Pd(0)- S-propyl-2-aminobenzothioate immobilized onto functionalized magnetic nanoporous MCM-41 as efficient and recyclable nanocatalyst for the Suzuki, Stille and Heck cross coupling reactions

Article abstract of DOI:10.1002/aoc.4282

The present work describes the use of Pd(0)- S-propyl-2-aminobenzothioate Complex immobilized onto functionalized magnetic nanoporous MCM-41(Fe₃O₄@MCM-41@Pd-SPATB) as efficient and recyclable nano-organometallic catalyst for C–C bond formation between various aryl halides with phenylboronic acid (Suzuki reaction), aryl halides with triphenyltin chloride (Stille reaction), and aryl halides with n-butyl acrylate (Heck reaction). All the reactions were carried out in PEG-400 as green solvent with short reaction time and good to excellent yields. This catalyst was characterized by FT-IR spectroscopy, XRD, TGA, VSM, ICP-OES, TEM, EDX and SEM techniques. Ease of operation, high efficiency, recovery and reusability for five continuous cycles without significant loss of its catalytic activities or metal leaching are the noteworthy features of the currently employed heterogeneous catalytic system.

Full text of DOI:10.1002/aoc.4282

Received: 27 October 2017
DOI: 10.1002/aoc.4282
Revised: 26 December 2017
Accepted: 26 December 2017
F U L L P A P E R
Pd(0)‐ S‐propyl‐2‐aminobenzothioate immobilized onto
functionalized magnetic nanoporous MCM‐41 as efficient
and recyclable nanocatalyst for the Suzuki, Stille and Heck
cross coupling reactions
1
2
1
1
Mohsen Nikoorazm
| Farshid Ghorbani | Arash Ghorbani‐Choghamarani
| Zahra Erfani
1
Department of Chemistry, Faculty of
Science, Ilam University, P. O. Box
The present work describes the use of Pd(0)‐ S‐propyl‐2‐aminobenzothioate
Complex immobilized onto functionalized magnetic nanoporous MCM‐
69315516, Ilam, Iran
2
Department of Environment, Faculty of
4
1(Fe O @MCM‐41@Pd‐SPATB) as efficient and recyclable nano‐organome-
3
4
Natural Resource, University of Kurdistan,
6177‐15177 Sanandaj, Iran
tallic catalyst for C–C bond formation between various aryl halides with
6
phenylboronic acid (Suzuki reaction), aryl halides with triphenyltin chloride
Correspondence
(Stille reaction), and aryl halides with n‐butyl acrylate (Heck reaction). All
Mohsen Nikoorazm, Department of
Chemistry, Faculty of Science, Ilam
University, P.O. Box 69315516, Ilam, Iran.
Email: e_nikoorazm@yahoo.com
the reactions were carried out in PEG‐400 as green solvent with short reaction
time and good to excellent yields. This catalyst was characterized by FT‐IR
spectroscopy, XRD, TGA, VSM, ICP‐OES, TEM, EDX and SEM techniques. Ease
of operation, high efficiency, recovery and reusability for five continuous cycles
without significant loss of its catalytic activities or metal leaching are the
noteworthy features of the currently employed heterogeneous catalytic system.
Funding information
Ilam University
KEYWORDS
3 4
C‐C bond formation, Fe O @MCM‐41@Pd‐SPATB, heck reaction, Stille reaction, Suzuki reaction
1
| INTRODUCTION
In the past decade, the design of highly efficient and
recyclable catalysts has become a very important matter
for reasons of economic and environmental impact.
[11]
Carbon–carbon coupling reactions such as the Suzuki–
Miyaura, Stille and Heck–Mizoroki reactions have been
widely used as significant procedures in modern synthetic
organic chemistry for academic and industrial process
including the pharmaceuticals, herbicides, agrochemicals,
polymers, liquid crystal materials, hydrocarbons, UV
One strategy has focused on combining the high selectiv-
ity and activity of homogeneous catalysts with the ease of
[12]
separation and recycling of heterogeneous catalysts.
For this aim, immobilization strategy used for linking
homogeneous catalysts to various solid supports to facili-
tate catalysts separation and recycling, as well as product
[
1–6]
screens, and advanced materials.
Mostly palladium
[
13]
complexes as efficient and active catalyst are used to cata-
lyze these Carbon–carbon couplings reactions as they
offer high product yields, high selectivity and compatibil-
ity with many functional moieties. Homogeneous Pd
catalysts are not used in industrial applications because
of the difficulty in separating and recycling, and possibil-
separation.
Among the different classes of supports
available for this kind of catalysis, nanoparticle such as
magnetic iron oxide and mesoporous silica material
(especially MCM‐41) are ideal heterogeneous supports.
Because this type of supports can be used as efficiently
[7]
bridge and fill the gap between homogeneous and hetero-
[8–10]
[14,15]
ity of the high leaching of metal.
In order to solve this
geneous catalysts.
More recently, the consolidation
problem, new strategies should be employed.
of functionalized mesoporous silica materials with
Appl Organometal Chem. 2018;e4282.
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Copyright © 2018 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.4282

