Pd- Dithizone grafted onto magnetic nanoparticles and study of its catalyticactivity in C-C and C-N coupling reactions

Article abstract of DOI:10.1002/aoc.3839

In this paper, we report a simple, facile and efficient method for the synthesis of Fe₃O₄/SiO₂-DTZ-Pd. The immobilized palladium was an efficient catalyst without addition of phosphine ligands for Stille, Heck and N-arylation reactions. This method has some advantages such as high yields and easy work up of products. In addition, the catalyst can be recovered using a magnet and reused several times without significant loss of its catalytic activity. This catalyst was characterized by various physico-chemical techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and inductively coupled plasma (ICP).

Full text of DOI:10.1002/aoc.3839

Received: 14 October 2016
DOI: 10.1002/aoc.3839
Revised: 30 November 2016
Accepted: 18 March 2017
F U L L PA P E R
Pd‐ Dithizone grafted onto magnetic nanoparticles and study of its
catalyticactivity in C‐C and C‐N coupling reactions
Arash Ghorbani‐Choghamarani
| Hossein Rabiei | Fatemeh Arghand
Department of Chemistry, Faculty of
Science, Ilam University, P.O. Box
69315516, Ilam, Iran
In this paper, we report a simple, facile and efficient method for the synthesis of
Fe3O4/SiO2‐DTZ‐Pd. The immobilized palladium was an efficient catalyst without
addition of phosphine ligands for Stille, Heck and N‐arylation reactions. This
method has some advantages such as high yields and easy work up of products.
In addition, the catalyst can be recovered using a magnet and reused several times
without significant loss of its catalytic activity. This catalyst was characterized by
various physico‐chemical techniques such as scanning electron microscopy
(SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and
inductively coupled plasma (ICP).
Correspondence
A. Ghorbani‐Choghamarani, Department of
Chemistry, Ilam University, P.O. Box
69315516, Ilam, Iran.
Email: arashghch58@yahoo.com;
a.ghorbani@mail.ilam.ac.ir
Funding information
Ilam University
KEYWORDS
amination, dithizone, Fe3O4/SiO2‐DTZ‐Pd, Heck reactions, heterogeneous catalysis, stille reaction
1 | INTRODUCTION
that easily separated from the reaction media with an external
magnet.[11] Furthermore, magnetic nanoparticles are useful
An intriguing aspect of modern chemical research is catalytic
reactions that has important strategy in fundamental research
and industrial applications and play an important role in the
synthesis of fine chemicals and advanced functional mate-
rials.[1,2] Generally, catalysts are divided into two groups:
Most are homogeneous and the others are heterogeneous sys-
tems.[3] Despite beneficial effects with a homogeneous cata-
lyst, it has significant drawbacks including low catalyst
stability, difficulties in recovery and regeneration, possible
toxicity caused by residual metal species, deactivation of
the catalyst and high cost of the catalyst.[4,5] Therefore, the
heterogenization of homogeneous catalysts can help in their
use for practical processes to overcome the problems men-
tioned above.[6] In the same context, metal complexes have
been immobilized on various supports such as mesoporous
silica, alumina, zeolites, organic polymers and magnetic
nanoparticles.[7–10]
for biomedical applications and industrial applications that
covered a broad spectrum such as magnetic seals in motors,
magnetic inks for bank cheques.[12]
The chemistry of organopalladium has made notable
progress over the last 30 years. That progress is still
continuing without any end. Carbon–carbon and carbon–
heteroatom couplings are most important reactions in
organic synthesis[13] due to they formed new bonds with
carbon under extremely mild conditions. Most of these
cross‐coupling reactions have been reported to be pro-
moted by Pd salts and complexes. Palladium catalyzed
cross‐coupling reactions being widely applied for the syn-
thesis of fine chemicals, functional materials, industrial
starting materials, pharmaceuticals and biologically active
compounds.[14]
Herein we report the synthesis and characterization of a
palladium complex immobilized on Fe3O4 (Fe3O4/SiO2‐dtz‐
Pd), which exhibits a high catalytic activity in the Heck and
Stille cross‐coupling reactions and synthesis of anilines from
aryl halides.
