Palladium nanoparticles supported on magnetic copper ferrite nanoparticles: The synergistic effect of palladium and copper for cyanation of aryl halides with K4[Fe(CN)6]

Article abstract of DOI:10.1016/j.molcata.2014.10.029

In this paper, for the first time, palladium nanoparticles were supported on (3-aminopropyl) triethoxysilane-modified copper ferrite nanoparticles. The obtained catalyst was characterized using FT-IR, TEM, EDX, AAS, XRD, and TGA analyses. The prepared heterogeneous catalyst showed superior activity toward cyanation of aryl iodides and bromides with K₄[Fe(CN)₆] compared to the Fe₃O₄ supported palladium nanoparticles, unfunctionalized CuFe₂O₄ nanoparticles, homogeneous Pd(OAc)₂, CuCl₂, and CuI catalysts. The heterogeneous and low Pd loading catalyst was recycled for four consecutive runs with small drops in catalytic activity.

Full text of DOI:10.1016/j.molcata.2014.10.029

Accepted Manuscript
Title: Palladium Nanoparticles Supported on Magnetic Copper
Ferrite Nanoparticles: The Synergistic Effect of Palladium and
Copper for Cyanation of Aryl Halides with K [Fe(CN) ]
4
6
Author: Mohammad Gholinejad Afsaneh Aminianfar
PII:
S1381-1169(14)00484-1
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2014.10.029
MOLCAA 9331
To appear in:
Journal of Molecular Catalysis A: Chemical
Received date:
Revised date:
Accepted date:
10-9-2014
30-10-2014
31-10-2014
Please cite this article as: M. Gholinejad, A. Aminianfar, Palladium
Nanoparticles Supported on Magnetic Copper Ferrite Nanoparticles: The
Synergistic Effect of Palladium and Copper for Cyanation of Aryl Halides
with K [Fe(CN) ], Journal of Molecular Catalysis A: Chemical (2014),
4
6
http://dx.doi.org/10.1016/j.molcata.2014.10.029
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Palladium Nanoparticles Supported on Magnetic Copper Ferrite Nanoparticles: The
Synergistic Effect of Palladium and Copper for Cyanation of Aryl Halides with
K [Fe(CN) ]
4
6
a*
a
Mohammad Gholinejad Afsaneh Aminianfar
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), P. O. Box
4
5195-1159, Gava zang, Zanjan 45137-6731, Iran.
Email: gholinejad@iasbs.ac.ir
Abstract
In this paper, for the first time, palladium nanoparticles were supported on (3-
aminopropyl)triethoxysilane-modified copper ferrite nanoparticles. The obtained catalyst was
characterized using FT-IR, TEM, EDX, AAS, XRD, and TGA analyses. The prepared
heterogeneous catalyst showed superior activity toward cyanation of aryl iodides and bromides
with K
4
[Fe(CN)
6
] compared to the Fe
3
O
4
supported palladium nanoparticles, unfunctionalized
, CuCl , and CuI catalysts. The heterogeneous
CuFe
2
O
4
nanoparticles, homogeneous Pd(OAc)
2
2
and low Pd loading catalyst was recycled for four consecutive runs with small drops in catalytic
activity.
Keywords: Magnetic, Palladium, Copper, Synergistic, Cyanation
1
Page 1 of 25

