A magnetic palladium nickel carbon nanocomposite as a heterogeneous catalyst for the synthesis of distyrylbenzene and biphenyl derivatives

Article abstract of DOI:10.1039/d1nj01762d

A magnetic palladium nickel carbon (Fe3O4@Pd@Ni/C) nanocomposite has been synthesized using a simple one-pot procedure via a hydrothermal approach. Ferric nitrate, palladium acetate, and nickel nitrate were dissolved in water together with glucose, and the mixture was heated in an autoclave. The Fe3O4@Pd@Ni/C nanocomposite was characterized via XRD, TEM, FE-SEM, VSM, EDS, and XPS studies. The catalytic abilities of the Fe3O4@Pd@Ni/C nanocomposite were investigated for the synthesis of distyrylbenzene and 9,10-distyrylanthracene derivatives. This method shows obvious advantages, such as the recyclability of the catalyst, simple experimental operation, and the obtaining of good to excellent yields.

Full text of DOI:10.1039/d1nj01762d

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A magnetic palladium nickel carbon nanocomposite
as a heterogeneous catalyst for the synthesis of
distyrylbenzene and biphenyl derivatives†
Cite this: New J. Chem., 2021,
45, 11697
Habiballah Shafie and Khodabakhsh Niknam
*
A magnetic palladium nickel carbon (Fe3O4@Pd@Ni/C) nanocomposite has been synthesized using a simple
one-pot procedure via a hydrothermal approach. Ferric nitrate, palladium acetate, and nickel nitrate were
dissolved in water together with glucose, and the mixture was heated in an autoclave. The Fe3O4@Pd@Ni/C
nanocomposite was characterized via XRD, TEM, FE-SEM, VSM, EDS, and XPS studies. The catalytic abilities
of the Fe3O4@Pd@Ni/C nanocomposite were investigated for the synthesis of distyrylbenzene and 9,10-
distyrylanthracene derivatives. This method shows obvious advantages, such as the recyclability of the
catalyst, simple experimental operation, and the obtaining of good to excellent yields.
Received 10th April 2021,
Accepted 2nd June 2021
DOI: 10.1039/d1nj01762d
rsc.li/njc
These reactions include the amination of phenols,27 the
deoxygenation and reductive homocoupling of phenols,28 the
Introduction
In recent years, the number of studies focusing on the conversion of protected phenols into olefins,29 and the reductive
development and synthesis of multi-metallic nanoparticles has amidation of aryl-triazine ethers.30
increased.1 Generally, they have been prepared for use as
Conjugated organic materials, those constructed from
catalysts due to their enhanced properties, such as physical p-conjugated molecules, have received increasing attention owing
and chemical stability, high selectivity for the target materials, to their potential applications in the field of optoelectronics.
and catalytic activity, when compared with equivalent catalysts Recently, 1,4-distyrylbenzene and 9,10-distyrylanthracene
based on single metals.1–8 Moreover, during preparation, they derivatives have received increased attention due to their
have been designed with capping agents to allow control of the organic-based photoluminescence, organic light-emitting diode
shape, size, and crystal structure.9–12 Among the various hybrid (OLED), fluorescence, and electroluminescence applications and
multi-metallic nanoparticles, those hybrids containing iron their photophysical properties.31–38
oxide (Fe3O4) have attracted much attention owing to their
Herein we report the preparation of the magnetic nano-
magnetic recoverability.1,6–9 Most prepared hybrid multi- composite Fe3O4@Pd@Ni/C (Scheme 1) as a new hetero-
metallic nanoparticles have been applied as catalysts in C–C geneous catalyst for the synthesis of 1,4-distyrylbenzene,
bond formation.1–8 The application of palladium species as 9,10-distyrylanthracene, and biphenyl derivatives.
