Fe3O4@SiO2@ l -arginine@Pd(0): A new magnetically retrievable heterogeneous nanocatalyst with high efficiency for C-C bond formation

Article abstract of DOI:10.1002/aoc.3424

The surface of Fe₃O₄@SiO₂ nanoparticles was modified using l-arginine as a green and available amino acid to trap palladium nanoparticles through a strong interaction between the metal nanoparticles and functional groups of the amino acid. The proposed green synthetic method takes advantage of nontoxic reagents through a simple procedure. Characterization of Fe₃O₄@SiO₂@l-arginine@Pd(0) was done using Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, vibrating sample magnetometry and inductively coupled plasma analysis. The catalytic activity of Fe₃O₄@SiO₂@l-arginine@Pd(0) as a new nanocatalyst was investigated in C-C coupling reactions. Waste-free, use of green medium, efficient synthesis leading to high yield of products, eco-friendly and economic catalyst, excellent reusability of the nanocatalyst and short reaction time are the main advantages of the method presented.

Full text of DOI:10.1002/aoc.3424

Full paper
Received: 3 November 2015
Revised: 23 November 2015
Accepted: 4 December 2015
Published online in Wiley Online Library: 9 February 2016
(wileyonlinelibrary.com) DOI 10.1002/aoc.3424
Fe O @SiO @L-arginine@Pd(0): a new
3
4
2
magnetically retrievable heterogeneous
nanocatalyst with high efficiency for C–C
bond formation
Arash Ghorbani-Choghamarani* and Gouhar Azadi
3 4 2
The surface of Fe O @SiO nanoparticles was modified using L-arginine as a green and available amino acid to trap palladium
nanoparticles through a strong interaction between the metal nanoparticles and functional groups of the amino acid. The pro-
posed green synthetic method takes advantage of nontoxic reagents through a simple procedure. Characterization of
Fe
electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, vibrating sample magnetometry and inductively
coupled plasma analysis. The catalytic activity of Fe @SiO @L-arginine@Pd(0) as a new nanocatalyst was investigated in C–C
3 4 2
O @SiO @L-arginine@Pd(0) was done using Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning
O
3 4
2
coupling reactions. Waste-free, use of green medium, efficient synthesis leading to high yield of products, eco-friendly and eco-
nomic catalyst, excellent reusability of the nanocatalyst and short reaction time are the main advantages of the method pre-
sented. Copyright © 2016 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: C–C bond formation; Fe O @SiO @L-arginine@Pd(0); retrievable
3
4
2
Importantly, magnetic separation of the magnetic nanoparticles
is more effective than filtration or centrifugation, easy, economi-
cal and promising for industrial applications. Supported metal
nanoparticles play a vital role in a wide range of applications,
particularly in the scope of catalysis. Among the various metal
nanoparticles, platinum group metals are used most extensively
Introduction
[11]
To design novel catalysts with high activity, selectivity and resistance
to deactivation is one of the long-term goals for research scientists.
In chemistry, a heterogeneous catalyst refers to the form and phase
of the catalyst differing from those of the reactants. The great major-
ity of practical heterogeneous catalysts are solids. Among a number
of advantages of heterogeneous catalysts can be listed ease of
[
1]
as catalysts for
hydrogenation,
a
great many industrial applications in
[
12]
[13]
[14]
hydroformylation,
carbonylation,
and so
[2]
on. Over the past few decades, palladium nanoparticles have also
been applied as useful catalysts for C–C coupling reactions like
Suzuki–Miyaura coupling reactions on account of the economic
handling and recyclability.
Fabrication of nanoparticles with desired properties through
modification of their surfaces has attracted growing attention in re-
cent years. There is an increasing interest in the synthesis, charac-
terization and surface modification of magnetic nanoparticles
because of their potential applications in biotechnology, biomedi-
[15]
benefits. Loading palladium active species onto solid materials
develops a cost-effective and green route for the wide applications
of palladium-based catalysts in the areas of cross-coupling reactions.
Carbon–carbon bond forming reactions such as the Suzuki–Miyaura
cross-coupling reaction represent some of the most important
transformations in organic synthesis, which are of great significance
in the fields of agrochemicals, functional materials and pharmaceu-
ticals. With the fast development of palladium-based catalysts,
Suzuki–Miyaura reactions now can be carried out under rather mild
[
3–6]
cine, environmental chemistry, material science and catalysis.
