Magnetic MCM-41 nanoparticles as a support for the immobilization of a palladium organometallic catalyst and its application in C-C coupling reactions

Article abstract of DOI:10.1039/c9nj02727k

In this study, the surface of magnetic MCM-41 nanoparticles (MCM-41/Fe₃O₄) was modified by 3-Aminopropyltriethoxysilane (APTES) and further, 1-methyl imidazole was anchored on their surface using cyanuric chloride as a linker. Then, Pd²⁺ ions were immobilized on the surface of the modified MCM-41/Fe₃O₄ (Pd-imi-CC@MCM-41/Fe₃O₄), and its application was studied as a magnetically recyclable nanocatalyst in carbon-carbon coupling reactions between a wide range of aryl halides and butyl acrylate, methyl acrylate, acrylonitrile, phenylboronic acid, or 3,4-difluorophenylboronic acid under the conditions of a phosphine-free ligand and an air atmosphere. This catalyst has the advantages of both the Fe₃O₄ nanoparticles and mesoporous MCM-41. The structure of the catalyst was characterized via TEM, SEM, EDS, WDX, N₂ adsorption-desorption isotherm, XRD, TGA, FT-IR, and AAS. Also, the recovered catalyst was characterized via SEM, AAS and FT-IR. All the products from the carbon-carbon coupling reaction were obtained with excellent yields and high TON and TOF values, which indicate the high efficiency and activity of this catalyst. The selectivity of this catalyst was studied with various aryl halides bearing different functional groups. Furthermore, the heterogeneity and stability of Pd-imi-CC@MCM-41/Fe₃O₄ was studied via AAS, and leaching and poisoning tests. According to the results, this heterogeneous catalyst can be reused several times.

Full text of DOI:10.1039/c9nj02727k

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Magnetic MCM-41 nanoparticles as support for the
immobilization of organometallic catalyst of palladium and its
application in C-C coupling reactions
Received 00th January 20xx,
Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x
Bahman Tahmasbi , Arash Ghorbani-Choghamarani
www.rsc.org/
In this work, surface of magnetic MCM-41 nanoparticles (MCM-41/Fe
3 4
O ) modified by 3-
aminopropyltriemtoxysilane (APTES) and further 1-methyl imidazole was anchored on its surface
2
+
using cyanuric chloride as linker. Then, Pd ions were immobilized on the surface of modified
MCM-41/Fe (Pd-imi-CC@MCM‐41/Fe ) and further its application was studied as
3
O
4
3 4
O
magnetically recyclable nanocatalyst in carbon-carbon coupling reactions between wide range of
aryl halides and butyl acrylate, methyl acrylate, acrylonitrile, phenylboronic acid, or 3,4-
diflorophenylboronic acid under phosphine-free ligand and air atmosphere. This catalyst has
advantages of both Fe
characterized using TEM, SEM, EDS, WDX, N
3
O
4
nanoparticles and mesoporous MCM-41. Catalyst structure was
adsorption–desorption isotherms, XRD, TGA,
2
FT-IR, and AAS techniques. Also, recovered catalyst was characterized by SEM, AAS and FT-IR
techniques. All products from carbon-carbon coupling reaction were obtained with excellent yields
and high TON and TOF values, which were indicate the high efficiency and activity of this
catalyst. Selectivity of this catalyst was studied in various aryl halides which are bearing different
functional groups. Heterogeneity and stability of Pd-imi-CC@MCM‐41/Fe O was studied by AAS
3 4
technique, leaching test and poisoning test. Therefore, this heterogeneous catalyst can be reused for
several times.
*
Address correspondence to B. Tahmasbi, Department of Chemistry, Ilam University, P.O. Box 69315516, Ilam, Iran;
Tel/Fax: +98 841 2227022; E-mail address: bah.tahmasbi@gmail.com
This journal is © The Royal Society of Chemistry 20xx
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biologically
active
compounds,
pharmaceuticals,
hydrocarbons, polymers, and advanced materials [30-41].
1
Introduction
In recent years, a rapid growth in the development of Traditionally, palladium-phosphine complexes are highly
novel supported materials (such as supported catalysts and efficient catalysts for the formation of carbon-carbon bonds
reagents) were extended in various fields of chemistry, [42, 43]. However, phosphorous ligands suffer from several
medicine, and biology sciences and especially in catalysis drawbacks such as thermal instability, toxicity, expensive and
field [1-7]. Designing and preparation of heterogeneous non‐recoverability.
catalysts by immobilization of homogenous species on solid
supports is one of the important routes for the developing of
novel and efficient catalytic protocols [8-13]. According to
green chemistry concept, magnetic nanoparticles (MNPs) and
mesoporous materials are as outstanding heterogeneous
support in catalytic transformations [14-16]. Magnetic
nanoparticles such as Fe
3
O
4
have a wide range of unique 2 Results and discussion
features such as easy preparation and functionalization, air
stability, nontoxicity, moisture resistance and especially facile
removing with assistance of external magnet from the
reactions mixture [17-25]. However, the major disadvantages
of magnetic nanoparticles are low surface area and low
durability. On the other hand, mesoporous materials such as
MCM-41 have a wide range of unique features such as
considerable durability, high specific surface area, air
tolerance, large and uniform pore size, high thermal and
mechanical stability [26-29]. However, the major
disadvantages of mesoporous materials are time consuming,
difficulty, and expensive conventional work-up procedures,
such as centrifugation or filtration. In order to combine
advantages of both magnetic nanoparticles and mesoporous
2.1 Catalyst preparation
In the first step, Pd-imi-CC@MCM‐41/Fe
3
O
4
was
prepared based on Scheme 1. Initially, the hydroxyl
groups on the surface of Fe nanoparticles were
functionalized and coated by silica layer [44] and further
these nanoparticles were doped in MCM-41 skeleton to
3
O
4
prepare
MCM‐41/Fe
nanoparticles
magnetic
) [45]. At next step, MCM‐41/Fe
were modified by
MCM-41
nanoparticles
(
3
O
4
3 4
O
(3-
aminopropyl)triethoxysilane. Subsequently, the amino
groups were reacted with cyanuric chloride, followed by
reaction with 1-methylimidazole to synthesis imi-
CC@MCM‐41/Fe
particles have
CC@MCM‐41/Fe O . This resulting nanomaterial
3
O
4
[46]. In final step, palladium
materials, Fe
MCM-41, which led to magnetic MCM-41 nanoparticles.
Fe /MCM-41 has a large surface area, which can be
3 4
O was doped into mesoporous channels of
been immobilized on imi-
O
4
3
4
3
characterized by transmission electron microscopy
(TEM), scanning electron microscopy (SEM), energy-
dispersive X-ray spectroscopy (EDS), wavelength
recovered and reused using external magnet and can be
considered as ideal and excellent support for catalytic
applications. In this regards, we are reporting a new
phosphine‐free complex of palladium on magnetic MCM-41
nanoparticles as efficient and reusable nanocatalyst for the C-
C coupling reactions. Because C-C coupling reactions are
powerful methods in modern synthetic of organic chemistry
for the preparation of natural products, agrochemicals,
2
dispersive X-ray spectroscopy (WDX), N adsorption–
desorption isotherms, X-ray diffraction (XRD),
thermogravimetric analysis (TGA), Fourier transform
infrared spectroscopy (FT-IR), and atomic absorption
spectroscopy (AAS) techniques.
