A novel copper(II)-lanthanum(IIi) metal organic framework as a selective catalyst for the aerobic oxidation of benzylic hydrocarbons and cycloalkenes

Article abstract of DOI:10.1039/c5cy01448d

The synthesis and structure of a novel heteronuclear Cu^II and La^III metal organic framework (MOF) having pyridinedicarboxylic acid (CuLa-MOF) is reported. The obtained MOF with the formula {[Cu_0.5La₂(HPDC)(PDC)₂(SO₄)(H₂O)₂]H₂O}_n (PDC: 3,5-pyridinedicarboxylate) has a 3D non-porous lattice with a single type of octahedrally coordinated Cu^II and two distinct nonacoordinated La^III ions, with sulphate being a linker between the Cu^II and La^III centers. CuLa-MOF exhibits catalytic activity to promote the aerobic autooxidation of benzylic hydrocarbons and the aerobic oxidation of cycloalkenes. Compared with a homogenous catalyst, Cu(OAc)₂, CuLa-MOF, as a heterogeneous catalyst, exhibits similar activity, but the solid is recyclable with some minor decrease in activity from the first to the second catalytic cycle; after which, a steady activity is observed, as determined by the coincidence of temporal evolution of the reaction upon reuse.

Full text of DOI:10.1039/c5cy01448d

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DOI: 10.1039/C5CY01448D
Journal Name
ARTICLE
Novel Copper(II)-Lanthanum(III) Metal Organic Framework as
Selective Catalyst for the Aerobic Oxidation of Benzylic
Hydrocarbons and Cycloalkenes.
Received 00th January 20xx,
Accepted 00th January 20xx
P. Cancino,a,b A. Vega,b,c A. Santiago-Portillo,d S. Navalon,d M. Alvaro,d P. Aguirre,a E. Spodine,*a,b
H. García,*d
DOI: 10.1039/x0xx00000x
www.rsc.org/
The synthesis and structure of
a
novel heteronuclear CuII and LaIII metal organic framework (MOF), having
pyridinedicarboxylic acid (CuLa-MOF) is reported. The obtained MOF of formula [Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n
(PDC: 3,5-pyridinedicarboxylate), has a 3D non-porous lattice with a single type of octahedrally coordinated CuII and two
distinct nonacoordinated LaIII ions, sulphate being a linker between the CuII and LaIII centers. The CuLa-MOF exhibits catalytic
activity to promote the aerobic autooxidation of benzylic hydrocarbons, and the aerobic oxidation of cycloalkenes.
Comparison with the homogenous catalyst, Cu(OAc)2, shows that the CuLa-MOF, as a heterogeneous catalyst, exhibits similar
activity, but the solid is recyclable with some minor decrease in the activity from the first to the second catalytic cycle, after
which a steady activity is observed, as determined by the coincidence of the temporal evolution of the reaction.
used as starting compounds in polymers and fine chemicals such as
in fragrances, agrochemicals, glues or medicines.[11] Preparation of
these compounds in absence of organic solvents, and using only
molecular oxygen as oxidizing reagent, is a continued target for the
development of green processes, more efficient and selective, and
Introduction
Metal organic frameworks (MOFs) or coordination polymers are with the generation of lesser amounts of toxic residues and
a relatively new class of crystalline porous materials with potential byproducts.[12] The use of heterogeneous catalysts can contribute to
application in catalysis.[1] These organic-inorganic hybrid materials achieve this target by promoting aerobic oxidations and allowing an
are formed by nodes of metal ions or metal clusters, interacting with easy separation of the products from the catalyst that eventually can
bi- or multi-podal organic linkers such as aromatic polycarboxylates. be recovered and recycled.
Nowadays, there is a vast number of MOFs with different topologies,
MOFs can have robust frameworks stable under reaction
conditions, decreasing the percentage of metal leaching into the
organic solution. MOFs have been successful heterogeneous
catalysts mainly for liquid-phase reactions.[13,14] Partial success has
been obtained using MOFs as support of radical initiators such as
morphologies and compositions, which are used for different
purposes.[2] Potential applications of these materials include gas
storage,[3,4] fluid separation,[4,5] biomedicine,[6] sensing,[7]
photocatalysis[8] and catalysis[9] among others.
[15]
[16,17]
In this context, there is a great current interest in exploiting the NHPI
or TEMPO
able to perform oxidations with molecular
potential that MOFs offer as heterogeneous catalysts for organic
O2. In other cases, MOFs have been used as catalysts for oxidation
reactions, particularly to promote aerobic oxidations.[10] Aerobic reactions using H2O2[18,19] or organic peroxides such as TBHP [19-24] as
oxidations of hydrocarbons are processes of large industrial oxidants or as radical initiators in combination with molecular O2.
importance for the manufacture of bulk chemicals and commodities, Other related reactions employ organic aldehydes, such as
isobutyraldehyde [25] or thimethylacetaldehyde[23], which with O2 and
with a proper metal catalyst can act as peracid precursors, have been
a
Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Sergio
Livingstone P 1007, Santiago, Chile. E-mail: espodine@uchile.cl
CEDENNA, Av. Libertador Bernando O`Higgins 3363, Santiago, Chile
Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Universidad
Andrés Bello, Quillota 980,Viña del Mar, Chile
Instituto de Tecnología Química and Departamento de Química, Universidad
Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, Spain.
E-mail: hgarcia@qim.upv.es
carried out using organic solvents. Howerver, there are also some
examples showing the ability of using MIL-101(Cr or Fe),[26], Co-[27,28]
or Cu-containing MOFs[29] as catalysts under solvent-free conditions
with the exclusive use of molecular O2 as oxidant. Regardless these
achievements there is still room to develop active, selective and
stable MOFs able to promote oxidation reactions using exclusively
molecular oxygen in the absence of any organic promoter.
b
c
d
Electronic Supplementary Information (ESI) available: [Structural diagrams and
catalytic data]. See DOI: 10.1039/x0xx00000x
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Less common are the heterogeneous catalysts based on Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
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lanthanide(III) ions. For example, lanthanide(III) based MOFs with CB21EZ, UK; e-mail: deposit@ccdc.cam.ac.uk.
DOI: 10.1039/C5CY01448D
arenedisulfonate ligands have been used as catalysts in the oxidation
of organic sulfur containing compounds and alkanes.[30] Moreover,
lanthanide carboxylates MOFs, as heterogeneous catalysts for
oxidation of olefins, have recently been reported in 2011 and 2012
by Sen et al..[31] However, to the best of our knowledge
heteronuclear copper(II)-lanthanide(III) MOFs have not been
reported to date as catalysts in oxidation reactions of benzylic and
cycloalkene substrates.
