Ni ion-containing immobilized ionic liquid on magnetic Fe3O 4 nanoparticles: An effective catalyst for the Heck reaction

Article abstract of DOI:10.1016/j.crci.2013.03.018

In this work, we synthesized Ni²⁺-containing 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium chloride ionic liquid on magnetic Fe₃O₄ nanoparticles. The catalytic activity of these novel nanocomposites was finally evaluate

Full text of DOI:10.1016/j.crci.2013.03.018

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C. R. Chimie xxx (2013) xxx–xxx
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´
Full paper/Memoire
Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction
*
Javad Safari , Zohre Zarnegar
Laboratory of Organic Compound Research, Department of Organic Chemistry, College of Chemistry, University of Kashan, PO Box 87317-51167, Kashan, Islamic
Republic of Iran
A R T I C L E I N F O
A B S T R A C T
In this work, we synthesized Ni2+-containing 1-methyl-3-(3-trimethoxysilylpropyl)
imidazolium chloride ionic liquid on magnetic Fe3O4 nanoparticles. The catalytic activity
of these novel nanocomposites was finally evaluated for the Heck reaction at 100 8C, and
can be reused after washing without loss in activity. The immobilized ionic liquid catalysts
proved to be effective and easily separated from the reaction media by applying an
external magnetic field. This procedure has many obvious advantages compared to those
reported in the previous literature, including avoidance of the use of the expensive Pd
catalysts, mild reaction conditions, high yields, and simplicity of the methodology.
Article history:
Received 20 October 2012
Accepted after revision 28 March 2013
Available online xxx
Keywords:
Fe3O4
Magnetic nanoparticles
Heck reaction
Ionic liquid
´
ß 2013 Published by Elsevier Masson SAS on behalf of Academie des sciences.
Heterogeneous catalyst
1. Introduction
In fact, the choice of a suitable supporting material is an
important factor that may affect the performance of the
Since the discovery of the Heck reaction by Heck and
Misoroki in the early 1970s, it has been recognized as one
of the most important synthetic pathways to arylated
olefins, important components for agrochemicals, phar-
maceuticals, and cosmetics production [1–3]. In the Heck
coupling reaction, usually aryl halides react with alkenes in
the presence of palladium and of a suitable base in a single
step under mild conditions [1]. Palladium catalysts used in
the Heck reaction usually contain phosphorus ligands;
because of palladium they have several setbacks asso-
ciated with their air-sensitivity and rapid decomposition
[3]. Moreover, phosphine ligands are expensive and
difficult to prepare and this, coupled with the high cost
of palladium metal, limits their industrial appeal. To
circumvent these problems, significant research efforts are
currently directed towards the design of cheaper metal
sources than palladium and more stable catalysts [4,5].
Heck reaction [6]. Moreover, compared with supported
palladium catalysts, supported transition metal (Cu, Co, Ni)
catalysts for the Heck reaction are much less expensive [5].
Recently, several publications have appeared on the
development of an immobilized Ni ion catalyst in Heck
and Suzuki cross-coupling reactions [5,7,8].
Ionic liquid (IL) technology offers a new and environ-
mentally benign approach toward modern synthetic chem-
istry [9–12]. ILs have interesting advantages, such as
extremely low vapor pressure, excellent thermal stability,
reusability, and talent to dissolve many organic and
inorganic substrates [10–12]; nowadays, supported ILs
containing different metal particles or ions have been used
as catalysts in different reactions, such as the Heck reaction
[13,14], hydrogenation [15–17]. Sasaki et al. prepared a Ni
ion-containingIL salt and a Niion-containingimmobilized IL
on silica for the Suzuki reaction [7]. Han et al. synthesized a
Ni2+-containing IL immobilized on silica to catalyze styrene
oxidation with H2O2 for producing benzaldehyde [18].
Though ILs possessed such promising advantages, their
widespread practical application was still hampered by
several drawbacks:
* Corresponding author.
E-mail addresses: zohrehzarnegar@yahoo.com, Safari@kashanu.ac.ir
(J. Safari).
