Synthesis of a new Pd(0)-complex supported on boehmite nanoparticles and study of its catalytic activity for Suzuki and Heck reactions in H2O or PEG

Article abstract of DOI:10.1039/c6ra02967a

Boehmite nanoparticles are a cubic orthorhombic structure of aluminum oxide hydroxide containing hydroxyl groups attached to their surface, which were prepared in water using commercially available materials. A moisture- and air-stable palladium S-methylisothiourea complex supported on boehmite nanoparticles (Pd(0)-SMTU-boehmite) was prepared using a very simple and inexpensive procedure without an inert atmosphere using commercially available materials. This nanostructure compound was used as an excellent organometallic catalyst for Suzuki and Heck reactions in H₂O or PEG-400. The synthesized nanoparticles were characterized using FT-IR, XRD, BET, TGA, TEM, SEM, EDS and ICP-OES techniques. Nitrogen adsorption/desorption measurements indicated that the boehmite nanoparticles have a BET surface area of about 122.8 m² g^-1. This heterogeneous nanocatalyst was easily separated from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of palladium from the catalyst was examined using hot filtration and ICP-OES techniques.

Full text of DOI:10.1039/c6ra02967a

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: A. Ghorbani-
Choghamarani, B. Tahmasbi and P. Moradi, RSC Adv., 2016, DOI: 10.1039/C6RA02967A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

Page 1 of 13
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
RSC Advances
RSCPublishing
ARTICLE
Synthesis of new Pd(0)ꢀcomplex supported on
boehmite nanoparticles and study of its catalytic
Cite this: DOI: 10.1039/x0xx00000x
activity for Suzuki and Heck reactions in H O or PEG
2
∗
Arash GhorbaniꢀChoghamarani, Parisa Moradi and Bahman Tahmasbi
Received 00th January 2012,
Accepted 00th January 2012
Department of Chemistry, Faculty of Science, Ilam University, P. O. Box 69315516, Ilam, Iran.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Boehmite nanoparticle is a cubic orthorhombic structure of aluminum oxide hydroxide
containing attached hydroxyl groups to its surface, which prepared in water using commercial
available materials. A moistureꢀ and airꢀstable palladium Sꢀmethylthio urea complex supported
on Boehmite nanoparticles (Pd(0)ꢀSMTUꢀboehmite) was prepared by very simple and
inexpensive procedure without inert atmosphere using commercially available materials. This
nanostructure compound was used as an excellent organometallic catalyst for the Suzuki and
Heck reactions in H O or PEGꢀ400. The synthesized nanoparticles were characterized by FTꢀ
2
IR, XRD, BET, TGA, TEM, SEM, EDS and ICPꢀOES techniques. Nitrogen
adsorption/desorption measurement indicated that boehmite nanoparticles had BET surface
2
area about 122.8 m /g. This heterogeneous nanocatalyst was easily separated from the reaction
mixture and reused for several consecutive runs without significant loss of its catalytic
efficiency or palladium leaching. The leaching of palladium from catalyst has been examined
by hot filtration and ICPꢀOES techniques.
∗
Address correspondence to A. GhorbaniꢀChoghamarani, Department of Chemistry, Ilam University, P.O. Box
6
9315516, Ilam, Iran; Tel/Fax: +98 841 2227022; Eꢀmail address: arashghch58@yahoo.com or
a.ghorbani@mail.ilam.ac.ir
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