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Cl
NH2
N
N
NH2
Cl
N
HN
O Si
O
O
O Si
O
Si
O
M
C
M
O
-
4
1
/
F
O
e3
Cyanuric chloride
O
O4
M
Cl
C
M
Toluene, Reflux, 24h
N
-
N
4
1
/
nPr-NH @MCM-41/Fe O
2
3
4
O
F
Cl
N
NH
e
3
O
4
Si
O
O
N
N
Cl
CC@MCM-41/Fe O4
3
N
N
N
Cl
N
N
1
-methyl imidazole
N
N
HN
N
Cl
Toluene, Reflux, 24h
N Cl
O
N
Pd
N
Si
O
O
N
N
N
M
C
N
N
HN
M
N
-
N
4
1
/
Cl
N
O
O
F
O
N
e
NH
N
1. Pd(OAc)2, N2
Si
O
N
3
O
4
Si
O
O
Cl
DMSO, 3 h, r.t.
o
M
N
2
. 60 C, 12 h
Pd
C
M
o
N
imi-CC@MCM-41/Fe O4
3.100 C, 4 h
N
3
-
4
1
/
O
N
F
N
N
e
NH
3 O
Si
O
O
4
Pd-imi-CC@MCM-41/Fe O4
3
3 4
Scheme 1. Synthesis of Pd-imi-CC@MCM‐41/Fe O .
2.2 Catalyst characterization
The particles size and morphology of Pd-imi-
CC@MCM‐41/Fe were studied by scanning electron
3
O
4
microscopies (SEM) technique. SEM image of this catalyst
are shown in Figure 1. Uniform and nearly spherical
nanoparticles of Pd-imi-CC@MCM‐41/Fe O are shown in
3 4
SEM image. SEM image was confirmed that particles of
catalyst were prepared nanometer scale.
3 4
Also, TEM images of Pd-imi-CC@MCM‐41/Fe O shown
in Figure 2. As it can be seen the catalyst was obtained with
average size of less than 100.
.
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3 4
Figure 1. SEM image of Pd-imi-CC@MCM‐41/Fe O .
3 4
Figure 2. TEM images of Pd-imi-CC@MCM‐41/Fe O .
In order to determine the elements content of Pd-imi-
CC@MCM‐41/Fe , EDS analysis was performed (Figure
). As depicted, the EDS result shows the presence of iron,
oxygen, silica, carbon, nitrogen, chlorine and as well as
palladium species in described nanomaterial, which is in good
agreement with the content of the final catalyst. WDX
3
O
4
3
3 4
analysis (X-Ray Mapping) of Pd-imi-CC@MCM‐41/Fe O is
shown in Figure 4. This analysis exhibits homogeneous
distributions of iron, oxygen, silica, carbon, nitrogen, chlorine
and palladium in the structure.
Also, the exact amount of palladium content of Pd-imi-
CC@MCM‐41/Fe
3 4
O was measured by atomic absorption
-
spectroscopy (AAS) technique that was found to be 1.89 × 10
3
-1
mol g .
4
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Figure 3. EDS diagram of Pd-imi-CC@MCM‐41/Fe O .
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Figure 4. Elemental mapping of (a) iron, (b) oxygen, (c) silica, (d) carbon, (f) nitrogen, (g) chlorine and (h) palladium for Pd-imi-
CC@MCM‐41/Fe
3
4
O .
The normal XRD and low angle XRD patterns of XRD patterns of magnetic MCM-41 nanoparticles, imi-
magnetic MCM-41 nanoparticles and Pd-imi- CC@MCM‐41/Fe and Pd-imi-CC@MCM‐41/Fe
CC@MCM‐41/Fe are shown in Figures 5 and 6. In normal (Figure 5) several peaks in 2θ values of 30.7º, 35.6º, 43.3º,
3
O
4
3 4
O
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O
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3.8º, 57.7º and 62.8º were observed, which were nanoparticles,
imi-CC@MCM‐41/Fe
3
O
4
and
Pd-imi-
View Article Online
CC@MCM‐41/Fe
3
O
4
.
DOI: 10.1039/C9NJ02727K
corresponded to crystal planes of Fe
mesoporous channels of MCM-41. These results confirmed
that the Fe -doped into mesoporous channels of MCM-41
did not lead to changes in the crystal phase of Fe . These
results are in agreement with standard XRD pattern of Fe
3 4
O -doped into
1000
3
O
4
a
8
6
00
00
3
O
4
3
O
4
nanoparticles [47]. Also, a broad peak at 20-28º is related to
silica skeleton. A good agreement was observed between
b
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400
200
0
normal XRD pattern of MCM‐41/Fe
patterns of imi-CC@MCM‐41/Fe
CC@MCM‐41/Fe , which it was confirmed the stability of
MCM‐41/Fe nanoparticles after modification.
3
O
4
with normal XRD
O and Pd-imi-
3
4
3
O
4
3
O
4
0
2
4
6
8
10
Also, the peak positions of 2θ at 40.7° (200), 46.8° (220),
and 67.5° (331) in normal XRD pattern of Pd-imi-
2
θ / degree
Figure 6. Low angle XRD patterns of magnetic MCM-41
nanoparticles (a) and Pd-imi-CC@MCM‐41/Fe (b).
CC@MCM‐41/Fe
These peaks are not presented in XRD patterns of
MCM‐41/Fe and imi-CC@MCM‐41/Fe . This result
confirmed that Pd(0) successfully immobilized on
MCM‐41/Fe [28, 33].
3 4
O are related to Pd(0) in the catalyst.
3
O
4
3
O
4
3 4
O
The thermogravimetric analysis was used to determine
qualitative and quantitative analysis of organic groups, which
3
O
4
Also, low angle XRD patterns of magnetic MCM-41 were immobilized on the surface of MCM‐41/Fe O .
3
4
nanoparticles and Pd-imi-CC@MCM‐41/Fe
performed, which are presented in Figure 6. The low angle performed using a heating rate of 15°C/min under an air
XRD pattern of MCM‐41/Fe shows the several peaks of atmosphere between room temperature to 700 °C.
θ value at 2θ ≈ 2.18˚, 2θ ≈ 4.5˚ and 2θ ≈ 5.5˚ that is due to
3
O
4
were TGA/DTA analysis of Pd-imi-CC@MCM‐41/Fe O was
3
4
3
O
4
2
3 4
TGA/DTA diagrams of Pd-imi-CC@MCM‐41/Fe O are
the hexagonal channel unit cell of MCM-41 [47, 48]. The
mentioned peaks, appear in very low intensity due to
immobilization of organic layers and palladium complex in
MCM-41 channels [45, 47].
shown in Figure 7, which shows the weight loss of the
organic functional groups as it decomposes upon heating. The
TGA curve of this catalyst shows the several steps of weight
losses. The mass loss in low temperatures (25 %), is
correspondence to the removal of organic solvents and water
[49]. Second weight loss is 30 %, which was observed at 200-
00 °C is due to calcination of organic moieties that was
immobilized on MCM‐41/Fe nanoparticles. Final weight
loss is 5%, which was observed at high temperatures, may be
related to thermal transformation of crystal phase of Fe O
3 4
Pd
1
400
5
1200
Pd
3 4
O
1
000
800
Pd
nanoparticles and condensation of the silanol groups of
MCM-41 [29, 47].