1631-0748/$ – see front matter ß 2013 Published by Elsevier Masson SAS on behalf of Acade´mie des sciences.
http://dx.doi.org/10.1016/j.crci.2013.03.018
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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Scheme 1. Heck reaction catalyzed by IL–Ni(II)–MNPs.
ꢀ
ꢀ
ꢀ
high viscosity, which resulted in only a minor part of
ionic liquids taking part in the catalyzed reaction;
homogeneous reaction, which was difficult for product
separation and catalyst recovery;
consequently, high cost for the use of relatively large
amounts of ILs [19,20].
Therefore, in order to solve these problems mentioned
earlier, an immobilized IL catalyst combining the advanta-
geous characteristics of ionic liquids, inorganic acids and
solid acids had been proposed [21,22].
Fig. 1. Compared FT-IR spectra of (a) magnetic nanoparticles (MNPs), (b)
IL–Ni(II)–MNPs.
During the past decades, advances in nanoscience and
nanotechnology have pushed forward the synthesis of
functional magnetic nanoparticles (MNPs), which is one of
the most active research areas in the field of advanced
materials. MNPs that have unique magnetic properties and
other functionalities have enabled a wide spectrum of
applications [23]. Iron oxide magnetic nanoparticles
(Fe3O4–MNPs) are approximately 20–30 nm in size and
contain a single magnetic domain with a single magnetic
moment and exhibit superparamagnetism [24]. Addition-
ally, recent studies show that MNPs are excellent supports
for catalysts [25,26]. The supported catalysts proved to be
effective and easily separated from the reaction media by
applying an external magnetic field.
could be recovered easily and reused many times without
significant loss of its catalytic activity.
2. Results and discussion
2.1. Characterization of the prepared IL–Ni(II)–MNPs
Scheme
2 shows the sequence of events in the
functionalization of MNPs with IL–Ni2+. In the first step,
magnetite nanoparticles of 18–20 nm were prepared by
the coprecipitation of iron(II) and iron(III) ions in an
alkaline solution at 85 8C using the method described by
Massart [27]. Then, 1-methyl-3-(3-trimethoxysilylpropyl)
imidazolium chloride (IL) was prepared from the reaction
In this paper, we synthesized a Ni2+-containing immo-
bilized IL on magnetite Fe3O4 nanoparticles and carried out
studies of its catalytic activity for the Heck coupling of aryl
halides and olefins (Scheme 1). The heterogeneous catalyst
Scheme 2. Preparation steps for fabricating IL–Ni(II)–functionalized magnetic Fe3O4 nanoparticles.
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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3
Fig. 2. SEM image of (a) magnetic nanoparticles (MNPs), (b) IL–Ni(II)–MNPs.
of N-methyl imidazole with (3-chloropropyl) trimethox-
ysilane at 80 8C [28]. Then, IL was added to an acetonitrile
solution of NiCl2 in a 250 mL round-bottom flask and
refluxed for 24 h; IL–Ni(II) was then obtained. In a second
step, the external surface of MNPs was coated with IL–
Ni(II) to obtain IL–Ni(II)–MNPs (Scheme 2).
Fig. 1 shows the Fourier transform infrared (FT-IR)
spectra of both the unfunctionalized and functionalized
MNPs. The Fe–O stretching vibration near 580 cmꢁ1, the O–
H stretching vibration near 3432 cmꢁ1, and the O–H
deformed vibration near 1625 cmꢁ1 were observed in both
Fig. 2(a) and (b). The significant features observed in
Fig. 1(b) are the appearance of the peaks at 1007 cmꢁ1 (Si–
O stretching), at 1612 cmꢁ1 (C5N stretching) and at
2800 cmꢁ1 (–CH2 stretching). A peak at about 3390 cmꢁ1
can be observed in Fig. 1(b), which indicates the formation
of an hydrogen bond (C–HꢂꢂꢂꢂCl interaction) that has been
observed in analogous compounds containing the 1-
methyl-3-methylimidazolium cation [MmIM]+ and
NiCl42ꢁ ([MmIM]2[NiCl4]) on the MNPs [18]. These results
provided evidence that IL–Ni+2 was successfully attached
to the surface of the Fe3O4 nanoparticles.