RSC Advances
Page 2 of 13
View Article Online
DOI: 10.1039/C6RA02967A
RSC Advances
RSCPublishing
ARTICLE
ratio on the synthesis of boehmite has been studied by L. Rajabi
et al. [4]. Despite several studies on morphology, properties and
preparation of boehmite, there are few reports on the
modification of nano boehmite surface that have been reported
as heterogeneous catalyst [12ꢀ14]. Therefore, an attempt has
been made to modify surface of boehmite nanoparticles in this
work. In this regards, palladium Sꢀmethylthio urea complex has
been supported on boehmite nanoparticles and applied as an
excellent and reusable nano organometallic catalyst for the CꢀC
coupling reactions, because crossꢀcoupling reactions were used
as a powerful method in modern synthetic organic chemistry
for the preparation of natural products, advanced materials,
agrochemicals, pharmaceuticals, herbicides, biologically active
compounds, polymers, UV screens, preparation of
hydrocarbons and liquid crystal materials [15ꢀ19].
1
Introduction
Boehmite is an aluminum oxide hydroxide (γꢀAlOOH)
particles, which the surface of boehmite nanoparticles covered
with hydroxyl groups. Boehmite is structure consists of double
sheets of octahedral with aluminum ions at their centers and the
sheets themselves are composed of octahedral chains and has a
cubic orthorhombic structure. Also, boehmite nanoparticles was
not moistureꢀor air sensitive, and was synthesized in H O at
room temperature without inert atmosphere using available
materials such as Al(NO ) .9H O and NaOH. Boehmite has
important applications in the preparation of catalysts in
petrochemical and petroleum refining processes [1]. Boehmite
is an important precursor material for the preparation of
ceramic membranes and coatings [1ꢀ3]. Boehmite is also used
for building units and directing template in the preparation of
core/shell materials [2], which has been extensively used as
2
3
3
2
catalyst, optical material, cosmetic products, vaccine adjuvants, 2 Results and discussion
pillared clays and sweepꢀflocculation for fresh water treatment
and adsorbent [2ꢀ4], due to its unique properties such as good 2.1 Catalyst preparation
porosity and thermal stability, high specific surface area (>120 In continuation of our studies on the application of immobilized
2
m /g) [5, 6]. Another important application of boehmite is metal complex on boehmite nanoparticles in organic reactions
producing αꢀAl O by calcinations at high temperatures [6]. [3, 12], herein, we report the preparation and characterization of
2
3
Furthermore, boehmite has excellent properties such as Pd(0) complex supported on Boehmite nanoparticles. Initially,
chemical resistance, good mechanical strength, good the nano Boehmite has been prepared via addition of NaOH to
conductivity, high hardness, transparency, low cost, high the solution of Al(NO ) .9H O as source of aluminum at room
3
3
2
abrasive and corrosion resistance, excellent biocompatibility, temperature. Subsequently, boehmite nanoparticles were
relatively and controllable synthesis [7, 8]. The chemical and modified with 3ꢀchloropropyltrimethoxysilane (CPTMS) then
physical properties of boehmite nanoparticles are very grafting of Sꢀmethylisothiourea (SMTU) on the prepared nPrꢀ
dependent on the experimental factors of its synthesis, such as Clꢀboehmite
achieve
Sꢀmethylisothioureaꢀfunctionalized
the nature of Al(III)ꢀsalt, pH, temperature, time of aging and boehmite nanoparticles (SMTUꢀboehmite). Finally Pd
etc. Therefore, numerous methods have been reported for the nanoparticles have been supported on SMTUꢀboehmite (Pd(0)ꢀ
preparation of boehmite nanoparticles such as hydrothermal SMTUꢀboehmite) by the concise route that outlined in Scheme
(
HS) [9], sol–gel [10], and hydrolysis of aluminum [11]. Also 1.
effect of temperature, ultrasonic waves, time and Al/OH molar
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 2

Page 3 of 13
RSC Advances
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
ARTICLE
Scheme 1. Synthesis of Pd(0)ꢀSMTUꢀboehmite.
2
.2 Catalyst characterizations
The prepared nanoparticles have been characterized by SEM, TEM,
EDS, TGA, XRD, BET, FTꢀIR and ICPꢀOES techniques.
Pd
The XRD patterns of boehmite nanoparticles and Pd(0)ꢀSMTUꢀ
boehmite are shown in Figure 1. As it can be seen in Figure 1, the
boehmite phase was characterized by the peak positions at the 2θ
values of 14.40, 28.41, 38.55, 46.45, 49.55, 51.94, 56.02, 59.35,
Pd
6
5.04, 65.56, 68.09, and 72.38 from the XRD patterns, which could
be attributed for the (0 2 0), (1 2 0), (0 3 1), (1 3 1), (0 5 1), (2 0 0),
1 5 1), (0 8 0), (2 3 1), (0 0 2), (1 7 1), and (2 5 1) reflections,
Pd
(
respectively. This XRD patterns of boehmite nanoparticles is
conforming to the standard boehmite nanoparticles XRD spectrum
and the all peaks can be confirmed the crystallization of boehmite
with an orthorhombic unit cell [14, 20]. Also the XRD pattern of
Pd(0)ꢀSMTUꢀboehmite contains a series of peaks (39°, 46° and 67°)
which are indexed to the Pd (0) on the surface of boehmite [21ꢀ24],
which they have overlapped with 0 3 1, 1 3 1, 2 3 1, 0 0 2 and 1 7 1
reflections.
1
0
30
50
θ / degree
70
2
Figure 1. The XRD pattern of boehmite nanoparticles (black line)
and Pd(0)ꢀSMTUꢀboehmite (red line).
Figure 2 shows the FTꢀIR spectrums of boehmite, nPrꢀClꢀboehmite,
SMTUꢀboehmite and Pd(0)ꢀSMTUꢀboehmite. The FTꢀIR spectrum
of the boehmite nanoparticles (Spectrum a) shows two strong bands
at 3086 and 3308 cm , which are attributed to the both symmetrical
and asymmetrical modes of the OꢀH bonds on the surface of
boehmite nanoparticles [3, 14]. In FTꢀIR Spectrums aꢀd, several
−
1
−1
peaks that appear at 480, 605 and 735 cm can be related to the
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 3