600
400
c
b
a
200
0
1
0
30
2θ / de 5g 0r ee
70
Figure 5. Normal XRD patterns of magnetic MCM-41
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5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/C9NJ02727K
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3 4
Figure 7. TGA/DTA diagram of Pd-imi-CC@MCM‐41/Fe O .
Nitrogen adsorption–desorption isotherms of mesoporous CC@MCM‐41/Fe
MCM‐41/Fe and Pd-imi-CC@MCM‐41/Fe are shown due to the grafting of organic layers and Pd-complex into
in Figure 8. Based on the IUPAC classification, the channels of MCM-41 nanoparticles. The pore volume of
MCM‐41/Fe material displayed an isotherm of type IV, MCM‐41/Fe and Pd-imi-CC@MCM‐41/Fe are 0.7
which is according to mesoporous material [47, 50]. Based on cm g and 0.1 cm g , respectively, and pore volume of
Brunauer-Emmett-Teller (BET), the surface area of catalyst is lower than MCM‐41/Fe , which is due to the
MCM‐41/Fe and Pd-imi-CC@MCM‐41/Fe are 911 grafting of organic layers and Pd-complex into channels of
3
O
4
is lower than MCM‐41/Fe
3 4
O which is
3
O
4
3 4
O
3
O
4
3
O
4
3 4
O
3
-1
3 -1
3
O
4
3
O
4
3 4
O
2
and 8.5 m /g, respectively. The BET surface area of Pd-imi- MCM-41 [47].
a
24
b
4
2
00
00
0
12
0
ADS
0.5
p/p0
DES
ADS
DES
1
0
1
0
0.5
p/p0
2 3 4 3 4
Figure 8. N adsorption–desorption isotherm of MCM‐41/Fe O (a) and Pd-imi-CC@MCM‐41/Fe O (b).
The FT-IR spectra for Fe
MCM-41, MCM‐41/Fe
CC@MCM‐41/Fe
CC@MCM‐41/Fe
bands at 438 and 570 cm in the FT-IR spectrum of Fe
3
O
4
nanoparticles, mesoporous vibrations of Fe-O bonds [17, 33], which these bands are
nPr-NH @MCM‐41/Fe present in FT-IR spectrum of MCM‐41/Fe (Figure 9,
4, imi-CC@MCM‐41/Fe
and Pd-imi- spectrum c). The several peaks at 458, 810, and 1083 cm in
are shown in Figure 9. The strong FT-IR spectrum of mesoporous MCM-41 (Figure 9, spectrum
3
O
4,
2
3
O
4
,
3 4
O
-1
3
3
O
O
3 4
O
4
-
1
3
O
4
a) are corresponded to the symmetric and asymmetric Si–O–
nanoparticles (Figure 9, spectrum b) are related to the Si vibrations in silica [29, 48], which these bands are present
8
| J. Name., 2012, 00, 1-3
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in FT-IR spectrum of MCM‐41/Fe
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
O
4
. Also, a stretching the bending vibrational mode of the O–H bands on the surface
View Article Online
-1
-1
vibrational mode at 951 cm in the FT-IR spectrum of of nanoparticles were indicated by a banDdOaI:t101.6103309-/1C69N35J0c27m27K,
MCM‐41/Fe
from salinization of the magnetic nanoparticles [33, 45] nanoparticles [33, 51].
which is not indicate in FT-IR spectra of MCM-41and Fe
Functionalization of MCM‐41/Fe
nanoparticles. All of these results are important witness for 9, spectrum d) was confirmed by C-H bands vibrations that is
3 4
O
may be corresponded to the Fe-O-Si bonds which is due to the presence of an adsorbed water layer on the
3
O
4
3 4
O with APTES (Figure
-1
the successful preparation of MCM‐41/Fe
3
O
4
.
observed at 2930 cm [49, 52], which these peaks not
-1
The bands adsorption above 3000 cm are due to indicate in FT-IR spectra a-c. The broad adsorption band at
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-1
symmetrical and asymmetrical stretching vibrations of 1500-1630 cm in FT-IR spectra e-g may be related to the
hydroxyl groups on the nanoparticles surface [44, 51]. Also, C=N and C=C bands, which overlapped with bending
vibrational
mode
of
the
O–H
bands.
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Page 10 of 21
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/C9NJ02727K
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 9. FT-IR spectrums of mesoporous MCM-41 (a), Fe
3
O
4
nanoparticles (b), MCM‐41/Fe
3
O
4
(c), nPr-NH
2 3 4
@MCM‐41/Fe O (d),
CC@MCM‐41/Fe (e), imi-CC@MCM‐41/Fe
3
O
4
3
O
4
(f) and Pd-imi-CC@MCM‐41/Fe O
3 4
(g).
In order to obtain the best conditions for Suzuki coupling
reaction, various parameters such as the amount of catalyst,
solvent, base and temperature were examined in coupling
2
.3 Catalytic activity of Pd-imi-CC@MCM‐41/Fe
3 4
O
in Suzuki and Heck reactions
Catalytic activity of Pd-imi-CC@MCM‐41/Fe
studied in C-C coupling reactions such as Suzuki (Scheme 2) model reaction. Results of these experiments were
and Heck (Scheme 4) coupling reactions.
3
O
4
was reaction of iodobenzene with phenylboronic (PhB(OH) ) as
2
summarized in Table 1. Based on outlined results in Table 1,
the best results were obtained in the presence of 8 mg (1.5
1
0 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
mol%) of Pd-imi-CC@MCM‐41/Fe
solvent using Na CO (3 mmol) as base at 80 °C (Table 1, mol%) of Pd-imi-CC@MCM‐41/Fe
entry 3). When the model reaction was examined at 60 °C entry 3) and lower amounts of Pd-imi-CC@MCM‐41/Fe
Table 1, entry 14), the product yield was 48%. As shown in (5 mg) gave a lower yield (69%) of products (Table 1, entry
Table 1, model reaction did not proceed in the absence of Pd- 2).
3
O
4
in PEG-400 as green best results were obtained in the presence ofV8iewmArtgicle(O0n.l4in5e
2
3
3
O
4 DaOsI:c1a0t.1a0l3y9s/tC(9TNaJ0b2l7e271K,
3
O
4
(
imi-CC@MCM‐41/Fe
3
O
4
(Table 1, entry 1). Meanwhile, the
N
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Cl
N
Pd
N
N
M
C
O
N
N
N
NH
M
-
Si
O
4
1
/
O
F
e
3
O
4
Pd-imi-CC@MCM-41/Fe O (1.5 mol%)
X
3
4
R
R'
R'
B(OH)2
Na CO
2 3
R'
R
+
o
R'
PEG-400, 80 C
X= Cl, Br, I
Scheme 2. Carbon-Carbon coupling reaction of aryl halides with PhB(OH)
CC@MCM‐41/Fe
2
or 3,4-diF-PhB(OH) in the presence of Pd-imi-
2
3
O
4
Table 1. Optimization of Suzuki reaction conditions for coupling of calculated TOF value for coupling of iodobenzene with
iodobenzene with phenylboronic acid in the presence of Pd-imi-
CC@MCM‐41/Fe
-1
2
PhB(OH) is 98 h (Table 2, entry 1) that is higher than
3
O
4
.
-1
-1
bromobenzene (35.2 h ) or chlorobenzene (2.5 h ).