In the recent decades, magnetic nanoparticles are attrac-
tive candidates as heterogeneous catalysts owing stability,
high surface area, high activity and their magnetic properties
Appl Organometal Chem. 2017;e3839.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3839

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GHORBANI‐CHOGHAMARANI ET AL.
2 | EXPERIMENTAL SECTION
2.1 | Materials
2.6 | General procedure for C–C coupling
reaction using aryl halides and triphenyltin
chloride (Stille reaction)
The reagents and solvents used in this work were all pur-
chased from Sigma‐Aldrich, Fluka or Merck Chemical Com-
panies and utilized without further purification. Powder XRD
was collected with a Rigaku‐Dmax 2500 diffractometer with
nickel filtered Cu Kα radiation (λ = 1.5418 °A, 40 kV). The
particle morphology was examined using SEM with an
FESEMTESCAN MIRA3. TEM of the NPs were recorded
using a Zeiss‐EM10C TEM. Supermagnetic properties of cat-
alyst was measured on Vibrating Sample Magnetometer
(VSM) MDKFD operating at room temperature.
The catalytic activity of the synthesized Fe3O4/SiO2‐DTZ‐Pd
nanocatalyst was investigated with the Stille reaction that was
carried out as follow: a mixture of aryl halide (1.0 mmol),
triphenyltin chloride (0.5 mmol), Na2CO3 (3.0 mmol) and
Fe3O4/SiO2‐DTZ‐Pd (0.005 g) was added to PEG (2.0 ml)
as solvent. The reaction mixture was stirred at 80 °C and
the progress of the reaction was monitored using TLC. After
completion of the reaction, the catalyst was separated using
an external magnet and washed with diethyl ether and reused
for the next experiment; the mixture was diluted with
diethylether and water. The organic layer was separated, then
the solvent was evaporated and pure biphenyl derivatives
were obtained in good to excellent yields.
2.2 | Preparation of Fe3O4 MNPs
Bare Fe3O4 magnetic nanoparticles were prepared according
to our recently reported work via chemical coprecipitation
method using FeCl3 6H2O and FeCl2 6H2O in basic solution
at 80 °C.[15]
2.7 | General procedure for C–C coupling
reaction using aryl halides with butyl acrylate
(Heck reaction)
A mixture of aryl halide (1.0 mmol), butyl acrylate
(1.2 mmol), K2CO3 (3.0 mmol) and Fe3O4/SiO2‐DTZ‐Pd
(0.007 g) was added to PEG (2.0 ml) as a solvent. The reac-
tion mixture was stirred at 100 °C and the progress of the
reaction was monitored using TLC. After completion of the
reaction, the mixture was cooled to room temperature and
the catalyst was separated using an external magnet and
washed with diethyl ether. The reaction mixture was
extracted with water and diethyl ether. The organic layer
was separated, and the solvent was evaporated and pure prod-
ucts were obtained in good to excellent yields.
2.3 | Preparation of Fe3O4‐(3‐chloropropyl)
triethoxysilane (CPTES)
The obtained magnetic nanoparticles (MNPs) powder (1.5 g)
was dispersed in a mixture of EtOH and water (25 ml, 1:1 by
volume) by sonication for 30 min. Then 3‐chloropropyl
triethoxysilane (95%, 3 ml) was added to the mixture and
stirred at room temperature under nitrogen atmosphere for
8 h. Then product was washed with deionized water and
EtOH and magnetically decanted and dried at room tempera-
ture overnight.
2.8 | General procedure for N‐arylationusing
2.4 | Preparation of Fe3O4/SiO2‐DTZ
aryl halides with aqueous ammonia
Chloro‐functionalized MNPs (1.0 g) and dithizone
(3.0 mmol) were dispersed in DMF (10 ml) by sonication
for 10 min. The reaction mixture was stirrer for 30 h at
100 °C. The product was isolated using an external magnet,
washed thoroughly with DMF and dried under vacuum for
12 h.