Elemental analysis
The C, N, S and H contents were determined using a Carlo-Erba
EA-1108 microanalyzer, and the Cu analysis was done using an
atomic absorption spectrophotometer, Shimadzu model AA-6200.
Thermogravimetric analysis
The thermogravimetric analyses were done on a NETZCH Iris
equipment. The TGA curves were registered in the 20-700ºC range,
under nitrogen atmosphere (20 mL/min) using a 10ºC/min heating
rate.
In the present work we report the synthesis of a new
heterometallic CuII and LaIII coordination polymer (CuLa-MOF) of
formula {[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n that shows
catalytic activity for the aerobic oxidation in free-solvent conditions
of benzylic substrates and cycloalkenes, without any aldehyde or
hydroxylimide as co-oxidant.
X-Ray powder diffraction (XRPD)
The X-ray powder diffraction patterns were recorded in the
refraction mode using a Philips X’Pert diffractometer using the Cu Kα
radiation ( λ = 1.54178 Å) as the incident beam, PW3050/60 (2h) as
Goniometer, PW 1774 spinner as sample stage, PW 3011 as detector,
incident mask fixed with 10 mm. PW3123/10 for Cu was used as a
monochromator. PW3373/00 Cu LFF was used as X-ray tube with
power scanning of 45 kV and 40 mA current. The sample powder was
loaded into a holder and levelled with a glass slide before mounting
it on the sample chamber. The specimens were scanned between 2
and 70º with the scan rate of 0.02 s-1.
Experimental Section
Reagents
All the reagents were of analytical grade and supplied by
Sigma Aldrich. Benzylic substrates were distilled immediately before
use in the catalytic reactions, in order to remove possible radical
quenchers or avoid the initial presence of hydroperoxides.
Synthesis of {[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n, was obtained by
hydrothermal synthesis. Briefly, 1 mmol of 3,5 pyridindicarboxylic
acid (H2PDC), 0.25 mmol of lanthanum oxide (La2O3) and 0,5 mmol of
copper sulfate pentahydrate (CuSO4·5H2O) were mixed with 8 mL of
water in a Teflon vessel. The reaction mixture was heated at 170 ºC
for 72 h in a Parr autoclave. Then, the reaction mixture was cooled
for 10 h till room temperature. The products were filtered off and
dried at room temperature. Blue crystals, together with a blue
microcrystalline solid were obtained; the crystals were separated
manually from the bulk product, being suitable to single crystal X-ray
Table 1. Crystallographic Parameters for
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n
Empiric formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C42H28CuLa4N6O36S2·2(H2O)
1912.05
293(2)
0.71073
Triclinic
diffraction.
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n
The
bulk
product
was
by
identified
powder
as
X-ray
P1
̅
9.4008 (5)
11.5017 (6)
13.7959 (7)
108.560 (1)
106.079 (2)
97.892 (2)
1316.50 (12)
1
diffraction. Yield: 30%. Elemental analysis (Calc %): C: 26.4 ; H: 1.7 ;
N: 4.5 ; S: 3.4 ; Cu: 3.4% ; (Exp %): C: 25.8 ; H: 1.5 ; N: 4.3 ; S: 3.3 ; Cu:
3.3%.
b (Å)
c (Å)
Single Crystal X-Ray Diffraction
α (deg)
β (deg)
The data were collected on
a Bruker Smart Apex
γ (deg)
diffractometer at 293 K, using separations of 0.3º between frames,
and 10 s by frame. Data integration was made using SAINTPLUS.[32]
The structure of {[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]·H2O}n was
solved by direct methods using XL SHELXTL[33] and completed (non-H
atoms) by Fourier difference synthesis. Refinement until
convergence was obtained using XL SHELXTL and SHELXL97.[34] All
hydrogen atoms were calculated in idealized positions on geometric
basis and refined with restrictions. Table 1 summarizes the methods
used and displays the main structural parameters obtained for
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2] ·H2O}n.
Volume (Å3)
Z
Density (Mg m-3)
2.412
-1
)
3.775
F(000)
919
Fit quality on F2
1.039
Final R indices (I > 2σ(I))
0.0278
0.0296
0.0765
0.0782
CCDC 1417605 contains the supplementary crystallographic
data for {[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2] ·H2O}n . These data can
be obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif, or from the
Indices (all data)
2 | J. Name., 2012, 00, 1-3
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Journal Name
Nitrogen sorptometry
ARTICLE
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DOI: 10.1039/C5CY01448D
The surface area of {[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n was
measured using the Brunauer-Emmett-Teller (BET) method on a
Micromeritics ASAP 2010 equipment after degassing the sample.
The result of the physical characterization of the catalyst by N2
sorptometry show that the specific area is approximately 0.0147 m2g-
1 and the pore volume 0.0137 cm3g-1, with the adsorption isotherm
being of type III according to the IUPAC classification (Figure S1).
Catalytic reactions
In a typical reaction, 20 mmol of organic substrate was placed
into the two neck bottom flask (25 mL capacity) together with 20 mg
of catalyst. These mixtures were stirred at 120 ºC under molecular
oxygen atmosphere (1 atm) for the required time. For cyclooctene,
cycloheptene and cyclohexene the reactions were carried out in
closed reinforced glass vessels that can stand a pressure of 5 bars.
After the reaction time, the catalyst was filtered through a Nylon
filter (0.2 μm) and extracted with toluene, and the reaction mixture
analyzed by GC. Nitrobenzene was used as an external standard. The
products were identified by GC and GC-MS, using available
commercial samples. As previously reported, the corresponding
hydroperoxides were analyzed by adding an excess of
triphenylphosphine to aliquot samples, and quantifying the
corresponding trihphenylphosphine oxide formed due to the
presence of hydroperoxide.[26,35] Mass balances based on the initial
moles of indane were higher than 95 %.
Figure 1. a) View along [100], b) View along [010], c) View along [001]
directions. Legend: Cyan: Cu; green: La; yellow: S; red: O; grey: C; blue: N;
white: H.
O10; La1-O11v), a water molecule (La1-O1W), and sulfate oxygen
atom (La1-O13), as shown in Figure S3. In contrast, coordination
around La2 is defined by five oxygen atoms from four PDC2- ligands
(La2-O1; La2-O5; La2-O9vi; La2-O11v; La2-O12v), three oxygen atoms
from two sulfate ions (La2-O13; La2-O14i; La2-O15) and one water
molecule (La2-O2W), as shown in Figure S4.
The reusability of the catalyst was tested for the oxidation of
indane or cyclooctene. After the reaction time, the reaction mixture
was filtered off, the catalyst dried and reused directly without further
treatment for a subsequent run with fresh indane or cyclooctene.