1
. Introduction
Aryl nitriles are important moieties of numerous biological, agrochemicals, pharmaceutical, and
natural products [1,2]. The nitrile compounds can be easily converted into several important
functional products such as acids, amides, aldehydes, ketones, and amines [3]. For more than a
century, the traditional methods for the synthesis of aryl nitriles were the Rosenmund–von Braun
[
4-8], Sandmeyer and ammoxidation reactions [9-10]. However, ammoxidation reaction typically
°
has performed under harsh reaction conditions, such as elevated temperatures (220-550 C) and
under high pressure conditions. Also, via the Rosenmund–von Braun and Sandmeyer methods,
aryl iodides, bromides and aryl diazonium salts can be converted to aryl nitriles using
stoichiometric amount of CuCN at high reaction temperature (150-250 °C) [3].
Over the last few years, in order to reduce the mentioned drawbacks and meet today's criteria of
sustainable synthesis, different transition metal-catalyzed methodologies for the preparation of
aryl nitriles from the reaction of aryl halide and cyanide sources have been reported. For this
purpose, different catalysts such as palladium [11], copper [12-20], nickel [21], and rhodium [22]
were developed. In addition, different metal-or metalloid-bound cyanide sources such as KCN
[23-26], CuCN [4-10], NaCN [27-29], Zn(CN)
2 4 6
[30-36], TMSCN [37-38], and K [Fe(CN) ] [39-
4
3] were employed for the cyanation of aryl compounds. Furthermore, in recent years extensive
attention has been paid to using of nonmetallic organic cyanide sources such as acetone
cyanohydrins, benzylthiocyanate, ammonium bicarbonate, formamide, malononitrile, benzyl
nitrile, azobisisobutyronitrile, acetonitrile, and ammonium iodide-DMF [44]. Despite the low
4 6 4 6
reactivity of K [Fe(CN) ] in comparison to the some of the other cyanide sources, K [Fe(CN) ]
was known as a general, nontoxic, inexpensive, and easily handled cyanide source.
2
Page 2 of 25

Copper catalyzed cyanation of aryl ioddies and bromides using K
under harsh reaction condition such as high temperature or microwave heating conditions [12-
0]. However, using palladium precatalysts for the cyanation of aryl halides affected this
4 6
[Fe(CN) ] usually performed
2
reaction to performed under mild reaction conditions in comparison to the copper precatalysts.
Though the significant efficiency in some of the reported palladium catalyzed cyanation
reactions, these reactions usually were performed under high loading of expensive palladium
precatalysts in the presence of phosphane ligands under homogeneous reaction conditions [11].
In particular, phosphanes are excellent ligands for the stabilization of the palladium species.
However, phosphanes are usually toxic, unrecoverable, thermally unstable, and their synthesis is
difficult. On the other hand, less attention has been paid to use of heterogeneous palladium
catalysts in the cyanation reaction of aryl halides.
Nowadays, bimetallic nanoparticles have been known as efficient catalysts for various catalytic
reactions. The synergistic combination of two metals enhanced their catalytic performance,
activity, selectivity, and stability in compared to corresponding monometallic catalysts [45]. In
addition, mass decreasing of bimetallic catalyst relative to the individually using of metals in
reactions such as Sonogashira in which usually a second metal is required, is other advantage of
bimetallic catalysts [46].
Ferrites nanoparticles are important magnetic materials, which are used for various applications
such as drug delivery, magneto-thermal therapy, microwave absorbent sensors, and as catalyst
for many organic transformations [47]. In recent years, there has been growing interest in the
application of copper ferrite nanoparticles as a recyclable catalyst in the different copper
catalyzed organic reactions [48-60]. Very recently, we have introduced copper ferrite
nanoparticles as an efficient catalyst for odorless carbon sulfur bond formation reactions [61].
3
Page 3 of 25