A mixture of aryl halide (1 mmol), aqueous ammonia (28%)
(2 ml) and 0.005 g of Fe3O4/SiO2‐DTZ‐Pd was added to a
round‐bottom flask in neat conditions The reaction mixture
was stirred at 60 °C and the progress of the reaction was mon-
itored using TLC. After completion of the reaction, the cata-
lyst was separated using an external magnet and the product
was extracted by water and ethyl acetate. The organic layer
was separated and the solvent was evaporated and pure prod-
ucts were obtained.
2.5 | Preparation of Fe3O4/SiO2‐DTZ‐Pd.
Fe3O4/SiO2‐DTZ (0.5 g), was added to a round‐bottom flask
containing EtOH (20 ml) and Pd (OAc)2 (0.25 mmol). The
mixture was stirred vigorously under reflux for 20 h. Then,
NaBH4 (0.3 mmol) was added to the reaction mixture and
reaction was continued for another 2 h. The resulting solid
was isolated using a magnetic field. The corresponding mod-
ified magnetic nanoparticles were thoroughly washed with
EtOH and dried under vacuum at room temperature.
2.9 | Results and discussion
The MNPs/SiO2‐DTZ‐Pd complex was synthesized by sev-
eral steps, which was shown in Scheme 1. First, MNPs was
reacted with 3‐(chloropropyl) triethoxysilane. The reaction
of the chloro‐functionalized MNPs with dithizone produced

GHORBANI‐CHOGHAMARANI ET AL.
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SCHEME 1 Synthesis of MNPs/SiO2‐DTZ‐Pd
dithizone‐functionalized Fe3O4. Finally, Fe3O4/SiO2‐DTZ‐
Pd was obtained via coordination of palladium with MNPs/
SiO2‐DTZ surface.
Catalyst characterization was performed using transmis-
sion electron microscopy, X‐ray diffraction, Fouriertransform
infrared spectroscopy, energy dispersive X‐ray spectroscopy,
vibrating sample magnetometer and scanning electron
microscopy. XRD pattern of Fe3O4/SiO2‐DTZ‐Pd sample is
shown in Figure 1. In the corresponding curve, six character-
istic diffraction peaks appeared at 2θ = 30.1(220), 35.3(311),
43.0(400), 53.4(422), 56.9(511) and 62.5(440). Besides the
characteristic peaks of Fe3O4 core, three additional peaks
can be observed at 2θ = 39.3(111), 45.49(110) and 67.1
(100), are indexed to Pd(0) indicating the presence of Pd(0)
in the prepared nanocatalyst.[16]
FIGURE 2 SEM images of Fe3O4/SiO2‐DTZ‐Pd
The shape and size of the Fe3O4/SiO2‐DTZ‐Pd were
determined by SEM (Figure 2). Moreover, the TEM image
of the Fe3O4/SiO2‐DTZ‐Pd catalyst shows that the function-
alized magnetic nanoparticles possess almost spherical mor-
phology (Figure 3).
The elemental composition of the Fe3O4/SiO2‐DTZ‐Pd
catalyst performed by EDS analysis, which the results shown
in Figure 4. The distribution of the elements (atomic percent)
in the complex was determined as Si = 1.49%, Fe = 29.15%,
O = 62.38% and Pd = 5.59%. Exact loading of Pd on the
FIGURE 3 TEM images of Fe3O4/SiO2‐DTZ‐Pd
magnetic nanoparticles was determined by inductively
coupled plasma atomic emission spectroscopy (ICP‐OES)
that was to be 1.65 mmol g−1
.
The magnetic properties of MNPs/SiO2‐DTZ Pd were
determined using vibrating sample magnetometry
(Figure 5). It can be seen that the magnetic saturation values
of the catalyst is 51 emu g−1. The decrease of the saturation
magnetization suggests the presence of some palladium parti-
cles on the surface of the magnetic supports.[17]
The palladium catalyzed C‐C and C‐N bond forming
reactions are of the most important transformations in organic
reactions. The catalytic activity of MNPs/SiO2‐DTZ‐Pd was
evaluated in the C–C coupling reaction of aryl halides with
triphenyltinchloride (Stille reaction), butyl acrylate (Heck
reaction) and amination of aryl halides with aqueous
ammonia.
