Palladium immobilized on amidoxime-functionalized magnetic Fe3O4 nanoparticles: A highly stable and efficient magnetically recoverable nanocatalyst for sonogashira coupling reaction

Article abstract of DOI:10.1002/aoc.3390

We describe the synthesis of a novel Fe₃O₄/amidoxime (AO)/Pd nanocatalyst by grafting of AO groups on Fe₃O₄ nanoparticles and subsequent deposition of Pd nanoparticles. Prior to grafting of AO, the 2-cyanoethyl-

Full text of DOI:10.1002/aoc.3390

Full paper
Received: 12 August 2015
Revised: 29 August 2015
Accepted: 1 September 2015
Published online in Wiley Online Library: 5 October 2015
(wileyonlinelibrary.com) DOI 10.1002/aoc.3390
Palladium immobilized on amidoxime-
functionalized magnetic Fe3O4 nanoparticles: a
highly stable and efficient magnetically
recoverable nanocatalyst for sonogashira
coupling reaction
Hojat Veisia*, Alireza Sedrpoushanb, Behrooz Malekic, Malak Hekmatid,
Masoud Heidarib and Saba Hemmatia
We describe the synthesis of a novel Fe3O4/amidoxime (AO)/Pd nanocatalyst by grafting of AO groups on Fe3O4 nanoparticles and
subsequent deposition of Pd nanoparticles. Prior to grafting of AO, the 2-cyanoethyl-functionalized Fe3O4 nanoparticles prepared
through combining 2-cyanoethyltriethoxysilane and Fe3O4 were treated with hydroxylamine. The AO-grafted Fe3O4 nanoparticles
were then used as a platform for the deposition of Pd nanoparticles. The catalyst was characterized using Fourier transform infra-
red spectroscopy, X-ray diffraction, scanning and transmission electron microscopies, vibrating sample magnetometry,
wavelength- and energy-dispersive X-ray spectroscopies and inductively coupled plasma analysis. Fe3O4/AO/Pd is novel
phosphine-free recyclable heterogeneous catalyst for Sonogashira reactions. Interestingly, the novel catalyst could be recovered
in a facile manner from the reaction mixture by applying an external magnet device and recycled seven times without any signif-
icant loss in activity. Copyright © 2015 John Wiley & Sons, Ltd.
Keywords: Fe3O4/AO/Pd; magnetic nanoparticles; heterogeneous catalyst; Pd nanoparticles; Sonogashira
The immobilization methods used to deposit Pd into heteroge-
Introduction
neous solid beds have been studied extensively, and diverse sup-
ports such as clay,[5] carbon nanofibres,[6] montmorillonite,[7]
In the past few decades, much attention has been paid to research
magnetic mesoporous silica,[8] zeolites[9] and metal oxides[10] have
dedicated to the development of environmentally compatible pro-
cesses. Along with this awareness, industries have started
implementing safer practices such as waste prevention using new
catalysts. In this regard, the design of environmentally benign, eco-
nomical, practical and efficient processes for catalyst separation
and reuse has attracted much attention as a central focus area in
green chemistry research in the twenty-first century. Supported
metal nanoparticles (NPs) are excellent catalysts for a variety of re-
actions because of their large surface-to-volume ratio, remarkable
efficiency, topological properties, interaction between them and
supports, and their heterogenization on various oxide and carbon
supports that allow their recovery.[1] In particular, iron oxide mag-
netic nanoparticles (MNPs) have received considerable attention
because they are biocompatible and can be recovered easily from
reaction mixtures using a simple external magnetic field.[2]
Conventionally, the fixation of NPs on supports is mostly carried
out by the reduction of metal salts in the presence of the support
followed by an adequate thermal treatment.[3] Mesoporous sup-
ports (MCM-41, SBA) are frequently used as supports for Pd NPs–
MNPs.[4a–c] Other supports, such as polymer-coated MNPs,[4d–g]
ionic-liquid-modified MNPs[4h] and sulfonated graphene-decorated