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NIKOORAZM ET AL.
magnetic nanoparticles (MNPs), within a single material
to develop novel porous magnetic nanostructure which
have the advantages and properties of both mesoporous
Silica (thermal and mechanical stability, large pore
Volume and high surface area for catalyst loading) and
magnetic nanoparticles (simple in synthesis, fast separa-
tion, low cost, high surface area and low toxicity), is
undoubtedly of great interest for practical applications
such as catalytic applications, magnetic storage and
recording, for sensors, environmental, and biomedical
sonication and N atmosphere. After the completed of
2
the reaction for 30 min, the Fe O nanoparticles was
3
4
[
21]
isolated and dried at 80 °C in vacuum.
In the next step,
Fe O nanoparticles (0.05 g) were dispersed in ethanol
3
4
(20.0 ml) for 30 min using ultra sonication. Then, the
suspension was centrifuged and the solid was in a mixture
of NH (0.5 ml), deionized water (10 ml) and ethanol
3
(20 ml). The system was kept under vigorous mechanical
stirring for 30 min, and then (0.03 g) of TEOS was added
dropwise. At the end of the addition, the mixture was kept
under stirring at room temperature, for 6 h. The coated
nanoparticles (Fe O @nSiO ) were separated with the
[16–20]
applications.
Therefore owing to the context of reuse
of palladium, Herein we report synthesis and spectro-
scopic characterization of a Pd‐SPATB complex supported
on functionalized magnetic nanostructured MCM‐41
3
4
2
aid of a magnet, and washed with ethanol and water sev-
eral times. Then, the coated Fe O @nSiO nanoparticles
3
4
2
(
Fe O @MCM‐41@Pd‐SPATB), which has been applied
were dispersed in a mixture of NH (0.6 ml), deionized
3
4
3
as a novel and efficient nano‐organometallic catalyst with
excellent catalytic activity and selectivity in Carbon–
carbon coupling reactions in PEG‐400 as green solvent.
water (40 ml), ethanol (30 ml) and CTAB (0.15 g). After
stirring at room temperature for 30 min, 0.4 g of TEOS,
added slowly to the solution and continued to stir for
6
h. The solid products were collected by magnetic separa-
tion, washed with plenty of ethanol/deionized water, and
subsequently dried in a vacuum oven at 80 °C for 12 h.
After this period, to remove organic template CTAB,
ethanol (100 ml) and 5 ml of 2 mol L‐ HCl was added
to the 0.1 g of produced nanocomposite, then the mixture
was kept under stirring at room temperature, for 48 h.
The solid products were collected by magnetic separation,
and subsequently dried in a vacuum oven at 80 °C for
24 h. Finally, we obtained the Fe3O4@MCM‐41.
2
2
| EXPERIMENTAL
.1 | Materials and techniques
1
The tetraethyl orthosilicate (TEOS), cationic surfactant
cetyltrimethylammonium bromide (CTAB, 98 %), solvents
and other materials were purchased from Sigma‐Aldrich,
Merck or Flucka Chemical Companies and were used as
received without further purification.
Nanostructures were identified using a Holland
Philips X’pert X‐ray powder diffraction (XRD) diffractom-
eter, with monochromatized Cu Ka radiation under the
conditions of 40 kV and 30 mA. Thermogravimetric
analyses (TGA) of the samples were recorded between
2
.3 | Preparation of MPTMS
functionalized mag mesoporous silica
Fe O @MCM‐41‐SH)
(
3
4
3
0 ‐ 800 °C using Shimadzu DTG‐60 automatic thermal
To a suspension of Fe O @MCM‐41 (4.8 g, 80 °C) in
3
4
analyzer. Fourier transform infrared (FT‐IR) spectra
n‐hexane, 4.8 g of (3‐mercaptopropyl) trimethoxysilane
(MPTMS) was added slowly and then refluxed for 24 h.
The separated solid was collected by magnetic separation,
washed with n‐hexane and dried under vacuum.
were recorded with FTIR spectrophotometer (Bruker,
‐
1
Germany) Vertex 70 in the range of 400 4000 cm . The
particle size and morphology were examined using SEM
with a FESEM‐TESCAN MIRA3, and also using TEM
with a High resolution TEM JEOL, JEM‐2100F, 200KV
transmission electron microscope. VSM measurements
were performed using a vibrating sample magnetometer
2
.4 | Preparation of heterogeneous Pd‐
SPATB complex immobilized onto
magnetic nanoporous MCM‐41
(
VSM) MDKFD. The content of Pd was measured using
inductively coupled plasma‐optical emission spectrometry
ICP‐OES).
(
Fe O @MCM‐41@Pd‐SPATB)
3
4
(
For the preparation of Fe O @MCM‐41@Pd‐SPATB, 0.5 g
3
4
of functionalized Fe O @MCM‐41 and S‐propyl‐2‐
3
4
aminobenzothioate (1.2 mmol) in ethanol was refluxed
for 3 h. The resulting solid was washed with ethanol, col-
lected by magnetic separation and dried under vacuum
and designated as Fe O @MCM‐41@SPATB. Ultimately,
2
.2 | Synthesis of Fe O @MCM‐41
3
4
The first, a mixture of FeCl .6H O (2 g) and FeCl .4H O
3
2
2
2
(0.8 g) was dissolved in 10 ml of deionized water under
3
4
N atmosphere. Then, the mixture was added to solution
the Fe O @MCM‐41@Pd‐SPATB was prepared by
2
3 4
containing 100 ml of 1.0 mol L‐ NH .H O and 0.4 g
1
stirring a mixture of Pd (OAc) (0.168 g, 0.63 mmol) and
3
2
2
of cetyltrimethylammonium bromide (CTAB) under
0.250 g Fe O @MCM‐41@SPATB in ethanol (20 ml) for
3
4