RSC Advances
Page 4 of 13
View Article Online
RSC Advances
DOI: 10.1039/C6RA02967A
ARTICLE
absorption of AlꢀO bonds [12]. Also, the nitrate impurity vibration at
−
1
1
650 cm and the vibrations of hydrogen bands OH…OH by two
ꢀ
1
strong absorption bands at 1164 and 1069 cm were observed in FTꢀ
IR spectrum [3, 4]. In the FTꢀIR spectra of nPrꢀClꢀboehmite
(Spectrum
b),
The
presence
of
the
anchored
chloropropyltrimethoxysilane is confirmed by C–H stretching
−1
vibrations that appears at 2955 cm and also OꢀSi stretching
ꢀ
1
vibration modes that appear at 1073 cm [26]. In the FTꢀIR spectra
of SMTUꢀboehmite (Spectrum c), the existence of the grafted Sꢀ
methylisothiourea groups is identified by C=N vibrations that appear
−1
at 1638 cm , which this band has been shifted to lower frequency
−1
(
1631 cm ) in the catalyst (Spectrum d), which indicates the
formation of palladium complex on surface of functionalized nano
boehmite [27].
Figure 3. TEM images of Pd(0)ꢀSMTUꢀboehmite.
Figure 2. FTꢀIR spectra of (a) boehmite, (b) nPrꢀClꢀboehmite, (c)
SMTUꢀboehmite and (d) Pd(0)ꢀSMTUꢀboehmite.
The orthorhombic structure of boehmite nanoparticles was
confirmed by SEM (Figure 4) technique. TEM image (Figure 3)
revealed more accurate information on the morphology and particles
size of the palladium nanoparticles. It can be seen that most of the
palladium nanoparticles are in nano size with an average diameter
about 5ꢀ10 nm.
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 4

Page 5 of 13
RSC Advances
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
ARTICLE
The nitrogen adsorptionꢀdesorption isotherms of boehmite
nanoparticles is shown in Figure 6. The N physical adsorption and
2
desorption isotherms were adopted at 120 °C to obtain surface areas,
which the Brunauer–Emmett–Teller (BET) surface area for boehmite
2
nanoparticles was obtained in 122.8 m /g. When the Pd complex
loaded on boehmite nanoparticles, the BET specific surface areas
2
decreased from 122.8 to 82.90 m /g. As shown in Table 1, BET
analysis of boehmite nanoparticles shows a pore diameter of 1.64 nm
3
and a pore volume of 0.22 cm /g.
The pore volume and pore diameter of Pd(0)ꢀSMTUꢀboehmite is
lower than boehmite nanoparticles. On the basis of these results, the
well grafting of organic groups including palladium on the boehmite
nanoparticles is verified.
1
80
b
1
20
BET of
boehmi
te
6
0
BET of
catalyst
0
0
0.5
1
p/p0
Figure 4. SEM images of boehmite (a) and Pd(0)ꢀSMTUꢀboehmite
b).
(
Figure 6. Nitrogen adsorption–desorption isotherms of boehmite
nanoparticles and Pd(0)ꢀSMTUꢀboehmite.
In order to prove the presence of palladium metal on the surface of
functionalized boehmite, EDS technique has been applied. The EDS
spectrum of Pd(0)ꢀSMTUꢀboehmite was shown in Figure 5. As
shown in Figure 5, EDS spectrum of Pd(0)ꢀSMTUꢀboehmite shows
the presence of Al, O, Si, C, S, N and as well as Pd species in Pd(0)ꢀ
SMTUꢀboehmite. Also for quantitative analysis and find out the
exact amount of palladium, ICPꢀOES has been applied. According to
the inductively coupled plasma (ICP) analysis, the exact amount of
palladium in the heterogeneous catalyst has been calculated that it to
Table 1. Textural parameters deduced from nitrogen sorption
isotherms of boehmite nanoparticles and Pd(0)ꢀSMTUꢀboehmite
S
BET
Pore diam.
Pore vol.
sample
2
3
(
m /g) By BJH method (nm) (cm /g)
boehmite nanoparticles
Pd(0)ꢀSMTUꢀboehmite
122.8
82.90
1.64
1.21
0.22
0.19
ꢀ
1
be 2.55 mmol g .
Figure 7 shows the TGA analysis of boehmite nanoparticles, SMTUꢀ
boehmite and Pd(0)ꢀSMTUꢀboehmite. The results were confirmed
by TGA analysis data by showing 16% weight loss from 25ꢀ250 °C
for nano boehmite, which is due to desorption of water and
dehydration of surface hydroxyl groups [25]. The total mass loss of
the SMTUꢀboehmite was approximately 29% from 300ꢀ800 °C,
which is attributed to the decomposition of immobilized organic
moieties on the nano boehmite surface. Meanwhile, weight loss
about 40% from 250 to 800 °C is occurred for Pd(0)ꢀSMTUꢀ
boehmite. On the basis of these results, the well grafting of organic
groups including palladium complex on the boehmite nanoparticles
is verified.
Thermal stability of the Pd(0)ꢀSMTUꢀboehmite was also considered.
As shown in Figure 6, this catalyst was stable even at 300 ºC.
Figure 5. EDS spectrum of Pd(0)ꢀSMTUꢀboehmite.
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 5