FIGURE 1 XRD pattern of Fe3O4/SiO2‐DTZ‐Pdnanoparticles

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GHORBANI‐CHOGHAMARANI ET AL.
TABLE 1 C–C coupling of iodobenzenewithtriphenyltin chloride in
the presence of Fe3O4/SiO2‐DTZ‐Pd under various conditions
Base
Catalyst Temp Time Yield
Entry Solvent
(mmol)
(mg)
(°C)
(min)
(%)
1
PEG
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
0
2
5
7
5
5
5
5
5
5
5
5
5
5
5
80
24 h
25
25
25
25
25
25
25
25
25
25
25
5 h
5 h
25
0
45
2
PEG
80
80
80
80
80
80
80
80
80
80
80
Rt
3
PEG
92
4
PEG
96
5
DMF
DMSO
75
6
68
7
Dioxane Na2CO3
40
FIGURE 4 EDS analysis of Fe3O4/SiO2‐DTZ‐Pd
8
H2O
PEG
PEG
PEG
PEG
PEG
PEG
PEG
Na2CO3
KOH
86
9
54
10
11
12
13
14
15
NaOH
K2CO3
Et3N
50
85
35
Na2CO3
Na2CO3
Na2CO3
Trace
68
60
100
95
aReaction conditions: iodobenzene (1 mmol), triphenyltin chloride (0.5 mmol),
base (3 mmol), Fe3O4/SiO2‐DTZ‐Pd (.0005 g), solvent (2 mL) at 80 °C.
(Table 1, entries 4–8). After the solvent screening, PEG
was chosen as solvent of reaction. Next studies focused on
the influence of the base on the reaction. The reactions were
carried out under similar conditions using different bases
such as Na2CO3, K2CO3, KOH, NaOH and Et3N; the
obtained yields were 96%, 85%, 54%, 50% and 35%, respec-
tively (Table 1, entries 9–12). As shown in Table 1, it was
found that Na2CO3 was an effective base for the reaction
with the highest yield. To investigate the effect of tempera-
ture on the outcome of coupling reaction, we performed
the reaction at difference temperatures: room temperature,
60, 80 and 100 °C (Table 1, 13–15). Based on these
obtained results in Table 1, temperature of 80 °C was
selected. Next, using the optimized procedure,
triphenyltinchloride and various aryl halides possessing both
electron releasing and electron‐withdrawing groups were
employed. As shown in Table 2, reactions of aryl iodides
were done in short time, while the aryl bromides and aryl
chlorides required longer reaction times.
FIGURE 5 Magnetization curves for Fe3O4/SiO2‐DTZ‐Pd
2.10 | Evaluation of the catalytic activity of
MNPs/SiO2‐DTZ‐Pd through the Stille reaction
Initially, we employed iodobenzene and triphenyltinchloride
in PEG as a solvent in the presence of Na2CO3 as base at
80 °C as model substrates for the optimization of the reaction
conditions (Scheme 2).
Different parameters were investigated for this model
reaction including the use of different molar ratio of cata-
lyst, variety of solvents, bases, and temperature (Table 1).
In order to explore the role of this nanocatalyst in the out-
come of C‐C coupling reaction, several experiments were
carried out using different amounts of catalyst (Table 1,
entries 1–4). The resulting optimum amount of the catalyst
was (0.005 g) of MNPs/SiO2‐DTZ‐Pd (Table 1, entry 3),
which increasing of this amount did not show any signifi-
cant change in yield.
When the reaction was carried out in different solvents
such as Dioxane, DMF, DMSO, water and PEG under the
same reaction conditions, the products were obtained in
poor to good yields of 40%, 75%, 68%, 86% and 96%
2.11 | Evaluation of the catalytic activity of
MNPs/SiO2‐DTZ‐Pd through the Heck reaction
The next part of the study focused on the utility of this cata-
lyst in Heck reaction. To standardize the reaction conditions,
a series of reactions were performed using several bases and
solvents, and different temperatures and molar ratio of cata-
lyst (Table 3). Initially, the experiment was performed using
SCHEME 2 Fe3O4/SiO2‐DTZ‐PdcatalyzedStille reaction

GHORBANI‐CHOGHAMARANI ET AL.