NIKOORAZM ET AL.
3 of 13
2
0 h under reflux conditions. Afterward, For the reduc-
tion of Pd(II) present in the resulting catalyst, NaBH4
0.022 g, 0.057 mmol) was added and then refluxed under
temperature. Then catalyst was separated by an external
magnet and the reaction mixture was extracted with
diethyl ether and water. The organic layer was dried over
Na SO (1.5 g) and after evaporation of the diethyl ether,
(
the same conditions for 2 h. The final product was sepa-
rated by magnet, and washed with ethanol and dried at
room temperature. The detailed preparation route for
Fe O @MCM‐41@Pd‐SPATB is shown in Scheme 1.
2
4
the pure product was obtained.
3
4
2.7 | Selected spectral data
1
4
‐methoxy‐1,1'‐biphenyl (Table 2, entry 4): H NMR
2
.5 | General procedure for the synthesis
(
(
400 MHz, CDCl ): δ = 7.65‐7.54 (m, 4H), 7.47‐7.43
t, J= 7.6 Hz, 2H), 7.36‐7.29 (tt, J= 7.6, 1.2 Hz, 1H),
3
H
of biphenyl derivatives
A mixture of an aryl halide (1 mmol), phenylboronic acid
or Ph SnCl (0.5 mmol), K CO3 (3 mmol), and
7.03‐7.01 (dt, J= 8.8, 2.4 Hz, 2H), 3.89 (s, 3H) ppm.
1
butyl 3‐(p‐tolyl)acrylate (Table 6, entry 2):: H NMR
3
2
Fe O @MCM‐41@Pd‐SPATB was added to a reaction ves-
(400 MHz, CDCl ): δ = 7.69‐7.65 (d, J= 16 Hz, 1H), 7.49‐
3
4
3
H
sel. The resulting mixture was stirred in PEG‐400 at 80 °C
for an appropriate time and the progress of the reaction
was monitored by thin‐layer chromatography (TLC).
After completion of the reaction, the catalyst was sepa-
rated using an external magnet and washed with ethyl
acetate. The reaction mixture was extracted with ethyl
acetate and H O, and dried over anhydrous Na SO
4
7.47 (d, J= 8 Hz, 2H), 7.25‐7.23 (d, J= 8 Hz, 2H), 6.47‐6.43
(d, J= 16 Hz, 1H), 4.27‐4.24 (t, J= 6.6 Hz, 2H), 2.43 (s, 3H),
1.78‐1.71 (m, 2H), 1.52‐1.46 (m, 2H), 0.99 (t, J= 7.6 Hz,
3H) ppm.
3
| RESULT AND DISCUSSION
2
2
(
1.5 g). Then the solvent was evaporated and pure Biphe-
3
4
.1 | Characterization of Fe O @MCM‐
3
4
nyl derivatives were obtained in good to excellent yields.
1@Pd‐SPATB
The structure of Pd(0)‐ SPATB complex anchored on to
the surface of magnetic MCM‐41 (Fe O @MCM‐41@Pd‐
2
.6 | General procedure for the synthesis
3
4
of butyl Cinnamate derivatives
SPATB) as a novel and recyclable heterogeneous
nanocatalyst was studied and fully characterized by FT‐
IR, XRD, EDS, TEM, SEM, VSM, and TGA analysis.
The SEM images of Fe O @MCM‐41 and
A mixture of aryl halide (1 mmol), an butyl acrylate
(1.2 mmol), K CO (3 mmol), and Fe O @MCM‐41@Pd‐
2
3
3 4
SPATB (0.006 g, 0.94 mol%) was stirred in PEG‐400 at
20 °C for an appropriate time and progress of the
3
4
1
Fe O @MCM‐41@Pd‐SPATB are shown in Figure 1. As
3
4
reaction was monitored using TLC. After completion of
the reaction, the mixture was cooled down to room
shown in these images, the morphologies of the
Fe O @MCM‐41 and Fe O @MCM‐41@Pd‐SPATB are
3
4
3 4
3 4
SCHEME 1 Synthesis of Fe O @MCM‐41@Pd‐SPATB