The absence of active species leached from the solid to the solution
was assured by the Sheldon’s hot filtration test. In this case, the
reaction was initiated under the typical oxidation conditions
indicated above and the solid catalyst filtered at the time required
for a conversion around 40 %. Then, the clear solution was allowed
to react further at 120 ºC in the absence of any solid.
The carboxylic acid ligands are found in two different forms in
the structure: partially protonated (HPDC-) or totally deprotonated
(PDC2-). These carboxylate groups present diverse coordination
modes: tridentate, coordinating one LaIII atom as chelate (O1-La1-
O2), and another LaIII center in a monodentate bridging mode (La1-
O1-La2). Besides, the carboxylate group of HPDC- is bonded in a
monodentate form to a LaIII center (La2-O5). In contrast, the oxygen
atom O7 of one of these carboxylate groups does not present
coordination with any metallic center; the charge is compensated by
hydrogen bond interactions between the deprotonated carboxylic
group and two water molecules coordinated with two neighboring
LaIII ions (O7-O1w = 2.704(4) ; O7-O2w = 2.602(4) Å).
Results and Discussion
Structural description
The heteronuclear copper(II)-lanthanum(III) metal organic
framework,
monoacid
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n
3,5-pyridinedicarboxylate; PDC:
(HPDC:
3,5-
The extended framework defines a 3D system, being a non-
porous structure. The inorganic polymer grows along the a, b and c
axes, thus forming a covalent three dimensional structure. The
connectivity is through the carboxylate and sulfate groups, which act
as bridges between the CuII and LaIII centers (Figure 1).
pyridinedicarboxylate) crystallizes in the triclinic system with space
group P1̅
. The coordination environment around CuII is well
described as slightly elongated octahedral. The CuII atom lies on a
crystallographic inversion center, occupying a special position of type
b [0012]. Its first coordination sphere is completed by two oxygen
The calculated X-ray powder diffractogram (XRPD) pattern
obtained from the single crystal parameters matches the
atoms from two different sulfate groups, in a trans configuration,
that are equivalent (Cu1-O16; Cu1-O16i), and four N atoms from four
deprotonated pyridine dicarboxylic ligands (PDC2-) (Cu1-N1; Cu1-N2;
Cu1-N1i; Cu1-N2i) as shown in Figure S2. On the other hand, there
are two different LaIII centers, both being nonacoordinated. The
coordination around La1 is completed by seven oxygen atoms from
six PDC2- ligands (La1-O1; La1-O2; La1-O3ii; La1-O4iii; La1-O8iv; La1-
experimental
pattern
of
bulk
{[Cu0,5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n (Figure 2a). Thus, the
results confirm that the compound used in the catalytic experiments
exactly corresponds to the species whose structure was obtained
from single crystal XRD data.
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DOI: 10.1039/C5CY01448D
a)
b)
100
100
80
60
40
20
0
a)
2)
b)
100
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60
40
20
0
80
60
40
20
0
1)
0
10
20
30
40
50
0
10
20
30
40
50
Time (h)
Time (h)
0
100 200 300 400 500 600 700 800
10 20 30 40 50 60 70
2 ()
Temperature (°C)
Figure 3. (a) Time conversion plot for the aerobic oxidation of indane using
CuLa-MOF as catalyst during four consecutive uses. (b) Time selectivity plot
of the main products observed for the aerobic oxidation of indane using CuLa-
MOF as catalyst. Reaction conditions: Catalyst (20 mg, 0.05 mol % Cu),
substrate (20 mmol), 120 ºC, O2 atmosphere. Legend a): 1st use (), 2nd use
(○), 3th use (□) and 4th use (Δ). Legend b): 1-indanyl hydroperoxyde (○),
indanone (□), indanol (▲) and hydroperoxide+indanol+indanone (●).
Figure 2. (a) XRD pattern of [Cu0,5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n.
simulated (1) and experimental (2). (b)
{[Cu0.5La2(HPDC)(PDC)2(SO4)(H2O)2]H2O}n.
Thermogram of
The thermal stability of the catalyst was studied by
thermogravimetric analysis (TGA) (Figure 2b). The compound
presents a weight loss of 1.5 % in the 20 to 165 ºC temperature range,
corresponding to crystallization water molecules. The coordinated
water molecule is lost at 205 ºC. A temperature-programed
decomposition (TPD) showed that the loss weight between 205 - 360
ºC corresponds to CO2 molecules from the carboxylic groups of the
PDC2- ligands. Finally, between 360 – 700 ºC a weight loss of
approximately 40 % corresponds to the total decomposition of the
organic material and the breaking down of the sulfate group that
begins at 438 ºC. At 700 ºC the weight loss is not complete; the
remaining mass corresponds to Cu and La oxides formed in the
thermic decomposition process.
Importantly, CuLa-MOF can be recovered from the reaction
mixture and reused four consecutive runs under the same
conditions. It was observed that the catalyst undergoes a certain
deactivation from the first to the second cycle, but then it maintains
essentially the same activity for the third and fourth cycle.
Interestingly, the selectivity towards hydroperoxide/ol/one is similar
within ±10 % for all the four runs, being over 90 % for conversions
lower than 70 % and, then, decreasing to about 80 % for complete
conversion. When using CuLa-MOF as catalyst, 1-indanone
represents about 80 % of the product mixture at complete
conversion.
Catalytic activity
This selectivity data compares favorably respect to the use of
MIL-101(Fe) or MIL-101(Cr) as catalysts under similar reaction
conditions.[26] For these two MIL-101 MOFs the selectivity to 1-
indanone at full indane conversion represents about 65 and 40 % for
Fe and Cr, respectively.[26] This difference in selectivity could be
explained considering that the reaction occurs on the surface of the
CuLa-MOF catalyst, due to the negligible internal porosity (CuLa-MOF
surface area < 5 m2 g-1). In the case of MIL-101(Fe) or MIL-101(Cr) the
reaction takes place in the cavities of these MOFs and, therefore, the
occurrence of over oxidation is more likely in these cases.
Interestingly, the selectivity of CuLa-MOF is also higher respect to the
use of homogeneous radical initiators such as TBHP or AIBN where
selectivity at full indane conversions were lower than 60 %, therefore
showing the beneficial role of CuLa-MOF to promote the selective
aerobic oxidation.[26]
After characterizing the new CuLa-MOF, the catalytic activity of
the novel material for the aerobic oxidation of hydrocarbons was
evaluated. Aimed at this purpose, the catalytic activity of CuLa-MOF
was initially explored for benzylic oxidation of a series of aromatic
hydrocarbons, and subsequently, the activity for the epoxidation of
three cycloalkenes was determined.