The SEM image shows that magnetite (Fe3O4) nano-
particles have a mean diameter of about 18 nm and a
nearly spherical shape (Fig. 2(a)). Fig. 2(b) shows that IL–
Ni(II)–MNPs particles are larger, with a smoother surface,
while silica is uniformly coated on them to form a silica
shell.
Fig. 3 presents the X-ray diffraction patterns of the
prepared MNPs and IL–Ni(II)–MNPs. The position and
relative intensities of all the peaks confirm well with
standard XRD pattern of Fe3O4 (JCPDS card No. 79-0417),
indicating the retention of the crystalline cubic spinel
structure of Fe3O4–MNPs. The XRD patterns of the particles
show six characteristic peaks of a cubic iron oxide phrase
(2u = 30.35, 35.95, 43.45, 53.70, 57.25, 62.88, 71.37, 74.46).
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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Fig. 5. Magnetization curves for the prepared magnetic nanoparticles
(MNPs) and IL–Ni(II)–MNPs at room temperature.
Fig. 3. XRD patterns of (a) magnetic nanoparticles (MNPs), (b) IL–Ni(II)–
MNPs.
displayed in Fig. 4. The EDS results indicated the presence
of Ni, Cl, Si, and Fe in the composites, which indicates that
the iron oxide nanoparticles have been coated by NiCl2.
According to the above analysis, it could be concluded that
IL–Ni(II)–MNPs have been successfully synthesized.
The magnetization curves of Fe3O4 nanoparticles and
IL–Ni(II)–MNPs are shown in Fig. 5. The room temperature
specific magnetization (M) versus applied magnetic field
(H) curves of the samples indicate a saturation magnetiza-
tion value (Ms) of 40.5 emu/g, lower than that of bare MNPs
(60.1 emu/g) due to the coated shell. In Fig. 5, we can also
see that both magnetization curves follow a Langevin
behavior over the applied magnetic field and that
coercivity (HC) could be ignored, which can be considered
as superparamagnetism [26].
These are related to their corresponding indices (2 2 0),
(3 1 1), (4 0 0), (3 3 1), (4 2 2), (3 3 3), (4 4 0) and (5 3 1),
respectively [26]. It is implied that the resultant nano-
particles are pure Fe3O4 with a spinel structure. The crystal
size of Fe3O4ꢂMNPs nanoparticles can be determined from
the XRD pattern by using the Debye–Scherrer equation
(Fig. 3(a)):
0:94
l
Dðh k lÞ ¼
b
cosu
where D(h k l) is the average crystalline diameter, 0.94 is
the Scherrer constant, is the X-ray wavelength, is the
is the Bragg
l
b
half-width of X-ray diffraction lines and
angle, in degree.
u
2.2. Evaluation of the catalytic activity of IL–Ni(II)–MNPs in
the Heck reaction
Here, the (3 1 1) peak of the highest intensity was
picked out to evaluate the particle diameter of the
nanoparticles. Fe3O4–MNPs were calculated to be 18 nm.
Fig. 3(b) depicts the XRD pattern of the prepared IL–Ni(II)–
MNPs, with the diffraction peaks of both NiCl2 (JCPDS card
No. 01-1143) and Fe3O4 (JCPDS card No. 79-0417).
The Heck reaction is one of the most important C–C
bond formation reactions in organic synthesis. A variety of
parameters, such as solvent, catalyst, base and tempera-
ture can influence the reactivity of the Heck coupling [29].
The benefits of N,N-dimethylformamide (DMF) as a solvent
or solvating ligands are well known [29,30]. In this study,
the IL–Ni(II)–MNPs were investigated as the catalysts in
the model Heck coupling reaction of iodobenzene, and
ethyl acrylate. This was performed in order to carry out the
To confirm the composition of the functionalized MNPs,
we considered the EDS spectrum of IL–Ni(II)–MNPs
Table 1
Optimizing the Heck reaction conditions in the presence different bases
and amounts of catalysta.