4
of 13
NIKOORAZM ET AL.
FIGURE 2 The EDS spectrum of Fe
3
O
4
@MCM‐41@Pd‐SPATB
analysis of Fe O @MCM‐41@Pd‐SPATB surface mor-
3
4
phology demonstrated the well‐ordered mesostructures
with uniform pore dimension and hexagonal structure
and agglomeration of many ultrafine spherical like
particles which display dark magnetite cores surrounded
by a shell.
The XRD patterns of Fe O @MCM‐41 and
3
4
Fe O @MCM‐41@Pd‐SPATB are shown in Figure 4. As
3
4
seen from the small‐angle XRD patterns in Figure 4a,
The XRD pattern of Fe O @MCM‐41 shows a very
3
4
intense reflection at 2θ = 2.36° for d100 plane and also
two additional high order peaks with low intensity reflec-
tions at 2θ = 3.95° and 4.39° for d110 and d200 planes
respectively, typically confirming the presence of ordered
[21]
hexagonal mesoporous structure of MCM‐41.
The
wide‐angle XRD for the Fe O @MCM‐41@Pd‐SPATB
3
4
sample are shown in Figure 4 b. The characteristic peaks
at 2θ=30.25°, 35.6°, 43.8°, 53.9°, 57.0° and 62.8° assigned
to magnetite were observable for samples which agrees
with the standard Fe O (cubic phase) XRD spectrum
3
4
and demonstrated that catalyst had been successfully syn-
thesized without damaging the crystal structure of
[
13]
o
Fe O .
The broad peak at 2θ = 20–30 corresponds to
3
4
amorphous silica, which indicates that the silica is suc-
cessfully coated on the surface of the Fe O nanoparti-
3
4
[
49]
cles.
Also the XRD pattern of Fe O @MCM‐41@Pd‐
3
4
FIGURE 1 (a) SEM images of Fe
Fe @MCM‐41@Pd‐SPATB
3 4
O @MCM‐41 and (b)
SPATB exhibits a series of peaks (39.9°, 46.4° and 67.5°)
which are indexed to Pd(0) on the surface of
3 4
O
[
28]
Fe O @MCM‐41. The comparison study of small‐angle
3
4
agglomerations of small spherical regular particles with
uniform nanometer sized.
The energy dispersive spectrum (EDS) evidently
shows the presence of Pd, Fe, Si, O, N, S and C species
in the catalyst (Figure 2).
XRD patterns of Fe O @MCM‐41 and Fe O @MCM‐
3
4
3 4
41@Pd‐SPATB shows that after grafting of Pd through
complex formation into Fe O @MCM‐41, the reflections
3
4
with weaker intensities are observed.
Figure 5 shows FT‐IR spectra of (a) Fe O (b)
3
4
HR TEM images of the Fe O @MCM‐41@Pd‐SPATB
Fe O @MCM‐41 (c) Fe O @MCM‐41@nPr‐SH (d)
3
4
3
4
3 4
are shown in Figure 3. Based on the TEM micrograph,
Fe O @MCM‐41@SPATB and (e) Fe O @MCM‐41@Pd‐
3
4
3 4

NIKOORAZM ET AL.
5 of 13
FIGURE 4 XRD patterns of (a) small angle of Fe
and Fe @MCM‐41@Pd‐SPATB and (b) wide angle of
Fe @MCM‐41@Pd‐SPATB
3
O
4
@MCM‐41
3 4
O
3 4
O
on the surface of Fe O @MCM‐41 was indicated by the
3
4
‐1
appearance of two peaks at 2981 and 2936 cm , assigned
to the C–H stretching vibrations, also S‐H stretching vibra-
tion modes as a weak band that appears at 2450 cm‐
1
(
Figure 5c). Reaction of S‐propyl‐2‐aminobenzothioate
with SH immobilized on Fe O @MCM‐41 produces
3
4
Fe O @MCM‐41@ATBA in which the presence of car-
3
4
‐1
bonyl group is indicated by the 1623 cm band in its FT‐
IR spectrum (Figure 5d). Figure (5e) shows the FT‐IR spec-
trum after covalent bonding of Pd ions onto
Fe O @MCM‐41@SPATB the broad band in the range
3 4
FIGURE 3 The HR TEM micrographs of Fe O @MCM‐41@Pd‐
SPATB
3
4
‐1
1
400–1650 cm is attributed to the formation of palladium
[
1]
complex.
The superparamagnetic property of Fe
(a) and Fe @MCM‐41@Pd‐SPATB (b) were investi-
gated using VSM at room temperature (Figure 6). VSM
measurements for Fe @MCM‐41 nanoparticles show
that the saturation magnetization (M
Figure 6 (a), while M of Fe @MCM‐41@Pd‐SPATB is
SPATB respectively. The FT‐IR spectrum of the Fe O4
O @MCM‐41
3 4
3
nanoparticles (spectrum a) shows the strong absorptions
O
3 4
near 579 and 444 cm‐ and 3000–3500 cm due to Fe–O
1
‐1
[29]
and O–H stretching vibrations,
1 sample (spectrum b) the peaks at 3445 cm is due to
for the Fe O @MCM‐
O
3 4
3
−
4
1
_1
4
) is 13.02 emu g
s
the stretching vibrating absorption of O–H band in the
s
O
3 4
_
1
surfaced hydroxyl groups, also three characteristic peaks
decreased to 12.11 emu g Figure 6 (b). On the basis of
these results, the successful grafting of organic layers
‐1
‐1
‐1
at 460 cm , 958 cm and 1081 cm corresponded to bend-
ing, symmetric stretching and asymmetric stretching, Si‐
O–Si vibrations respectively. Immobilization of MPTMS
including palladium complex on Fe O @MCM‐41 is
3 4
verified.
[30]
[31]