In this context, for the first time, stabilization of palladium nanoparticles on (3-
aminopropyl)triethoxysilane-modified copper ferrite nanoparticles is described. The new catalyst
was successfully applied for the cyanation of aryl iodides and bromides under heterogeneous and
low palladium loading conditions.
2
. Experimental Section
.1. General
2
All chemicals were purchased from Sigma-Aldrich, Acros and Merck and were used without
further purification. Thin layer chromatography was carried out on silica gel 254 analytical
sheets obtained from Fluka. Column chromatography was carried out on silica gel 60 Merck
(
230-240 mesh) in glass columns (2 or 3 cm diameter) using 15-30 grams of silica gel per one
1
13
gram of the crude mixture. H NMR spectra were recorded at 250 and 400 MHz and C NMR
were recorded at 100 MHz in CDCl using TMS as internal standard. Thermogravimetric
3
analysis (TGA) was conducted from room temperature to 600 °C in an oxygen flow using a
NETZSCH STA 409 PC/PG instrument. FT-IR spectra were recorded on a Bruker Vector 22. X-
ray diffraction (XRD) was recorded on Philips X'PertPro. Energy dispersive X-ray analysis
(
EDX) was obtained using Carl Zeiss iGMA instrument. The structures of the prepared
materials were observed by transmission electron microscopy (Philips CM-120).
2
.2.
Preparation of the catalyst
CuFe
2
O
4
nanoparticles were synthesized by procedures described previously [90]. 500 mg of
NPs were dispersed in 20 mL dry toluene for 30 min using
as-synthesized CuFe
2
O
4
ultrasound assistance. To the resulting solution, 2 mmol of 3-aminopropyltriethoxysilane was
added and mixture was refluxed for 24 h under argon atmosphere. The (3-
2 4
aminopropyl)triethoxysilane functionalized CuFe O NPs was subjected to magnetic
4
Page 4 of 25

separation, and was washed sequentially with EtOH (3×20 mL) and dried under vacuum for
2
4 h. Then, 500 mg of functionalized CuFe O NPs were dispersed in 20 mL EtOH for 30
2
4
min and to this solution, a solution of PdCl
2
(12.5 mg, 0.07 mmol) in 10 mL hot water was
added. To the resulting mixture, solution of 1 mmol NaBH in 5 mL water was added and the
4
mixture was stirred for 12 h at room temperature. The solid catalyst was separated by
external magnet, washed sequentially with EtOH (3×20 mL) and dried under vacuum for 24
h.
2
.3.
General procedure for the cyanation of aryl bromides and iodides using
Pd@CuFe O NPs
2
4
To a 10 mL glass tube aryl halide (1 mmol), K FeCN (0.6 mmol, 220 mg), K CO (1.5 mmol,
4
6
2
3
2
07 mg), catalyst (10 mg), and 2 mL DMF were added and mixture was stirred for appropriate
reaction time at 120 °C under argon atmosphere. The progress of the reaction was monitored by
GC analysis. After completion of the reaction, reaction mixture was washed with 5 mL water and
crude product was isolated using dichloromethane (5 × 1 mL). Organic extracts were combined
together, evaporated and purified by flash chromatography using hexane/EtOAc to give the
desired aryl cyanide products.
3
. Results and Discussion
2 4 3 2 2 3 3 2
CuFe O nanoparticles were synthesized using Cu(NO ) .3H O and Fe(NO ) .9H O via
conventional co-precipitation method without using any capping agent or surfactant [60]. Copper
ferrite nanoparticles-supported palladium catalyst was synthesized according to the procedure
summarized in Scheme 1.
5
Page 5 of 25

(
EtO) Si
NH2
3
O
Si
NH2
O
O
Toluene, reflux, 24 h
CuFe O NPs
2
4
PdCl , NaBH
O
O
O
2
4
Si
NH2
Pd NP
EtOH-H O
2
°
2
4 h, 60 C
Scheme 1. Synthesis of Copper ferrite nanoparticles-supported palladium nanoparticles
Pd@CuFe NPs.
2
O
4
The loading of palladium in the catalyst was determined using atomic absorption spectroscopy
-1
(
AAS) and a amount of 0.1 mmol.g was obtained. Also, thermalgravimetric analysis showed
three steps of weight losses and confirmed presence of supported organic functional group (0.72
-1
mmol.g ) (Figure 1). The first weight loss occurred between 25 and 100 °C, with an observed
weight loss of 3.36% related to the loss of H O. The second weight loss occurred between 100-
00 °C which may be related to the physisorbed 3-aminopropyl)triethoxysilane group and third
weight loss between 100-500 °C is related to the supported 3-aminopropyl)triethoxysilane
organic group on CuFe NPs [62].
2
2
2
O
4
6
Page 6 of 25