Entry
Catalyst (g)
Base
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
0.010
0.010
0.010
0.010
0.08
Na2CO3
NaOAc
K2CO3
Et3N
4
4
30
39
45
70
60
80
80
–
4
4
Et3N
4
0.012
0.014
–
Et3N
4
Et3N
4
Et3N
24
a
Iodobenzene (0.01 mol) ethyl acrylate (0.01 mol) and base (0.01 mol)
in N,N-dimethylformamide (DMF) as a solvent at 90 8C.
b
Fig. 4. EDS spectrum of IL–Ni(II)–MNPs.
Determined by GC using mesitylene as the internal standard.
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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5
Table 2
temperatures, even if the reaction time was prolonged,
only low yields were obtained, and that the higher the
temperature, the better is the yield. The efficiency of the
reaction is mainly affected by the amount of catalyst and
the temperature. As indicated in Table 2, the best results
have been obtained at 100 8C. This reaction can be
considered as very mild for the Heck reactions, even for
nickel catalysts.
Based on the above observations, we conducted the
same reactions using various aryl halide and olefins in the
presence of 0.012 g of IL–Ni(II)–MNPs under optimal
conditions. As expected, satisfactory results were
observed, and the results are summarized in Table 3. No
catalytic activity was observed within 4 h with bromo-
benzene, but after 8 h, a substrate conversion of 28% was
reported. However, some catalytic activity was observed in
the coupling reactions of chlorobenzene with methyl
acrylate, even after 10 h (conversion of 10%). This trend is
consistent with the increasing strength of carbon–halide
bonds from aryl iodide to aryl chloride [29] (Table 3,
Entries 1–3).
On the other hand, aryl iodides are better reaction
partners than bromides, which gave only poor conversions
(less than 30%), even after extended reaction times
(>24 h). Bases, such as Et3N are well suited, whereas
inorganic bases, such as K2CO3 or NaOAc result in poor
yields (Table 1, Entries 1–3).
The reusability is one of the important properties of
this catalyst. After completion of the reaction, the
catalyst was washed with DMF and acetone, dried and
used directly with fresh substrates under identical
conditions, without further purification. It was shown
Optimizing the Heck reaction conditions at different temperaturesa.
Entry
Temperature (8C)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
50
70
10
8
11
58
71
80
97
97
97
–
80
6
90
4
100
110
120
120
4
4
4
24
a
Iodobenzene (0.01 mol) ethyl acrylate (0.01 mol), Et3N (0.01 mol) and
0.012 gr IL–Ni(II)–MNPs in N,N-dimethylformamide (DMF) as the solvent.
b
Determined by GC using mesitylene as the internal standard.
Heck vinylation reaction in
a simple, efficient and
inexpensive way. So, initially, the reactions were per-
formed in DMF as a solvent with different bases at 90 8C in
the presence of IL–Ni(II)–MNPs as the catalyst. A variety of
bases, including Na2CO3, NaOAc, K2CO3 and Et3N, were
employed to improve the yield for the synthesis of ethyl
cinnamate. The results are presented in Table 1. An
excellent yield was found with base Et3N (Table 1, entry 4)
at 90 8C for 4 h. When the reaction was carried out in the
presence of the catalyst (0.012 g), it led to the desired
product in 80% yield in 4 h at 90 8C (Table 1, Entry 6). The
catalytic activity of IL–Ni(II)–MNPs was evident when no
product was obtained in the absence of the catalyst (Table
1, Entry 8).
In the following study, we examined the effect of
temperature on the reaction. We found out that, at lower
Table 3
Heck coupling reaction of aryl halide and olefins catalyzed by IL–Ni(II)–MNPsa.
Entry
Aryl halide
Olefins
Product
Time (h)
4
Yield (%)b
97
1
O
I
O
O
O
O
2
4
98
O
O
I
O
3
4
4
8
88
28
O
I
O
O
O
O
O
O
Br
O
5
10
10
O
Cl
O
O
O
a
Aryl halide (0.01 mol), olefin (0.01 mol) and Et3N (0.01 mol) in N,N-dimethylformamide (DMF) solvent at 100 8C.