MNPs,[4i] are also employed for the stabilization of Pd NPs. Phos-
phine and amine ligands grafted on MNPs are also common for this
purpose.[4j–o]
been investigated. A current challenge in this area is the develop-
ment of efficient immobilized systems that can simultaneously fulfil
the usual targets of achieving high turnover numbers and facilitate
recovery and reuse as well as the need for obtaining Pd-free final
products,[11,12] meeting the strict purity specifications for the phar-
maceutical industry.[13,14]
The Sonogashira cross-coupling of aryl halides with terminal al-
kynes has been employed for the synthesis of several compounds
bearing internal alkyne moieties, including biologically active mole-
cules and functional polymers.[15–17] Toxic and expensive homoge-
neous palladium phosphine complexes, which are rarely
*
Correspondence to: Hojat Veisi, Department of Chemistry, Payame Noor
University, Tehran, Iran. E-mail: hojatveisi@yahoo.com
a Department of Chemistry, Payame Noor University, Tehran, Iran
b Institute of Industrial Chemistry, Iranian Research Organization for Science and
Technology, Tehran, Iran
c
Hakim Sabzevari University, Department of Chemistry, PO Box 397, Sabzevar, Iran
d Department of Pharmaceutical Chemistry, Faculty of Pharmaceutical Chemistry,
Pharmaceutical Sciences Branch, (IAUPS), Tehran, Iran
Appl. Organometal. Chem. 2015, 29, 834–839
Copyright © 2015 John Wiley & Sons, Ltd.

Fe3O4/AO/Pd as an effective nano catalyst in the sonogashira reaction
recoverable without elaborate and wasteful procedures,[18] have
been used as catalysts for the Sonogashira reaction. Phosphines
could be a more serious economic burden than even the
palladium itself in some cases.[19] From an economic and
environmental standpoint, it is desirable to use solid catalysts
without the use of hazardous phosphine additives as a greener
alternative to conventional homogeneous processes.[19] Indeed,
phosphine-free Sonogashira coupling processes under homoge-
neous as well as heterogeneous conditions have been
reported.[20–25] In the work reported here, in continuation of
our studies of the synthesis of novel supported catalysts,[26] we
decided to design and synthesize novel amidoxime (AO)-func-
tionalized Fe3O4 NPs for the subsequent deposition of palladium
NPs (Fe3O4/AO/Pd) (Scheme 1). After characterization,
Sonogashira reactions were selected to investigate the catalytic
activity and recyclability (Scheme 2).
Experimental
Preparation of magnetic Fe3O4 NPs
Scheme 2. Possible mechanism of Sonogashira coupling reaction using
Naked Fe3O4 NPs were prepared by chemical coprecipitation of Fe3
+ and Fe2+ ions with a molar ratio of 2:1. Typically, FeCl3Á6H2O (5.838
g, 0.0216 mol) and FeCl2Á4H2O (2.147 g, 0.0108 mol) were dissolved
in 100 ml of deionized water at 85°C under nitrogen atmosphere
and vigorous mechanical stirring (500 rpm). Then, 10 ml of 25%
NH4OH was quickly injected into the reaction mixture in one por-
tion. The addition of the base to the Fe2+/Fe3+ salt solution resulted
in the immediate formation of a black precipitate of MNPs. The re-
action continued for another 25 min and the mixture was cooled to
room temperature. Subsequently, the resultant ultrafine magnetic
particles were treated using magnetic separation and washed sev-
eral times with deionized water.
Fe3O4/AO/Pd.
refluxed under argon atmosphere at 100°C for 48 h. The product
was separated by filtration, washed with ethanol and dried under
vacuum for 24 h at 50°C. The precipitated product (Fe3O4/Ethyl-
CN) was dried at room temperature under vacuum. Then, the 2-
cyanoethyl-functionalized MNPs (1 g) were immersed in NH2OH
aqueous solution (50 ml, 50%) at 65°C for 5 h (Scheme 1). The
AO-functionalized MNPs (Fe3O4/AO) were filtered off, washed with
distilled water several times and dried.