Aerobic oxidation of indane was efficiently promoted by CuLa-
MOF using 0.05 Cu mol % at 120 ºC. Figure 3 shows the temporal
evolution of indane conversion and the major products formed (see
Figure S5 for other minor products also observed). As can be seen,
the corresponding indanyl hydroperoxide appears as primary
oxidation product, as well as the benzylic ol/one products. During the
course of the reaction, the selectivity of the hydroperoxide decreases
and indanone becomes the major product with selectivity above 80
% for complete indane conversion. These selectivity values are better
than those previously reported using MIL-101(Fe) and similar to
those of MIL-101(Cr), as catalysts for the aerobic oxidation of indane
under similar reaction conditions.[26] It is worth commenting that
attempts to activate the catalyst at 120 ºC under vacuum did not
result in an increase of the catalytic activity. This observation is not
unexpected considering the chemical structure of the CuLa-MOF
were CuII as active center is not coordinated with water molecules,
whose removal to liberate some coordination positions around the
metal center is among the main reasons for catalyst activation.[26]
The fact that thermal activation of CuLa-MOF is not needed
represents an advantage compared to other reported MOF catalysts
such as MIL-101(Cr)[21,22,26,36] or MIL-101(Fe)[21,26,36,37] that typically
require thermal activation to remove water or solvent molecules
coordinated to the active metal centers.[38]
Stability of CuLa-MOF under the reaction conditions was
supported by XRPD; comparing the diffraction pattern of the fresh
catalyst with that of the three and four times used catalyst, no
significant variations were observed (Figure 4a). In addition, chemical
analysis of CuII by quantitative inductively coupled plasma (ICP)
measurements in the liquid phase after the first use shows the
presence of about 1.5 % (10.5 μg) of the initial amount of CuII (0.7
mg) present in the fresh catalyst dissolved in the solution. Then, the
CuII leaching decreases from the first to the forth use with values of
0.9, 0.6 and 0.2 wt% of Cu respect to the fresh catalyst. Control
experiments, in which the amounts of leached CuII in the different
catalyst cycles were evaluated as homogeneous catalyst to promote
benzylic oxidation of indane, showed that these amounts of CuII
leached contribute in fact in a certain percentage to the aerobic
oxidation when CuLa-MOF is used as solid catalyst (Figure 4b).
However, experiments using the CuII leach resulted in significantly
slower conversion reaction rates (Figure 4b) and lower selectivities
(Figure S6) respect to experiments in which CuLa-MOF was used as
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a)
C
b)
100
80
60
40
20
0
100
80
B
A
60
10 20 30 40 50 60
0
10
20
t (h)
30
40
50
2 (
)
40
20
0
Figure 4. (a) XRPD of fresh (A), three (B) and four times used catalyst (C). (b)
Time conversion plot for the aerobic oxidation of indane the heterogeneous
CuLa-MOF catalyst (close symbol) and the homogeneous Cu(OAc)2 catalyst
(open symbols). Legend panel (b): CuLa-MOF (); Amount of Cu employed as
homogeneous catalyst corresponding to the 1.5 (□), 0.8 (Δ) and 0.3 wt% (○)
of the leached Cu from the solid catalyst to the solution. Reaction conditions:
Catalyst (20 mg, 0.05 mol % for CuLa-MOF or the indicated amounts of
Cu(OAc)2), substrate (20 mmol), 120 ºC, O2 atmosphere (1 atm).
0
10
20
Time (h)
30
40
50
Figure 5. Time-conversion plot for the aerobic oxidation of indane using CuLa-
MOF (■), after filtering the catalyst at ~40 % conversion in the absence (○)
and in the presence of TEMPO added at this conversion (Δ). Reaction
conditions: Catalyst (20 mg), indane (20 mmol), 120 ºC, O2 atmosphere (1
atm).
catalyst. For example, the combined selectivity to hydroperoxide/-
ol/-one using CuLa-MOF was found to be 97 % at 60 % conversion
while using the corresponding amount of Cu(OAc)2 equivalent to that
found in the leachates, the selectivity was below < 80 % at the same
conversion (Figure S6).
forming a peroxyl radical that in the propagation steps forms
hydroperoxy and another indanyl radical.[26,27] To support this
proposal, i.e. the involvement of carbon centered radicals in the
oxidation, a well-known radical scavenger, TEMPO, was added in a
hot filtration experiment.
The stability of CuLa-MOF as catalyst is higher than that reported
for a commercial Cu-MOF, namely Basolite C 300 (Cu3(BTC)2, (BTC:
1,3,5-benzenetricarboxylate), this catalyst becomes transformed in
metallic Cu nanoparticles when used for the aerobic oxidation of
thiols to disulfides.[39]
Figure 5 also shows the influence of addition of TEMPO on the
time conversion plot on a hot filtration experiment. As observed, the
presence of TEMPO inhibits almost completely the oxidation of
indane after removal of the solidcatalyst, indicating that the most
likely reaction intermediates of the process have carbon centered
radical character.
Related with catalyst stability, a productivity test using a large
amount of indane (40 mL, 325 moles) and low amount of catalyst (2
mg, 0.001 mmol as Cu) working at 120 ºC under O2 atmosphere (1
atm) was performed. Under these extremely low catalyst content
The catalytic activity of CuLa-MOF was compared to that of
Cu(OAc)2 as homogeneous CuII catalyst, using the same CuII content
as the CuLa-MOF solid (Figure 6). It was observed that the required
amounts of Cu(Oac)2 were dissolved in indane. Although the exact
coordination of dissolved Cu(Oac)2 is surely different than that of
CuLa-MOF or its leachate, it provides a useful information about the
catalytic activity of solubilized CuII compounds in indane. To address
the issue about the possible role of LaIII as catalyst, either in nodal
positions or upon leaching, a control experiment in which lanthanum
carbonate was used as homogeneous catalyst for indane oxidation
was performed. The reaction was followed for twenty-four hours,
without observing any conversion. This experimental fact supports
the lack of catalytic activity of LaIII to promote hydrocarbon
oxidation. A commercial Cu-MOF, namely Cu3(BTC)2, was also
included in the comparison. It was determined that the
homogeneous system resulting from dissolved Cu(Oac)2 promoted
the aerobic oxidation of indane faster than CuLa-MOF under similar
conditions. The activity of CuLa-MOF and Cu3(BTC)2 was on the other
hand similar at initial times, although at longer reaction times CuLa-
MOF outperforms Cu3(BTC)2 as catalyst (Figure 6a). Also,
hydroperoxide/-ol/-one selectivity using CuLa-MOF catalyst was
higher than that of Cu3(BTC)2 and coincident at moderate
conversions, and also higher than that of Cu(Oac)2 (Figure 6b). This
catalytic behavior can be interpreted considering that the solubility
of Cu(Oac)2 allows better accessibility to CuII sites than when this
transition metal is forming part of the structure of the solid catalyst.