Determined by GC using mesitylene as the internal standard.
b
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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3. Conclusions
Ni2+-containing ILs immobilized on the MNPs have
been synthesized and were used as a heterogeneous
catalyst for the Heck reaction. IL–Ni(II)–MNPs displayed
good catalytic activities under mild conditions towards
iodobenzene and bromobenzene with olefins. This method
offers several advantages, including high yield, short
reaction time, simple work-up procedure, easiness of
separation, and recyclability of the magnetic catalyst, as
well as its ability to tolerate a wide variety of substitutions
in the reagents.
Fig. 6. Recyclability of IL–Ni(II)–MNPs in the reaction of iodobenzene
(0.01 mol) ethyl acrylate (0.01 mol), Et3N (0.01 mol), with N,N-
dimethylformamide (DMF) as the solvent (GC yield).
4. Experimental method
High-purity chemical reagents were purchased from
Merck and Sigma. All the materials were of commercial
reagent grade. 1H NMR and 13C NMR spectra were recorded
with a Bruker DRX-400 spectrometer at 400 and 100 MHz,
respectively. FT-IR spectra were obtained with potassium
bromide pellets in the 400–4000 cmꢁ1 range with a
PerkinElmer 550 spectrometer. The element analyses (C,
H, N) were obtained with a Carlo Erba Model EA 1108
analyzer, and were carried out on a PerkinElmer 240c
analyzer. Nanostructures were characterized using a Hol-
land Philips Xpert X-ray powder diffraction (XRD) diffract-
that the catalyst could be reused for the next cycle
without any appreciable loss of its activity. Similarly,
reusability studies for the sequential reaction were also
carried out, and the catalyst was found to be reusable
for five cycles (Fig. 6). As observed in Fig. 7, the XRD
pattern of the recovered nanocatalyst was indexed
according to the magnetite phase (JCPDS card No. 01-
1143 for Fe3O4 and JCPDS card No. 75. 1609 for NiCl2),
and so, there is no considerable change in its magnetic
phase. Thus, the magnetite nanocatalyst is stable in the
Heck reaction.
In this simple and reliable protocol, we have reported
the synthesis of a new catalyst for the Heck reaction.
Additionally, the supported catalyst proved to be effective
and easily separated from the reaction media by applying
an external magnetic field. This heterogeneous catalyst
could be recovered easily and reused many times without
significant loss of its catalytic activity.
ometer (Cu K
speed of 28/min from 108 to 1008 (2
a
, radiation,
l
= 0.154056 nm), at a scanning
). Scanning electron
u
microscope (SEM) images were recorded with a FEI Quanta
200 SEM operated at 20 kV accelerating voltage. The
samples for SEM examination were prepared by spreading
a small drop containing nanoparticles onto a silicon wafer
and were dried almost completely in air at room tempera-
ture for 2 h, and then were transferred onto SEM conductive
tapes. The transferred samplewas coated witha thinlayerof
gold before measurement. Gas chromatography–mass
Fig. 7. XRD patterns of the recovered IL–Ni(II)–MNPs after four recoveries.
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

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7
spectroscopy (GC–MS) (Shimadzu + 17A, Ver 3) (column:
DB-5ms, control mode: split, injection: 260 8C) was used to
determine the yield of the Heck reactions.
for 60 min. The resulting suspension was mechanically
stirred, followed by the addition of a solution of ethanol
(95%, 100 mL) containing IL–Ni(II) (6 g) and concentrated
ammonia (28%, 1 mL). Stirring under Ar was continued
for 36 h. The modified magnetite nanoparticles were
magnetically separated and washed three times
with ethanol (95%, 50 mL) and dried under vacuum for
24 h.
4.1. Preparation of the magnetic Fe3O4 nanoparticles (MNPs)
Fe3O4–MNPs were prepared using the simple chemical
coprecipitation method described in the literature [26].
Typically, 20 mmol of FeCl3ꢂ6H2O and 10 mmol of
FeCl2ꢂ4H2O were dissolved in 75 mL of distilled water in
a three-necked round-bottom flask (250 mL) under Ar
atmosphere for 1 h. Thereafter, under rapid mechanical
stirring, 10 mL of NaOH (10 M) were added into the
solution within 30 min with vigorous mechanical stirring
and ultrasound treatment under continuous Ar atmo-
sphere bubbling. After being rapidly stirred for 1 h, the
resultant black dispersion was heated to 85 8C for 1 h. The
black precipitate formed was isolated by magnetic
decantation, exhaustively washed with double-distilled
water until neutrality, and further washed twice with
ethanol and dried at 60 8C under vacuum.