catalysts in C–C coupling reactions is well known, and it has
received considerable attention in both industrial and academic
Experimental
research.13–18 Therefore, multi-metallic nanoparticles containing
palladium and iron oxide have attracted more attention due to General
the high catalytic performance of palladium and the magnetic
All reagents were purchased from the Merck and Aldrich Chemical
Companies. Reaction monitoring was accomplished using TLC
on silica gel (PolyGram SILG/UV254) plates. Melting points
recoverability of Fe3O4.19–25
Nickel is a metal that has been recently used as a catalyst in
C–C bond formation and organic transformations. In most of
these coupling or transformation reactions, 2,4,6-trichloro-
1,3,5-triazine (TCT) has been used as an efficient and
mild reagent accompanied by nickel-catalyzed species.25–30
Department of Chemistry, Faculty of Nano and Bio Science and Technology,
Persian Gulf University, Bushehr 75169, Iran. E-mail: niknam@pgu.ac.ir
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1nj01762d
Scheme 1 The preparation of the Fe3O4@Pd@Ni/C nanocomposite.
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were determined in open capillary tubes using Barnstead the catalyst was removed using an external magnet and was
Electrothermal 9100 BZ circulating oil melting point apparatus. washed with dichloromethane (3 ꢁ 5 mL). Having extracted the
The compounds were visualized using 1H-NMR (400 MHz) and reaction mixture from dichloromethane and water, the organic
13C NMR (100 MHz) spectroscopy, and spectra were recorded phase was dried over Na2SO4. The evaporation of the solvent gave
using a Bruker Avance instrument in CDCl3 or DMSO-d6 solvent the products. For further purification, the products were passed
with tetramethylsilane (TMS) as an internal standard. FT-IR through a short column of silica gel using n-hexane as the eluent.
spectroscopy (Shimadzu FT-IR 8300 spectrophotometer) was
[It is worth mentioning that in the case of 1,4-dihalobenzene
employed for the characterization of the products. X-ray (1 mmol), the following conditions were used: phenylboronic
diffraction (XRD) data were obtained using a Bruker D8 acid derivative (2.4 mmol) and Na2CO3 (2.5 mmol) in water
Advance Theta–2theta diffractometer. Energy dispersive X-ray (3 mL); Fe3O4@Pd@Ni/C catalyst (0.1 g, 4.38 mol% with respect
(EDX) spectroscopy (SiriusSD, England) was used for catalyst to the Pd content); oil bath at 80 1C].
analysis. All of the products are known compounds and were
1
characterized via H and 13C NMR spectra (see the ESI†) and
compared with the literature.1,32,33,36,39
Results and discussion
Preparation of palladium nickel ferrite (Fe3O4@Pd@Ni/C
nanocomposite)
Initially, the magnetic palladium nickel carbon (Fe3O4@Pd@
Ni/C) nanocomposite was prepared via the reaction of iron(III)
nitrate, palladium acetate, and nickel nitrate in deionized water
in the presence of glucose. The structure and physical and
chemical properties of the double salt were investigated using
FT-IR, EDS, XRD, XPS, SEM, and TEM methods.
Fe(NO3)3ꢀ9H2O solution (1 M, 2 equiv.), Pd(OAc)2 solution (1 M,
0.5 equiv.), and Ni(NO3)2ꢀ6H2O solution (1 M, 0.5 equiv.) were
dispersed in 10 mL of distilled water and added to a mixture
containing glucose solution (1 M). After being stirred for about
30 min, the mixture was transferred into a Teflon-lined
stainless-steel autoclave. The autoclave was maintained at
180 1C for 24 h and then naturally cooled to ambient temperature.
The precipitate was filtered, washed with water and ethanol, and
dried at 100 1C. Finally, the nanocomposite was obtained after
keeping the temperature at 250 1C for 3 h. The synthesized
Fe3O4@Pd@Ni/C nanocomposite was characterized using
different methods, including SEM, TEM, IR, XRD, EDS, and XPS.
