Magnetic nanoporous MCM-41 supported ionic liquid/palladium complex: An efficient nanocatalyst with high recoverability

Article abstract of DOI:10.1002/aoc.4862

In this study, a novel magnetic mesoporous MCM-41 silica supported ionic liquid/palladium complex (Fe₃O₄@MCM@IL/Pd) with core-structure was prepared and characterized and its catalytic performance was developed under green conditions

Full text of DOI:10.1002/aoc.4862

Received: 7 November 2018
DOI: 10.1002/aoc.4862
Revised: 29 December 2018
Accepted: 24 January 2019
F U L L P A P E R
Magnetic nanoporous MCM‐41 supported ionic
liquid/palladium complex: An efficient nanocatalyst with
high recoverability
Somayeh Abaeezadeh | Dawood Elhamifar
| Meysam Norouzi
| Masoumeh Shaker
Department of Chemistry, Yasouj
In this study, a novel magnetic mesoporous MCM‐41 silica supported ionic
liquid/palladium complex (Fe3O4@MCM@IL/Pd) with core‐structure was pre-
pared and characterized and its catalytic performance was developed under
green conditions. The Fe3O4@MCM@IL/Pd was prepared via a post grafting
method and was characterized using Fourier transform infrared spectroscopy,
thermal gravimetric analysis, wide‐ and low‐angle powder X‐ray diffraction,
scanning electron microscopy, transmission electron microscopy, vibration
sample magnetometer and energy‐dispersive X‐ray analyses. This was applied
as an efficient and recoverable nanocatalyst for the one‐pot synthesis of
pyrano[2,3‐d]pyrimidine derivatives under ultrasonic conditions. The catalyst
was magnetically recovered and reused for 12 consecutive cycles without
significant loss of its activity and selectivity.
University, Yasouj 75918‐74831, Iran
Correspondence
Dawood Elhamifar, Department of
Chemistry, Yasouj University, Yasouj
75918‐74831, Iran.
Email: d.elhamifar@yu.ac.ir
KEYWORDS
core–shell, magnetic mesoporous silica, pyrano[2,3‐d]pyrimidines, supported Pd‐catalyst, ultrasonic
conditions
1 | INTRODUCTION
particles have a broad range of potential applications in
the areas of nanocatalysis,[9,10] data storage,[11,12] targeted
In recent years, many efforts have been made to prepare
and synthesize magnetic nanoparticles (MNPs) for their
application in a variety of fields such as biotechnology,
drug delivery, computers, and so on. In general, the per-
formance and application of these nanoparticles are influ-
enced by their proper design and synthesis. Until now,
various magnetic nanoparticles have been prepared and
applied in various chemical processes. The most common
MNPs are pure metal nanoparticles, metal oxides, ferrites
and metal alloys.[1–5] Among different kinds of MNPs,
iron oxide nanoparticles have attracted a lot of attention
between chemists owing to their unique properties such
as easy preparation, high ability to be modified with var-
ious functional groups, tuning structural order, low toxic-
ity, low cost, high surface area, easy availability, excellent
recoverability and reusability, and low toxicity.[6–8] These
drugs,[13,14] bioelectrochemistry,[15] adsorption, etc.[16–18]
However, magnetic iron oxides suffer from several prob-
lems such as being unstable in acidic and alkaline condi-
tions, aggregation over long periods of time and oxidation
in the presence of air. Therefore, various strategies have
been developed for stabilizing magnetic nanoparticles
(NPs).[19,20] Among the different species, silica is the most
commonly used material to stabilize magnetic NPs. In
particular, magnetic mesoporous silica core–shells with
a magnetic core and mesoporous silica shell are an attrac-
tive group of magnetic nanocomposites that have the
advantages of both magnetic nanoparticles and mesopo-
rous materials, such as uniform pore size distribution,
large surface area, easy functionalization with appropri-
ate practical groups, high pore volume and excellent
selectivity.[21–31] To date
a
number of magnetic
Appl Organometal Chem. 2019;e4862.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 11
https://doi.org/10.1002/aoc.4862

2 of 11
ABAEEZADEH ET AL.
mesoporous silicas with different functional groups are
prepared and applied in a number of chemical processes.
Some of newly developed systems include Fe3O4@NH2‐
mesoporous silica@polypyrrole/Pd,[32] Fe3O4@MCM‐41‐
MCM‐41 type silica supported ionic liquid/palladium
complex [Fe3O4@MCM@IL/Pd] with core–shell struc-
ture has been designed, prepared and characterized and
its catalytic application was developed in the one‐pot syn-
thesis of pyrano[2,3‐d]pyrimidine derivatives under green
conditions (Scheme 1).