The product selectivity on the other hand is influenced by the nature
of the reaction surface in where oxidation is taking place.[26]
conditions, conversions around 60
% were reached without
observing noticeable decrease of activity (Figure S7). Importantly,
the selectivity towards the corresponding benzylic hydroperoxide,
alcohol and ketone was still higher than 90 %.
Additionally, information with respect to the role of leached Cu
and the oxidation mechanism was obtained by hot filtration tests. In
these experiments, the reaction is initiated in the presence of CuLa-
MOF and, then, the solid removed while the reaction mixture is still
hot close to the reaction temperature. The clear liquid solution in the
absence of solid particles is allowed to continue the reaction while
observing that in the absence of solid catalyst, indane oxidation
progresses from about 38 % till 72 %. Figure 5 shows a comparison
of the temporal profile of indane conversion in the presence of CuLa-
MOF and in the hot filtration experiment. The results of the hot
filtration test cannot be fully explained by the low percentage of Cu
leached from the solid to the liquid phase as the control experiment,
using this small concentration of soluble Cu(OAc)2, reveals. Based on
precedent data from literature, in which removal of the solid acting
as radical initiator, does not alter the temporal profile for benzylic
oxidations, it is here proposed that the hydroperoxide present in the
reaction mixture, and being generated from the beginning of the
reaction, in combination with small amounts of copper ions, is
responsible for the progress of the oxidation reaction in the absence
of solid CuLa-MOF. [26,27,40,41]
This proposal assumes the operation of a radical chain
mechanism in which indanyl radicals react with molecular oxygen
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Journal Name
a)
b)
a)
b)
View Article Online
DOI: 10.1039/C5CY01448D
100
100
100
80
60
40
20
0
100
80
60
40
20
80
60
40
20
0
80
60
40
20
0
0
0
0
20
40
60
80
100
0
10
20
Time (h)
30
40
50
10
20
Time (h)
30
40
50
0
20
40
60
80
100
Conversion (%)
Conversion (%)
Figure 7. Time conversion (a) and selectivity (b) plot for the aerobic oxidation
of indane using CuLaPDC as catalyst (■) in the presence of DMSO (Δ) or p-
benzoquinone (○) as radical quencher. Reaction conditions: Catalyst (20 mg
or 0.011 mmol of Cu), substrate (20 mmol), DMSO or p-benzoquinone (20 mol
% respect indane), 120 ºC, O2 atmosphere (1 atm).
Figure 6. Time-conversion (a) and selectivity-conversion (b) plot for the
aerobic oxidation of indane in the presence of the heterogeneous solid
catalysts CuLa-MOF (■) and Cu3(BTC)2 (○) or the homogeneous Cu(AcO)2 salt
(Δ). Reaction conditions: Catalyst (20 mg or 0.011 mmol of Cu), substrate (20
mmol), 120 ºC, O2 atmosphere (1 atm).
these two compounds having strong affinity for metal ions would
inhibit oxidation. As it can be seen in Figure S8, this was the case and
the activity of CuLa-MOF for indane oxidation becomes considerably
diminished when any of these two ligand molecules are present.
According with these facts, we propose that the reaction mechanism
should involve a step on oxygen activation by the metal ions of the
MOF that requires some interaction between molecular oxygen and
the metal centers.[26] As previously reported, CuII ions have the ability
to interact with molecular O2 leading to the formation of CuII
superoxo species able to activate C-H bonds, such as those
The influence of the oxygen pressure on the benzylic oxidation
of indane was determined by performing the reaction under inert
atmosphere or in the presence of air or oxygen. It was observed that
indane conversion increases significantly with oxygen pressure
(Figure S8). Under inert atmosphere, no oxidation took place.
However, if after having started the reaction under Ar for 24 h and
observing no conversion, the atmosphere is suddenly changed from
Ar to O2, then evolution of oxidized products is observed, at a similar
rate as in the case in which the reaction is started under oxygen.
To learn more about the reaction mechanism and, particularly,
the nature of the reactive oxygen species that could be involved in
the process, two reactions were carried out, where
dimethylsulfoxide (DMSO) or p-benzoquinone was present. DMSO is
a selective quencher of HO· radicals, while p-benzoquinone is
encountered in the benzylic substrates employed in the present
[41, 46]
work.
The scope of CuLa-MOF as catalyst for benzylic
oxidations was expanded by studying a series of alkyl aromatic
compounds (Figures S9-S12). The results are summarized in Table 2
and Figure S14. Table 1 shows that all the alkyl aromatics undergo
the expected benzylic oxidation with a rate (Figure S14) that
increases for tertiary benzylic positions (cumene) and with the
presence of two benzylic groups (indane) with respect to secondary
benzylic groups (sec-butyl-, isobutyl- and n-butylbenzenes), in
accordance with the relative stability of the corresponding benzylic
radicals.
·-
selective for the quenching of O2 and HOO· radicals.[26,42] The
obtained results are shown in Figure 7 in which temporal profiles of
a reaction in the absence of any quencher is also included for
comparison. Figure 7 shows that the presence of p-benzoquinone
completely inhibits indane oxidation, while the presence of DMSO
has a marginal influence on the time conversion plot. This marginal
influence could be due to polarity changes of the medium by DMSO
including oxygen solubility. However, the complete inhibition of the
oxidation by p-benzoquinone strongly suggests the involvement of
superoxide or hydroperoxyl radical as the active oxygen species
responsible for the benzylic oxidation.
Table 2. Aerobic oxidation of aromatic benzylic hydrocarbons using
CuLa-MOF as catalyst.a
Conversion
(%)
Main reaction
products
Selectivity
(%)
n-Butylbenzene
~ 30
1-Phenyl-1-
butylhydroperoxid
e
1-phenyl-1-butanol
Butyrophenone
(1-Hydroperoxy-2-
methylpropyl)benz
ene
Phenylisopropyl
ketone
Benzoic acid
Acetophenone
Cumyl
~ 30
~35
~35
Other quenchers that were also used to get additional
information on the oxidation process were benzoic acid and DMF
(Figure S9). The rationale behind the use these compounds as
quenchers was to poison free coordination positions around metal
ions to avoid interaction of these metal ions with oxygen or
substrates.[43, 44] A generally accepted paradigm in catalysis by MOFs
is that active sites should be metal ions occupying nodal positions in
MOF structures having free coordination positions.[37, 44, 45] These
coordination positions will activate substrates and reagents, but if a
ligand is present in the reaction mixture it can compete favorably
with substrates and reagents, the ligand should lead to an apparent
deactivation of the catalyst. In precedents in the literature it has
been found that carboxylic acids having similar coordination strength
as typical MOF linkers can be poisons for oxidation of benzylic
alcohols.[16]
Isobutylbenzene
~ 60
24
~68
~8
Cumene
100
84
~ 86
~ 7
hydroperoxide
Acetophenone
sec-Butylbenzene
~ 45
~ 47
Propiophenone
[a] Reaction conditions: Catalyst (20 mg), substrate (20 mmol), O2
atmosphere (1 atm), 120 ºC and reaction time depending of the
substrate to achieve the indicated conversion (Figures S9 to S12).