5 of 7
TABLE 2 C‐C coupling reaction of aryl halides with
triphenyltinchloridecatalyzed by Fe3O4/SiO2‐DTZ‐Pdat 100 °C
Entry
X
R
Time (min) Yield (%)
M.p. (°C)
1
I
H
25
55
92
95
90
88
93
95
87
90
80
93
89
67–69[18]
86–88[19]
45–47[20]
67–69[18]
44–47[20]
83–87[20]
161–163[18]
73–76[21]
52–55[18]
112–115[21]
67–70[18]
SCHEME 3 Fe3O4/SiO2‐DTZ‐Pd catalysed Heck reaction
2
I
4‐OCH3
4‐CH3
H
The reactivity of the catalyst in the presence of different
bases was also investigated. Among the tested bases
(Na2CO3, K2CO3, KOH, NaOH and Et3N) the best choice
was K2CO3 due to the highest yield of product (Table 3, entry
11). Subsequently, the influence of different solvents was
examined (Table 3, entries 5–8). Among the solvents exam-
ined, the highest yield was achieved when using PEG
(Table3, entry 3). Next, effect of temperature on the outcome
of reaction, the reaction was carried out at different tempera-
tures such as room temperature, 60, 80 and 100 °C (Table 3,
entries 14–17). Based on these obtained results, temperature
of 100 °C was selected.
3
I
75
4
Br
30
5
Br 4‐CH3
Br 4‐Cn
Br 4‐oh
Br 4‐cl
65
6
60
7
55
8
45
9
Br 4‐Cho
Br 4‐NO2
145
50
10
11
Cl
H
180
aReaction condition: Aryl halide (1 mmol), Ph3SnCl (0.5 mmol), Na2CO3
(3 mmol), Cat. (5 mg), PEG (2 ml).
After optimizing the reaction conditions, the catalytic
activity of MNPs/SiO2‐DTZ‐Pd for Heck reaction was
explored with respect to various aryl halides and butyl acry-
late, as listed in Table 4.
TABLE 3 C–C coupling of iodobenzenewithbutyl acrylate in the
presence of Fe3O4/SiO2‐DTZ‐Pd under various conditions
Base
Catalyst Temp Time Yield
Entry Solvent
(mmol)
(mg)
(°C)
(min)
(%)
2.12 | Evaluation of the catalytic activity of
MNPs/SiO2‐DTZ‐Pd through the N‐arylation
reaction
1
PEG
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
2
5
100
100
100
100
100
100
100
100
100
80
240
30
30
20
30
30
30
30
30
30
30
30
30
240
30
30
30
36
2
PEG
55
3
PEG
7
93
The activity of described catalyst was investigated througha
reaction of aryl halides with NH3.H2O for amination reaction
of various aryl halides. Initially, we examined the reaction
of iodobenzene with aqueous ammonia (28%) in
4
PEG
10
7
95
5
DMF
DMSO
84
6
7
78
7
Dioxane K2CO3
7
Trace
80
TABLE 4 C‐C coupling reaction of aryl halides with
triphenyltinchloridecatalyzed by Fe3O4/SiO2‐DTZ‐Pdat 100 °C
8
H2O
PEG
PEG
PEG
PEG
PEG
PEG
PEG
PEG
PEG
K2CO3
KOH
7
9
7
75
Time Yield
(min) (%)
M.p.