SO3H@[HMIm][HSO4],[33]
Fe3O4@MCM‐41@Ni‐
P2C,[34] Fe3O4@MCM‐41‐SO3H,[35] (α‐Fe2O3)‐MCM‐41‐l‐
prolinium nitrate,[36] Fe3O4@SiO2 hollow mesoporous
spheres,[37]
Fe3O4@MCM‐41@Pd‐SPATB[38]
and
Fe3O4@MCM‐41‐Im@MnPor.[39]
2 | EXPERIMENTAL
On the other hand, pyrano[2,3‐d]pyrimidine deriva-
tives are an important class of organic compounds owing
to their pharmacological and therapeutic properties
such as antitumor, antihypertensive, antibacterial and
antileishmanial activity.[40–43] Although several methods
have been developed until now for the synthesis of the
pyrano[2,3‐d]pyrimidine derivatives using different cata-
lysts systems, some of these protocols suffer from disad-
vantages of long reaction times, homogenous catalysts,
product separation, toxic solvent and catalyst recovery.
Therefore, owing to the biological importance of
pyrano[2,3‐d]pyrimidines, the development of new and
improved approaches for the design and preparation of
efficient catalytic systems is important for the synthesis
of pyrano[2,3‐d]pyrimidine derivatives under better
conditions than before.
2.1 | Synthesis of Fe3O4@MCM‐41
In order to synthesize Fe3O4@MCM‐41, first Fe3O4@SiO2
NPs were prepared according to a well‐known proce-
dure.[60] Then, 0.6 g of Fe3O4@SiO2 nanoparticles were
added in a solution of distilled water (50 mL) and EtOH
(110 mL) and dispersed under ultrasonic irradiation at
30 °C for 30 min. In the next step, 3 mL of aqueous ammo-
nia solution (25%) and 1 g of cetyltrimethylammonium
bromide (CTAB) were added to the resulting mixture
and it was mechanically stirred at room temperature for
10 min. Then 0.7 mL of tetramethoxysilane (TMOS) was
added dropwise and the resulting mixture was stirred for
2 h at room temperature. After that, this was statically
heated at 100 °C for 48 h. Finally, the resulting material
was separated using an external magnet, washed by
deionized water and dried at 70 °C for 10 h. The CTAB
template was removed from the synthesized material by
According to aforementioned subjects, in continuous
of our recent studies and due to the importance of sup-
ported catalytic systems in chemical processes,[44–59]
herein for the first time a novel magnetic mesoporous
calcination at 400 °C for 6 h[61]
.
SCHEME 1 Preparation of Fe3O4@MCM‐41@IL/Pd nanocatalyst

ABAEEZADEH ET AL.
3 of 11
ethanol and dried. The recovered catalyst was reused in
the next run under the same conditions as the first one.
This process was repeated and the results showed that
the catalyst could be recovered and reused at least 11
times without noticeable loss of catalytic activity.
2.2 | Synthesis of Fe3O4@MCM‐41@IL
The Fe3O4@MCM‐41@IL nanomaterial was prepared as
follows: 1.0 g of Fe3O4@MCM‐41 nanoparticles were
suspended in 50 mL of toluene and sonicated for
20 min at room temperature. Then, 0.53 mmol of 1‐
methyl‐3‐(3‐trimethoxysilylpropyl)imidazolium chloride
was added and the mixture refluxed under argon atmo-
sphere for 24 h in an oil bath. The resulting solid was
separated using an external magnet, washed completely
with ethanol and labeled as Fe3O4@MCM‐41@IL.
3 | RESULTS AND DISCUSSION
In order to synthesize the Fe3O4@MCM‐41@IL/Pd
catalyst, magnetic iron oxide nanoparticles were first
modified by a mesoporous MCM‐41 silica shell through
a sol–gel approach. The Fe3O4@MCM‐41 was then
2.3 | Synthesis of Fe3O4@MCM‐41@IL/Pd
reacted
with
1‐methyl‐3‐(3‐trimethoxysilylpropyl)
imidazolium chloride to prepare an ionic liquid contain-
ing Fe3O4@MCM‐41@IL material. Finally, the latter
nanomaterial was treated with palladium acetate to
deliver Fe3O4@MCM‐41@IL/Pd catalyst (Scheme 1).