4.5. Heck arylations catalyzed by IL–Ni2+–MNPs
In
a typical Heck arylation reaction, iodobenzene
(0.01 mol), ethyl acrylate (0.01 mol) triethylamine
(0.01 mol) and DMF (20 mL) were added to the IL–
Ni(II)–MNPs (0.01 g was dissolved in 5 mL of DMF) in a
50-mL flask equipped with a heating arrangement and a
stirrer and the temperature was set at 100 8C. Samples
were drawn at regular intervals and analyzed by GC to
determine the percentage conversions. After the reaction
was completed, the catalyst was separated by an external
magnet.
4.2. Synthesis of 1- methyl -3-(3-trimethoxysilylpropyl)-1H-
imidazol-3-ium chloride (IL)
Acknowledgements
1-Methylimidazole (13.6 mL, 0.17 mol) and (3-chloro-
propyl) trimethoxysilane (31 mL, 0.17 mol) were refluxed at
80 8C for 3 days in the absence of any catalyst and solvent
underAratmosphere.The unreactedmaterialswerewashed
with diethyl ether (3 ꢃ 8 mL). The diethyl ether was
removed under reduced pressure at room temperature,
and then was heated under high vacuum, to yield a
yellowish viscous liquid. The isolated yield was 98% [28].
FT-IR (KBr, cmꢁ1): 1656, 1612, 1584. 1H NMR (400 MHz,
CDCl3): dH (ppm): 10.22 (broad, 1H, Are-H), 7.59 (1H, dd,
J = 7.89 and 2.86 Hz, Are-H), 7.26 (1H, dd, J = 7.89 and
2.79 Hz, Are-H), 4.06 (2H, t, J = 7.25 Hz, –NCH2), 3.86 (3H, s,
–NCH3), 3.30 (9H, s, OCH3), 1.74 (2H, tt, J = 7.14 Hz, –CH2),
0.37 (2H, t, J = 7.09 Hz, SiCH2). 13C NMR (100 MHz, CDCl3,
We gratefully acknowledge the financial support from
the Research Council of the University of Kashan through
Grant NO (159198/VI).
References
[1] M. Adeli, E. Mehdipour, M. Bavadi, J. Appl. Polym. Sci. 116 (2010)
2188.
[2] M. Adeli, Z. Zarnegar, R. Kabiri, J. Appl. Polym. Sci. 113 (2008)
2072.
[3] E.M. Skaa, A. Gnieweka, I. Pryjomska-Raya, A.M. Trzeciaka, H. Grabow-
skab, M. Zawadzkib, Appl. Catal. A: Gen. 393 (2011) 195.
[4] W.M. Motswainyana, M.O. Onani, S.O. Ojwach, B. Omondi, Inorg. Chim.
Acta 391 (2012) 93.
[5] Y. Yang, R. Zhou, S. Zhao, Q. Li, X. Zheng, J. Mol. Catal A: Chem. 192
(2003) 303.
[6] M. Vinoba, V. Selvaraj, M. Alagar, J Colloid Interface Sci. 322 (2008)
537.
TMS):
dC = 138.13, 123.34, 121.58, 58.53, 51.66, 36.51,
24.32, 18.2, 7.03. Anal. calcd.: C, 48.45; H, 8.39; N, 8.69.
Found: C, 48.35; H, 8.32; N, 8.79.
[7] C. Zhong, T. Sasaki, M. Tada, Y. Iwasawa, J. Catal. 242 (2006) 357.
[8] A. Houdayer, R. Schneider, D. Billaud, J. Ghanbaja, J. Lambert, Synthetic
Met. 151 (2005) 165.
[9] A.K. Burrell, R.E.D. Sesto, S.N. Baker, T.M. McCleskey, G.A. Baker, Green
Chem. 5 (2007) 449.