Therefore, the reactivity of aryl halides are as:
PhI>PhBr>PhCl. Also as shown in Table 2, aryl halydes
with electron-withdrawing groups are more reactive than
aryl halydes bearning an electron-donating group. For
example, the calculated TOF values for coupling of 4-
bromoanisole, 4-bromotoluene, bromobenzene, 4-
Bromonitrobenzene and 4-Bromobenzonitrile with
Catalyst
(mg)
Temperature Time Yield
Entry
Solvent Base
a
(ºC)
80
80
80
80
80
80
80
80
80
80
80
80
80
60
40
(min) (%)
1
2
3
4
5
6
7
8
9
-
5
8
10
8
8
8
8
8
8
8
8
8
8
8
PEG Na
PEG Na
PEG Na
PEG Na
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
200
40
40
40
60
60
40
35
60
60
60
60
60
60
-
69
98
98
64
21
97
98
77
56
30
64
61
48
H
2
O
Na
EtOH Na
DMSO Na
DMF Na
Dioxane Na
-1
PhB(OH)2 are 27.7, 42.2, 35.2, 65.3 and 86 h ,
respectively. Based on these data, the reactivity of para-
functionalized bromobenzenes can be sorted as: 4-CN>4-
1
0
1
2
3
PEG
PEG
PEG
PEG
PEG Na
PEG Na
3
Et N
NO
2
>H>4-Me>4-OMe. Also, the calculated TOF value
is 30.3 h-
(Table 2, entry 19), which is higher than 4-
1
1
1
NaOEt
NaOH
KOH
for coupling of 3-bromoanisole with PhB(OH)
2
1
-1
bromoanisole (27.7 h ), because electron-withdrawing
60 Trace effect of parafanctional groups are hgiher than
metafunctional groups.
14
15
2
CO
CO
3
2
3
a
Isolated yield.
In order to extend the scope of this procedure, the
3 4
Catalytic activity of Pd-imi-CC@MCM‐41/Fe O was
coupling of various aryl halides with 3,4-
diflorophenylboronic acid (Table 2, entries 21-28) were
investigated. As expected, aryl iodides exhibit more
reactivity than aryl bromides. As shown in Table 2, high
catalytic activity of Pd-imi-CC@MCM‐41/Fe O and
3 4
high TON and TOF values of obtained products were
explored with differnt aryl halides and phenylboronic
acid derivatives (Table 2). Aryl halides having electron-
donating or electron-withdrawing groups on aromatic
ring converted to biphenyl products in high yields and
high TON and TOF values. High TOF and TON values
were shows the highly efficiency of Pd-imi-
observed in carbon-carbon coupling reactions.
3 4
CC@MCM‐41/Fe O in C-C coupling reactions as a
The selectivity of this catalytic system was investigated
for the coupling of 1-bromo-4-chorobenzene with
phenylboronic acid (Table 2, entry 2) and 3,4-
hetereogeneous catalyst. As shown in Table 2, the
coupling of phenylboronic acid with aryl iodide is faster
than aryl bromide or aryl chloride. For example, the
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1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
diflorophenylboronic acid (Table 2, entry 27). As shown catalyst, which C-O coupling was not observVeiedw aArnticdle pOnulirnee
in Scheme 3, chloro functional group was not coupled biphenyl from Suzuki reaction wasDO
with phenylboronic acid derivatives, and coupling of yield. Therefore, this procedure is efficient and capable
bromo functional group was observed. Also the coupling for wide range of various aryl halides.
of 4-bromophenol with phenylboronic acid (Table 2,
o
I:
b
1
t
0
a
.1
i
0
n
3
e
9
d
/C9
i
N
n
J0
g
2
o
727K
o
d
entries 17 and 18) was examined in the presence of this
Table 2. Catalytic C-C coupling reaction of aryl halides using phenylboronic acid and 3,4-diflorophenylboronic acid
in the presence of Pd-imi-CC@MCM‐41/Fe O .
3 4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
phenylating
Time Yield
(min) (%)a
TOF Melting point Reported M.P.
Entry
Aryl halide
TON
-1
reagent
(h )
(ºC)
[Ref.]
I
1
PhB(OH)
PhB(OH)
2
2
40
50
98
95
65.3
98.0
65-68
66-68 [52]
Br
2
3
4
5
6
63.3
63.3
61.3
64.7
61.3
76.0
42.2
46.0
86.2
16.7
6
4
9-72
5-46
71-73 [17]
45-47 [29]
82-84 [29]
80-84 [29]
Oil [33]
Cl
Br
I
PhB(OH)
PhB(OH)
PhB(OH)
PhB(OH)
2
2
2
2
90
80
95
92
97
92
Me
80-82
MeO
NC
Br
45
8
1-83
Oil
I
220
Me
Br
7
8
9
PhB(OH)
PhB(OH)
PhB(OH)
2
55
45
98
96
90
65.3
64.0
60.0
71.3
85.3
27.7
1
11-114
113-115 [53]
45-47 [29]
82-84 [29]
O N
2
I
2
2
44-47
Me
Br
130
81-83
MeO
Br
Cl
1
0
PhB(OH)
PhB(OH)
2
2
100
88
89
58.7
59.3
35.2
2.5
6
6
5-68
5-68
66-68 [52]
66-68 [52]
11
24 h
Cl
1
2
PhB(OH)
2
210
95
63.3
18.1
8
0-83
80-84 [29]
NC
1
2 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Br
View Article Online
DOI: 10.1039/C9NJ02727K
1
1
3
4
PhB(OH)
PhB(OH)
2
2
90
88
90
58.7
60.0
39.1
32.7
54-56
Oil
55-57 [33]
OHC
OHC
Br
Cl
110
Oil [53]
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
5
6
PhB(OH)
PhB(OH)
2
2
260
90
85
60.0
56.7
13.8
2.4
1
11-115
60-163
113-115 [53]
O N
2
Cl
Br
Br
24 h
1
1
162-164 [28]
HO
17
PhB(OH)
PhB(OH)
2
2
120
120
50
89
91
97
90
59.3
60.7
64.7
60.0
29.7
30.3
77.6
30.0
59-163
Oil
162-164 [28]
Oil [53]
HO
MeO
1
1
8
9
I
3
,4-diF-
3
3
9-41
9-41
39-41 [52]
39-41 [52]
PhB(OH)
2
2
Br
3
,4-diF-
20
120
PhB(OH)
I
Br
I
3,4-diF-
2
2
2
2
1
2
3
4
75
90
96
97
92
86
87
97
64.0
64.7
61.3
57.3
58.0
64.7
51.2
43.1
36.8
27.5
49.7
55.4
4
2-43
-
PhB(OH)
2
2
Me
NC
3,4-diF-
1
04-106
Oil
-
PhB(OH)
3
,4-diF-
100
125
70
-
PhB(OH)
2
H CO
3
3
,4-diF-
Oil
-
PhB(OH)
2
2
2
H CO
Br
Br
3
3
,4-diF-
25
5
9-60
-
PhB(OH)
Cl
Br
3
,4-diF-
26
70
1
17-120
119-120 [52]
PhB(OH)
O N
2
a
Isolated yield.
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Cl
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Br
R
R
B(OH)2
View Article Online
DOI: 10.1039/C9NJ02727K
Br
+
Pd-imi-CC@MCM-41/Fe O
3 4
R
Cl
R
R
Na CO , PEG-400, 80 °C
2
3
R= F or H
R
1
00 %
0%
Br
+
B(OH)2
O
Pd-imi-CC@MCM-41/Fe O
3
4
OH +
Na CO , PEG-400, 80 °C
2
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
HO
Br
1
00 %
0%
Scheme 3. Selectivity in C-C coupling in the presence of Pd-imi-CC@MCM‐41/Fe O .