The designed nanocatalyst was characterized by several
techniques such as Fourier transform infrared spectros-
copy (FTIR), vibration sample magnetometer, wide‐ and
low‐angle powder X‐ray diffractionpowder X‐ray diffrac-
tion, scanning electron microscopy, transmission electron
microscopy, energy‐dispersive X‐ray and thermal gravi-
metric analyses.
For the preparation of Fe3O4@MCM‐41@IL/Pd
nanocatalyst, typically 1 g of Fe3O4@MCM‐41@IL was
added in dimethyl sulfoxide (DMSO, 20 mL) and soni-
cated for 10 min at room temperature. After complete dis-
persion of this material, 1.5 mmol of Pd (OAc)2 salt was
added into reaction vessel and the obtained mixture was
first stirred at room temperature for 24 h and then heated
for 2 h at 80 °C. After that, the resulting material was
magnetically separated, washed completely with DMSO,
dried at 65 °C for 10 h and labeled as Fe3O4@MCM‐
41@IL/Pd.
The FTIR analysis of prepared magnetic Fe3O4,
Fe3O4@MCM‐41 and Fe3O4@MCM‐41@IL/Pd materials
are revealed in Figure 1. For all samples, the FTIR analy-
sis exhibited a specific absorption peak for the Fe–O bond
at 588 cm−1 and also the stretching vibration of the O–H
bond was observed at 3419 cm−1 (Figure 1). For
Fe3O4@MCM‐41 and Fe3O4@MCM‐41@IL/Pd samples
the new peaks observed at 823, 1078 cm−1 were due to
symmetric and asymmetric vibrations of the Si–O–Si
bond (Figures 1b, 1c). For the Fe3O4@MCM‐41@IL/Pd,
the new signals observed at 2923, 1417 and 1623 cm−1
were assigned, respectively, to aliphatic C–H, C=C and
C=N bonds of grafted alkyl imidazolium groups
(Figure 1c). These data confirm the successful immobili-
zation of silica and ionic liquid moieties onto magnetic
iron oxide cores.
2.4 | General method for the synthesis of
pyrano[2,3‐d]pyrimidine derivatives using
Fe3O4@MCM‐41@IL/Pd nanoparticles
For this, aldehyde (1 mmol), malononitrile (1 mmol),
barbituric acid (1 mmol) and Fe3O4@MCM‐41@IL/Pd
(0.001 g, 0.014 mol%) were added to a reaction vessel.
The resulting mixture was placed in an ultrasonic bath
at 40 °C. The reaction progress was monitored by TLC.
After finishing the process, 10 mL of hot ethanol was
added to the reaction mixture and the Fe3O4@MCM‐
41@IL/Pd catalyst was removed using an external
magnet. The pure products were obtained after recrystal-
lization in a mixture of water and EtOH.
The vibration sample magnetometer analysis of the
Fe3O4@MCM‐41@IL/Pd catalyst is shown in Figure 2.
According to this analysis, a magnetic saturation value of
30 emu/g was observed for the catalyst, indicating the good
paramagnetic property of the material. It is important to
note that the reduction of the magnetic properties of the
Fe3O4@MCM‐41@IL/Pd catalyst compared with Fe3O4
NPs[55] can be due to the presence of a non‐magnetic meso-
porous shell around the magnetic iron oxide cores.
The scanning electron microscopy analysis was per-
formed to study the morphology of the Fe3O4@MCM‐
41@IL/Pd nanocatalyst. This showed well‐distributed
2.5 | General procedure for the recovery
of Fe3O4@MCM‐41@IL/Pd nanocatalyst
The
recovery
of
the
Fe3O4@MCM‐41@IL/Pd
nanocatalyst was tested in the synthesis of pyrano[2,3‐d]
pyrimidine derivatives under optimized conditions. For
this, after completion of the reaction, the Fe3O4@MCM‐
41@IL/Pd nanocatalyst was separated from the reaction
mixture using an external magnetic field. After that, the
Fe3O4@MCM‐41@IL/Pd nanocatalyst was washed with

4 of 11
ABAEEZADEH ET AL.
FIGURE 1 FTIR spectra of (a) Fe3O4, (b) Fe3O4@MCM‐41 and (c) Fe3O4@MCM‐41@IL/Pd materials
FIGURE 2 Vibration sample magnetometer analysis of Fe3O4@MCM‐41@IL/Pd nanocatalyst
particles with spherical shape and an average particle size
of 80 nm (Figure 3). These types of nanomaterials are
very important in different fields of chemistry processes
such as catalysis, adsorption and chromatography.