RSC Advances
Page 6 of 13
View Article Online
RSC Advances
DOI: 10.1039/C6RA02967A
ARTICLE
1
1
10
00
Table 2. Optimization of reaction conditions for the CꢀC
coupling reaction of iodobenzene with phenylboronic acid in
the presence of Pd(0)ꢀSMTUꢀboehmite
9
8
7
6
5
0
0
0
0
0
a
b
c
Amount
of base
(mmol)
3
3
Catalyst
Temperature Time Yield
a
Entry
Solvent Base
(mg)
(ºC)
(min) (%)
b
1
2
3
4
5
6
7
8
9
ꢀ
H
H
H
H
2
2
2
2
O
O
O
O
Na
Na
Na
Na
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
80
80
80
80
80
80
80
80
80
80
80
80
60
r.t.
360
35
25
20
25
25
25
25
25
25
25
30
40
45
ꢀ
3
5
7
5
5
5
5
5
5
5
5
5
5
85
90
91
88
70
22
15
10
15
32
90
93
94
0
200
400
600
800
3
3
3
3
3
3
3
3
◦
Temperature( C)
PEG Na
EtOH Na
DMSO Na
DMF Na
Figure 7. TGA diagram of boehmite (a), SMTUꢀboehmite (b) and
Pd(0)ꢀSMTUꢀboehmite (c).
H
H
H
H
H
2
2
2
2
2
2
O
O
O
O
O
O
NaOEt
Et
KOH
1
1
1
1
0
1
2
3
3
N
3
2
.3 Catalytic activity of Pd(0)ꢀSMTUꢀboehmite in the
CꢀC coupling reactions
Na
Na
Na
2
2
2
CO
CO
CO
3
3
3
1.5
1.5
1.5
Crossꢀcoupling reactions such as Suzuki and Heck reactions are
powerful tools for the preparation of natural products, advanced
materials, agrochemicals, pharmaceuticals and biologically active
compounds [28ꢀ37]. Therefore, we investigated catalytic activity of
Pd(0)ꢀSMTUꢀboehmite as a new heterogeneous and high reusable
nanocatalyst for the CꢀC coupling through Suzuki reaction. For this
purpose, the coupling of iodobenzene with phenylboronic acid has
been selected as a simple model reaction to establish the feasibility
of the strategy and optimize the reaction conditions, and the results
are summarized in Table 2. We examined the effect of different
parameters (including solvent, base, reaction temperature, and
amounts of Pd(0)ꢀSMTUꢀboehmite) on the outcome of CꢀC coupling
reaction of iodobenzene with phenylboronic acid (Table 2). The
catalyst is not thermal, air, or moisture sensitive and hence inert
atmosphere was not employed in all reactions. Interestingly, the
reaction did not proceed in the absence of Pd(0)ꢀSMTUꢀboehmite
even after 6 hour (Table 2, entry 1). In order to choose the reaction
14
H
a
b
Isolated yield, No reaction.
After the optimization of the reaction conditions, we examined the
catalytic activity of Pd(0)ꢀSMTUꢀboehmite for various substrates
and the results are shown in Table 3. Various aryl iodides (Table 3,
entries 1, 2 and 12), bromides (Table 3, entries 3ꢀ8, 13 and 14) and
chlorides (Table 3, entries 9ꢀ11) were converted into corresponding
biphenyls. However, the completing reaction including aryl
chlorides was slower than aryl iodides and bromides. The aryl
halides including electronꢀdonor and electronꢀwithdrawing
functional groups have been successfully converted to corresponding
biphenyls in short reaction times with good to excellent yields (Table
3
). Therefore, the experimental procedure is very simple and
convenient, and has the ability to tolerate a variety of different
functional groups such as OH, CN, NO , alkyl and OCH under the
2
3
reaction conditions.
media, different solvents such as PEG, DMF, DMSO, H O and
ethanol were used (Table 1, entries 5ꢀ9) and the best result was
obtained in H O in the presence of 0.005 gr (0.8 mol%) of Pd(0)ꢀ
SMTUꢀboehmite (Table 2, entry 14). Also, the effect of nature and
amount of base was studied, which inferior results were obtained
2
We also applied optimized reaction conditions to coupling of aryl
halides with 3,4ꢀdifluoro phenylboronic acid. However, 3,4ꢀdifluoro
phenylboronic acid showed less reactivity toward the coupling
reaction than unfunctionalized phenylboronic acid. In this aim,
iodobenzene, bromobenzene and 4ꢀnitrobromobenzene reacted with
2
using NaOEt, KOH, and Et N (Table 1, entries 9ꢀ11). Excellent
3
3
,4ꢀdifluoro phenylboronic acid and the corresponding crossꢀ
biphenyl yields were obtained using 1.5 mmol of sodium carbonate
at room temperature. As shown in Table 2, iodobenzene (1 mmol) in
the presence of catalytic amount of Pd(0)ꢀSMTUꢀboehmite (0.005 g,
.8 mol%) and Na CO (1.5 mmol) reacted with phenylboronic acid
1 mmol) in H O at room temperature as ideal reaction conditions
coupling products was obtained in the reasonable yields (Table 3,
entries 13ꢀ15). Therefore, these results revealed that this
methodology is effective for a wide range of aryl halides and
phenylboronic acid deriavatives.
0
(
2 3
2
for the formation of corresponding biphenyl.
Table 3. Catalytic CꢀC coupling reaction of aryl halides using phenylboronic acid or 3,4ꢀdifluoro phenylboronic acid in the
presence of Pd(0)ꢀSMTUꢀboehmite (0.005 g, 0.8 mol%) under optimized conditions.
a
Entry
Aryl halide
Iodobenzene
4ꢀIodotoluene
ArꢀB(OH)
2
Time (min) Yield (%)
Melting point (ºC) [Ref.]
Reported melting point (ºC) [Ref.]
1
2
3
4
5
C
C
C
C
C
6
6
6
6
6
H
5
H
5
H
5
H
5
H
5
B(OH)
2
2
2
2
2
45
90
94
87
92
85
90
68
67ꢀ68 [17]
44ꢀ47 [17]
67ꢀ68 [17]
44ꢀ47 [17]
83 [21]
B(OH)
B(OH)
B(OH)
B(OH)
45ꢀ46
66ꢀ68
44ꢀ46
86ꢀ88
Bromobenzene
4ꢀBromotoluene
4ꢀBromobenzonitrile
90
180
50
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 6