FT-IR spectra of the prepared nanocomposite are presented
in Fig. 1. FT-IR analysis of the nanocomposite (Fe3O4@Pd@Ni/C)
shows characteristic peaks at around 449 cmꢂ1 and 576 cmꢂ1
,
which can be assigned to the presence of metal–oxide (FeꢂO and
Ni–O) vibrations. The FT-IR spectrum of the recovered nano-
composite showed no obvious changes in comparison with the
freshly synthesized catalyst (Fig. 1b).
The morphology of the nanocomposite (Fe3O4@Pd@Ni/C)
was investigated via SEM and TEM methods. SEM images
demonstrate that the obtained nanocomposite has a uniform
structure, and aggregate spheres are detected on the carbon
backbone (Fig. 2). TEM and high-resolution TEM images are
shown in Fig. 3. The TEM images clearly revealed the uniform
sphere-shaped morphology with an obvious lattice, and the
corresponding HR-TEM images also confirmed the crystallite size
of the synthesized nano-composite (PdNiFe3O4). The diameter of
the nano-magnetic (Fe3O4) core was around 388 nm and
TEM images of the catalyst show Pd and Ni nanoparticles with
near-spherical morphology, which were aggregated on the nano-
magnetic core. Also, the obtained histogram (Fig. 4) confirmed
General procedure for the synthesis of distyrylbenzenes
The Fe3O4@Pd@Ni/C catalyst (0.075 g, 3.29 mol% with respect
to the Pd content) was added to a mixture of aryl halide
(1 mmol), alkene (1.2 mmol), and Na2CO3 (2.5 mmol) in DMF
(3 mL), and this was heated in an oil bath at 120 1C. The
reaction was continuously followed via TLC to completion.
After completion, the catalyst was removed using an external
magnet and was washed with dichloromethane (3 ꢁ 5 mL).
Having extracted the reaction mixture from dichloromethane
and water, the organic phase was dried over Na2SO4. The
evaporation of the solvent gave the products. For further
purification, the products were passed through a short column
of silica gel using n-hexane as the eluent.
[It is worth mentioning that in the cases of 1,4-
dihalobenzene and 9,10-dibromonanthracene (1 mmol), the
following conditions were used: alkene (2.4 mmol) and Na2CO3
(2.5 mmol) in DMF (3 mL); Fe3O4@Pd@Ni/C catalyst (0.15 g,
6.58 mol% with respect to the Pd content); oil bath at 120 1C].
General procedure for the synthesis of biphenyls
The Fe3O4@Pd@Ni/C catalyst (0.05 g, 2.19 mol% with respect
to the Pd content) was added to a round-bottom flask (10 mL)
containing aryl halide (1 mmol), phenylboronic acid derivative
(1.2 mmol), and sodium carbonate (2.5 mmol) in water (3 mL),
and this was heated in an oil bath at 80 1C. The reaction was
continuously followed using TLC to completion. After completion,
Fig. 1 FT-IR spectra of the nanocomposite: (a) fresh Fe3O4@Pd@Ni/C and
(b) the catalyst after recovery.
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Fig. 2 SEM images of the nanocomposite (Fe3O4@Pd@Ni/C).
that the size distribution of the nanoparticles in this nano-
composite was narrow and normal, with average values between
80 and 90 nm.
The EDX pattern of the nanocomposite (Fe3O4@Pd@Ni/C) is
shown in Fig. 5. This analysis indicated the presence of the
constituent elements Pd, Fe, Ni, O, N, and C in the nanocomposite.
The C, Fe, Ni, and Pd content levels in Fe3O4@Pd@Ni/C were
determined to be 8.02%, 30.69%, 30.66%, and 12.38% (w/w),
respectively.
Fig. 4 A histogram showing the nanoparticle size distribution in the
nanocomposite.
The structure of the synthesized magnetic palladium nickel
carbon nanocomposite (Fe3O4@Pd@Ni/C) was studied via XRD
analysis.