Preparation of Fe3O4/AO/Pd(0)
Preparation of Fe3O4/AO
Fe3O4/AO (500 mg) was dispersed in CH3CN (30 ml) using an ultra-
sonic bath for 30 min. Subsequently, a yellow solution of PdCl2 (30
mg) in 30 ml of acetonitrile was added to the dispersion of Fe3O4/
AO and the mixture was stirred for 10 h at 20–25°C. Then, the
Fe3O4/AO/Pd(II) thus obtained was separated by magnetic decanta-
tion and washed successively with CH3CN, water and acetone to re-
move the unattached substrates.
The obtained MNP powder (500 mg) was dispersed in 50 ml of
toluene solution by sonication for 20 min, and then triethoxyethyl
cyanide (3 mmol) was added to the mixture. The mixture was
The reduction of Fe3O4/AO/Pd(II) using hydrazine hydrate was
performed as follows. An amount of 50 mg of Fe3O4/AO/Pd(II)
was dispersed in 60 ml of water, and then 100 μl of hydrazine
hydrate (80%) was added. The pH of the mixture was adjusted
to 10 with 25% ammonium hydroxide and the reaction was
carried out at 95°C for 2 h. The final product, Fe3O4/AO/Pd(0),
was washed with water and dried in vacuum at 40°C. Scheme 1
depicts the synthetic procedure of Fe3O4/AO/Pd. The concentra-
tion of Pd in Fe3O4/AO/Pd was 1.83 wt% (0.17 mmol gÀ1), which
was determined using inductively coupled plasma atomic emis-
sion spectroscopy (ICP-AES) and energy-dispersive X-ray spec-
troscopy (EDX).
General procedure for sonogashira coupling reactions
In a typical reaction, 10 mg of Fe3O4/AO/Pd (10 mg = 0.0017 mmol
Pd) was placed in a 25 ml Schlenk tube, and 1 mmol of aryl halide in
5 ml of dimethylformamide (DMF) was added with phenylacetylene
(1.5 mmol) and Et3N (2 mmol). The mixture was then stirred for the
desired time at 80°C. The progress of the reaction was monitored
Scheme 1. Synthetic route to Fe3O4/AO/Pd.
Appl. Organometal. Chem. 2015, 29, 834–839
Copyright © 2015 John Wiley & Sons, Ltd.
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H. Veisi et al.
using TLC. After the reaction was over, the catalyst was removed
using an external magnet. The filtrate was then extracted with ethyl
acetate followed by washing with brine solution. The organic part
thus obtained was dried with sodium sulfate and the solvent was
then removed by rotary evaporation under reduced pressure. The
product thus obtained was further purified before undergoing
spectroscopic analysis.
hydroxylamine treatment, the CN stretching band is absent and
signals appear at 3300 cmÀ1 attributable to the N–H stretching of
amine generated through AO functionalization. Thus it is evident
that the cyano groups are converted into AO groups for the
metal–ligand coordination.
TEM images of the Fe3O4/AO/Pd catalyst reveal that the Pd NPs
with nearly spherical morphology are grafted on AO-functionalized
Fe3O4 NPs (Fig. 2). In the TEM images, Fe3O4 NPs of 15–20 nm in
diameter and Pd NPs of ca 3 nm entrapped in iron oxide are
observed. An SEM image of the final catalyst shows the formation
of uniform and mono-dispersed NPs (Fig. 3).