3
4
3 4
Also, catalytic activity of Pd-imi-CC@MCM‐41/Fe O
has the present of 0.012 g (contaning 2.27 mol% of palladium) of
been studied in Heck cross coupling reaction, which is outlined catalyst (Table 3, entry 4). As shown in Table 3, the model
in Scheme 4. In order to found the best reaction conditions, the reaction was not proceeded in the absent of catalyst (Table 3,
coupling of iodobenzene with butyl acrylate was selected as entry 1) and also low yield of product was observed in the
model reaction. Effect of various parameters (such as solvent, precent of lower amounts of catalyst (Table 3, entries 2 and 3).
temperature, amount of catalyst, and nature of base) were Among the various solvents (Table 3, entries 5-9) and bases
studied in model reaction and the results of these studies are (Table 3, entries 9-13), the best results were observed in PEG-
summarized in Table 3. The coupling of iodobenzene with 400 as solvent and sodium carbonate as base. In the
butyl acrylate has been examined in the presence of different temperature effect study (Table 3, entries 13 and 14), the best
amount of Pd-imi-CC@MCM‐41/Fe
including yield of product and time reaction) were obtained in
3 4
O
and the best results results were obtained at 120 °C.
(
N
Cl
N
Pd
N
N
M
C
O
N
N
N
NH
M
-
Si
O
4
1
/
O
F
e
3
O
4
R2
Pd-imi-CC@MCM-41/Fe O (2.27 mol%)
3
4
X
R1
Na CO
2
3
R1
R2
+
2
o
R = COOBu, COOMe, CN
PEG-400, 120 C
3 4
Scheme 4. Heck coupling reaction in the presence of Pd-imi-CC@MCM‐41/Fe O .
Table 3. Optimization conditions for the coupling of iodobenzene
with butyl acrylate in the presence of Pd-imi-CC@MCM‐41/Fe
8
9
12
Dioxane NaCO
DMF NaCO
3
120
120
120
120
120
120
100
100
80
18
97
40
80
59
47
61
3
O
4
.
12
12
12
12
12
12
3
Catalyst
Temperature Time Yield
10
11
12
13
14
PEG
PEG
KOH
Et
100
100
100
100
80
Entry
Solvent Base
a
(mg)
(ºC)
(min) (%)
3
N
1
2
3
4
5
6
7
-
5
PEG NaCO
PEG NaCO
PEG NaCO
PEG NaCO
PEG NaCO
3
3
3
3
3
3
3
120
120
120
120
120
Reflux
120
600
80
80
80
70
-
PEG NaOEt
PEG NaOH
PEG NaCO
3
51
68
96
98
33
97
10
12
15
12
12
a
Isolated yield.
H
2
O
NaCO
DMSO NaCO
100
75
1
4 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
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Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The scope of this procedure was extended for the respectively. Based on these data, the reactivViietwyAortifclepOanrliane-
coupling of various aryl halides with butyl acrylate in the functionalized aryl halides are h
presence of Pd-imi-CC@MCM‐41/Fe
aryl halides (including electron-donating and electron- ortho-functional groups.
withdrawing functional groups on aromatic ring) were
converted to corresponding products with good yields
and high TON and TOF values. As shown in Table 4, the
coupling of para-functionalized aryl halides is faster than
ortho-functionalized aryl halides. For example, the
D
ig
O
h
I:
e
10
r
.10
t
3
h
9
a
/C
n
9NJ
o
0
r
2
t
7
ho-
2
7K
3
O
4
(Table 4). All functionalized aryl halides due to steric hindrance of
In order to extend the scope of this procedure, the
coupling of aryl halides with methyl acrylate (Table 4,
entries 6-10) and acrylonitrile (Table 4, entries 11-15)
were investigated and all products were obtaind in good
yields with high TON and TOF values.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
calculated TOF values for coupling of 4-iodotoluene and
-1
2
-iodotoluene with butyl acrylate are 25.9 and 11.8 h ,
Table 4. Coupling of aryl halides with butyl acrylate, methyl acrylate and acrylonitrile in the presence of Pd-imi-
CC@MCM‐41/Fe O .
3 4
Time
Yield
(%)
Melting point
(ºC)
Reported melting
point (ºC)
-1
Entry
Aryl halide
Alkene
TON TOF (h )
a
(min)
I
1
2
3
4
Butyl acrylate
80
96
89
42.3
39.2
31.7
11.8
Oil
Oil
Oil [48]
Oil [54]
I
Butyl acrylate
200
Me
I
Butyl acrylate
Butyl acrylate
Butyl acrylate
Methyl acrylate
Methyl acrylate
220
110
100
65
95
96
98
94
97
41.8
42.3
43.2
41.4
42.7
11.4
23.1
25.9
38.2
34.2
Oil
Oil
Oil [33]
Oil [29]
Oil [17]
Oil [55]
55-57 [56]
OMe
I
MeO
Me
I
5
6
7
Oil
I
28-30
54-56
I
75
Me
I
8
9
Methyl acrylate
Methyl acrylate
180
160
87
91
38.3
40.1
12.8
15.0
Oil
Oil
Oil [57]
[58]
OMe
I
Me
I
1
0
1
Methyl acrylate
Acrylonitrile
Acrylonitrile
90
93
93
90
41.0
40.1
39.6
27.3
24.6
16.4
86-88
Oil
88-91 [56]
Oil [54]
MeO
MeO
I
1
100
145
I
12
Oil
Oil [59]
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J. Name., 2013, 00, 1-3 | 15
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Ple Na se ew dJ oo u nr no at l ao df jCu hs et mm i sa t rr yg ins
Page 16 of 21
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
I
View Article Online
DOI: 10.1039/C9NJ02727K
1
1
1
3
4
5
Acrylonitrile
Acrylonitrile
Acrylonitrile
130
170
200
95
94
97
41.8
41.4
42.7
19.3
14.6
12.8
Oil
Oil
Oil
Oil [54]
Me
I
Oil [17]
Me
I
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-
OMe
a
Isolated yield.
2
.4Reusability of the Catalyst
The
CC@MCM‐41/Fe
iodobenzene with PhB(OH)
recoverability
and
reusability
of
Pd-imi-
3
O
4
was examined in the coupling of
. The obtained results from reusing
2
of this catalyst were summarized in Figure 10. For this aim, in
the end of the each reaction run, the catalyst was recovered by
an external magnet and washed with ethyl acetate to obtain the
product. The recovered catalyst was reused for next run. As
shown in Figure 10, this catalyst can be reused up to 8 times
without significant loss in its catalytic activity or any increase
in reaction time. TON value for 8 times reusing of this catalyst
is 520. Also, the average isolated yields is 97.5%.
1
00
80
6
4
2
0
0
0
0
1
2
3
4
5
6
7
8
Run number
Figure 10. Recyclability of Pd-imi-CC@MCM‐41/Fe
coupling of iodobenzene with PhB(OH)
3
O
4
in the
2
.
2.5 characterization of recovered catalyst
In order to show the structure stability of Pd-imi-
CC@MCM‐41/Fe after recycling, separated catalyst was
3 4
Figure 11. SEM images of recycled Pd-imi-CC@MCM‐41/Fe O .