Fig. 6 shows the XRD pattern of this nanocomposite. As can
be seen from the XRD spectrum of the nanocomposite, the
diffraction peaks at 2y values of 18.7, 30.4, 35.7, 43.4, 54.1, 57.6,
63.1, and 68.31 can be attributed to Fe3O4. Moreover, the
diffraction peaks at 2y values of 34.1, 37.5, and 60.31 correspond
to nickel. The diffraction peaks at 2y values of 40.4, 46.8, and
68.31 correspond to the Pd planes of the nanocomposite.1
Fig. 5 EDX spectra of (a) the fresh nanocomposite (Fe3O4@Pd@Ni/C) and
(b) the recovered material after eight cycles.
Through a comparison with the XRD patterns of the constituent
components (palladium, nickel oxide, and nickel ferrite), it is
indicated that the nanocomposite is made up of these elements.
Magnetic hysteresis measurements of Fe3O4@Pd@Ni/C were
done using an applied magnetic field at r.t., with the field being
Fig. 3 TEM (a) and HR-TEM (b) images of the nanocomposite
(Fe3O4@Pd@Ni/C).
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16.54%, 0.86%, 1.31%, and 1.77%, respectively (Fig. 8a). As
displayed in Fig. 8b, the peaks at 284.32 eV, 284.93 eV, 286.1 eV,
287.16 eV, and 288.8 eV can be attributed to carbon in C–C/
CQC, C–N, C–O, CQO, and O–CQO bonds, respectively.
In Fig. 8c, the peaks located at 399.10 eV, 399.95 eV, 400.89 eV,
and 401.76 eV can be assigned to nitrogen in N-pyridinic,
N-pyrrolic, N-graphitic, and N-oxidised forms, respectively.
The Pd XPS spectrum in Fig. 8d shows a double peak at binding
energies (BEs) of 335.34 and 340.78 eV, corresponding to Pd 3d5/2
and Pd 3d3/2, respectively. The BEs of the doublet for Pd 3d5/2 and
Pd 3d3/2 are characteristic of Pd(0). In addition, the double Pd 3d5/2
and Pd 3d3/2 peaks at 336.15 and 341.98 eV, and 337.16
and 342.88 eV correspond to PdO and Pd(OH)x, respectively.
The amounts of Pd(0), PdO, and Pd(OH)x are 2.23%, 2.18%, and
0.92%, respectively.
The Ni XPS spectrum shows 2p3/2 and 2p1/2 peaks at 855.6
and 872.98 eV, and 856.78 and 873.88 eV, as shown in Fig. 8e,
which are characteristic of Ni2+ and Ni3+, respectively. This
indicates that the Ni nanoparticles were oxidized owing to
exposure to air or under reaction conditions during the
preparation of the catalyst. Furthermore, Fig. 8f shows the
XPS signals from the Fe 2p region, which indicate that Fe2+
and Fe3+ formed Fe3O4. Fe 2p3/2 and Fe 2p1/2 peaks are seen at
710.23 and 723.28 eV, and 711.88 and 725.08 eV, and these
could be attributed to Fe2+ and Fe3+, respectively.
The ICP data show 4.67% w/w palladium in Fe3O4@Pd@Ni/
C. Because of the Pd content, the nanocomposite catalyst was
treated with concentrated HCl and HNO3 to digest the Pd
species, followed by ICP analysis. The Pd, Ni, and Fe content
levels in Fe3O4@Pd@Ni/C were determined to be 4.67%,
41.38%, and 35.14% w/w, respectively. Here, 0.075 g of catalyst
is used per 1 mmol of aryl-halide, which is equivalent to
0.0035 g of Pd metal, corresponding to 3.29 mol% catalyst
per 1 mmol of aryl-halide used.
After the preparation and characterization of the Fe3O4@Pd@
Ni/C nanocomposite, its catalytic activity was investigated for
C–C bond formation via the Heck reaction and Suzuki coupling
reaction.