Results and discussion
The elemental composition was determined using EDX analysis
and the results, shown in Fig. 4, indicate Si, O, C, N, Fe and Pd signals
that are provided by Fe3O4/AO/Pd. For further characterization of
the sample, WDX coupled with quantified FESEM mapping of the
sample was also carried out (Fig. 5). WDX can provide qualitative
information about the distribution of various chemical elements
in the catalyst matrix. Looking at the compositional maps of Fe, Si,
C, N, Pd, and mainly the combined composition image, the pres-
ence of Pd NPs with good dispersion is clearly distinguished in
the composite.
Fe3O4/AO/Pd was prepared using the concise route outlined in
Scheme 1. Naked magnetic Fe3O4 NPs were prepared through a
chemical coprecipitation method, and subsequently were coated
with 2-cyanoethyltriethoxysilane to afford AO-functionalized MNPs
in the presence of hydroxylamine. Ultimately, the reaction of AO
groups with PdCl2 and subsequent reduction led to the corre-
sponding Pd NPs supported on MNPs. Finally, the mixture was col-
lected using an external magnet, followed by drying in vacuum.
The Pd content in the Fe3O4/Ethyl-CN/Pd catalyst was determined
as 1.83 wt% (0.17 mmol gÀ1) using ICP-AES. The characterization
of the catalyst was carried out using Fourier transform infrared
(FT-IR) spectroscopy, transmission electron microscopy (TEM), scan-
ning electron microscopy (SEM), EDX, wavelength-dispersive X-ray
spectroscopy (WDX), ICP analysis and vibrating sample magnetom-
etry (VSM).
Figure 1 shows FT-IR spectra of Fe3O4, Fe3O4/Ethyl-CN and Fe3O4/
AO. The spectrum of the MNPs alone shows a stretching vibration
at 3381 cmÀ1 which incorporates the contributions from both sym-
metric and asymmetric modes of the O–H bonds which are at-
tached to the surface of iron atoms.[26] The bands at low
wavenumbers (≤700 cmÀ1) arise from vibrations of Fe–O bonds of
iron oxide, which for the bulk Fe3O4 samples appear at 570 and
375 cmÀ1 but for Fe3O4 NPs at 624 and 572 cmÀ1, a blue shift
due to the size reduction.[27–29] The presence of an adsorbed water
layer is confirmed by a stretching vibrational mode of water at 1622
cmÀ1. The FT-IR spectra of Fe3O4/Ethyl-CN and Fe3O4/AO show
Fe–O vibrations in the same vicinity. The introduction of cyano
groups to the surface of Fe3O4 is confirmed by the bands at 1009,
2245 and 2952 cmÀ1 assigned to the Fe–O–Si, CN and C–H
stretching vibrations, respectively. The cyanide signal appears at
2245 cmÀ1 in the spectrum of Fe3O4/Ethyl-CN. Interestingly, after
Figure 2. TEM image of Fe3O4/AO/Pd.
Figure 1. FT-IR spectra of (a) Fe3O4, (b) Fe3O4/Ethyl-CN and (c) Fe3O4/AO.
Figure 3. SEM image of Fe3O4/AO/Pd.
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Appl. Organometal. Chem. 2015, 29, 834–839

Fe3O4/AO/Pd as an effective nano catalyst in the sonogashira reaction
the immobilization of Pd NPs in the composite. As a result, the
modified MNPs show a typical superparamagnetic behaviour and
can be separated from a reaction mixture using an external magnet.
The catalytic activity of the prepared catalyst (Fe3O4/AO/Pd) was
evaluated in the Sonogashira coupling reaction. In order to deter-
mine the optimized reaction conditions, the reaction between
iodobenzene and phenylacetylene was chosen as a model reaction
(Table 1). The effects of various factors such as solvent, base,
amount of catalyst and temperature were studied (Table 1). Results
indicate that using Et3N as a base, DMF as a solvent and 0.1 mol%
catalyst at 80°C affords the highest yield of the product (Table 1,
entry 10). In continuation of the work, the catalytic activity of our
pre-catalyst Fe3O4/AO/Pd(II) was checked using the optimized
conditions (Table 1, entry 10). It does not lead to a better yield than
Fe3O4/AO/Pd.