Magnetic nanoparticles are efficient, readily available and have
high surface area resulting in high catalyst loading capacity and
outstanding stability as heterogeneous supports for catalysts. They
show the same and sometimes even higher activity than their
[
7–9]
corresponding homogeneous analogues.
Therefore, combining
[16–18]
conditions with great proficiency and selectivity.
the attractive properties of nanotechnology with the above
mentioned advantages of heterogeneous catalysts increases the
importance of these catalysts.
3 4
Magnetic nanoparticles especially Fe O coated with silica
(
Fe @SiO ) are emerging as interesting supports for the immobi-
O
3 4
2
* Correspondence to: Arash Ghorbani-Choghamarani, Department of Chemistry,
Faculty of Science, Ilam University, PO Box 69315516, Ilam, Iran. E-mail:
arashghch58@yahoo.com or a.ghorbani@mail.ilam.ac.ir
lization of homogeneous catalysts. Different from many traditional
porous supports, nonporous magnetic nanoparticles induce the
distribution of catalytically active sites throughout the outer
Department of Chemistry, Faculty of Science, Ilam University, PO Box 69315516,
Ilam, Iran
[
10]
surface; thus, the pore diffusion constraint is practically avoided.
Appl. Organometal. Chem. 2016, 30, 247–252
Copyright © 2016 John Wiley & Sons, Ltd.

A. Ghorbani-Choghamarani and G. Azadi
For the reasons mentioned above, in this paper we report the
synthesis of a novel magnetic Fe /silica nanoparticle-supported
palladium (Fe @SiO @L-arginine@Pd(0)) catalyst for the first time
and evaluate the catalytic activity of the prepared catalyst. The
Suzuki–Miyaura coupling reaction was employed as a model
reaction.
Preparation of Fe
3 4 2
O @SiO
3 4
O
Fe was readily synthesized using a chemical co-precipitation
3 4
O
O
3 4
2
[
22]
method similar to a previously reported one,
followed by a
was
SiO -coating procedure. Briefly, 2.00 g of the obtained Fe O
2
3 4
dispersed in a mixture of 50 mL of ethanol, 20 mL of deionized
water and 10.0 mL of concentrated aqueous ammonia solution,
followed by the addition of 3.36 g of PEG and 2 mL of
tetraethylorthosilicate (TEOS). This solution was stirred mechani-
cally for 38 h at room temperature. Then the product, Fe O @SiO ,
Experimental
3
4
2
was separated using an external magnet, washed with deionized
water and ethanol three times and dried at room temperature.
Materials
All reactants were purchased from Merck Chemical Company and
Aldrich and used without further purification. Fourier transform
infrared (FT-IR) spectra were recorded as KBr pellets using a Bruker
VRTEX 70 model FT-IR spectrophotometer. Powder X-ray diffraction
Preparation of Fe
3
O
4
@SiO
2
@L-arginine@Pd(0)
In the second step, Fe
3
O
4
@SiO @L-arginine nanocatalyst was synthe-
2
(XRD) patterns were collected with a Rigaku-Dmax 2500 diffractom-
sized using the following procedure. An amount of 1 g of Fe @SiO
2
3
O
4
eter with nickel filtered Cu Kα radiation (λ = 1.5418 Å, 40 kV).
Supermagnetic properties of the catalyst were measured with a
vibrating sample magnetometer (MDKFD) operating at room
temperature. Thermogravimetric analysis (TGA) was carried out
with a Shimadzu DTG-60 instrument.
was suspended in deionized water (20 mL) and sonicated until it
became highly dispersed. Then, 2 g of L-arginine was added and
the mixture stirred at 90 °C for 15 h. Fe O @SiO @L-arginine nanopar-
3 4 2
ticles were separated from the aqueous solution by applying an
external magnet, washed with distilled water several times and then
dried in an oven overnight. The whole synthesis was done under
nitrogen atmosphere. In the last step, incorporation of palladium
General procedure for C–C coupling reaction of aryl halides
onto the Fe
by mixing the Fe
in absolute ethanol (30 mL). The mixture was refluxed for 24 h. Pd
II) ions were adsorbed onto the magnetic nanocarrier and reduced
by NaBH to produce Fe @SiO @L-arginine@Pd(0). Finally, the syn-
thesized Fe @SiO @L-arginine@Pd(0) nanosolid as a black powder
was separated from the suspension using magnetic decantation,
washed with absolute ethanol and dried under vacuum at room
temperature (1).