Page 7 of 13
RSC Advances
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
ARTICLE
6
7
8
9
4ꢀBromonitrobenzene
4ꢀBromophenol
4ꢀBromochlorobenzene
Chlorobenzene
4ꢀChloronitrobenzene
4ꢀChlorobenzonitrile
Iodobenzene
C
C
C
C
C
C
6
6
6
6
6
6
H
H
H
H
H
H
5
5
5
5
5
5
B(OH)
B(OH)
B(OH)
B(OH)
B(OH)
B(OH)
2
2
2
2
2
2
25
90
90
185
50
90
360
420
390
99
96
98
93
93
97
89
91
98
110ꢀ113
157ꢀ160
69ꢀ71
67ꢀ69
111ꢀ114
87ꢀ89
39ꢀ41
40ꢀ42
119ꢀ120
111ꢀ113 [21]
157ꢀ160 [21]
70ꢀ71 [17]
67ꢀ68 [17]
111ꢀ113 [21]
83 [21]
1
0
1
2
3
4
1
1
1
1
3,4ꢀdiFꢀC
3,4ꢀdiFꢀC
6
6
6
H
5
H
5
H
5
B(OH)
B(OH)
B(OH)
2
2
2
ꢀ
ꢀ
ꢀ
Bromobenzene
4ꢀBromonitrobenzene 3,4ꢀdiFꢀC
a
Isolated
yield
Catalytic cycle for this C–C bond formation reaction in the
presence of Pd(0)ꢀSMTUꢀboehmite was outlined in Scheme 2
[
38, 39].
Scheme 2. Mechanism of the Pd(0)ꢀSMTUꢀboehmiteꢀcatalyzed Suzuki reaction.
In order to extend applications of the catalytic activity of Pd(0)ꢀ in PEG using 0.016 g (2.56 mol%) of Pd(0)ꢀSMTUꢀboehmite
SMTUꢀboehmite, this catalyst was investigated in the CꢀC (Table 4, entry 4). Also, the reaction was significantly affected
coupling through Heck reaction. The Pd(0)ꢀSMTUꢀboehmite by the nature and amount of base. Therefore, to found the best
has been tested as heterogeneous catalyst in the crossꢀcoupling reaction conditions, the effect and amount of base was
of iodobenzene with butyl acrylate to ascertain the best described (Table 4, entries 8ꢀ11) and the best results were
conditions reaction. The effect of solvent (DMF, DMSO, H O, obtained using 1.5 mmol of Na CO . Becase, the coupling
2
2
3
EtOH or PEG), temperature (room temperature to 120 °C), reaction yields were susceptible to temperature changes.
amounts of catalyst, nature and amount of base (Et N, Na CO , Therefore, to found the best reaction conditions, different bases
3
2
3
KOH or NaOEt) on the outcome of the coupling of was examined in model reaction (Table 4, entries 11ꢀ14). As
iodobenzene with butyl acrylate were examined. A summary of shown in Table 4, the best result was obtained with Na CO
2
3
the results is shown in Table 4. The reaction did not perform in (1.5 mmol) in the presence of 16 mg (2.56 mol%) of Pd(0)ꢀ
the absence of Pd(0)ꢀSMTUꢀboehmite (Table 4, entries 4 and SMTUꢀboehmite in PEGꢀ400 as solvent at 120 °C (inferior
1
0). Among of different solvents, the best results were obtained results were observed at 80 and 100 °C).
Table 4. Optimization of reaction conditions for the CꢀC coupling reaction of iodobenzene with butyl acrylate
a
Entry
Catalyst (mg)
Solvent
PEG
PEG
PEG
PEG
Base Amounts of base (mmol) Temperature (ºC) Time (min)
Yield (%)
b
1
2
3
4
5
6
7
8
ꢀ
Na CO
3
3
3
3
3
3
3
3
120
120
120
120
120
120
120
120
360
80
50
15
15
15
15
15
ꢀ
92
90
95
Trace
64
2
3
3
3
3
3
3
3
10
12
16
16
16
16
16
Na CO
2
Na CO
2
Na CO
2
H O
Na CO
2
2
DMSO Na CO
EtOH
PEG
2
Na CO
80
Trace
2
NaOEt
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 7