The transmission electron microscopy image of the
Fe3O4@MCM‐41@IL/Pd nanocatalyst demonstrated that
the Fe3O4@MCM‐41@IL/Pd nanocatalyst has a core–
shell structure with a black core and mesoporous shell
(Figure 4).
The energy‐dispersive X‐ray spectrum of the designed
catalyst confirmed the presence of expected Si, N, O, C,
Pd and Fe elements in the structure of Fe3O4@MCM‐
41@IL/Pd (Figure 5).
The thermal stability study of Fe3O4@MCM‐41@IL/Pd
nanocatalyst was performed using thermal gravimetric
analysis (Figure 6). This analysis was carried out in a tem-
perature range of 0–800 °Celsius. The weight loss in the
first stage up to 150 °C indicates the removal of water

ABAEEZADEH ET AL.
5 of 11
FIGURE 3 Scanning electron microscopy image of Fe3O4@MCM‐41@IL/Pd nanocatalyst
FIGURE 4 Transmission electron
microscopy image of the Fe3O4@MCM‐
41@IL/Pd nanocomposite
and organic solvents remaining from the synthesis steps.
In the second stage, the weight loss in the range 151–
250 °C can be assigned to the removal of CTAB surfactant
maintained during synthesis process. In the final stage,
the weight loss at temperature range of 251–700 °C was
due to the decomposition and elimination of organic

6 of 11
ABAEEZADEH ET AL.
FIGURE 5 Energy‐dispersive X‐ray spectrum of the Fe3O4@MCM‐41@IL/Pd nanocatalyst
FIGURE 6 Thermal gravimetric analysis results of the Fe3O4@MCM‐41@IL/Pd nanocatalyst
parts (ionic liquid groups) from the structure of the
Fe3O4@MCM‐41@IL/Pd nanocatalyst. These observa-
tions are in good agreement with FTIR and energy‐
dispersive X‐ray analyses, confirming the high thermal
stability and successful immobilization of the expected
organic and inorganic moieties onto/into material
framework.
The presence of magnetic nanoparticles in the
Fe3O4@MCM‐41@IL/Pd was investigated by wide‐angle
powder X‐ray diffraction (PXRD) analysis (Figure 7). This
analysis showed that the Fe3O4@MCM‐41@IL/Pd has
crystalline structure, the same as magnetic iron oxide
nanoparticles, with seven spinel peaks at 2θ of 30.35,
36.2, 46.5, 54.4, 57.3, 63.02 and 75 ° that match the stan-
dard pattern of magnetic iron oxide nanoparticles (JCPDS
card, file no. 85‐1436).[57] This confirms the high stability
of magnetic cores during the catalyst preparation process.
The low‐angle PXRD analysis of Fe3O4@MCM‐41@IL/
Pd nanocatalyst showed a peak at 2.1 ° that is attributed
to the mesoporous structure of the MCM‐41 shell
(Figure 8).
After successful characterization, the Fe3O4@MCM‐
41@IL/Pd was applied as effective heterogeneous
nanocatalyst for the one‐pot synthesis of pyrano[2,3‐d]

ABAEEZADEH ET AL.
7 of 11
FIGURE 7 Powder X‐ray diffraction pattern (PXRD) of the Fe3O4@MCM‐41@IL/Pd nanocatalyst
FIGURE 8 Low‐angle PXRD analysis of the Fe3O4@MCM‐41@IL/Pd nanocatalyst
pyrimidine derivatives under green conditions (Table 1).
In order to optimize the conditions, the effect of different
parameters such as catalyst loading, solvent and tempera-
ture was investigated in the model reaction between
benzaldehyde, malononitrate and barbituric acid
(Table 1). As shown in Table 1, to study the effect of the
catalyst on the progress of the reaction, the model
reaction was carried out in the absence of the
Fe3O4@MCM‐41@IL/Pd at 40 °C under ultrasonic irradi-
ation (Table 1, entry 1). In this case, only a trace amount
of product was obtained after 40 min. In the next, differ-
ent amounts of catalyst were added and it was observed
that, by increasing the catalyst loading from 0.01 to
0.02 mol%, the conversion was increased and the best
result was obtained using 0.014 mol% of catalyst
(Table 1, entries 2–6). Also, the temperature effect was
investigated and the best conversion was resulted at
40 °C under ultrasonic irradiation (Table 1, entry 3). In
addition, various solvents such as CH3CN, EtOH, toluene
and H2O were also examined and the results were com-
pared with those under solvent‐free conditions. As
shown, in EtOH and H2O a moderate conversion resulted
(Table 1, entries 7, 8), whereas in toluene and acetonitrile
a low yield of product was obtained (Table 1, entries 9,
10). This may attributed to both better polarity and the
protic nature of EtOH and water. Interestingly, under

8 of 11
ABAEEZADEH ET AL.