Figure 4. EDX spectrum of the catalyst.
Using these optimized reaction conditions, the efficiency of the
catalyst was studied in the Sonogashira reaction of various aryl ha-
lides. The results are summarized in Table 2. Aryl iodides (entries 1–
6) and aryl bromides (entries 7–13) with various functional groups
efficiently react with phenylacetylene to produce Sonogashira
products in good to excellent yields (Table 2). This catalytic system
was also applied for the reactions of aryl chlorides (Table 2, entries
14–16). It is clear from Table 2 that aryl chlorides couple with
phenylacetylene in moderate yields within 10–12 h reaction times.
The heterogeneity of the catalyst was evaluated to study
whether the reaction using the solid Pd catalyst occurs on the
Fe3O4/AO surface or is catalysed by Pd species leached in the liquid
phase. To address this issue, two separate experiments were con-
ducted with iodobenzene and phenylacetylene. In the first experi-
ment, the reaction was terminated after 10 min; at this juncture,
the catalyst was separated from the reaction mixture using an ex-
ternal magnet and the reaction was continued with the filtrate for
Figure 5. FESEM image of Fe3O4/AO/Pd and elemental maps of Fe, Si, C, N
and Pd atoms of Fe3O4/AO/Pd.
Table 1. Optimization of reaction conditions for reaction of
iodobenzene with phenylacetylenea
In order to obtain information about the superparamagnetic
property of the prepared nanocatalyst, magnetization curves of
Fe3O4 NPs and of the final catalyst (Fe3O4/AO/Pd) at room temper-
ature were determined using VSM (Fig. 6). It is worth mentioning
that the decrease in the magnetization value of Fe3O4/AO/Pd
(55.4 emu gÀ1) in comparison with Fe3O4 NPs (62.1 emu gÀ1) con-
firms the immobilization of organic groups on the surface and also
Entry
Solvent
Base Pd (mol%) T (°C) t (h) Yield (%)b
1
2
3
4
5
6
7
8
9
DMF
H2O
K2CO3
K2CO3
K2CO3
K2CO3
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.15
0.0
80
80
80
80
80
80
80
80
80
80
80
80
80
50
100
80
80
80
10
12
12
12
70
55
60
60
55
50
65
65
70
96
70
65
Trace
80
96
80
92
0
EtOH
CH3CN
H2O–EtOH (1:1) K2CO3
H2O–EtOH (1:2) K2CO3
H2O–EtOH (2:1) K2CO3
0.4
0.25
1.5
No solvent
DMF
K2CO3
Na2CO3
Et3N
12
10
0.5
10 DMF
11 DMF
12 DMF
13 DMF
14 DMF
15 DMF
16 DMF
17 DMF
18 DMF
NaHCO3
K3PO4
No base
Et3N
5
5
12
5
Et3N
0.5
Et3N
2
Et3N
0.5
24
Et3N
aReaction conditions: iodobenzene (1.0 mmol), phenylacetylene (1.2
mmol), catalyst, base (2 mmol) and solvent (3 ml).
bIsolated yield.
Figure 6. Room temperature magnetization curves of Fe3O4, and Fe3O4/
AO/Pd.
Appl. Organometal. Chem. 2015, 29, 834–839
Copyright © 2015 John Wiley & Sons, Ltd.
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H. Veisi et al.
Table 2. Sonogashira reaction of various aryl halides using Fe3O4/AO/
Pd as catalysta
Entry
R
X
Time (h)
Yield (%)b
1
H
I
0.5
0.5
0.5
1
96
98
96
88
95
92
96
92
90
85
92
88
95
85
75
65
2
4-CH3O
4-CH3
2-CH3
4-Cl
I
3
I
4
I
5
I
0.5
0.5
1
6
3-NO2
H
I
7
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Figure 7. Recycling of the Fe3O4/AO/Pd catalyst in successive Sonogashira
coupling reactions under similar conditions.