RSC Advances
Page 8 of 13
View Article Online
RSC Advances
DOI: 10.1039/C6RA02967A
ARTICLE
9
16
16
16
16
16
16
PEG
PEG
PEG
PEG
PEG
PEG
Et N
KOH
3
3
1.5
1.5
1.5
1.5
120
120
120
100
80
10
20
20
20
20
20
96
41
97
80
65
15
3
1
1
1
1
1
0
1
2
3
4
Na CO
2
3
3
3
3
Na CO
2
Na CO
2
Na CO
r.t.
2
a
Isolated yield.
After the optimization of the reaction conditions, we extended to afford the corresponding products and the all products were
the catalytic activity of Pd(0)ꢀSMTUꢀboehmite for other obtained in good to excellent yields.
substrates and the results are summarized in Table 5. Therefore, We also applied optimized reaction conditions to coupling aryl
optimized reaction conditions was applied to wide range of aryl halides with acrylonitrile (Table 5, entries 11ꢀ15). The aryl
iodides (Table 5, entries 1ꢀ3 and 13ꢀ15), bromides (Table 5, iodides, bromides and chlorides reacted with acrylonitrile to
entries 4ꢀ8 and 12) and chlorides (Table 5, entries 9ꢀ11) using produce the corresponding crossꢀcoupling products in good to
butyl acrylate under the optimized reaction conditions. Aryl excellent yields. However, acrylonitrile showed high reactivity
bromides and aryl iodides need less reaction times compared to toward the coupling reaction than butyl acrylate. Therefore,
those corresponding aryl chlorides (Table 5, entries 9ꢀ11 and these results revealed that this methodology is effective for a
1
3). As shown in Table 5, this methodology is applicable for wide range of alkenes and aryl halides.
wide range of aryl halides with electronꢀdonor and electronꢀ
withdrawing functional groups that reacted with butyl acrylate
Table 5. Coupling of aryl halides with butyl acrylate or acrylonitrile in the presence of catalytic amounts of Pd(0)ꢀSMTUꢀboehmite
(
16 mg, 2.56 mol%).
a
Entry
Aryl halide
Iodobenzene
Alkene
Time (min)
20
Yield (%)
1
2
3
4
5
6
7
Butyl acrylate
Butyl acrylate
Butyl acrylate
Butyl acrylate
Butyl acrylate
Butyl acrylate
Butyl acrylate
97
96
93
91
96
89
93
4ꢀIodotoluene
4ꢀIodoanisole
4ꢀBromotoluene
4ꢀBromoanisole
4ꢀBromophenol
Bromobenzene
270
260
16.5 h
12 h
17 h
8 h
1
ꢀBromoꢀ3ꢀ
8
9
Butyl acrylate
3 h
88
(
trifluoromethyl)benzene
Chlorobenzene
4ꢀChlorophenol
Chlorobenzene
Bromobenzene
Iodobenzene
Butyl acrylate
Butyl acrylate
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
16 h
24h
300
150
60
88
94
93
96
94
88
90
1
0
1
2
3
4
5
1
1
1
1
1
4ꢀIodoanisole
4ꢀIodotoluene
215
180
a
Isolated yield.
addition, migratory insertion, betaꢀhydride elimination and
The formation of the products through Heck reaction can be reductive elimination [40ꢀ42].
explained by a plausible mechanism as shown in Scheme 3. As
shown in Scheme 3, the full catalytic cycle involves oxidative
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 8