4.3. Synthesis of the Ni2+-containing IL
[10] R. Sheldon, Chem. Commun. 23 (2001) 2399.
[11] J.S. Wilkes, Green Chem. 4 (2002) 73.
[12] N. Jain, A. Kumar, S. Chauhan, S.M.S. Chauhan, Tetrahedron 61 (2005)
1015.
[13] K. Selvakumar, A. Zapf, M. Beller, Org. Lett. 4 (2002) 3031.
[14] B. Karimi, D. Enders, Org. Lett. 8 (2006) 1237.
[15] J. Dupont, G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner, S.R. Teixeira, J.
Am. Chem. Soc. 124 (2002) 4228.
[16] C.P. Mehnert, E.J. Mozeleski, R.A. Cook, Chem. Commun. 24 (2002)
3010.
[17] C.P. Mehnert, R.A. Cook, N.C. Dispenziere, M. Afework, J. Am. Chem. Soc.
124 (2002) 12932.
[18] G. Liu, M. Hou, J. Song, Z. Zhang, T. Wu, B. Han, J. Mol. Catal. A Chem. 316
(2010) 90.
[19] S. Sahoo, P. Kumar, F. Lefebvre, S.B. Halligudi, Appl. Catal. A 354 (2009)
17.
[20] L.L. Zhu, Y.H. Liu, J. Chen, Ind. Eng. Chem. Res. 48 (2009) 3261.
[21] W. Chen, Y.Y. Zhang, L.B. Zhu, J.B. Lan, R.G. Xie, J.S. You, J. Am. Chem. Soc.
129 (2007) 13879.
The Ni2+-containing IL was synthesized according to the
method reported by other authors [18]. In the experiment,
anhydrous NiCl2 (0.65 g, 0.05 mol), IL (3.23 g, 0.10 mol) and
anhydrous acetonitrile (100 mL) were added into a 250-mL
round-bottom flask; the mixture was refluxed at 363 K for
24 h under Ar atmosphere until a transparent blue solution
was obtained. After cooling down, acetonitrile was
evaporated under vacuum. A blue viscous liquid was
obtained after the solution had been washed by toluene,
which was dried under vacuum for 24 h to afford IL–Ni(II).
4.4. Modification of magnetic nanoparticles with IL–Ni2+ (IL–
Ni(II)–MNPs)
[22] J. Miao, H. Wan, G. Guan, Catal. Commun. 12 (2011) 353.
[23] A. Kong, P. Wang, H. Zhang, F. Yang, S.P. Huang, Y. Shan, Appl. Catal. A:
Gen. 417–418 (2012) 183.
Freshly prepared magnetite nanoparticles (2 g) were
suspended in ethanol (95%, 250 mL), and sonicated
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018

G Model
CRAS2C-3743; No. of Pages 8
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J. Safari, Z. Zarnegar / C. R. Chimie xxx (2013) xxx–xxx
[24] J. Zhu, J. He, X. Du, R. Lu, L. Huang, X. Ge, Appl. Surf. Sci. 257 (2011)
9056.
[28] A. Chrobok, S. Baj, W. Pudło, Andrzej Jarze bski, Appl. Catal. A: Gen. 366
(2009) 22.
[25] A. Hu, G.T. Yee, W. Lin, J. Am. Chem. Soc. 127 (2005) 12486.
[26] J. Safari, Z. Zarnegar, M. Heydarian, Bull. Chem. Soc. Jpn. 85 (2012),
http://dx.doi.org/10.1246/bcsj.20120209.
[29] W.H. Yang, C.S. Lee, S. Pal, Y.N. Chen, W.S. Hwang, I.J.B. Lin, J.C. Wang, J.
Organomet. Chem. 693 (2008) 3729.
[30] X. Gai, R. Grigg, M.I. Ramzan, V. Sridharan, S. Collard, J.E. Muir, Chem.
Commun. (2000) 2053.
[27] R. Massart, IEEE Trans. Magn. 17 (1981) 1247.
Please cite this article in press as: Safari J, Zarnegar Z. Ni ion-containing immobilized ionic liquid on magnetic Fe3O4
nanoparticles: An effective catalyst for the Heck reaction. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.03.018