3 4
O
characterized by SEM, FT-IR and AAS techniques. The particle
size and morphology of catalyst after recycling studied by SEM
technique. The SEM images of recovered catalyst was shown in
Figure 11. As it can be seen, the morphology and size of
catalyst after recycling is as same as fresh catalyst. These
results indicate that the size and morphology of catalyst doesn’t
changed after recycling.
Also, the recovered Pd-imi-CC@MCM‐41/Fe
3
O
4
was
characterized by FT-IR technique and compared to fresh
catalyst. FT-IR spectra of recovered catalyst and fresh catalyst
are shown in Figure 12, which there is no any change in FT-IR
of recovered catalyst compared with fresh one. These results
are
strong
evidence
3
for
stability
of
Pd-imi-
CC@MCM‐41/Fe
O
4
after recycling, therefore this catalyst can
be recovered and recycled without any change in its structure.
1
6 | J. Name., 2012, 00, 1-3
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Page 17 of 21
New Journal of Chemistry
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ARTICLE
presence of PVP (8 mg) and Pd-imi-CC@MCM‐41/Fe (8
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
O
4
View Article Online
mg, 1.5 mol%) was performed underDO
condition (in PEG as solvent, sodium carbonate as base at 80
C). In this study, any change was not observed in the
I: 10.1039/ 2727K
optimizedC9NreJ0action
°
conversion of starting materials to products and reaction was
completed after 40 min, which suggests that Pd-imi-
CC@MCM‐41/Fe O is heterogeneous in nature. Therefore,
3 4
during the C-C coupling reaction, the palladium doesn’t
leached into reaction solution and heterogeneous (supported)
palladium is as only catalyst in described reaction.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2.7 Leaching Study of the catalyst
In order to explore the heterogeneous nature of Pd-imi-
CC@MCM‐41/Fe , leaching study of this catalyst was performed.
3
O
4
In this regard, coupling of iodobenzene with phenylboronic acid was
selected as model reaction. In order to determine the palladium
concentration in reaction solution, catalyst was removed after 40 min
without cooling and further the remained reaction solution was
analyzed by AAS. In this analysis, the palladium concentration in
Figure 12. FT-IR spectrums of Pd-imi-CC@MCM‐41/Fe
3
O
4
(a)
and recovered Pd-imi-CC@MCM‐41/Fe
3
O
4
(b).
-1
solution was very small, which found to be 0.000056 mmol mL . It
could be found that a very small amount of palladium in reaction
solution did not have a significant effect on the reaction progress.
Therefore completion of the reaction could be attributed to the
heterogeneous palladium species. These results proves that Pd-imi-
2
.6 Poisoning test
Poisoning
test
was
commonly
used
for
homogeneity/heterogeneity nature of catalysis procedures,
which was often performed using PVP or mercury [60-62].
3 4
CC@MCM‐41/Fe O has heterogeneous nature.
As shown in Scheme 1, palladium is immobilized on modified
2.8 Comparison of the Catalyst
MCM-41/Fe
3 4
O structure by covalent bond. If little amount of
the palladium leached into reaction solution during C-C The efficiency of Pd-imi-CC@MCM‐41/Fe
3
4
O was studied by
coupling reaction, both heterogeneous (supported) and comparing of obtained results from previously reported catalysts
homogeneous (leached) palladium play as catalyst in the with this catalyst for the coupling of 4-iodotoluene with
reaction. However, if insoluble ligand (which can coordinate phenylboronic acid. Results of this comparison are summarized in
with palladium) is added in the reaction mixture, the catalytic Table 5. As shown, in the presence of Pd-imi-CC@MCM‐41/Fe O
3 4
activity of homogeneous (leached) palladium will be stopped. as catalyst, the reaction yield is higher and reaction time is lower
Pyridines are known ligands, which easily coordinated with than previously reported catalysts. Also, the higher TON and TOF
palladium [63]. Therefore, herein commercially available PVP values was observed in the presence of Pd-imi-CC@MCM‐41/Fe
was selected for the poisoning test study. In order to consider than other catalysts. Also, several previously reported procedures
homogeneity/heterogeneity nature of
Pd-imi- were applied microwave irradiation (Table 5, entries 11 and 12) or
CC@MCM‐41/Fe
the Suzuki coupling reaction of ultrasonic sonication (Table 5, entry 12) to perform Suzuki coupling
iodobenzene (1 mmol) with phenylboronic acid (1 mmol) in the reaction.
3 4
O
O ,
3 4
Table 5. Comparison of Pd-imi-CC@MCM‐41/Fe
procedures.
3
O
4
in the coupling of 4-Iodotoluene with phenylboronic acid with previously reported
a
Time
(min)
180
240
90
TOF Yield (%)
Entry
Catalyst
Reaction conditions
O, Et N, 80 ºC
PEG-400, Na CO , 80 °C
O, Na CO , 80 °C
O, K CO , 100 ºC
EtOH/H O, K CO , 80 ºC
TON
-1
(h ) [Reference]
1
2
3
Pd(0)-ABA-Fe
Pd-Arg-boehmite
3
O
4
H
2
3
171
84
108
57
21.1
72
96 [17]
91 [38]
87 [51]
2
3
Pd(0)–SMTU–boehmite
H
2
2
3
N,N'-bis(2-pyridinecarboxamide)-1,2-
benzene palladium complex
Pd/Au NPs
4
H
2
2
3
240
93
23
93 [64]
5
6
7
2
2
3
24h
12h
180
21
94
190
0.89
7.8
63
86 [65]
94 [66]
95 [67]
Pd NP
CA/Pd(0)
H
2
O, KOH, 100 ºC
O, K CO , 100 ºC
O (1:1), 80
H
2
2
3
Polymer anchored Pd(II)
Schiff base complex
Pd@SBA-15/ILDABCO
SBA-16-2 N-Pd(II)
K
2
CO
3
, DMF: H
ºC
2
8
9
480
182
22
91 [68]
K
2
CO
EtOH, K
solvent-free, K
400 W), 50 ºC
O, K CO , MW, 60 ºC,
ultrasonic sonication
3
, H
2
O, 80 ºC
, 60 ºC
CO , MW
120
120
194
194
97
97
97 [69]
97 [70]
1
0
2
CO
3
2
3
1
1
Pd nanocatalyst
5
18
75
225
150
72 [71]
75 [72]
(
H
2
2
3
12
Pd NPs@CMC/AG
30
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 17
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Ple Na se ew dJ oo u nr no at l ao df jCu hs et mm i sa t rr yg ins
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ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
EtOH, Cs
2 3
CO , reflux
View Article Online
1
3
CNT-Fe3O4@(A-V)-silica-Pd
480
45
62
7.75
93 [73]
conditions
DOI: 10.1039/C9NJ02727K
9
6 [this
work]
14
Pd-imi-CC@MCM‐41/Fe O
2
3
PEG-400, Na CO , 80 °C
65.3 98.0
3
4
room
separated using an external magnet and washed with diethyl
ether. Then, the reaction mixture was extracted with H O and
diethyl ether. The organic layer was dried over anhydrous
Na SO (1.5 g). The diethyl ether was evaporated and pure
products were obtained in 88 to 98% of yields.
temperature,
Pd-imi-CC@MCM‐41/Fe
3
O
4
was
3 Experimental
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3.1. Preparation of the catalyst
In the first step, amino-functionalized magnetic MCM-41
nanoparticles (nPr-NH @MCM‐41/Fe prepared
according to new reported procedure [44]. In the next step, 1
g of nPr-NH @MCM‐41/Fe was dispersed in toluene and
mixed with 2.5 mmol of cyanuric chloride (CC). Then, this
mixture was stirred under reflux conditions for 24 h. The
resulting solid (CC@MCM‐41/Fe
assistance of external magnet, washed with ethanol and dried
at room temperature. Then, CC@MCM‐41/Fe (1g) was
dispersed in 50 mL toluene by sonication for 20 min, and 1-
methylimidazole (5 mmol) was added to the reaction mixture.