TABLE 1 The effect of solvent, temperature and catalyst loading on the synthesis of pyrano[2,3‐d]pyrimidine derivativesa
Entry
Catalyst
Catalyst loading (mol %)
Temperature (°C)
Time (min)
Solvent
Yield (%)b
1
—
—
40
40
40
40
25
50
40
40
40
40
40
40
40
10
10
10
10
10
10
10
10
10
30
30
—
Trace
68
2
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41@IL/Pd
Fe3O4@MCM‐41
0.010
0.014
0.02
—
3
—
96
4
—
95
5
0.014
0.014
0.014
0.014
0.014
0.014
10 mg
10 mg
—
67
6
—
95
7
H2O
90
8
EtOH
Acetonitrile
Toluene
—
83
9
48
10
11
12
35
Trace
Trace
Fe3O4@MCM‐41@IL
—
aReaction conditions: benzaldehyde (1 mmol), malononitrile (1 mmol) and barbituric acid (1 mmol) under ultrasonic waves.
bIsolated yields.
solvent‐free media an excellent yield of desired product
was obtained under the same conditions as before
(Table 1, entry 3). The latter result may also be attributed
to the higher concentration of starting materials under
solvent‐free media compared with the solvent‐charged
ones. Accordingly, the use of 0.014 mol% of catalyst under
solvent‐free media at 40 °C using ultrasonic waves was
selected as the optimized conditions. To investigate the
neat effect of supported palladium species in the catalytic
process, in other studies the catalytic ability of Pd‐free
Fe3O4@MCM‐41 and Fe3O4@MCM‐41@IL was checked
and compared with that of the Fe3O4@MCM‐41@IL/Pd.
Interestingly, both Pd‐free nanocomposites delivered only
a trace amount of product (Table 1, entries 11 and 12).
This result successfully confirms that the reaction process
is actually catalyzed by the supported palladium species.
TABLE 2 Preparation of pyrano[2,3‐d]pyrimidine derivatives in the presence of Fe3O4@MCM‐41@IL/Pd nanocatalysa
Entry
Aldehyde
Time (min)
Yield (%)b
Melting point (°C) Found
Melting point (°C) Reported
1
2
3
4
5
6
7
C5H6CHO
10
25
10
10
20
20
15
96
90
94
92
88
90
93
222–224
244–245
228–230
256–258
230–232
268–271
226–230
224–225[62]
242–243[63]
225–226[63]
254–256[62]
226–227[63]
266–270[62]
228–230[64]
2,4(Cl)C6H5CHO
3‐NO2C6H5CHO
2‐NO2C6H5CHO
4‐MeC6H5CHO
4‐MeOC6H5CHO
4‐BrC6H5CHO
aReaction conditions: aldehyde (1 mmol), malononitrile (1 mmol), barbituric acid (1 mmol) and Fe3O4@MCM‐41@IL/Pd (0.014 mol%) at 40 °C under ultrasonic
waves.
bIsolated yield.

ABAEEZADEH ET AL.
9 of 11
Next, to consider the ability and generality of the
catalyst and optimized conditions, the efficiency of the
Fe3O4@MCM‐41@IL/Pd nanocatalyst was investigated
in the conversion of different aldehyde substrates for
the one‐pot synthesis of pyrano[2,3‐d]pyrimidine deriva-
tives (Table 2). As shown, both electron‐donating
aldehydes (such as 4‐methylbenzaldehyde and 4‐
methoxybenzaldehyde) and electron‐withdrawing alde-
hydes (such as 3‐nitrobenzaldehyde, 2‐nitrobenzaldehyde
and 2,4‐dichlorobenzaldehyde) were applied as substrates
and delivered corresponding pyrano[2,3‐d]pyrimidines
in high to excellent yield in relatively short times. This
confirms the high efficiency of the designed catalyst for
the preparation of a wide range of biologically useful
pyrano[2,3‐d]pyrimidines.
The study showed that the catalyst could be recovered
and reused at least 11 times while keeping its perfor-
mance (Table 3).