Page 9 of 13
RSC Advances
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
ARTICLE
Scheme 3. Mechanism of the Pd(0)ꢀSMTUꢀboehmiteꢀcatalyzed Heck reaction.
In order to show the efficiency of described catalytic system, Pd(0)ꢀSMTUꢀboehmite catalyst that have advantages of air or
the obtained results for the model compounds in this project moisture stable, ease of preparation and catalyst recycling
was compared with previously reported procedures in the without significant loss of catalytic activity (Figure 8). As
literature. Comparison of the results shows a better catalytic shown in Figure 6, the catalyst can be reused over 5 times in the
activity of Pd(0)ꢀSMTUꢀboehmite in Suzuki reaction (Table 6). coupling of iodobenzene with phenylboronic acid or coupling
As shown in Table 6, many catalysts have been reported for the of 4ꢀiodotoluene with butyl acrylate without any significant loss
CarbonꢀCarbon coupling reactions that most of them have some of its catalytic activity or palladium leaching. The average
drawbacks or limitations such as use of homogeneous catalysts isolated yield for 5 successive cycles in Suzuki and Heck
that is difficult to separate catalyst from the reaction mixture, reactions were 96 % and 92.6% respectively, which clearly
using excess of catalyst or phenylboronic acid, hazardous demonstrates the practical recyclability of this catalyst. Metal
organic solvents, high temperature and long reaction times. leaching of the catalyst was studied by hot filtration test and
Meanwhile, in this work, CꢀC bond forming through Suzuki ICP analysis. Based on the results from ICPꢀOES analysis, the
reaction has been carried out in water at room temperature with amount of palladium in fresh catalyst and the recovered catalyst
ꢀ
1
ꢀ1
short reaction times. Also this new catalyst is comparable with after 5 runs were 1.64 mmol g and 1.62 mmol g ,
previously reported catalysts in terms of price, nonꢀtoxicity, respectively, which indicated that Pd leaching of the catalyst
stability and easy separation. Moreover, the mesoporous silica was very low. In order to examine leaching of palladium in
such as MCMꢀ41, SBAꢀ15 or some nanoparticles such as TiO2 reaction mixture and heterogeneity of described catalyst, we
NPs, which have been used as catalyst supports in the organic performed hot filtration in the Heck reaction through coupling
reactions, requires high temperature for calcination and a lot of of iodobenzene and butyl acrylate. In this study we found the
time and tedious conditions to prepare. Also some of previously yield of product in the half time of the reaction was 55%. Then
reported catalysts such as heteropolyacids, ionic liquids or the reaction was repeated and in half time of the reaction, the
some polymers are more expensive. Also, some of catalyst separated and allowed the filtrate to react further. The
heterogeneous supports such as Fe O nanoparticles require yield of reaction in this stage was 58% that confirmed the
3
4
inert atmosphere and tedious conditions to prepare. Meanwhile, leaching of palladium hasn’t been occurred.
preparation of boehmite nanoparticles was not air, or moisture
sensitive, therefore this nanomaterial was prepared in water at
room temperature without inert atmosphere. Here, we used the
Table 6. Comparison results of Pd(0)ꢀSMTUꢀboehmite with other catalysts for the coupling of iodobenzene with phenylboronic acid
a
Entry
Catalyst (mol% of Pd)
Polymer anchored Pd(II)
Condition
Time (min)
Yield (%)
Ref.
1
K CO , DMF: H O (1:1), 80 ºC
5h
99
[15]
2
3
2
Schiff base complex (0.5 mol%)
Fe O /SiO –DTZ–Pd (0.5 mol %)
2
3
4
5
6
7
Na CO , PEG, 60 ºC
130
90
120
12h
12 h
120
94
97
99
88
95
94
[17]
[28]
[29]
[30]
[31]
[32]
3
4
2
2
3
Pd@SBAꢀ15/ILDABCO (0.5 mol%)
SBAꢀ16ꢀ2 NꢀPd(II) (0.5 mol%)
NHCꢀPd(II) complex (1.0 mol%)
Pd NP (1.0 mol%)
K CO , H O, 80 ºC
2 3 2
EtOH, K CO , 60 ºC
2
3
THF, Cs CO , 80 ºC
2
3
H O, KOH, 100 ºC
2
CA/Pd(0) (0.5ꢀ2.0 mol%)
H O, K CO , 100 ºC
2
2
3
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 9

RSC Advances
Page 10 of 13
View Article Online
RSC Advances
DOI: 10.1039/C6RA02967A
ARTICLE
[33]
[34]
[35]
[36]
[37]
8
9
PdCl (0.05 mol%)
Pd/Au NPs (4.0 mol%)
PdꢀMPTATꢀ1 (0.02 g)
LDHꢀPd(0) (0.3 g)
PANIꢀPd (2.2 mol%)
DMF, Cs CO , 130 ºC
120
24h
8h
10h
4h
95
88
95
96
91
94
95
2
2
3
EtOH/H O, K CO , 80 ºC
2
2
3
1
1
1
1
1
0
1
2
3
4
NaOH, DMF: H O (1:5), 85 ºC
2
K CO , 1,4ꢀdioxane: H O (5:1), 80 ºC
2
3
2
K CO , 1,4ꢀdioxane: H O (1:1), 95 ºC
2
3
2
PdꢀSMTUꢀboehmite (0.8 mol%)
Pd(0)ꢀSMTUꢀboehmite (0.32 mol%)
H O, Na CO , room temperature
45
75
This work
This work
2
2
3
H O, Na CO , 80 ºC
2
2
3
a
Isolated yield
1
00
8
0
a
b
6
0
4
0
2
0
0
5
4
3
2
Run number
1
Fig 8. Recyclability of Pd(0)ꢀSMTUꢀboehmite in the coupling of
iodobenzene with phenylboronic acid (a) and coupling of 4ꢀ
iodotoluene with butyl acrylate (b).
In order to show the structure stability of catalyst after recycling,
recovered catalyst has been characterized by FTꢀIR and XRD
techniques. The recovered catalyst was investigated by XRD pattern
(Figure 9) and FTꢀIR (Figure 10). FTꢀIR and XRD pattern of
recovered Pd(0)ꢀSMTUꢀboehmite indicates that this catalyst can be
recycled without any change in its structure.
1
0
30
50
θ / degree
70
2
Figure 9. The XRD pattern of boehmite nanoparticles (black line) Figure 10. FTꢀIR spectra of (a) fresh Pd(0)ꢀSMTUꢀboehmite and
and Pd(0)ꢀSMTUꢀboehmite after 10 runs recycling (red line).
recovered Pd(0)ꢀSMTUꢀboehmite (b).
3
Conclusions
In summary, a novel type of boehmiteꢀrecoverable nanocatalyst
Pd(0)ꢀSMTUꢀboehmite) was synthesized from immobilization of
(
Pd nanoparticles on functionalized boehmite nanoparticles. This
catalyst showed excellent catalytic activity, high reusability and air
or moisture stability for the Heck and Suzuki reactions in water or
PEGꢀ400. The advantages of this protocol are the use of a
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 10