Initially, the carbon–carbon coupling reaction between iodo-
benzene and ethyl acrylate was selected as a model reaction,
and the reaction time and yield were measured in the presence
of the Fe3O4@Pd@Ni/C nanocomposite while varying reaction
parameters such as the solvent, catalyst loading, base, and
reaction temperature (Scheme 2 and Table 1).
Fig. 6 Top panel: the XRD patterns of (a) fresh Fe3O4@Pd@Ni/C and (b)
the material after recovery. Bottom panel: the XRD peaks of the nano-
composite (Fe3O4@Pd@Ni/C) compared with the standard patterns of Pd,
NiO, and NiFe2O4.
swept from ꢂ15 000 to 15 000 Oersted. As shown in Fig. 7, these
nanoparticles exhibited superparamagnetic characteristics, as
the M (H) hysteresis loop for the sample was completely
reversible. The hysteresis loop reached saturation at the max-
imum applied magnetic field value. The magnetic saturation
value of the catalyst was 18 emu gꢂ1 at r.t.
X-ray photoelectron spectroscopy (XPS) analysis was carried
out to further measure the chemical composition of
Fe3O4@Pd@Ni/C. The survey spectrum of Fe3O4@Pd@Ni/C
displays that the nanocomposite consists of C, N, O, Pd, Ni,
and Fe elements, with atomic percentages of 72.78%, 6.74%,
As shown in Table 1, the model reaction was not accomplished
in the absence of catalyst, even after 24 h at 120 1C (Table 1,
entry 1).
The model reaction was carried out in the presence of
palladium acetate (0.01 g, 9 mol% Pd), and the corresponding
product was obtained in 84% yield after 12 h at 120 1C (Table 1,
entry 2).
The model reaction was carried out in the presence of nickel
nitrate and did not give any product (Table 1, entry 3). The best
results were achieved in the presence of the Fe3O4@Pd@Ni/C
nanocomposite (0.075 g, 3.29 mol% Pd) in DMF (3 mL) with
sodium carbonate (2.5 mmol) at 120 1C. Decreasing the amount
Fig. 7 The VSM spectrum of the nanocomposite (Fe3O4@Pd@Ni/C).
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Fig. 8 (a) The XPS survey spectrum of the Fe3O4@Pd@Ni/C nanocomposite, and high-resolution (b) C 1s, (c) N 1s, (d) Pd 3d, (e) Ni 2p, and (f) Fe 2p XPS
spectra.
The reaction was studied in the presence of the
Fe3O4@Pd@Ni/C nanocomposite in various solvents, such as
toluene, dioxane, water, acetonitrile, and dimethylacetamide
(DMA), and the reaction proceeded in DMF and DMA solvents
Scheme 2 The model reaction for Heck coupling.
(Table 1, entries 11–15).
Since 1,4-distyrylbenzenes and 9,10-distyrylanthracenes
have photoelectronic and fluorescence properties,1–6 [1–6], in
this study we have focused on the synthesis of series of these
compounds using the magnetic palladium nickel nanocomposite
as a new catalyst. For this purpose, we used the Heck reactions
shown in Schemes 3 and 4.
As shown in Schemes 5, 1,4-diiodobenzene (4) reacted with
ethyl acrylate or methyl acrylate (2) or styrene derivatives (5)
under the optimized conditions, and the corresponding
products (6a–6c and 7a–7c) were obtained with yields in the range
of 72–86%. Moreover, when 2,5-dimethyl-1,4-diiodobenzene and
of Fe3O4@Pd@Ni/C nanocomposite led to a decrease in the
product yield (Table 1, entries 4 and 5). The model reaction was
also carried out in the presence of other bases, including
K2CO3, Na3PO4, and Et3N in DMF at 120 1C, and Na2CO3 was
the best base for this reaction (Table 1, entries 4–10). In another
effort, the model reaction carried out at lower temperatures
with DMF as the solvent gave the corresponding product in
lower yield (Table 1, entry 16).