In the final study, the catalytic performance of our
designed catalyst was compared with some recently
reported heterogeneous catalysts in the synthesis of
pyrano[2,3‐d]pyrimidine derivatives (Table 4). For this,
the condensation between benzaldehyde, malononotrile
and barbituric acid was selected as the reaction model.
The results showed that the efficiency of the present
catalyst in terms of reaction temperature, reaction time
and especially recycling time was much better than that
in most previous systems.
The revocability and reusability of the catalyst were
also investigated. For this aim, the nucleophilic conden-
sation between benzaldehyde, malononitrile and
barbituric acid under optimized conditions was selected
as a model reaction. After each run, the catalyst was
removed using an external magnetic field and washed
with EtOH. Then, the recovered catalyst was reused in
the next run under the same conditions as the first one.
4 | CONCLUSION
In summary, a novel palladium‐containing magnetic
mesoporous silica (Fe3O4@MCM‐41@IL/pd) was pre-
pared and applied as an effective nanocatalyst in the syn-
thesis of biologically active pyrano[2,3‐d]pyrimidines.
The characterization techniques confirmed the high sta-
bility and good incorporation/immobilization of organic
and inorganic moieties into/onto the catalyst framework.
This nanocatalyst was applied under solvent‐free media
and delivered pyrano[2,3‐d]pyrimidine products in high
to excellent yield. The catalyst was magnetically recov-
ered and reused at least 11 times without a significant
decrease in efficiency. Other advantages of this catalytic
system were that reaction could be performed at moder-
ate temperature and very short times, the easy product
and catalyst separation and the high stability and durabil-
ity of the catalyst under the applied conditions. Other
applications of this catalyst in some organic transforma-
tions are under testing in our laboratory.
TABLE 3 Recoverability and reusability of the Fe3O4@MCM‐
41@IL/pd nanocatalyst under ultrasonic conditions
Run Time (min) Yield (%) Run Time (min) Yield (%)
1
2
3
4
5
6
10
10
10
10
10
12
96
94
95
95
94
92
7
12
14
14
14
18
18
90
92
90
90
88
86
8
9
10
11
12
TABLE 4 Comparison of catalytic activity of Fe3O4@MCM‐41@IL/pd nanocatalyst with several known catalysts in the synthesis of
pyrano[2,3‐d]pyrimidine derivatives
Entry
Catalyst
Conditions
Recovery time
Reference
[65]
1
2
3
4
5
6
L‐Proline
EtOH, 25 °C, 40 min
H2O, 25 °C, 35 min
—
5
[64]
[62]
[62]
[63]
Fe3O4@cellulose
DABCO (SO3H) (Cl2)
DABCO (SO3H)(HSO2)
SBA‐Pr‐SO3H
H2O, reflux, 10 min
3
H2O, 90 °C, 7 min
5
Solvent free, 140 °C, 15 min
Solvent free, 40 °C, 10 min
—
12
Fe3O4@MCM‐41@IL/pd
This work
Abbreviations: DABCO: 1,4‐diazabicyclo[2.2.2]octane.

10 of 11
ABAEEZADEH ET AL.
[24] J. Liu, Z. Zhao, P. Shao, F. Cui, Chem. Eng. J. 2015, 262, 854.
ACKNOWLEDGEMENTS
[25] H. Kefayati, M. Golshekan, S. Shariati, M. Bagheri, Chin. J.
Catal. 2015, 36, 572.
The authors thank the Yasouj University and the Iran
National Science Foundation for supporting this work.
[26] B. Karami, S. J. Hoseini, K. Eskandari, A. Ghasemi, H.
Nasrabadi, Catal. Sci. Tech. 2012, 2, 331.
ORCID
[27] T. Ogoshi, S. Kanai, S. Fujinami, T.‐a. Yamagishi, Y.
Nakamoto, J. Am. Chem. Soc. 2008, 130, 5022.
Dawood Elhamifar https://orcid.org/0000-0003-4889-9505
Meysam Norouzi https://orcid.org/0000-0002-0715-9968
[28] S. T. Fardood, A. Ramazani, S. Moradi, J. Sol‐Gel Sci. Technol.
2017, 82, 432.
[29] J. Kim, J. E. Lee, J. Lee, J. H. Yu, B. C. Kim, K. An, Y. Hwang,
C.‐H. Shin, J.‐G. Park, J. Kim, J. Am. Chem. Soc. 2006, 128, 688.