2 4
Figure 1. Thermogravimetric diagram of Pd@CuFe O NPs
-1
-1
The presence of stretching mode for Fe-O band at 575 cm , Cu-O at 438 cm and the broad
-1
peak at 3432 cm for surface O-H groups in FT-IR confirmed the structure of prepared copper
-1
-1
ferrite nanoparticles. However, appearance of two new peaks at 585 cm and 1008 cm which
may be related to the Fe-O-Si [63] and Cu-O-Si [64] bonds confirms the structure of
Pd@CuFe O catalyst (Figure 2).
2 4
7
Page 7 of 25

Figure 2. FT-IR spectrums of CuFe O NPs (left) and Pd@CuFe O catalyst (right)
2
4
2
4
Figure 3 shows TEM image of Pd@CuFe O catalyst, in which palladium nanoparticles with
2
4
average size of 5-10 nm were assembled on 40-60 nm (3-aminopropyl)triethoxysilane
functionalized copper ferrite nanoparticles. In addition, EDX (SEM) spectrum of catalyst
showed the presence of palladium species in the catalyst (Figure 4).
8
Page 8 of 25

2 4
Figure 3. TEM images of Pd@CuFe O NPs
2 4
Figure 4. EDX spectrum of Pd@CuFe O NPs
The X-ray diffraction (XRD) analysis of catalyst confirmed formation of catalyst by screening
Bragg’s reflections related to CuFe O nanoparticles [62] in 2θ = 18.3, 30.3, 35.6, 57.1, 62.98
2
4
and Bragg’s reflections related to palladium [65] in 2θ= 40.1, 46.7, 68.1.
9
Page 9 of 25

Figure 5. XRD pattern of the catalyst
Hypothesizing the synergistic effect of the palladium and copper nanoparticles in the catalyst,
4 6
cyanation reaction of iodobenzene with K Fe(CN) in the presence of 10 mg catalyst (0.001
mmol Pd) and K
2
CO
3
as a base in DMF at different temperatures was studied. The results
°
showed that after 7 h reaction proceeded well at 120 C and benzonitrile as the product was
obtained in 97% GC yield (Table 1).
4 6
Table 1 Reaction of iodobenzene with K Fe(CN) in the presence of catalyst at different
temperatures
I
CN
Pd@CuFe O4
2
+
K Fe(CN)6
4
K CO , DMF (2 mL)
2
3
7
h
1
0
Page 10 of 25

Entry
T (°C)
100
Yield%
72
1
2
3
110
89
120
97
In order to demonstrate the synergistic effect between two metals, reaction of iodobenzene with
K Fe(CN) as a model reaction under different reaction conditions in the absence of
4
6
Pd@CuFe
was prepared using similar method to preparation of Pd on CuFe
scheme 2). AAS showed the amount of palladium on Fe nanoparticles was 0.12 mmol per
gram which is approximately same as the Pd on CuFe . Then, the obtained catalyst was tested
2
O
4
was studied. First of all, palladium nanoparticles supported on Fe
3
O
4
nanoparticles
2
O
4
to give Pd@Fe
3 4
O
catalyst
(
3 4
O
2
O
4
for model reaction under similar optimized reaction conditions. However, GC analysis of the
reaction after 7 h showed only 13% conversion of iodobenzene to benzonitrile (Table 2, entry 2).
(
EtO) Si
NH2
3
O
Si
NH2
O
O
Toluene, reflux, 24 h
Fe O NPs
3
4
PdCl , NaBH
O
O
O
2
4
Si
NH2
Pd NP
EtOH-H O
2
°
2
4 h, 60 C
Scheme 2. synthesis of Copper ferrite nanoparticles-supported palladium nanoparticles
Pd@Fe O NPs
3
4
1
1
Page 11 of 25