Similarly, it is well known that removal of dimethylformamide
(DMF) frequently used as solvent in MOF synthesis is a necessary
44]
activation step for most catalytic reactions.[19,
Based on this
previous knowledge we wanted to determine if the presence of
6 | J. Name., 2012, 00, 1-3
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ARTICLE
O
Table 3. Aerobic oxidation of cycloalkenes using CuLa-MOF as catalyst.
O
View Article Online

DOI: 10.1039/C5CY01448D
O
O
CuLa-MOF
O2
(n)
Conversion
(%)
Selectivitya
(n)
(n)
Electrophilic addition to C=C(n)
(n)
(%)
n = 1, 2, or 3
Epoxide Alcohol Ketone HPOX.d
O
O
Cycloocteneb
Cyclooctenec
Cycloheptenec
Cyclohexenec
96
80
94
77
99.5
98.2
45.2
~ 1.0
-
-
< 0.5
1.8
+
(n)
(n)
-
-
-
54.8
68.0
< 1
30.6
< 1
Scheme 1. Proposed reaction mechanism for the aerobic oxidation of
cyloalkenes using molecular oxygen and CuLa-MOF as catalyst.
a The oxidation to the corresponding alcohol, ketone or hydroperoxide
takes place in the allylic position of the cycloakene.
Comparison of the catalytic activity of CuLa-MOF for this
process shows that this MOF is significantly more active than
commercial Cu3(BTC)2, although soluble Cu(OAc)2 exhibits higher
activity than CuLa-MOF. Again, this relative activity is not
unprecedented since soluble homogeneous catalysts exhibit higher
intrinsic activity than similar centers incorporated in an insoluble
material.
b Reaction conditions: Catalyst (20 mg, 0.05 mol %), substrate (20 mmol),
O2 (1 atm), 120 ºC, reaction time 48 h.
c Reaction conditions: Catalyst (20 mg, 0.05 molt %), substrate (20 mmol),
O2 (5 atm), 120 ºC and reaction time depending of the substrate to
achieve the indicated conversion (Figures S14-S16).
d. HPOX = Hydroperoxide.
However, the heterogeneous conditions allow easy recovery of
the catalyst by filtration or decantation, a recovery that is not
possible for homogeneous catalysts. A notable observation that
contrasts with the previous experiments of benzylic oxidations was
that hot filtration of CuLa-MOF stops completely epoxidation of
cyclooctene.
The negative influence of the steric hindrance around the
benzylic positions on the reaction rate observed for sec-
butylbenzene or isobutylbenzene with respect to cumene and n-
butylbenzene suggests that the substrate has to adsorb on the solid
catalyst surface to form the radicals. Besides benzylic oxidation and
as already indicated above, the activity of CuLa-MOF was also tested
for the aerobic epoxidation of cycloalkenes. The results are
summarized in Table 3. It was observed that in the presence of
oxygen at atmospheric pressure, CuLa-MOF promotes the
epoxidation of cyclooctene by oxygen with almost complete
selectivity at high conversion.
The behavior of cyclooctene contrasts with that of
cycloheptene and cyclohexene. In agreement with the literature,[15]
the allylic oxidation was almost the exclusive process observed for
cyclohexene, while cycloheptene exhibits an intermediate behavior
between cyclooctene and cyclohexene. In this case, both allylic
oxidation and epoxidation takes place with similar selectivity.
Although the influence of the size of the ring on the outcome of the
reaction has been observed previously and reported in the literature,
using NHPI adsorbed on Fe-BTC, no convincing explanation has been
given.[15] It seems that geometry and conformation of the
hydroperoxides and C=C double bonds in cycloalkenes should change
as a function of the ring size, and these conformations and
geometries favor epoxide for larger rings versus allylic oxidation in
medium size rings. The involvement of the corresponding
hydroperoxide in C=C epoxidation is supported by the detection of
this intermediate during the course of the reaction, particularly at
short reaction times. Scheme 1 summarizes the proposed reaction
mechanism for the aerobic epoxidation of cyclooctene using CuLa-
CuLa-MOF could be reused three times for the aerobic
epoxidation of cyclooctene, observing some decrease of the catalytic
activity in the second cycle, while the activity of CuLa-MOF is
maintained for the third and fourth cycle, as indicated by the time
conversion plot of the epoxidation, and the final yield at the end of
the reaction (Figure 8).
a)
b)
100
80
60
40
20
0
100
80
60
40
20
0
MOF, based on previous reports in the literature.[15,24,46]
.
Conclusions
0
10
20
Time (h)
30
40
50
0
10
20
30
40
50
Time (h)
Figure 8. (a) Time-conversion plots for the aerobic oxidation of cyclooctene
for the fresh (■), 2nd use (●), 3th use (▲) and 4th use (Δ) of CuLa-MOF catalyst.
Temporal evolution of cyclooctene oxide selectivity (○) for the first use and
hot filtration test when using fresh CuLa-MOF (□); (b) Time-conversion plot
for the aerobic oxidation of cyclooctene using the homogeneous Cu(OAc)2 salt
as homogeneous catalyst (Δ) or CuLa-MOF (■) or Cu-basolite (○) solids as
heterogeneous catalysts. Reaction conditions: Catalyst (20 mg or 0.011
mmol), substrate (20 mmol), oxygen atmosphere (1 atm), 120 ºC.
CuLa-MOF exhibits similar catalytic activity for benzylic
aerobic oxidation and epoxidation of cycloalkenes, but greater than
that of Cu3(BTC)2, which is a benchmark CuII MOF catalyst largely
used in the literature.[14,47] . Besides, the selectivity of the CuLa-MOF
is similar to that of Cu(OAc)2, which was used as homogeneous
catalyst. The catalyst is reusable with some minor decrease from the
first to the second catalytic cycle. The reaction mechanism seems to
follow the expected radical chain autooxidation for benzylic
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Journal Name
hydrocarbons, and epoxidation by a hydroperoxide intermediate for [12]
cycloalkenes.