REFERENCES
[30] W. Zhao, J. Gu, L. Zhang, H. Chen, J. Shi, J. Am. Chem. Soc.
2005, 127, 8916.
[1] T. Cheng, D. Zhang, H. Li, G. Liu, Green Chem. 2014, 16, 3401.
[2] N. Azgomi, M. Mokhtary, J. Mol. Catal. A: Chem. 2015, 398, 58.
[31] F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Angew. Chem.
Int. Ed. 2006, 45, 3216.
[3] S. Kango, S. Kalia, A. Celli, J. Njuguna, Y. Habibi, R. Kumar,
Prog. Polym. Sci. 2013, 38, 1232.
[32] Y. Snoussi, S. Bastide, M. Abderrabba, M. M. Chehimi,
[4] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.‐M.
Basset, Chem. Rev. 2011, 111, 3036.
Ultrason. Sonochem. 2018, 41, 551.
[33] H. Kefayati, S. J. Bazargard, P. Vejdansefat, S. Shariati, A. M.
[5] M. B. Gawande, P. S. Branco, R. S. Varma, Chem. Soc. Rev.
2013, 42, 3371.
Kohankar, Dyes Pigm. 2016, 125, 309.
[34] M. Nikoorazm, F. Ghorbani, A. Ghorbani‐Choghamarani, Z.
Erfani, Phosphorus, Sulfur Silicon Relat. Elem. 2018.
[6] J.‐D. Qiu, M. Xiong, R.‐P. Liang, H.‐P. Peng, F. Liu, Biosens.
Bioelectron. 2009, 24, 2649.
[35] N. Saadatjoo, M. Golshekan, S. Shariati, H. Kefayati, P. Azizi,
[7] S. Wang, Y. Tan, D. Zhao, G. Liu, Biosens. Bioelectron. 2008, 23,
J. Mol. Catal. A: Chem. 2013, 377, 173.
1781.
[36] S. Rostamizadeh, M. Nojavan, R. Aryan, E. Isapoor, M. Azad,
[8] J. Safari, S. Gandomi‐Ravandi, Z. Haghighi, RSC Adv. 2016, 6,
J. Mol. Catal. A: Chem. 2013, 374‐375, 102.
31514.
[37] Y. Zhu, Y. Fang, S. Kaskel, J. Phys. Chem. C 2010, 114, 16382.
[9] M. B. Gawande, V. D. Bonifácio, R. S. Varma, I. D. Nogueira,
N. Bundaleski, C. A. A. Ghumman, O. M. Teodoro, P. S.
Branco, Green Chem. 2013, 15, 1226.
[38] M. Nikoorazm, F. Ghorbani, A. Ghorbani‐Choghamarani, Z.
Erfani, Appl. Organomet. Chem. 2018.
[10] M.‐C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293.
[39] R. Hajian, A. Ehsanikhah, Chem. Phys. Lett. 2018, 691, 146.
[11] S. Sun, C. B. Murray, D. Weller, L. Folks, A. Moser, Science
2000, 287, 1989.
[40] E. M. Grivsky, S. Lee, C. W. Sigel, D. S. Duch, C. A. Nichol,
J. Med. Chem. 1980, 23, 327.
[12] V. Skumryev, S. Stoyanov, Y. Zhang, G. Hadjipanayis, D.
[41] L. R. Bennett, C. J. Blankley, R. W. Fleming, R. D. Smith, D. K.
Givord, J. Nogués, Nature 2003, 423, 850.
Tessman, J. Med. Chem. 1981, 24, 382.
[13] J. Klostergaard, C. E. Seeney, Maturitas 2012, 73, 33.
[42] A. R. Bhat, R. S. Dongre, R. S. Selokar, Int. J. Pharm. Biosci.
2014, 5, 422.
[14] S. C. McBain, H. H. Yiu, J. Dobson, Int. J. Nanomed. 2008, 3,
169.
[43] A. Agarwal, N. Goyal, P. M. Chauhan, S. Gupta, Biorg. Med.
Chem. 2005, 13, 6678.
[15] L. Zhang, Y. Zhai, N. Gao, D. Wen, S. Dong, Electrochem.
Commun. 2008, 10, 1524.
[44] D. Elhamifar, B. Karimi, J. Rastegar, M. H. Banakar,
[16] A. K. Geim, K. S. Novoselov, Nat. Mater. 2007, 6, 183.
ChemCatChem 2013, 5, 2418.
[17] V. Georgakilas, A. B. Bourlinos, R. Zboril, T. A. Steriotis, P.