Furthermore, reaction of iodobenzene with K
unfunctionalized copper ferrite nanoparticles under optimized reaction conditions afforded only
% GC yield for benzonitrile after 7 h (Table 2, entry 3). Also, the reaction of 1 mmol
iodobenzene with K Fe(CN) in the presence of 0.001 mmol Pd(OAc) , 1.5 mmol K CO at 120
4 6
[Fe(CN) ] in the presence of 10 mg
6
4
6
2
2
3
°
C in DMF was investigated. After 7 h, 31% (GC) conversion of iodobenzene to benzonitrile was
achived (Table 3, entry 4). The model reaction was also performed using 5 mol% of CuI or
CuCl under optimized reaction condition. However GC analysis of reaction showed only 4-5%
2
production of benzonitrile (Table 3, entries 5 and 6). In addition, using 10 mg of
unfunctionalized Fe
3 4
O NPs (containing 0.001 mmol Pd) as a catalyst for the reaction, gave trace
amount of benzonitrile as the product (Table 3, entry 7).
Table 2 Reaction of iodobenzene with K
4
Fe(CN)
6
in the presence of different catalysts
I
CN
Catalyst
+
K Fe(CN)
4 6
K CO , DMF (2 mL)
2
3
120 °C, 7 h
Entry
Catalyst
NPs (10 mg, containing 0.001 mmol Pd)
Yield%
1
2
3
4
5
6
7
Pd@CuFe
Pd@Fe
2
O
4
97
13
6
3
O
4
NPs (10 mg, containing 0.001 mmol Pd)
CuFe O NPs (10 mg)
2
4
Pd(OAc) (0.001 mmol)
31
4
2
CuI (0.05 mmol)
CuCl
2
(0.05 mmol)
NPs (10 mg)
5
Fe
3
O
4
trace
1
2
Page 12 of 25

8
9
Pd(OAc)
2
(0.001 mmol) + CuI (0.05 mmol)
88
91
82
Pd(OAc) (0.001 mmol) + CuCl (0.05 mmol)
2
2
10
3 4 2
Pd@Fe O (containing 0.001 mmol Pd) + CuCl (0.05 mmol)
From all above studies and results of Table 2, it is concluded that synergistic effect between
copper and palladium nanoparticles, plays an important role in the cyanation of iodobenzene
with K [Fe(CN) ]. In order to demanstrate the effect of copper species in the Pd@CuFe O on
4
6
2
4
it’s greater reactivity, the model reaction was studied using homogenous Pd and Cu togethre
Table 2, entries 8 and 9) and also in the presance of Pd@Fe and CuCl additive (Table 2,
(
3
O
4
2
entry 10). Results showed that presence of copper species have significant effect on palladium
catalysts compared to the individual using of Pd or Cu catalysts. These observations clearly
2 4 2 4
support important effect of CuFe O NPs in high reactivity of Pd@CuFe O catalyst.
In order to investigate the general application of palladium supported copper ferrite
nanaoparticles as a catalyst, reaction of structurally diverse aryl iodides and bromides with
4 6
K [Fe(CN) ] were studied (Table 3). The results indicated that reaction of aryl iodides proceeded
effectively and desired nitrile products were obtained in high to excellent yields. In addition, the
reactions of aryl bromides under similar optimized reaction conditions proceeded well and
corresponding products were obtained in high yields. The results of Table 3 indicated that
presence of electron withdrawing groups at the para-position of the aryl halides afforded high
yields compared to electron donating groups at the para-position. In addition, because of the
weakness of the carbon-iodide bond in aryl iodides, these compounds exhibit greater reactivity
compared to aryl bromides.
1
3
Page 13 of 25

4 6
Table 3 Reaction of structurally different aryl iodides and bromides with K Fe(CN) in the
presence of catalyst.
X
+
CN
Pd@CuFe O
2
4
K [Fe(CN) ]
4
6
R
K CO , DMF (2 mL)
2
3
R
1
20 °C
X= Br, I
a
Entry
1
ArX
Time (h)
7
Product
CN
Yield%
97
I
1
a
CN
I
2
3
10
20
95
93
Me
Me
1
b
I
CN
Me
I
Me 1c
CN
4
5
20
10
95
94
Me
Me
1d
CN
I
MeO
MeO
1e
CN
I
6
15
89
1
f
I
CN
7
8
2
2
98
98
O N
O N
2
2
1g
I
CN
Cl
Cl
1h
1
4
Page 14 of 25