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Table 1 Optimization of the reaction conditionsa
Catalyst
loading (g)
Temp.
(1C)
Yieldb
Time (h) (%)
Entry Solvent
Base
1
2
3
4
5
6
7
8
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Na2CO3
—
120
120
24
12
12
8
8
8
8
8
8
8
0
84
0
Na2CO3 0.01 (9 mol%)c
Na2CO3 0.01 (1.1 mol%)d 120
Na2CO3 0.025
Na2CO3 0.05
Na2CO3 0.075
Na2CO3 0.1
K2CO3 0.075
Na3PO4 0.075
Et3N
Na2CO3 0.075
Na2CO3 0.075
120
120
120
120
120
120
120
Reflux 8
Reflux 8
Reflux 8
Reflux 8
70
83
90
90
85
85
54
25
Trace
41
10
90
56
91
Scheme 4 The synthesis of 9,10-distyrylanthracenes in the presence of
Fe3O4@Pd@Ni/C as a catalyst.
9
DMF
DMF
10
11
12
13
14
15
16
17
0.075
Toluene
Dioxane
Acetonitrile Na2CO3 0.075
Water
DMA
DMF
DMF
Na2CO3 0.075
Na2CO3 0.075
Na2CO3 0.075
Na2CO3 0.075
120
80
140
8
8
8
a
Reaction conditions: iodobenzene (1 mmol), ethyl acrylate (1.2 mmol),
b
c
and base (2.5 mmol) in solvent (3 mL). Isolated yield. Pd(OAc)2 was
used as the catalyst. Ni(NO3)2 was used as the catalyst.
d
2,5-dimethoxy-1,4-diiodobenzene as ortho-substituted aryl halides
reacted with ethyl acrylate or styrene, the corresponding product 6c
or 7c was obtained in 83% yield after 8 h or 71% yield after 12 h,
respectively. In addition, when 1,4-dibromobenzene was used as
the aryl halide, it gave the corresponding products after longer
reaction times (24 h) and in lower yields (46–62% yields). Also, 1,4-
dichlorobenzene was treated with ethyl acrylate (2) under optimized
conditions, but after 36 h this gave only a trace of the product.
Subsequently, 9,10-dibromoanthracene (8) was reacted with
ethyl acrylate (2) and styrene derivatives (5) under the opti-
mized conditions, giving the corresponding products 9 and
10a–10c, respectively, in good to excellent yields (Scheme 6).
Encouraged by the obtained results from the Heck reaction,
we also investigated the potential of our Fe3O4@Pd@Ni/C
catalyst for use in the Suzuki cross-coupling reaction. First, a
coupling reaction between 4-iodoanisole and phenylboronic
acid was chosen as a model reaction (Scheme 7). Due to
environmental concerns, the reaction was only carried out with
water as the solvent and sodium carbonate as the base. Next, we
examined the effect of catalyst loading on the yield of the
coupling product. Based on the results, the optimized conditions
were chosen as follows: water (3 mL) as the solvent; Na2CO3
(2.5 mmol) as the base; a catalyst loading of 0.05 g (2.19 mol%
Scheme 5 The synthesis of distyrylbenzenes in the presence of
Fe3O4@Pd@Ni/C as a catalyst.
based on the Pd content); and heating at 80 1C. 4-Methoxy-
biphenyl was obtained as the corresponding product (13) after 80
min and in 91% yield. Using lower catalyst amounts gave longer
reaction times and lower yields.
Again, in this study, we focused on the reaction of 1,4-
diiodobenzene with phenylboronic acid derivatives under the
optimized conditions, and the obtained results are summarized
in Scheme 8. 1,4-Diiodobenzene reacted with aryl boronic
acids, including phenyl, 3-methyl-phenyl, 2-methyl-phenyl,
Scheme 3 The synthesis of distyrylbenzenes in the presence of
Scheme 6 The synthesis of 9,10-distyrylanthracenes in the presence of
Fe3O4@Pd@Ni/C as a catalyst.