Dallas, A. K. Stubos, C. Trapalis, Chem. Commun. 2010, 46,
1766.
[45] D. Elhamifar, A. Shabani, Chem. – Eur. J. 2014, 20, 3212.
[46] D. Elhamifar, B. Karimi, A. Moradi, J. Rastegar,
ChemPlusChem 2014, 79, 1147.
[18] V. Georgakilas, M. Otyepka, A. B. Bourlinos, V. Chandra, N.
Kim, K. C. Kemp, P. Hobza, R. Zboril, K. S. Kim, Chem. Rev.
2012, 112, 6156.
[47] D. Elhamifar, M. Nasr‐Esfahani, B. Karimi, R. Moshkelgosha,
A. Shábani, ChemCatChem 2014, 6, 2593.
[48] D. Elhamifar, F. Hosseinpoor, B. Karimi, S. Hajati, Microporous
Mesoporous Mater. 2015, 204, 269.
[19] Q. Zhang, H. Su, J. Luo, Y. Wei, Green Chem. 2012, 14, 201.
[20] P. Riente, C. Mendoza, M. A. Pericás, J. Mater. Chem. 2011, 21,
[49] D. Elhamifar, F. Shojaeipoor, O. Yari, RSC Adv. 2016, 6, 58658.
7350.
[50] D. Elhamifar, S. Kazempoor, J. Mol. Catal. A: Chem. 2016, 415,
[21] S. Rostamizadeh, A. M. Amani, G. H. Mahdavinia, H.
74.
Sepehrian, S. Ebrahimi, Synthesis 2010, 2010, 1356.
[51] D. Elhamifar, P. Badin, G. Karimipoor, J. Colloid Interface Sci.
2017, 499, 120.
[22] P. Sivaguru, K. Parameswaran, M. Kiruthiga, P. Vadivel, A.
Lalitha, J Iranian Chem Soc 2015, 12, 95.
[23] L. M. Rossi, N. J. Costa, F. P. Silva, R. Wojcieszak, Green Chem.
2014, 16, 2906.
[52] D. Elhamifar, D. Elhamifar, F. Shojaeipoor, J. Mol. Catal. A:
Chem. 2017, 426, 198.

ABAEEZADEH ET AL.
11 of 11
[53] D. Elhamifar, O. Yari, B. Karimi, J. Colloid Interface Sci. 2017,
500, 212.
[62] N. Seyyedi, F. Shirini, M. S. N. Langarudi, RSC Adv. 2016, 6,
44630.
[54] M. Norouzi, D. Elhamifar, R. Mirbagheri, Microporous
Mesoporous Mater. 2019, 278, 251.
[63] G. M. Ziarani, S. Faramarzi, S. Asadi, A. Badiei, R. Bazl, M.
Amanlou, DARU J. Pharma. Sci. 2013, 21, 3.
[55] Z. Ramazani, D. Elhamifar, M. Norouzi, R. Mirbagheri,
[64] A. Maleki, A. A. Jafari, S. Yousefi, Carbohydr. Polym. 2017, 175,
Composites, Part B 2019, 164, 10.
409.
[56] R. Mirbagheri, D. Elhamifar, M. Norouzi, New J. Chem. 2018,
42, 10741.
[65] M. Bararjanian, S. Balalaie, B. Movassag, A. Amani, J. Iranian
Chem. Soc. 2009, 6, 436.
[57] D. Elhamifar, Z. Ramazani, M. Norouzi, R. Mirbagheri,
J. Colloid Interface Sci. 2018, 511, 392.
How to cite this article: Abaeezadeh S,
Elhamifar D, Norouzi M, Shaker M. Magnetic
nanoporous MCM‐41 supported ionic
liquid/palladium complex: An efficient
nanocatalyst with high recoverability. Appl
Organometal Chem. 2019;e4862. https://doi.org/
10.1002/aoc.4862
[58] M. Norouzi, D. Elhamifar, R. Mirbagheri, Z. Ramazani,
J. Taiwan Inst. Chem. Eng. 2018, 89, 234.
[59] M. Norouzi, D. Elhamifar, R. Mirbagheri, Polyhedron 2018, 154,
229.
[60] J. Dai, H. Zou, R. Wang, Y. Wang, Z. Shi, S. Qiu, Green Chem.
2017, 19, 1336.
[61] Z.‐M. Cui, Z. Chen, C.‐Y. Cao, L. Jiang, W.‐G. Song, Chem.
Commun. 2013, 49, 2332.