphenylimidodiphosphinate) as catalysts [30]. The chloride and
the hydroxide species gave a similar low conversion of 27%, but
with a selectivity of 75% for indanone. On the other hand, the use
9
2
of Cu(TPIP) as catalyst permitted to increase the conversion to 10 C. Kremer, J. Torres, S. Domínguez, J. Mol. Struct., 2008, 879,
49%, but the main product was indanyl-1-hydroperoxide (31%), 130.
instead of the ketone [30].
11 A. C. Rizzi, R. Calvo, R. Baggio, M. T. Garland, O. Peña, M. Perec,
To the best of our knowledge the only heterometallic MOF
Inorg. Chem., 2002, 41, 5609.
based on copper(II) and lanthanide(III) ions used as catalyst for the 12 R. Baggio, M. T. Garland, Y. Moreno, O. Peña, M. Perec, E.
oxidation of aromatic benzylic compounds is CuLaPDC (PDC: 3,5- Spodine, J. Chem. Soc., Dalton Trans., 2000, 2061.
pyridindicarboxylate) [19]. The reported catalysts based on copper 13 I.P. Beletskaya, G.K.-I. Magomedov, A.Z. Voskovinikov, J.
II) or copper(II)/lanthanum(III) present a lower conversion than the Organomet. Chem., 1990, 385, 289.
reported in this work, using CuLuMOF with molecular oxygen as 14 K. Sinha, S.S. Sangani, A.D. Kehr, G.S. Rule, L. Jen-Jacobson,
(
oxidant, and solvent free conditions.
Biochemistry, 2016, 55 (44), 6115.
1
1
1
1
1
2
5 P. Cancino, V. Paredes-Garcia, P. Aguirre, E. Spodine, Catal. Sci.
Technol., 2014, 4, 2599.
Conclusions
6
A. Gómez-Paricio, A. Santiago-Portillo, S. Navalón, P.
Concepción, M. Alvaro, H. García, Green Chem., 2016, 18, 508.
7 D. Farrusseng, S. Aguado, C. Pinel, Angew. Chem. Int. Ed., 2009,
8, 7502.
8 A. Dhakshinamoorthy, M. Alvaro and H. Garcia, J. Catal., 2012,
89, 259.
The present work reports a new heterometallic metal organic
4
3 2 6 2 6 2 n
framework, {[Cu Lu (ODA) (H O) ]•10H O} (CuLuMOF) with an
active catalytic performance in the oxidation of olefins and
aromatic benzylic hydrocarbon compounds, using tert-butyl
hydroperoxide or molecular oxygen as oxidant. The lutetium(III)
ions enhance the oxidation reactions by increasing the catalytic
properties of the copper(II) ions. The change to more friendly
environmental solvent free conditions, using molecular oxygen as
the sole oxidant since the presence of a co-catalyst is not needed,
permitted to find better results than those previously reported for
heterogeneous copper(II) catalysts. The best catalytic performance
of CuLuMOF was obtained for cyclohexene with a conversion of
2
9 U. Junghans, C. Suttkus, J. Lincke, D. Lassig, H. Krautscheid, R.
Glaser, Microporous Mesoporous Mater., 2015, 216, 151.
0 P. Cancino, A. Santiago-Portillo, S. Navalon, M. Alvaro, P.
Aguirre, E. Spodine, H. Garcia, Catal. Sci. Technol., 2016, 6,
3
633.
1 F. Parra da Silva, R. V. Goncalves, L. M. Rossi, J. Mol. Catal. A.,
017, 426, 534.
2
2
2
2
2
2
2
2
2 A. Santiago-Portillo, S. Navalón, F. G. Cirujano, F. X. Labrés i
Ximena, M. Alvaro and H. Garcia, ACS Catal., 2015, 5, 3216.
3 A. N. Dhakshinamoorthy, M. Alvaro, H. Garcia, ChemSusChem,
95%, and for cumene with a conversion of 91% after four hours of
reaction.
2
012, 5, 46.
4 M. J. Burkitt and R. P. Mason, Proc. Natl. Acad. Sci. U. S. A.,
991, 88, 8440.
Acknowledgements
The authors acknowledge Proyecto Anillo ACT 1404 and Basal
1
5
R. Martin, S.Navalon, J. J. Delgado, J. J. Calvino, M. Alvaro, H.
Funding FB0807 (CEDENNA) for financial support. C. K. thanks CSIC
Garcia, Chem. Eur. J., 2011, 17, 9494.
(Uruguay) for financial support through Programa de Apoyo a
6 M. Zhang, L. Wang, H. Ji, B. Wu, X. Zeng, J. Natural Gas Chem.,
007, 16, 393.
Grupos de Investigación.
2
7 Luz, L., Leon, A., Boronat, M., Llabrés i Xamena, F. X. , Corma, A.,
Catal. Sci. Teccnol., 2013, 3, 371.
References
4
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Cat Pa ll ey as si es dS oc ni eo nt ca ed j &u s Tt me ca hr gn i on ls ogy
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DOI: 10.1039/C7CY01385J
Journal Name
COMMUNICATION
28 B. Orlinska, Tetrahedron Letters, 2010, 51, 4100.
29 Labrés i Xamena, F. X., Casanova, O., Galiasso Tailleur, R., García,
H., Corma, A., J. Catal. 2008, 255, 220.
30 H. Rudler, B. Denise, J. Mol. Catal. A: Chem., 2000, 57, 277.
This journal is © The Royal Society of Chemistry 20xx
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Catalysis Science & Technology
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