I
CN
9
5
9
97
92
Br
Br
1i
I
CN
1
0
CHO
CHO
1j
I
CN
11
12
13
5
95
71
78
OHC
OHC
OHC
OHC
1k
CN
CN
Br
Br
24
24
1
k
O N
O N
2
2
1g
Br
CN
CN
1
1
4
5
24
75
73
Cl
Cl
1
h
Br
30
Me
Me
1
b
a
Reaction conditions: ArX (1 mmol), K
4
6 2 3
FeCN (0.6 mmol), K CO (1.5 mmol), catalyst (10 mg,
containing 0.001 mmol Pd), and DMF (2 mL)
Finally, recycling property of the catalyst was studied for the reaction of iodobenzene with
[Fe(CN)] . After completion of each run, the catalyst was separated by external magnetic rod,
washed with diethyl ether and was subjected into another batch of the reaction (Figure 6).
K
4
6
1
5
Page 15 of 25

a
b
c
Figure 6. a) reaction mixture, b) isolation of catalyst from reaction by external magnet after 3
min, c) isolation of catalyst from reaction by external magnet after 8 min.
The result showed that catalyst is recoverable and was recycled for four consecutive runs with
small drops in catalytic activity (Figure 7).
4 6
Figure 7. Recycling of catalyst for the reaction of iodobenzene with K Fe(CN)
1
6
Page 16 of 25

A possible mechanism for the Pd@CuFe
mechanism for cyanation of aryl halides which occur on the surface of the catalyst (scheme 3)
40]. Reaction proceeded via the oxidative addition of aryl halide over catalyst followed by
2 4
O catalyzed cyanation reaction involves a well-known
[
cyanide anion transfer from K [Fe(CN)] and finally reductive elimination step afforded the aryl
4
6
cyanide product.
ArX
ArCN
Ar
Ar
Pd
CuFe O4
2
CN
X
[
Fe(CN) ]2
-n
n
-
3-n
X + [Fe(CN) ]
n-1
2 4
Scheme 3. Proposed mechanism for Pd@CuFe O catalyzed cyanation of aryl halides.
4
. Conclusion
In summary, preparation and characteriztion of palladium nanoparticles supported copper ferrite
nanoparticles is described. The new heterogeneous catalyst is an efficient and recyclable catalyst
in the cyanation of aryl iodides and bromides at low palladium loading condition in comparison
3 4 2 2 3 4
to the Fe O supported palladium nanoparticles, homogeneous Pd(OAc) , CuI, CuCl , Fe O , and
CuFe O nanoparticles. It may be concluded that the synergitic effect between palladim and
2
4
1
7
Page 17 of 25

copper species is responsible for the observed reactivity. The catalyst showed good recyclability
using external magnet and was reused for four times with small drops in catalytic activity.
Acknowledgment
The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research
Council and Iran National Science Foundation (INSF-Grant number of 93020713) for support of
this work.
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Research highlights
•
•
2 4
Pd@CuFe O NPs were synthesized and characterized for the first time.
The low loading Pd catalyst shows good activity in the cyanation of aryl iodides and
bromides.
•
•
Synergitic effect between Pd and Cu species is responsible for the observed reactivity.
The Magnetically recoverable catalyst was recycled for four times with small drops in
activity.
2
4
Page 24 of 25

Palladium Nanoparticles Supported on Magnetic Copper Ferrite Nanoparticles: The
Synergistic Effect of Palladium and Copper for Cyanation of Aryl Halides with
K
4
6
[Fe(CN) ]
a*
a
Mohammad Gholinejad Afsaneh Aminianfar
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), P. O. Box
4
5195-1159, Gava zang, Zanjan 45137-6731, Iran.
Email: gholinejad@iasbs.ac.ir
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Gava Zang, Zanjan
5137-66731, Iran; email: gholinejad@iasbs.ac.ir
4
2 4
Pd supported on CuFe O NPs were synthesized, characterized and successfully applied as magnetically
recyclable catalyst for the cyanation of aryl iodides and bromides.
2
5
Page 25 of 25