6
of 13
NIKOORAZM ET AL.
FIGURE
7
TGA thermograms of Fe
3
O
4
@MCM‐41 and
3 4
Fe O @MCM‐41@Pd‐SPATB
at above 650 °C as a result of the condensation of the
silanol groups.
Finally, to determine the exact amount of Pd in
Fe O @MCM‐41@Pd‐SPATB, ICP‐OES was used. From
3
4
FIGURE 5 FT‐IR spectra of (a) Fe
3
O
4
(b) Fe
3 4
O @MCM‐41(c)
this analysis, the Pd amount of the immobilized catalyst
Fe
Fe
3
O
O
4
3 4
@MCM‐41@nPr‐SH(d) Fe O @MCM‐41@SPATB and (e)
@MCM‐41@Pd‐SPATB.
‐3
on Fe O @MCM‐41 was found to be 1.59× 10 mol/g.
3
4
3
4
3
.2 | Evaluation of the catalytic activity of
Fe O @MCM‐41@Pd‐SPATB in Suzuki‐
3
4
Miyaura, Stille and Mizoroki–heck
reactions
After full characterization of the catalyst structure, the
catalytic activity of this magnetic mesoporous compound
was examined in C–C coupling reactions, namely Suzuki,
Stille and Heck reactions. At the onset of our work, the
catalytic activity of complex was investigated in Suzuki–
Miyaura cross coupling reactions. For this propose the
reaction between iodobenzene (1 mmol) with phenyl
boronic acid (1 mmol) using K CO as a base at 80 °C
2
3
was chosen as model reaction and the effects of various
parameters such as amount of catalyst, solvent, tempera-
ture and base were studied for this model reaction
(Table 1).
When the reaction was carried out in the absence of
catalyst, the desired product was not achieved after 6 h
(Table 1, entry 1). Thus, we tested different amount of
catalyst (Table 1, entries 2–4) and the best amount of cat-
alyst was found 4 mg (0.63 mol %) for this reaction
(Table 1, entry 3). In the next step, the influence of vari-
FIGURE
6
3 4
Magnetic curves of (a) Fe O @MCM‐41 and
(
b) Fe @MCM‐41@Pd‐SPATB
3 4
O
The thermogravimetric analysis (TGA) curves of
Fe O @MCM‐41 and Fe O @MCM‐41@Pd‐SPATB are
3
4
3 4
shown in Figure 7. The TGA of the synthesized
Fe O @MCM‐41 shows 3 % weight loss in one step at
3
4
between 25 to 100 °C due to desorption of water.
Fe O @MCM‐41@Pd‐SPATB sample showed a mass loss
3
4
about 5.6 % below 250 °C due to the removal of physically
adsorbed solvent and surface hydroxyl groups, the other
weight loss is in the region of 250–650 °C (about 15 %)
mainly related to the decomposition of immobilized
organic moieties on the Fe O @MCM‐41@Pd‐SPATB
ous solvents, PEG‐400, H O, THF, Toluene, DMSO,
2
EtOH, DMF, and 1,4‐Dioxan at 80 °C was studied
(Table 1, entries 4–11). The best results are obtained for
PEG‐400. Then, we investigated the effects of bases on
the reaction in PEG‐400 solvent. The different bases
3
4
[
32]
surface;
and the third weight loss (about 11%) appears

NIKOORAZM ET AL.
7 of 13
TABLE 1 Optimization of the solvent, base, temperature and concentration of catalyst for the synthesis of biphenyl in Suzuki reaction
a
Entry
Temperature (°C)
Solvent
Base
Catalyst amount (mg)
Time (min)
Yield
1
80
PEG‐400
K
K
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
3
‐
360
Trace
94
2
3
4
5
6
7
8
9
80
80
80
80
80
80
80
80
80
80
80
80
80
80
60
40
25
PEG‐400
PEG‐400
PEG‐400
1,4‐dioxane
DMSO
5
4
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
94
82
20
72
Toluene
THF
16
39
H
2
O
25
10
11
12
13
14
15
16
17
18
DMF
92
EtOH
82
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
Et
NaHCO
Na CO
KOH
3
N
92
3
83
2
3
88
Trace
90
K
2
K
2
K
2
CO
CO
CO
3
3
3
68
30
3 4
Reaction conditions: iodobenzene (1 mmol), phenyl boronic acid (1 mmol), base (3 mmol), Fe O @MCM‐41@Pd‐SPATB (4 mg, 0.63 mol%) and PEG‐400 (2 ml)
a
Isolated yield.
including NaHCO , KOH, (Et) N, Na CO and K CO
3
the reaction between the iodobenzene (1.0 mmol) and
3
3
2
3
2
were studied (Table 1, entries 3, 12–15). High yield and
Ph SnCl (0.5 mmol) in the presence of base (3 mmol)
3
shorter reaction time are obtained when K CO3 is
was probed as a model reaction. The catalytic reactions
were first carried out in the absence of catalyst, which
did not give a quantitative yield of products after 10 h
(Table 3, entry 1).
2
employed as base, therefore, we chose K CO as the base
2
3
in all of the coupling reactions. Also, the effect of temper-
ature was studied (Table 1, entries 3, 16–18). Optimum
reaction conditions base on the effect of temperature
shows that excellent yield of the product is obtained at
To investigate the effect of the catalyst, systematic
studies were carried out in the presence of different
amounts of the catalyst in PEG (Table 3, entries 2–4).
The best result is observed with 6 mg (0.94 mol%) of
Fe O @MCM‐41@Pd‐SPATB (Table 3, entry 4). Also,
8
0 °C. Therefore, the best result was obtained when the
reaction was carried out with Fe O @MCM‐41@Pd‐
3
4
SPATB (0.004 g), iodobenzene (1 mmol), phenyl boronic
3
4
acid (1 mmol) and K CO (3 mmol) in PEG‐400 at 80 °C
the effect of a series of bases on the activity of
2
3
(Table 1, entry 3).
Fe O @MCM‐41@Pd‐SPATB catalyst was studied and
3
4
To examine the utility and generality of this approach,
K CO was selected as the proper base (Table 3, entries
2
3
various aryl halides were reacted with phenyl boronic
acid in the optimal reaction conditions for the synthesis
of a wide variety of biphenyls. The biphenyl derivatives
were obtained in high yields and short reaction time
5–8). Beside, in order to find appropriate solvent, Several
solvents were also tested (Table 3, entries 9–14) among
them PEG‐400 gives the best result. Further optimization
was performed at different temperatures (Table 3, entries
15–17). A high yield of product canbe achieved at 80 °C.
After optimization, the Stille reaction of aryl halides
with Ph SnCl in the presence of Fe O @MCM‐41@Pd‐
(Table 2). As shown in Table 2, completion of the reaction
involving chlorobenzene was slower than for iodobenzene
or bromobenzene and requires more amount of
Fe O @MCM‐41@Pd‐SPATB (8 mg) and higher tempera-
3
3 4
SPATB (6 mg.0.94 mol%) in PEG‐400 at 80 °C were car-
ried out and the obtained results are listed in Table 4.
Catalytic cycle for Suzuki and Stille reaction in the
presence of Fe O @MCM‐41@Pd‐SPATB was outlined
3
4
ture (100 °C) (Table 2, entries 11‐13).
Also, we examined the catalytic activity of
Fe O @MCM‐41@Pd‐SPATB in the Stille cross‐coupling
3
4
3 4
reactions. In order to find out the best reaction conditions,
in Scheme 2.