F. J. Jiang, X. Zhu, B. Fu, J. Huang, G. Xiao, Chinese J. Catal.
View Article Online
2013, 34, 1683; O. A. Kholdeeva, Catal. Sci. Technol. 2014,
DOI: 10.1039/C5CY01448D
4, 1869.
[13]
A. Corma, H. García, F. X. Llabrés i Xamena, Chem. Rev.
2010, 110, 4606; J. Gascon, A. Corma, F. Kapteijn, F. X.
Llabrés i Xamena, ACS Catal. 2014, 4, 361; Z.-Y. Gu, J. Park,
A. Raiff, Z. Wei, H.-C. Zhou, ChemCatChem 2014, 6, 67; M.
Ranocchiari, J.A.V. Bokhoven, Phys. Chem. Chem. Phys.
2011, 13, 6388; C. Wang, M. Zheng, W. Lin, J. Phys. Chem.
Lett. 2011, 2, 1701; M. Yoon, R. Srirambalaji, K. Kim, Chem.
Rev. 2012, 112, 1196; P. García-García, M. Muller, A.
Corma. Chem Sci. 2014, 5, 2979.
Acknowledgements
Financial support by the Spanish Ministry of Economy and
Competitiveness (Severo Ochoa and CTQ2012-32315) is gratefully
acknowledged. Generalidad Valenciana is also thanked for funding
(Prometeo 2012/013). The authors ES, AV and PC thank
Financiamiento Basal (Proyecto FB0807) and Proyecto Anillo
ACT1404 for partial financial support. PC acknowledges financial
[14]
[15]
[16]
[17]
[18]
[19]
[20]
A. Dhakshinamoorthy, M. Opanasenko, J. Čejka, H. Garcia,
Catal. Sci. Technol. 2013, 3, 2509.
support from CONICYT, “Programa de Formación de Capital Humano
Avanzado”, Beca Doctorado Nacional 21110228.
A. Dhakshinamoorthy, M. Alvaro, H. Garcia, J. Catal. 2012,
289, 259.
References
A. Dhakshinamoorthy, M. Alvaro, H. Garcia, ACS Catal.
2011, 1, 48.
[1]
[2]
H. Furukawa, K.E Cordova, M. O'Keeffe, O.M. Yaghi, Science
2013, 341, 1230444.
A. Dhakshinamoorthy, M. Alvaro, H. Garcia, ChemCatChem
2010, 2, 1438.
N. Stock, S. Biswas, Chem. Rev. 2012, 112, 933; S. Qiu, Zhu,
G., Coord. Chem. Rev. 2009, 253, 2891; W. Xuan, C. Zhu, Y.
Liu, Y. Cui, Chem. Soc. Rev. 2012, 41, 1677; S. T. Meek, J.A.
Greathouse, M.D. Allendorf, Adv. Mater. 2011, 23, 249.
Z. Saedi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I.
Mohammadpoor-Baltork, Catal. Comm. 2012, 17, 18.
J. Sun, G. Yu, Q. Huo, Q. Kan, J. Guan, RSC Adv. 2014, 4,
38048.
[3]
J.-R. Li, Y. Ma, M. C. McCarthy, J. Sculleya, J. Yu, H.-K. Jeong,
P. B. Balbuena, H.-C. Zhou, Coord. Chem. Rev. 2011, 255,
1791; S. Ma, H.-C. Zhou, Chem. Comm. 2010, 46, 44; R. B.
Getman, Y.-S. Bae, C.E. Wilmer, R.Q. Snurr, Chem. Rev.
2012, 112, 703.
K. Brown, S. Zolezzi, P. Aguirre, D. Venegas-Yazigi, V.
Paredes-García, R. Baggio, M. Novak, E. Spodine, Dalton
Trans. 2009, 8, 1422; A. Dhakshinamoorthy, M. Alvaro, H.
Garcia, J. Catal. 2009, 267, 1; L. Hamidipour, F. Farzaneh,
Reac. Kinet. Mech. Cat. 2013, 109, 67; G.-Q. Song, Y.-X. Lu,
Q. Zhang, F. Wang, X.-K. Ma, X.-F. Huang, Z.-H. Zhang, RSC
Adv. 2014, 4, 30221; D. Jiang, T. Mallat, F. Krumeich, A.
Baiker, Catal. Commnun. 2011, 12, 602; T. Tonigold, Y. Lu,
B. Bredenkötter, B. Rieger, S. Bahnmüller, J. Hitzbleck, G.
Langstein, D. Volkmer, Angew. Chem. Int. Ed. 2009, 48,
7546.
[4]
[5]
[6]
J.-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869; Y.-
S. Bae, R. Q. Snurr, Angew. Chem. Int. Ed. 2011, 50, 11586.
B. Van De Voorde, B. Bueken, J. Denayer, D. De Vos, Chem.
Soc. Rev. 2014, 43, 5766.
P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P.
Couvreur, G. Férey, R. E. Morris, C. Serre, Chem. Rev. 2012,
112, 1232; A. C. McKinlay, R. E. Morris, P. Horcajada, G.
Férey, R. Gref, P. Couvreur, C. Serre, Angew. Chem. Int. Ed.
2010, 49, 6260.
[21]
O. A. Kholdeeva, I. Y. Skobelev, I. D. Ivanchikova, K. A.
Kovalenko, V. P. Fedin, A. B. Sorokin, Catal. Today 2014,
238, 54; N. V. Maksimchuk, K. A. Kovalenko, V. P. Fedin, O.
A. Kholdeeva, Chem. Commun. 2012, 48, 6812.
[7]
[8]
[9]
L. E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van
Duyne, J.T. Hupp, Chem. Rev. 2012, 112, 1105.
[22]
[23]
[24]
N. V. Maksimchuk, K. A. Kovalenko, V. P. Fedin, O. A.
Kholdeeva, Adv. Synth. Catal. 2010, 352, 2943.
C.-C. Wang, J.-R. Li, X.-L. Lv, Y.-Q. Zhang, G. Guo, Energy
Environ. Sci. 2014, 7, 2831.
Y. Qi, Y. Luan, J. Yu, X. Peng, G. Wang, Chem. Eur. J. 2015,
1589-1597.
A. Dhakshinamoorthy, A.M. Asiri, H. Garcia, Chem. Soc.
Rev. 2015, 44, 1922; A. Dhakshinamoorthy, H. Garcia,
Chem. Soc. Rev. 2014, 43, 5750.
U. Junghans, C. Suttkus, J. Lincke, D. Lassig, H. Krautscheid,
R.
Glaser,
Micropor.
Mesopor.
Mat.
(http://dx.doi.org/10.1016/j.micromeso.2015.01.050)
2015.