(°C)
10
11
12
13
14
15
16
17
NaOH
K2CO3
Et3N
7
70
Entry
X
R
Alkene
7
100
100
100
Rt
93
1
I
H
Butyl acrylate 30
Butyl acrylate 75
Butyl acrylate 65
Butyl acrylate 45
Butyl acrylate 110
Butyl acrylate 130
Butyl acrylate 3.5 h
Butyl acrylate 160
Butyl acrylate 190
92
95
90
88
93
95
87
90
80
83
90
93
Oil[22]
Oil[23]
Oil[22]
Oil[22]
Oil[22]
39–42[22]
Oil[24]
Oil[22]
57–61[22]
Oil[22]
7
65
2
I
4‐OCH3
4‐CH3
H
Na2CO3
K2CO3
K2CO3
K2CO3
K2CO3
7
88
3
I
7
Trace
42
4
Br
7
60
5
Br 4‐CH3
Br 4‐Cn
7
80
68
6
7
100
93
7
I
2‐OCH3
aReaction conditions: iodobenzene (1 mmol)butyl acrylate (1.2 mmol), base
(3 mmol), Fe3O4/SiO2‐DTZ‐Pd (0.007 g), solvent (2 ml) at 100 °C.
8
Br 4‐cl
9
Br 4‐NO2
iodobenzene (1.0 mmol) butyl acrylate (1.2 mmol), K2CO3
(3.0 mmol) and Fe3O4/SiO2‐DTZ‐Pd (0.007 g) in PEG as sol-
vent at 100 °C (Scheme 3).
Initially, the amount of catalyst was optimized (Table 3,
entries 1–4); it was observed that the best results were
obtained with 0.007 g of catalyst (Table 3, entry 3).
10
11
12
Br 3‐Br‐pyridin Butyl acrylate 90
Cl 4‐Cn
Cl
Butyl acrylate 14 h
Butyl acrylate 11 h
40–42[22]
Oil[22]
H
aReaction condition: Aryl halide (1 mmol), butyl acrylate (0.5 mmol), K2CO3
(3 mmol), Cat. (7 mg), PEG (2 ml).

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GHORBANI‐CHOGHAMARANI ET AL.
differentsolvents and various catalytic amounts of MNPs/
SiO2‐DTZ‐Pd (Table 5). It was observed that the best results
were obtained with 0.005 g of catalyst (Table 5, entry 2).
Then, the reaction was performed using different solvents that
the results are shown in Table 5. After optimizing the reaction
conditions, the amination reactions of various arylhalides
with NH3.H2O were tested. Results have been summarized
in Table 6.
For practical applications of heterogeneous systems, the
recyclability of a catalyst is an important factor. The recycla-
bility of Fe3O4/SiO2‐DTZ‐Pd was studied in the coupling
reaction of iodobenzene with butylacrylate and amination
reaction of iodobenzene with aqueous ammonia. In order to
reuse the catalyst, after reaction completion, it was separated
by a magnet and washed several times with ethyl acetate.
Then, it was dried in an oven at 50 °C and used in the next
run. The results show that this catalyst can be reused 5 times
without any significant loss in activity performance
(Figure 6). This result also demonstrated that the palladium
leaching of the catalyst was low.
FIGURE 6 Recyclability of Fe3O4/SiO2‐DTZ‐Pd in the coupling of
iodobenzene (1.0 mmol) with (a) butyl acrylate (1.2 mmol) and (b)
aqueous ammonia (2.0 mL) under reaction conditions
3 | CONCLUSIONS
In conclusion, Fe3O4/SiO2‐DTZ‐Pd was synthesized and
tested to evaluate its catalytic activity in Heck, Stille, and
N‐arylation reactions. Under the optimized conditions, the
catalyst displayed excellent catalytic activity in delivering
the desired products in good to excellent yields. This catalyst
was characterized by several techniques such as XRD, VSM,
TEM, SEM, EDS and ICPOES.
TABLE 5 Amination of iodobenzene with aqueous ammonia in the
presence of Fe3O4/SiO2‐DTZ‐Pd under various conditions
Entry
Solvent
Catalyst (mg)
Time (h)
Yield %
1
2
3
4
5
6
‐
0.003
0.005
0.007
0.005
0.005
0.005
9
5
4
5
5
5
70
90
92
90
65
77
‐
ACKNOWLEDGEMENTS
‐
We gratefully acknowledge financial support of this work by
Ilam University, Ilam, Iran.
‐
DMF
EtOH
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