8
of 13
NIKOORAZM ET AL.
TABLE 2 C–C coupling of aryl halides with phenylboronic acid in the presence of Fe
3
O
4
@MCM‐41@Pd‐SPATB (4 mg, 0.63 mol%) in PEG
at 80 °C
a
_1
Entry
Aryl halide
Time (min)
Yield (%)
TOF (h )
Melting point (°C)
[
22]
1
25
94
355.2
65‐67
[
23]
2
3
45
40
95
96
201.05
228.8
45‐47
[
22]
Oil
[
[
[
[
22]
4
5
6
7
60
50
45
60
93
92
93
90
147.6
175.3
196.8
142.8
82‐84
67‐68
42‐44
81‐83
79‐81
22]
22]
22]
[
22]
8
9
45
60
94
93
92
90
88
90
198.94
147.6
146.03
95.2
[
24]
113‐114
[
22]
[23]
[22]
1
1
1
1
0
1
2
3
60
70‐72
64‐66
81‐83
b
b
90
200
240
41.9
b
[23]
35.7
111‐113
a
Isolated yield.
b
3 4
Conditions were as follows: Fe O @MCM‐41@Pd‐SPATB (8 mg,1.26 mol%) at 100 °C.
In order to extend the general application of the
Fe O @MCM‐41@Pd‐SPATB as a catalyst, the ability of
this catalyst was investigated for C–C coupling through
the Heck reaction. The reaction of iodobenzene with n‐
butyl acrylate have been employed as the model reaction.
reaction had proceeded in high yield. Finally, different
temperatures were examined for the model reaction
(Table 5, entries 13–16) and high conversion of product
was achieved at 120 °C.
After the optimization of the reaction conditions, the
reaction of various aryl halide derivatives with n‐butyl
acrylate was then investigated to confirm the generality
of the present method. The results of this study are sum-
marized in Table 6.
3
4
The effect of the amount of catalyst, solvent (EtOH, H O,
2
Toluene, DMSO, DMF, 1, 4‐Dioxan and PEG), the nature
of the base (KOH, Et N, NaHCO , K CO or Na CO ) and
3
3
2
3
2
3
temperature (room temperature to 120 °C), on the out-
come of the coupling of iodobenzene with n‐butyl acrylate
was examined. A summary of the results is shown in
Table 5. As shown in Table 5 entry 1, the reaction did
not occur in the absence of Fe O @MCM‐41@Pd‐SPATB.
Catalytic cycle for Heck reaction in the presence of
Fe O @MCM‐41@Pd‐SPATB was outlined in Scheme 3.
3
4
The recovery and reusability of the catalysts is an
important factor in green chemistry and heterogeneous
catalysis. In another investigation, the recovery and
reusability of the Fe O @MCM‐41@Pd‐SPATB was
3
4
Among the different amount of catalyst tested, (6 mg,
.94 mol%) was found to be the most effective catalytic
amount since it gave the highest yield of the product
Tables 5, entry 4). Among the different solvents, the
0
3
4
investigated in the Suzuki–Miyaura reaction from
iodobenzene (1 mmol) with phenylboronic acid (1 mmol),
K CO (3 mmol), Fe O @MCM‐41@Pd‐SPATB (4 mg,
(
best yield is found in the presence of PEG‐400 (Table 5,
2
3
3 4
entry 4). Also, the reaction was significantly affected by
0.63 mol%) in PEG at 80 °C, Still reaction from
iodobenzene (1 mmol) with Ph SnCl (0.5 mmol), K CO
3
the nature of base and Using K CO3 as a base, the
2
3
2