3
O
4
@SiO
2
@L-arginine nanocomposite was carried out
with NaBPh
4
3 4
O @SiO
2
@L-arginine (0.5 g) and Pd(OAc) (0.25 g)
2
A mixture of aryl halide (1 mmol), sodium tetraphenylborate (NaPh
4
B;
@L-arginine@Pd(0) (5 mg,
.4 mmol% Pd) and poly(ethylene glycol) (PEG; 1 mL) as solvent
(
0
1
2 3 3 4 2
.5 mmol), Na CO (3 mmol), Fe O @SiO
4
3
O
4
2
3
O
4
2
was added to a 10 mL pressure-safe vial and stirred at 100 °C. After
completion of the reaction (monitored using TLC), the catalyst was
removed using an external magnet. The reaction mixture was diluted
with water and the resultant mixture extracted with diethyl ether to
isolate the products. The combined organic layers were dried over
anhydrous Na
pressure.
2
SO
4
, and the solvent was evaporated under reduced
Catalyst characterization
The surface structure of the materials was confirmed using FT-IR
spectroscopy. As shown in Fig. 1, the presence of vibration bands
À1
at 559–588 and 3400 cm , which are due to Fe–O and OH, respec-
General procedure for C–C coupling reaction of aryl halides
with phenylboronic acid
tively, demonstrates the existence of Fe
the synthesized materials. The sharp band at 1090 cm is due to
O
3 4
components in all of
À1
A mixture of aryl halide (1 mmol), phenylboronic acid (1 mmol),
2 3 3 4 2
Na CO (3 mmol), Fe O @SiO @L-arginine@Pd(0) (5 mg, 1.4 mmol
%
Pd)) and PEG (1 mL) as solvent was added to a 10 mL pressure-
safe vial and stirred at 100 °C. The reaction mixture was stirred for
an appropriate time. After completion of the reaction (monitored
using TLC), the catalyst was separated by applying an external mag-
net. The reaction mixture was diluted with water and the resultant
mixture extracted with ethyl acetate to isolate the products. The
combined organic layers were dried over anhydrous Na
2 4
SO , and
the solvent was evaporated under reduced pressure.
Results and discussion
Continuing our work on functionalizing magnetic nanoparticles with
[19–21]
various derivatives for catalysis applications,
in the research
reported here we decided to demonstrate the preparation of a novel
magnetic nanoparticle by anchoring L-arginine on the surface of
silica-coated iron oxide nanoparticles (Fe
Then treatment of Fe @SiO @L-arginine with Pd(OAc)
Fe @SiO @L-arginine@Pd(0).
3
O
4
@SiO
2
@L-arginine).
3 4
O
2
2
provides
3 4
O
2
3 4 2
Scheme 1. General route for the fabrication of Fe O @SiO @L-arginine@Pd(0).
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2016, 30, 247–252

Pd(0) supported on Fe O @SiO @L-arginine-catalysed Suzuki reaction
3
4
2
of bound water. As the TGA curve of the prepared nanocatalyst
shows, the organic parts are decomposed completely at 385 °C.
Figure 3 shows SEM images and energy-dispersive X-ray spec-
troscopy (EDS) pattern of the nanocatalyst. It can be seen that
3 4 2
Fe O @SiO @L-arginine@Pd(0) particles are spherical in shape with
slight agglomeration. The presence of Si, O and Fe signals in the
EDS pattern in Fig. 3 confirms that the iron oxide particles are
loaded into silica, and the higher intensity of Si peak compared with
Fe peaks shows Fe O nanoparticles are trapped by SiO . The EDS
3
4
2
analysis results confirm the elemental composition of the nanopar-
ticles and the existence of Pd in the prepared nanocatalyst. The
exact amount of Pd of Fe O @SiO @L-arginine@Pd(0) is found to
3
4
2
À3
À1
be 2.82 × 10 mol g , which was determined using inductively
coupled plasma optical emission spectrometry.
The magnetic properties were characterized using vibrating
sample magnetometry. The magnetization curve is shown in Fig. 4.