8
4-CH3O
4-CH3
2-CH3
4-Cl
2
9
2
10
11
12
13
14
15
16
5
4-methylbromobenzene and phenylacetylene, the presented pro-
cedure using Fe3O4/AO/Pd(0) as catalyst was compared with other
systems. It is evident from Table 3 that the present system gives
higher conversions and yields compared to other reported systems.
In view of industrial purposes and green chemistry, the reusabil-
ity of the catalyst was tested by carrying out repeated runs of the
reaction with the same batch of catalyst in the case of the model
reaction (Table 1). In order to regenerate the catalyst, after each cy-
cle it was separated using a magnet, and washed several times with
deionized water and ethanol. 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 seven times without any significant loss in activity (Fig. 7).
This high catalytic activity can be possibly related to the strong in-
teraction of Pd NPs with active sites of AO groups. Palladium
leaching of the catalyst was studied before and after the reaction
using ICP-AES analysis. The Pd content is found to be 1.83 and
1.71 wt% before and after the seven-reaction series, respectively,
which implies insignificant Pd leaching.
2.5
3
3-NO2
4-COCH3
H
2
10
10
12
4-CH3
2-CH3O
aReaction conditions: aryl halide (1 mmol), phenylacetylene (1.2 mmol),
Et3N (2 mmol), DMF (3 ml), catalyst (0.1 mol%) and 80°C.
bIsolated yield.
an additional 20 min. In the second experiment, the reaction was
terminated after 10 min. In both cases, the desired product is ob-
tained in the same yield (45%). The result of the magnetic separa-
tion experiment confirms the heterogeneous nature of the
catalyst. So, based on these evidences and the literature,[27] a reac-
tion mechanism for Sonogashira coupling with the prepared
nanocatalyst is proposed as shown in Scheme 2. Some of the Pd
NP species that are bound to the support undergo oxidative addi-
tion with aryl halide and are released to the solution, but some of
them still remain on the surface. After the reductive elimination
step the Pd NPs are recaptured by free AO groups on the surface
of the support and can start a new catalytic cycle. We speculate that
these simultaneous mechanisms are possible.
To investigate the practical applicability of the catalyst, we scaled
up the reaction of iodobenzene to 10 mmol with 12 mmol of
phenylacetylene under the optimized reaction conditions. Results
indicate that the reaction proceeds effectively and the desired
product is obtained in 94% isolated yield.
Firstly, the aryl halide reacts with the active palladium catalyst
(oxidative addition) to produce a Pd(II) intermediate (II). Then, the
acetylene moiety of phenylacetylene exchanges with halide on
the surface of the catalyst (III). Finally, III undergoes reductive elim-
ination to produce the expected product.
Conclusions
We have prepared and characterized novel Fe3O4 NP-supported Pd
NPs. The catalyst showed high activity in the Sonogashira coupling
reaction of aryl halides. The catalyst showed good stability and
could be recycled several times with only a small decrease in its
catalytic activity. These advantages make the process highly
valuable from the synthetic and environmental points of view.
Finally, to assess the present protocol with respect to other re-
ported methods for the Sonogashira coupling reaction between
Table 3. Comparison of activity of various catalysts in Sonogashira cou-
pling reaction of 4-methylbromobenzene with phenylacetylene
Acknowledgment
We are grateful to Payame Noor University for partial support of this
work.
Catalyst
Reaction conditions
Yield (%)
Ref.
Fe3O4/AO/Pd(0)
Et3N, DMF, 80°C, 2 h
90
84
This study
[28]
SiO2-pA-Cyan-Cys- NaOAc, DMF–H2O, 80°C, 7 h
Pd
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K3PO4, DMF, 80°C, 6 h
Et3N, NMP, 90°C, 72 h
13
40
[40]
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