NIKOORAZM ET AL.
9 of 13
TABLE 3 Catalytic results for the Stille reaction
a
Entry
Temperature (°C)
Solvent
Base
Catalyst (mg)
Time(min)
Yield
b
1
80
PEG‐400
K
K
K
K
2
2
2
2
CO
CO
CO
CO
3
3
3
3
‐
600
‐
2
3
4
5
6
7
8
9
80
80
80
80
80
80
80
80
80
80
80
80
80
70
60
25
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
EtOH
4
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
76
84
92
90
90
Trace
90
Trace
30
‐
NaHCO
Et
KOH
Na CO
3
3
N
2
3
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
10
11
12
13
14
15
16
17
DMSO
Toluene
THF
15
‐
1,4‐dioxane
H
2
O
77
78
44
‐
PEG‐400
PEG‐400
PEG‐400
3
The reaction mixture consisted of aryl halide (1.0 mmol), Ph SnCl (0.5 mmol), base (3 mmol), catalyst and 2 ml of solvent. Reaction time was 40 min.
a
Isolated yield.
b
No reaction.
TABLE 4 The Stille reaction of aryl halides with Ph3SnCl in the presence of Fe
3
O
4
@MCM‐41@Pd‐SPATB (6 mg, 0.94 mol%) in PEG at
8
0 °C
a
_1
Entry
Aryl halide
Time (min)
Yield (%)
TOF (h )
Melting point (°C)
[
[
[
[
22]
23]
22]
22]
1
40
94
150.1
64‐66
45‐47
83‐85
53‐55
63‐66
42‐44
81‐83
80‐82
2
3
4
5
6
7
8
45
55
93
88
84
90
88
87
89
131.9
102.8
63.3
85
[
[
[
[
22]
22]
22]
22]
55
105.2
80.7
70
75
70.04
47.3
120
[
23]
9
80
93
89
74.2
40.5
112‐114
[
22]
1
0
140
71‐73
a
Isolated yield.

10 of 13
NIKOORAZM ET AL.
mixture using an external magnet and washed with
diethyl ether to remove residual product, then reused for
the next run under the same reaction conditions as for
the first run. As shown in Figure 8, the Fe O @MCM‐
3
4
41@Pd‐SPATB can be recycled for at least five runs
without any significant loss of its catalytic activity or
palladium leaching.
Finally, hot filtration test was investigated to check
if the leached metal species are responsible for the cata-
lytic activity in Suzuki reaction iodobenzene with
phenylboronic acid as a model substrate in the presence
of Fe O @MCM‐41@Pd‐SPATB (4 mg, 0.64 mol%) at
3
4
80 °C in PEG‐400. In this experiment the product was
obtained after 13 min (in the half time of the reaction)
in 62% yield. Then the reaction was repeated but in the
half time of the reaction (after 13 min), the catalyst was
separated from the reaction mixture and the reaction mix-
ture was allowed to run for another 13 min. The yield of
reaction in this stage is 64% that confirmed the leaching
of palladium during the reaction hasn’t been occurred.
Also, to measure the exact leaching of palladium in
the catalyst, the amount of palladium in Fe O @MCM‐
SCHEME 2 Possible mechanism of Suzuki and Stille coupling
reactions
(3
mmol), Fe O @MCM‐41@Pd‐SPATB (6 mg,
3
4
3 4
0
.94 mol%) in PEG at 80 °C and Heck–Mizoroki cross‐
41@Pd‐SPATB was determined using ICP‐OES after five
recycles. The amount of Pd in catalyst was found to be
1.54× 10‐ mol/g based on ICP‐OES for catalyst after 5
runs reused. Therefore the catalyst can be recovered and
reused without any significant leaching Pd. The results
from hot filtration test and ICP‐OES technique show that
leaching of palladium during the reaction is negligible.
coupling reactions from iodobenzene (1 mmol) and
buthyl acrylate (1.2 mmol), K CO3 (3 mmol),
Fe O @MCM‐41@Pd‐SPATB (6 mg, 0.94 mol%) in PEG
at 120 °C. After completion of the reaction, the reaction
mixture was cooled to room temperature, the catalyst
was easily and rapidly separated from the reaction
3
2
3
4
TABLE 5 Catalytic results for the heck reaction
b
Entry
Temperature (°C)
Solvent
Base
Catalyst (mg)
Time (min)
Yield (%)
Trace
a
1
120
PEG‐400
K
K
K
K
2
2
2
2
CO
CO
CO
CO
3
3
3
3
None
24
2
3
4
5
6
7
8
9
120
120
120
120
120
120
120
120
120
120
120
120
110
100
80
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
PEG‐400
Toluene
DMSO
3
4
6
6
6
6
6
6
6
6
6
6
6
6
6
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
62
85
92
76
88
45
85
‐
NaHCO
Et
KOH
Na CO
3
3
N
2
3
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
0
1
2
3
4
5
6
68
84
‐
DMF
2
H O
EtOH
84
86
68
52
PEG‐400
PEG‐400
PEG‐400
3 4
Reaction conditions: aryl halide (1 mmol), n‐butyl acrylate (1.2 mmol), base (3 mmol), Fe O @MCM‐41@Pd‐SPATB (6 mg), and PEG‐400 (2 ml).

NIKOORAZM ET AL.
11 of 13
TABLE 6 The heck reaction of aryl halides with n‐butyl acrylate using heterogeneous Fe
3
O
4
@MCM‐41@Pd‐SPATB catalyst (0.94 mol%) at
1
20°C in PEG‐400
a
_1
Entry
Substrate
Product
Time (min)
Yield (%)
TOF (h )
Melting point (°C)
[25]
1
30
92
195.7
Oil
[
25]
2
3
40
90
90
86
145.06
Oil
[25]
60.9
Oil
[
[
25]
25]
4
5
40
90
91
89
145.3
63.1
Oil
Oil
[
[
25]
25]
6
7
100
100
86
81
54.9
51.7
Oil
Oil
[
26]
8
9
120
90
87
90
86
46.2
63.8
15.2
Oil
[
27]
40‐43
[25]
1
0
360
Oil
a
Isolated yield.
3 4
FIGURE 8 Reusability of Fe O @MCM‐41@Pd‐SPATB catalyst
for the Suzuki (column a), Stille (column b) and heck cross‐
coupling reactions (column c)
SCHEME 3 Possible mechanism of heck coupling reactions