The saturation magnetization of Fe O @SiO @L-arginine@Pd(0) is
3
4
2
À1
found to be ca 29 emu g , which is lower than that of bare
Fe O magnetic nanoparticles (67.22 emu g ).
À1 [25]
These results
3
4
indicate that the magnetization of Fe O decreases considerably
3
4
when coated with SiO and then Pd nanoparticles. Nevertheless,
2
the catalyst can still be separated from solution using an external
magnetic field.
The high-angle XRD pattern of the Fe O @SiO @L-arginine@Pd(0)
3 4 2
nanocomposite is shown in Fig. 5. This result means that the
nanocomposite has been successfully synthesized without dam-
Figure 1. Comparison FT-IR spectra of (a) Fe
3 4 2 3 4 2
O @SiO , (b) Fe O @SiO @L-
arginine and (c) Fe @SiO @L-arginine@Pd(0).
O
3 4
2
aging the crystal structure of the Fe
3 4
O core. The broad peaks
from 18° to 24° cover the area ascribed to amorphous silica.
Si–O–Si antisymmetric stretching vibration, being characteristic of
[
23]
the presence of a SiO
2
layer surrounding each Fe
O
3 4
nanoparticle.
À1
The peak at around 2856–2924 cm corresponds to aliphatic C–H
stretching of methylene groups, which is observable in the spectra
of the samples. According to Zhang et al. the wavenumber
À
À
separation, D, between the νas(COO ) and ν
s
(COO ) FT-IR bands
can be used to distinguish the type of the interaction between the
[
24]
carboxylate head and the metal atom.
1
In this study, D (1570–
À1
409 = 161 cm ) is ascribed to bridging bidentate. FT-IR spectra
3 4 2
show no major changes in the Fe O @SiO @L-arginine@Pd(0) (Fig. 1,
curve (c)) vibration bands, only a slight difference in intensity of
À1
bands in the 1400–1600 cm range can be noticed. Generally,
these observations indicate the immobilization of L-arginine on the
3 4 2
surface of Fe O @SiO .
3 4 2
The thermal stability of Fe O @SiO @L-arginine@Pd(0) nanoparti-
cles was investigated using TGA. The thermogram is presented in
Fig. 2. The weight loss below 200 °C is attributed to the removal
3 4 2
Figure 2. TGA curve of Fe O @SiO @L-arginine@Pd(0).
3 4 2
Figure 3. SEM images and EDS pattern of Fe O @SiO @L-arginine@Pd(0).
Appl. Organometal. Chem. 2016, 30, 247–252
Copyright © 2016 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

A. Ghorbani-Choghamarani and G. Azadi
Table 1. Optimization of base and solvent for synthesis of 4-
a
3 4 2
nitrobiphenyl catalysed by Fe O @SiO @L-arginine@Pd(0)
Entry
Solvent
Base
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
DMSO
EtOH
Na
Na
Na
Na
Na
2
2
2
2
2
CO
CO
CO
CO
CO
3
50
50
50
50
50
50
50
50
No reaction
No reaction
Trace
3
2
H O
3
Dioxane
PEG
3
No reaction
98
3
PEG
NaHCO
NaOH
Et
3
98
PEG
No reaction
No reaction
PEG
3
N
a
Reaction conditions: 1-bromo-4-nitrobenzene (1 mmol), NaBPh
0.5 mmol), base (3 mmol), Fe @SiO @L-arginine@Pd(0) (5 mg,
.4 mmol% Pd), solvent (1 mL) at 100 °C.
4
(
1
O
3 4
2
3 4 2
Figure 4. Vibrating sample magnetometry cure of Fe O @SiO @L-
arginine@Pd(0).
Table 2. Synthesis of biphenyl in the presence of various amounts of
a
catalyst at 100 °C
Entry
Catalyst (mg)
Time (min)
Yield (%)
1
2
3
4
5
0 (0 mmol%)
10
10
10
10
10
No reaction
1 (0.28 mmol%)
3 (0.8 mmol%)
5 (1.4 mmol%)
8 (2.2 mmol%)
74
80
98
98
a
Reaction conditions: iodobenzene (1 mmol), NaBPh
3 mmol), PEG (1 mL).