The reaction mixture was stirred under reflux conditions for
2
4
2
3 4
O )
2
3 4
O
3
.4. Selected spectral data
3,4-Difluoro-4'-nitro-1,1'-biphenyl: H NMR (400 MHz,
CDCl ): δ = 8.36-8.32 (dt, J= 8.8 Hz, J= 2 Hz, 2H), 7.73-
.70 (dt, J= 8.8 Hz, J= 2 Hz, 2H), 7.50-7.45 (m, 1H), 7.41-
.37 (m,1H), 7.36-7.31 (m,1H), ppm; C NMR (100 MHz,
): δ = 152.2, 152.1, 152.0, 151.9, 149.7, 149.6, 149.5,
49.4, 147.4, 145.4, 135.9, 135.84, 135.82, 135.7, 127.7,
24.3, 123.63, 123.60, 123.57, 123.54, 118.2, 118.0, 116.6,
1
3 4
O ) was separated using
3
H
7
7
3
O
4
1
3
CDCl
3
H
1
1
1
24 h under N
CC@MCM‐41/Fe
times and separated via magnetic decantation and dried at 50
ºC. In the final step, 0.5 g of imi-CC@MCM‐41/Fe and
.25 g of palladium acetate were dispersed in DMSO for 20
2
atmosphere. The resulting nanoparticles (imi-
1
9
3 H
16.4 ppm; F NMR (400 MHz, CDCl ): δ = -136.2 (d, 1F),
3
O
4
) were washed with ethanol for several
-
137.1 (d, 1F)ppm.
3
O
4
3
,4-Difluoro-3'-methoxy-1,1'-biphenyl: 1H NMR (400
MHz, CDCl ): δ = 7.44-7.38 (dd, J= 8 Hz, J= 4 Hz, 2H),
.35-7.32 (m, 1H), 7.29-7.24 (m, 1H), 7.16-7.13 (d, J= 12Hz,
H), 7.10 (s, 1H), 6.97-6.95 (d, J= 8 Hz, 1H), 3.91 (s, 3H)
0
3
H
2
min and stirred under N atmosphere at room temperature for
7
1
3
h and was allowed to continue for 12 h at 60 ºC. The
reaction mixture was allowed to continue for 4 h at 100 ºC.
The final product (Pd-imi-CC@MCM‐41/Fe was
13
ppm.
1
1
C NMR (100 MHz, CDCl
3
): δ= 160.0, 151.8, 151.3,
3
4
O )
51.2, 149.3, 148.8, 148.7, 140.6, 138.2, 130.0, 123.1, 123.0,
separated by magnetic decantation and washed by ethanol and
water to remove the unattached substrates and dried at room
temperature.
19
19.4, 117.6, 117.4, 116.2, 116.0, 113.1, 112.8, 55.3 ppm; F
): δ = -137.7 (d, 1F), -140.2 (d,
NMR (400 MHz, CDCl
3
H
1
F)ppm.
3
.2 General procedure for Suzuki reaction catalyzed by
[1,1'-Biphenyl]-3-carbaldehyde: 1H NMR (400 MHz,
CDCl ): δ = 10.14 (s, 1H), 8.42 (s, 1H), 8.17-8.15 (d, J= 8Hz,
A mixture of aryl halide (1 mmol), 1 mmol of 1H), 7.9-7.88 (t, J= 8Hz, 1H), 7.70-7.66 (m, 2H), 7.63-7.58
phenylboronic acid (PhB(OH) ) or 3,4-difluoro phenylboronic (q, J= 8 Hz, 1H), 7.54-7.50 (t, J= 8 Hz, 2H), 7.46-7.42 (m,
acid (3,4-diF-PhB(OH) ), Na CO
imi-CC@MCM‐41/Fe (0.008 g, 1.5 mol%) was stirred in 139.9, 132.5, 129.9, 129.0, 129.0, 128.9, 128.0, 127.9, 127.2
Pd-imi-CC@MCM‐41/Fe
3
O
4
3
H
2
1
3
2
2
3
(3 mmol, 0.318 g), and Pd- 1H) ppm.
3
C NMR (100 MHz, CDCl ): δ= 192.5, 141.6,
3
O
4
PEG-400 (1 mL) at 80 ºC and the progress of the reaction was ppm.
monitored by TLC. After completion of the reaction, the
mixture was cooled down, Pd-imi-CC@MCM‐41/Fe
separated using an external magnet and washed with ethyl δH= 7.64-7.62 (d, J= 8Hz, 2H), 7.49-7.45 (t, J= 8 Hz, 2H),
acetate. The remaining reaction mixture was extracted with 7.42-7.37 (six, J= 4 Hz, 2H), 7.23-7.21 (d, J= 8 Hz, 1H),
1
3
O
4
was
3
3-Methoxy-1,1'-biphenyl: H NMR (400 MHz, CDCl ):
H
2
O and ethyl acetate. The organic layer was dried over 7.17-7.15 (t, J= 4 Hz, 1H), 6.95-6.92 (dd, J= 8 Hz, J= 4 Hz,
anhydrous Na SO (1.5 g). Then ethyl acetate was evaporated 1H), 3.91 (s, 3H) ppm.
and pure biphenyl derivatives were obtained in 85 to 98% of
yields.
2
4
1
2-Methyl-1,1'-biphenyl: H NMR (400 MHz, CDCl ):
3
δ
H
= 7.51-7.47 (t, J= 8Hz, 3H), 7.44-7.40 (t, J= 8 Hz, 3H),
3
.3 General procedure for Heck reaction catalyzed by Pd- 7.35-7.32 (m,3H), 2.36 (s, 3H) ppm.
imi-CC@MCM‐41/Fe
3
O
4
',4'-Difluoro-[1,1'-biphenyl]-4-carbonitrile: 1H NMR
400 MHz, CDCl ): δ = 7.78-7.76 (d, J= 8Hz, 2H), 7.67-7.65
d, J= 8 Hz, 2H), 7.46-7.41 (m,1H), 7.38-7.34 (m,1H), 7.32-
3
A mixture of aryl halide (1 mmol), 1.2 mmol of alkene
butyl acrylate, methyl acrylate or acrylonitrile), Na CO (3
mmol, 0.318 g), and Pd-imi-CC@MCM‐41/Fe (0.012 g,
.27 mol%) was stirred in PEG-400 (1 mL) at 120 ºC and the
(
(
3
H
(
2
3
3
O
4
13
7
1
1
.28 (m, 1H) ppm. C NMR (100 MHz, CDCl
3
): δ= 151.9,
2
49.6, 143.5, 136.2, 132.8, 127.6, 123.4, 123.4, 123.4, 123.3,
progress of the reaction was monitored by TLC. After
completion of the reaction, the mixture was cooled down to
19
18.7, 118.2, 118.0, 116.4, 116.2, 111.6 ppm; F NMR (400
): δ = -136.4 (d, 1F), -137.6 (d, 1F)ppm.