12 of 13
NIKOORAZM ET AL.
TABLE 7 Comparison of the effect of Fe
3
O
4
@MCM‐41@Pd‐SPATB with other catalysts for Suzuki–Miyaura reaction using iodobenzene
and phenylboronic acid
Time
(h)
_
1
Entry
Catalyst (mol% of Pd)
Pd‐imino‐Py‐γ‐Fe (0.25 mol%)
Fe3O4/DAG/Pd(0.2 mol%)
Conditions
Et N, DMF, 100 °C
TOF (h )
Yield (%)
Ref.
[
[
[
[
[
[
[
[
33]
34]
35]
36]
37]
38]
39]
40]
1
2
O
3
3
0.5
760
95
2
3
4
5
6
7
8
9
K
K
2
CO
3
3
, EtOH/ H2O, 25 °C
, DMF/ H2O, 80 °C
0.16
0.5
2
3062
1000
31.08
32.6
98
100
97
Pd@Cu‐BDC/Py‐SI MOF(0.2 mol%)
Pd‐Py‐MCM‐41(1.56 mol%)
2
CO
Na
2
CO
3
, PEG, 80 °C
O, 80 °C
MCM‐41‐S‐Pd(0) (0.5 mol%)
MOF‐253·0.05PdCl2(0.23 mol%)
K
2
CO
3
,DMF‐H
2
6
98
KOAc, DMF:EtOH, 100 °C
Cs2CO3, EtOH, 80 °C
8
53.2
98
@Pd/meso‐TiO2/Pd@meso‐SiO
m‐6,6'‐Me bpy‐MOF‐PdCl (1 mol%)
Fe @MCM‐41@Pd‐SPATB(0.63 mol%)
2
(0.04 mol%))
0.16
15 390
8.25
99
2
2
K
K
2
2
CO
3
3
, Toluene, 85 °C
, PEG, 80 °C
12
0.41
99
3
O
4
CO
355.2
94
This work
3 4
TABLE 8 Comparison of the effect of Fe O @MCM‐41@Pd‐SPATB with other catalysts for heck–Mizoroki cross‐coupling reactions using
iodobenzene and buthyl acrylate
_
1
Entry
Catalyst (mol% of Pd)
Fe @SiO /Schiff base/Pd(II) (0.3 mol%)
Pd/Fe @PIL‐NH (0.011 mol%))
SiO @Fe –Pd (1 mol%)
Pd@MIL‐101 (0.15 mol%)
Pd(OAc) @MNP (0.5 mol%)
NHC–Pd(II) (1 mol%)
Pd/Fe (5 mol%)
Conditions
CO , DMF, 110 °C
N, 120 °C
Time (h)
TOF (h )
Yield (%)
Ref.
[
[
[
[
[
[
[
[
41]
42]
43]
44]
45]
46]
47]
48]
1
3
O
4
2
K
2
3
0.75
430
97
2
3
4
5
6
7
8
9
3
O
4
2
Et
3
0.66
8
12682
12.1
330
93
97
99
96
99
99
96
92
2
3
O
4
K
2
CO
CO
3
3
, DMF, 100 °C
, DMF, 120 °C
K
2
2
2
Et
Na
CO
N, DMF, 110 °C
CO , PEG, 120 °C
3
N, DMF, 100 °C
CO , DMA, 160 °C
, NMP, 130 °C
1.5
18
5
128
2
3
5.5
3
O
4
K
2
3
3.96
640
Fe
Fe
3
3
O
4
4
/DAG/Pd (0.3 mol%)
Et
3
0.5
0.5
O
@MCM‐41@Pd‐SPATB (0.94 mol%)
K
2
3
195.7
This work
In the next study, in order to compare the catalytic
MCM‐41 has been prepared and fully characterized using
FT‐IR, XRD, VSM, EDS, SEM, TEM and TGA techniques,
and successfully used as efficient and recyclable
nanocatalyst for the Suzuki, Still and Heck reactions under
mild experimental conditions. The given simple experi-
mental procedure in this work, avoided the use of organic
solvents which is in agreement with green chemistry prin-
ciples, utilization of an inexpensive and readily available
catalyst, good reactivity to generate the corresponding
products in good to excellent yields for all reactions are
the advantages of the present method. In addition, this
catalyst was easily separable from the reaction mixture by
external magnet and can be reused for five runs without
any significant loss of stability and activity.
potentiality of Fe O @MCM‐41@Pd‐SPATB with the
3
4
reported catalysts in the literature, we compared
the results of the coupling of iodobenzene with
phenylboronic acid (Table 7) and iodobenzene with buthyl
acrylate (Table 8) with the previously reported methods. As
shown in Table 7 and 8, in this work, C–C bond forming
reaction has been carried out in PEG‐400 as green solvent
and this catalyst shows shorter reaction time and higher
yield than the other catalysts. Especially this new catalyst
also is a proper catalyst in terms of stability, non‐toxicity,
price and easy separation than the previously reported
ones. In addition, the recyclability of this catalyst is faster
and easier than those of the other reported catalysts.
ACKNOWLEDGMENT
4
| CONCLUSION
The authors gratefully acknowledge Ilam University
Research Council for partial financial support of this
study.
In summary, Pd(0)‐ S‐propyl‐2‐aminobenzothioate
immobilized onto functionalized magnetic nanoporous

NIKOORAZM ET AL.
13 of 13
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