4
(0.5 mmol), base
(
of catalyst in the reaction of iodobenzene with NaBPh , starting
4
from 1 mg up to 8 mg, for which the best result was obtained in
the presence of 5 mg (1.4 mmol% Pd) of nanocatalyst. The results
are summarized in Table 2. Also, the use of higher amounts of
catalyst (8 mg) does not improve the result (Table 2, entry 5).
3 4 2
Figure 5. XRD pattern of Fe O @SiO @L-arginine@Pd(0).
Catalytic studies
3 4 2
Applying 5 mg (1.4 mmol%) of Fe O @SiO @L-arginine@Pd(0)
and Na CO as base in PEG as solvent at 100 °C are the best condi-
2
3
After full characterization of Fe O @SiO @L-arginine@Pd(0), the
3
4
2
tions for the C–C coupling reaction (Table 2, entry 4). We then
explored the synthesis of various biphenyl derivatives under the
established procedure, in order to probe the scope and generality
of the process (3). The results are summarized in Table 3.
After successful synthesis of a wide range of biphenyl com-
4 3 4 2
pounds with NaBPh , the catalytic activity of Fe O @SiO @L-
catalytic activity of the prepared nanocatalyst was tested in the syn-
thesis of biphenyl compounds. In order to get the best experimental
conditions, the C–C coupling reaction was optimized with respect to
solvent and base (2). The influence of various inorganic bases
demonstrates that Na CO and NaHCO give the best yield only
2
3
3
when PEG is used as solvent (Table 1, entries 5 and 6). Among the
other solvents studied, only traces or no products are obtained.
arginine@Pd(0) was also probed in the Suzuki reaction of various
aryl halides with phenylboronic acid. Initially the reaction between
In order to determine
a suitable catalytic amount of
1-bromo-4-nitrobenzene and phenylboronic acid as the model
Fe O @SiO @L-arginine@Pd(0), we then examined various amounts
3
4
2
Scheme 2. Synthesis of 4-nitrobiphenyl catalysed by Fe
arginine@Pd(0).
3 4 2
O @SiO @L-
Scheme 3. General scheme for the Suzuki reaction catalysed by
Fe @SiO @L-arginine@Pd(0).
O
3 4
2
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Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2016, 30, 247–252

Pd(0) supported on Fe O @SiO @L-arginine-catalysed Suzuki reaction
3
4
2
Table 3. C–C coupling reaction of aryl halides with NaBPh
Fe @SiO @L-arginine@Pd(0) as catalyst at 100 °C
4
using
Table 4. Optimization of various parameters for synthesis of 4-
a
O
3 4
2
nitrobiphenyl catalysed by Fe
3 4 2
O @SiO @L-arginine@Pd(0)
Entry
X
R
Time (min)
Yield (%)
M.p. (°C)
Entry Solvent Base Temperature Catalyst Time Yield (%)
(
°C)
(g)
(min)
[
26]
1
2
3
4
5
6
7
8
9
Br
I
4-NO
H
2
50
10
90
40
20
15
60
40
40
45
50
120
40
98
98
96
93
97
92
91
98
95
90
91
94
90
110–113
[
26]
27]
26]
26]
27]
1
2
3
4
PEG
PEG
PEG
PEG
Na
Na
Na
Na
2
CO
CO
CO
CO
3
100
100
100
100
1
3
35
35
35
35
70
75
60–64
[
I
4-OCH
3
84–86
2
3
[
97
I
4-CH
3
40–41
2
3
5
[
No
Br
Br
Br
Br
Br
Br
Br
Br
I
4-CHO
4-NC
55–57
2
3
0.00
[
reaction
No
79–81
[
26]
5
PEG
Na
2
CO
3
Room temp.
5
35
4-NH
2
55
[
27]
reaction
80
H
60–64
[
28]
6
7
PEG
PEG
Na
Na
2
CO
CO
3
80
50
5
5
35
35
2-COCH
3-CF
3
Oil
[
29]
No
10
11
12
13
3
Oil
220–225
2
3
[
30]
reaction
Trace
No
4-CO
4-CH
2
H
[
27]
8
9
PEG
PEG
Et
3
N
100
100
5
5
35
35
3
40–41
[30]
KOH
2
2-CO H
115–118
reaction
30
a
Reaction conditions: aryl halide (1 mmol), NaBPh
4
(0.5 mmol), Na
CO
2 3
10
11
12
13
PEG
NaHCO
Na CO
Na CO
Na CO
3
100
100
100
100
5
5
5
5
35
35
35
35
(3 mmol), catalyst (5 mg, 1.4 mmol% Pd), PEG (1 mL).