MHz, CDCl
3
H
1
8 | J. Name., 2012, 00, 1-3
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successfully applied for the selective C-C boVinewdArftioclremOnilninge
= 7.74- reactions. All products were obtaineDdOI:in10.1h0i3g9h/C9tNuJr0n2o7v27eKr
1
Butyl cinnamate: H NMR (400 MHz, CDCl
3
): δ
H
7
.70 (d, J= 16 Hz, 1H), 7.57-7.55 (m, 2H), 7.42-7.40 (t, J= 4 numbers (TON) and turnover frequency (TOF), which is
Hz, 3H), 6.50-6.46 (d, J= 16 Hz, 1H), 4.27-4.23 (t, J= 8 Hz, confirmed the high efficiency of this catalyst. Pd-imi-
H), 1.77-1.69 (quint, J= 8 Hz, 2H), 1.52-1.43 (sextet, J= 8 CC@MCM‐41/Fe O is composed from mesoporous MCM-
2
3
4
1
3
Hz, 2H), 1.02-0.98 (t, J= 8 Hz, 3H) ppm. C NMR (100 41 and Fe O magnetic nanoparticles, therefore it has
MHz, CDCl ): δ=167.1, 144.6, 134.5, 130.2, 128.9, 128.1, advantages of both mesoporous materials (such as high
3
3
4
1
18.3, 64.4, 30.8, 19.2, 13.8 ppm.
surface area) and magnetic nanoparticles (such as fast and
easy separation using an external magnet). Heterogeneity
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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2
3
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7
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2
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4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
Butyl 3-(4-methylphenyl)acrylate: H NMR (400 MHz, nature of Pd-imi-CC@MCM‐41/Fe O was studied by
CDCl ): δ = 7.72-7.68 (d, J= 16 Hz, 1H), 7.48-7.45 (d, J= 12 poisoning test and AAS technique.
3 H
Hz, 2H), 7.23-7.21 (d, J= 8 Hz, 2H), 6.45-6.41 (d, J= 16 Hz,
3
4
1
H), 4.26-4.22 (t, J= 8 Hz, 2H), 2.40 (s, 3H), 1.76-1.69
Acknowledgements
(quint, J= 8 Hz, 2H), 1.52-1.43 (sextet, J= 8 Hz, 2H), 1.02-
13
0
.98 (t, J= 8 Hz, 3H) ppm. C NMR (100 MHz, CDCl
3
):
Authors thank Ilam University and Iran National Science
δ=167.3, 144.6, 140.6, 131.7, 129.6, 128.1, 117.2, 64.4, 30.8, Foundation (INSF) for financial support of this research
21.5, 19.3, 13.8 ppm.
project.
1
Butyl 3-(2-methylphenyl)acrylate: H NMR (400 MHz,
CDCl ): δ = 78.03-7.99 (d, J= 16 Hz, 1H), 7.60-7.58 (d, J= 8
Hz, 1H), 7.31-7.30 (d, J= 4 Hz, 1H), 7.26-7.2 (t, J= 8 Hz,
3
H
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1
3
-(o-Tolyl)acrylonitrile: H NMR (400 MHz, CDCl
3
):
δ
7
H
= 7.75-7.71 (d, J= 16 Hz, 1H), 7.50-7.49 (d, J= 4 Hz, 1H),
.38-7.34 (d, J= 8 Hz, 1H), 7.33-7.29 (m, 1H), 7.27-7.25 (d,
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1
3
3
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9
.
.
7
.26-7.24 (d, J= 8 Hz, 2H), 5.87-5.83 (d, J= 16 Hz, 1H), 2.42
13
(s, 3H) ppm. C NMR (100 MHz, CDCl
3
): δ=150.5, 141.9,
1
30.9, 129.8, 127.4, 118.5, 95.1, 21.5 ppm.
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1
3 H
Cinnamonitrile: H NMR (400 MHz, CDCl ): δ = 7.53-
7.41 (m, 6H), 5.94-5.90 (d, J= 16 Hz, 1H) ppm.
1
1
1
Methyl 3-(o-tolyl)acrylate: H NMR (400 MHz, CDCl
3
):
δ
H
= 8.04-8.00 (d, J= 16 Hz, 1H), 7.59-7.57 (d, J= 8 Hz, 1H),
1
7.33-7.29 (t, J= 8 Hz, 1H), 7.26-7.23 (t, J= 8 Hz, 2H), 6.42-
1
3
6.38 (d, J= 16 Hz, 1H), 3.85 (s, 3H), 2.48 (s, 3H) ppm.
NMR (100 MHz, CDCl ): δ=167.5, 142.5, 137.7, 133.4,
30.8, 130.0, 126.4, 126.3, 118.8, 51.7, 19.8 ppm.
C
1
1
4. S. E. Hooshmand, B. Heidari, R. Sedghi, R. S. Varma, Green Chem.,
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2
019, 21, 381.
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5. B. Karimi, M. Tavakolian, F. Mansouri, H. Vali, ACS Sustainable
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Methyl cinnamate: H NMR (400 MHz, CDCl
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H
=
ChemistrySelect, 2019, 4, 1820.
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3
.75-7.71 (d, J= 16 Hz, 1H), 7.57-7.54 (m, 2H), 7.43-7.41 (m,
1
1
1
7. A. Ghorbani-Choghamarani, B. Tahmasbi, N. Noori, R. Ghafouri
1
3
H), 6.50-6.46 (d, J= 16 Hz, 1H), 3.84 (s, 3H) ppm. C NMR
): δ=167.4, 144.9, 134.4, 130.3, 128.9,
28.1, 117.8, 51.7 ppm.
nejad, J. Iran. Chem. Soc. 2017, 14, 681.
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8. M. G.Adimoolam, N. Amreddy, M. Rao Nalam, M. V.Sunkara, J.
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1
1
4
Conclusions
2
6
In conclusion, an efficient and reusable heterogeneous
catalyst (Pd-imi-CC@MCM‐41/Fe O ) was synthesized and
3 4
2
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View Article Online
10.1039/C9NJ02727K
Magnetic MCM-41 nanoparticles as support for immobilizatio
D
n
OI:
o
f
organometallic catalyst of palladium and its application in C-C coupling
reactions

Bahman Tahmasbi , Arash Ghorbani-Choghamarani
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Pd-imi-CC@MCM-41/Fe O
3
4
=
Fe O Nanoparticles
3 4
= Pd
R2
X
R2
B(OH)2
R1
Pd-imi-CC@MCM-41/Fe O (Cat.)
R1
3
4
R2
+
R2
Na CO , PEG, 80 °C
2 3
R3
X
R1
Pd-imi-CC@MCM-41/Fe3O4 (Cat.)
Na CO , PEG, 120 °C
R1
R3
+
2
3
Nanoboehmite was prepared in water using commercially materials. Then palladium has been
immobilized on its surface and applied as reusable organometallic nanocatalyst for C-C coupling
reactions. The pure products were obtained in high yields, excellent TON and TOF numbers which
were indicate the high efficiency of this catalyst. Selectivity of this catalyst was studied in various aryl
halides which are bearing different functional groups. Heterogeneity and stability of this catalyst was
studied by AAS technique, leaching test, poisoning test and characterization of recovered catalyst.
*
Address correspondence to B. Tahmasbi, Department of Chemistry, Ilam University, P.O. Box 69315516, Ilam, Iran; Tel/Fax: +98 841
2
227022; E-mail address: bah.tahmasbi@gmail.com