[10]
[11]
J. L. C. Rowsell, O. M. Yaghi, Micro. Meso. Mat. 2004, 73, 3.
K. Jorgensen, Chem. Rev. 1989, 89, 431; J. R. Monnier, Appl.
Catal. A.-Gen. 2001, 221, 73; R. A. Sheldon, J. K. Kochi,
1982.
[25]
Y. Liu, S. Liu, S. Liu, D. Liang, S. Li, Q. Tang, X. Wang, J. Miao,
Z. Shi, Z. Zheng, ChemCatChem 2013, 5, 3086.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 10
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
[26]
[27]
[28]
A. Santiago-Portillo, S. Navalón, F. G. Cirujano, F. X. Labrés [42]
i Ximena, M. Alvaro, H. Garcia, ACS Catal. 2015, 5, 3216.
A. N. Dhakshinamoorthy, M. Alvaro,ViewHA.rticGleaOrncliinae,
ChemSusChem 2012, 5, 46; M. J. Burkitt, R. P. Mason, Proc.
DOI: 10.1039/C5CY01448D
Natl. Acad. Sci. USA 1991, 88, 8440; R. Martin, S. Navalon,
J. J. Delgado, J. J. Calvino, M. Alvaro, H. Garcia, Chem. Eur.
J. 2011, 17, 9494.
F. X. Llabrés i Xamena, O. Casanova, R. Galiasso Tailleur, H.
Garcia, A. Corma, J. Catal. 2008, 255, 220.
G. Tuci, G. Giambastiani, S. Kwon, P. C. Stair, R. Q. Snurr, A.
Rossin, ACS Catal. 2014, 4, 1032; J. Hao, S. Li, L. Han, L.
Cheng, Q. Suo, Y. Xiao, X. Jiao, X. Feng, W. Bai, X. Song,
Inorg. Chim. Act. 2014, 421, 246.
[43]
[44]
I. Luz, A. Corma, F. X. Llabrés I Xamena, Catal. Sci. Technol.
2014, 4, 1829.
D.-Y. Hong, Y. K. Hwang, C. Serre, G. Férey, J.-S. Chang, Adv.
Func. Mater. 2009, 19, 1537.
[29]
[30]
D. Jiang, T. Mallat, D. M. Meier, A. Urakawa, A. Baiker, J.
Catal. 2010, 270, 26; I. Luz, A. León, M. Boronat, F. X. [45]
Llabrés i Xamena, A. Corma, Catal. Sci. Technol. 2013, 3,
371.
Y. K. Hwang, D.-Y. Hong, J.-S. Chang, S. H. Jhung, Y.-K. Seo,
J. Kim, A. Vimont, M. Daturi, C. Serre, G. Férey, Angew.
Chem. Int. Ed. 2008, 47, 4144.
F. Gándara, A. García-Cortés, C. Cascales, B. Gómez-Lor, E. [46]
Gutierrez-Puebla, M. Iglesias, A. Monje, N. Snejko, Inorg.
Chem. 2007, 46, 3475; F. Gándara, E. G. Puebla, M. Iglesias,
A. Ansari, P. Jayapal, G. Rajaraman, Angew. Chem. Int. Ed.
2015, 54, 564.
[47]
A. Dhakshinamoorthy, M. Opanasenko, J. Čejka, H. Garcia,
Adv. Synth. Catal. 2013, 355, 247; J. Liu, L. Chen, H. Cui, Z.
J., L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011.
D. M. Proserpio, N. Snejko, A. Monje, Chem. Mater. 2009,
21, 655.
[31]
[32]
R. Sen, S. Koner, D. K. Hazra, M. Helliwell, M. Mukherjee,
Eur. J. Inorg. Chem. 2011, 241, 241; R. Sen, D. Saha, S.
Koner, Catal. Lett. 2012, 142, 124.
Bruker, SAINT-NT. Bruker AXS Inc., Madison, Wisconsin,
USA. 1999; Bruker, SMART-NT and SADABS. Bruker AXS
Inc., Madison, Wisconsin, USA. 2001.
[33]
[34]
[35]
G. M. Sheldrick, Acta Cryst. 1990, A46, 467.
G. M. Sheldrick, Acta Cryst. 2008, A64, 112.
M. M. Fares, M. El-Khateeb, K. J. Asali, J. Inorg. Organomet.
Polym. 2003, 13, 143.
[36]
I. Y. Skobelev, A. B. Sorokin, K. A. Kovalenko, V. P. Fedin, O.
A. Kholdeeva, J. Catal. 2013, 298, 61; I. Y. Skobelev, K. A.
Kovalenko, V. P. Fedin, A. B. Sorokin, O. A. Kholdeeva,
Kinet. Catal. 2013, 54, 607.
[37]
[38]
H. K. Hwang, D.-Y. Hong, J.-S. Chang, H. Seo, M. Yoon, J.
Kim, S. H. Jhung, C. Serre, G. Férey, Appl. Catal. A.-Gen.
2009, 358, 249.
A. Vimont, F. Thibault-Starzyk, M. Datur, Chem. Soc. Rev.
2010, 39, 4928; J. W. Yoon, Y.-K. Seo, Y. K. Hwang, J.-S.
Chang, H. Leclerc, S. Wuttke, P. Bazin, A. Vimont, M. Daturi,
E. Bloch, P. L. Llewellyn, C. Serre, P. Horcajada, J.-M.
Grenche, A. E. Rodrigues, G. Férey, Angew. Chem. Int. Ed.
2010, 49, 5949.
[39]
[40]
A. Dhakshinamoorthy, M. Alvaro, P. Concepcion, H. Garcia,
Catal. Commun. 2011, 12, 1018.
J. Kim, S. Bhattacharjee, K.-E. Jeong, S.-Y. Jeong, W. S. Ahn,
Chem. Commun. 2009, 3904; I. Hermans, J. Peeters, P. A.
Jacobs, J. Org. Chem. 2007, 72, 3057.
[41]
P. Ryan, I. Konstantinov, R. Q. Snurr, L. J. Broadbelt, J. Catal.
2012, 286, 95.
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Catalysis Science & Technology
Page 10 of 10
View Article Online
DOI: 10.1039/C5CY01448D
Novel
Copper(II)-Lanthanum(III)
Metal
Organic
Framework as Selective Catalyst for the Aerobic
Oxidation of Benzylic Hydrocarbons and Cycloalkenes.
Patricio Cancino,a,b Andrés Vega,b,c Andrea Santiago-Portillo,d Sergio Navalon,d
Mercedes Alvaro,d Pedro Aguirre,a Evgenia Spodine,*a,b and Hermenegildo García,*d