EtOH
2
3
15
2
H O
2
3
Trace
No
DMSO
2
3
reaction
<5
reaction was selected and the reaction was examined under
various conditions (4).The results are presented in Table 4.
Excellent yield of biphenyl compound in the model reaction is
obtained with PEG as solvent in the presence of 5 mg (1.4 mmol
1
4
5
DMF
Na
2
CO
CO
3
100
100
5
5
35
35
1
Dioxane Na
2
3
9
a
Reaction conditions: aryl halide (1 mmol), PhB(OH) (1 mmol), base
2
%
Pd) of catalyst and Na CO3 as base at 100 °C. These were
(3 mmol).
2
selected as optimized reaction conditions. It can be seen that
when the model reaction is carried out at room temperature in
PEG no product is obtained. When the reaction is conducted at
8
0 or 50 °C, a lower yield of the biphenyl product is obtained
compared with reaction at 100 °C. The effects of solvent on
product yields were also investigated (Table 4, entries 11–14).
As can be seen, using other solvents such as EtOH, H O,
2
dimethylsulfoxide (DMSO), dioxane and dimethylformamide
(DMF) does not improve the yield of product or reaction time.
With these optimized conditions in hand, the scope of the
substrate was explored with various aryl halides having different
substituents (5). Various aryl halides were tested containing either
electron-donating or electron-withdrawing groups such as Me,
2 3
OMe, NO , CF , etc. As evident from Table 5, all the examined aryl
Scheme 5. General scheme for the Suzuki reaction catalysed by
halides couple with phenylboronic acid affording the corresponding
products with good to excellent yields. Additionally, aryl chlorides
were chosen as challenging substrates (Table 5, entries 11 and 12).
Fe O @SiO @L-arginine@Pd(0).
3
4
2
3 4 2
However, the catalytic efficiency of Fe O @SiO @L-arginine@Pd(0)
towards aryl chlorides is not satisfactory, which might be ascribed
to the strength of the C–Cl bond.
To provide evidence about the heterogeneity of the catalytic
reaction, we performed hot filtration for the synthesis of
4
-methylbiphenyl with phenylboronic acid. In this experiment we
obtain the product in half the time of the reaction, the yield being
0%. Then the reaction was repeated and in half time of the reac-
6
tion, the catalyst was separated by applying an external magnet,
and the filtrate was allowed to react further. We find that, after this
hot filtration, no further reaction is observed. The yield of reaction in
this stage is 65% that confirms the heterogeneity of the catalytic
reaction.
As evident from the results, the procedure is uniformly effective
for both electron-rich and electron-deficient aryl iodides and
bromides and delivers products with good to excellent yields in
short reaction time. In the final of our experimental work, the
catalyst was subjected to successive reactions. As can be seen, this
catalytic system can be recycled and reused up to five times
without significant loss of activity (Fig. 6).
Scheme 4. General scheme for the Suzuki reaction catalysed by
Fe O @SiO @L-arginine@Pd(0).
3 4 2
Appl. Organometal. Chem. 2016, 30, 247–252
Copyright © 2016 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

A. Ghorbani-Choghamarani and G. Azadi
Table 5. Suzuki reaction of various aryl halides with phenylboronic acid
Acknowledgement
a
3 4 2
catalysed by Fe O @SiO @L-arginine@Pd(0)
We gratefully acknowledge financial support of this work by Ilam
University, Ilam, Iran.
Entry
X
R
Time (min)
Yield (%)
1
2
3
4
6
7
8
9
Br
I
4-NO
2
35
15
97
91
90
91
98
92
95
92
90
40
10
H
I
4-OCH
4-CH
3
55
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I
3
60
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Br
Br
Br
Br
Cl
Cl
4-NC
H
30
30
[
[
[
2-COCH
3-CF
4-OCH
4-CN
4-NO
3
120
20
3
10
11
12
3
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Supporting information
Additional supporting information may be found in the online ver-
sion of this article at the publisher’s web-site.
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2016, 30, 247–252