Fe3O4@Pd@Ni/C as a catalyst.
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Scheme 7 The model reaction for Suzuki coupling.
Fig. 11 Yields after the recovery of the Fe3O4@Pd@Ni/C nanocomposite
in the reaction between 4-iodoanisol and phenyl boronic acid under the
optimized conditions (product 13).
Table 2 A comparison of Fe3O4@Pd@Ni/C with other reported reagents
and catalysts
Time Yield
Compound Catalyst and conditions
(h)
(%) Ref.
7b
7b
Pd(OAc)2, 130 1C in NMP
15
71
75
75
87
73
85
65
86
35
Fe3O4@Pd@Ni/C, 120 1C in DMF 12
Wittig method
Fe3O4@Pd@Ni/C, 120 1C in DMF 8
Pd(OAc)2, 140 1C in DMA
Fe3O4@Pd@Ni/C, 120 1C in DMF 8
Wittig method
Fe3O4@Pd@Ni/C, 120 1C in DMF 8
This work
36
This work
32
This work
36
This work
10a
10a
10b
10b
10c
10c
5
24
Scheme 8 The synthesis of biphenyl derivatives.
5
4-fluorophenyl, and 1-naphthyl examples, under the optimized
conditions in the presence of the Fe3O4@Pd@Ni/C nano-
composite, giving the corresponding products (14a–14e) in
good to excellent yields (Scheme 8). It worth mentioning
that when 4-methoxyphenyl boronic acid was treated with
1,4-diiodobenzene under the optimized conditions for
90 min, 4-iodo-40-methoxy-1,10-biphenyl (15) was obtained as
the major product (87% yield).
Finally, the recycling of the catalyst was examined after the
synthesis of compounds 3 and 13. After the completion of the
reactions, the catalyst was removed using an external magnet
(Fig. 9).
The obtained catalyst was washed with dichloromethane.
The recovered catalyst was successfully reused several times
without a significant loss of catalytic activity (Fig. 10 and 11).
To investigate the stability of the recovered catalyst, its
structure was studied using methods such as IR, EDX, and
XRD. The IR, EDX, and XRD spectra of the recovered nano-
composite showed no obvious changes in comparison with the
freshly synthesized catalyst (Fig. 1b, 5b and 6b).
Fig. 9 Images of (a) fresh catalyst powder, (b) the reaction mixture, and (c)
the recovery of the catalyst using an external magnet.
Finally, as shown in Table 2, the advantages and applicability
of the Fe3O4@Pd@Ni/C catalyst in the Heck reaction were
compared with other reported catalysts and reagents.
Conclusions
In summary, the hydrothermal preparation of a nanocomposite
(Fe3O4@Pd@Ni/C) was reported. The catalyst was characterized,
and it showed efficient abilities to catalyze the Heck and Suzuki
Fig. 10 Yields after the recovery of the Fe3O4@Pd@Ni/C nanocomposite
in the reaction between iodobenzene and ethyl acetoacetate under the
optimized conditions (product 3).
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14 B. Yuan, Y. Pan, Y. Li, B. Yin and H. Jiang, Angew. Chem., Int.
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vatives were prepared in the presence of the Fe3O4@Pd@Ni/C
nanocomposite as a recyclable catalyst in good to excellent
yields. The presented methodology is simple to operate, has
reasonable reaction times, involves a recoverable catalyst,
generates high yields, has an easy work-up procedure (using an
external magnet), and uses aqueous media and environmentally
benign mild reaction conditions for Suzuki reactions.
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21 S. Lee, W. Zhang, M. H. So, C. M. Che, R. Wang and R. Chen,
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We would like to thank the Iran National Science Foundation,
INSF, for financial support of this work via Proposal No.
95826900. The authors also acknowledge the Persian Gulf
University Research Council of Iran.
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