Page 11 of 13
RSC Advances
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
ARTICLE
commercially available, ecoꢀfriendly, cheap, chemically stable 4.3 Result of catalyst characterization
materials, the operational simplicity, practicability and good to high
yields, and more importance the catalyst can be synthesized readily IR (KBr) cm : 3384, 3098, 2101, 1631, 1568, 1418, 1111, 739,
from inexpensive and commercially available starting materials. 692, 624, 480; ICPꢀOES (amount of Pd) mol g : 2.55 × 10ꢀ3; BET
Also, nano boehmite is new support for heterogenization of (at 120 °C for 3h): as,BET = 82.90 m /g, V = 0.19 cm /g, r =1.21
ꢀ
1
ꢀ
1
2
3
p
p
homogeneous catalysts, which prepared by very simple procedure in nm; XRD (2θ / degree) at: 14.40, 28.41, 38.55, 39, 46, 46.45, 49.55,
water at room temperature using commercially available materials. 51.94, 56.02, 59.35, 65.04, 65.56, 67, 68.09, and 72.38;
The catalyst can be reused for 5 times without Pd leaching or any
significant loss of its activity.
4
.4 General procedure for the Suzuki reaction
4
Experimental
A mixture of aryl halide (1 mmol), phenylboronic acid (1 mmol) or
,4ꢀdifluoro phenylboronic acid (1 mmol), Na CO (1.5 mmol), and
3
2
3
Pd(0)ꢀSMTUꢀboehmite (0.005 g, 0.8 mol%) were added to a reaction
4
.1. Material
vessel. The resulting mixture was stirred in H O at room temperature
2
Chemicals and solvents used in this work were obtained from and the progress of reaction was monitored by TLC. After
SigmaꢀAldrich, Fluka or Merck chemical companies and used completion of the reaction, catalyst was separated and washed with
without further purification. boehmite nanoparticles and PdꢀSMTUꢀ ethylacetate. The reaction mixture was extracted with H O and
2
boehmite were identified using a Holland Philips X'pert Xꢀray ethylacetate and organic layer dried over anhydrous Na SO (1.5 g).
2
4
powder diffraction (XRD) diffractometer, at a scanning speed of Then the solvent was evaporated and pure biphenyl derivatives were
2
°/min from 2° to 80°. Thermogravimetric analyses (TGA) of the obtained in good to excellent yields.
samples were recorded using a Shimadzu PLꢀSTA 1500 device in
the temperature range 30–800 °C. The particle size and morphology
were examined by measuring SEM using FESEMꢀTESCAN
MIRA3, on an accelerating voltage of 30.0 kV and also using Zeissꢀ
EM10C transmission electron microscope (TEM). Nitrogen
adsorption/desorption isotherms were recorded at 120 °C with a
Brunauer Emmett Teller Analysis Adsorption BELSORP Mini II. IR
spectra were recorded as KBr pellets on a VRTEX 70 model
BRUKER FTꢀIR spectrophotometer. The content of Pd was
measured by inductively coupled plasmaꢀoptical emission
4
.5 General procedure for the Heck reaction
A mixture of aryl halide (1 mmol), alkene (1.2 mmol), Na CO (1.5
2
3
mmol), and Pd(0)ꢀSMTUꢀboehmite (0.016 g, 2.56 mol%) was stirred
in PEGꢀ400 at 120 ºC (progress of the reaction was monitored by
TLC). After completion of the reaction, the mixture was cooled to
room temperature and then catalyst was separated, washed with
diethyl ether and the reaction mixture was extracted with H O and
diethyl ether. The organic layer was dried over Na SO (1.5 g),
2
2
4
1
spectrometry (ICPꢀOES). H NMR spectra were recorded with a
Bruker DRXꢀ400 spectrometer at 400 MHz. Melting points were
measured with an Electrothermal 9100 apparatus.
evaporated to obtain pure products in 85 to 99% yields.
4
.6 Selected spectral data
1
4
.2 Preparation of catalyst
4
7
7
ꢀMethylꢀ1,1'ꢀbiphenyl: H NMR (400 MHz, CDCl ): δ = 7.66ꢀ
3 H
.64 (m, 2H), 7.58ꢀ7.56 (m, 2H), 7.52ꢀ7.47 (m, 2H), 7.41ꢀ7.37 (tt, J=
.2, 1.2 Hz, 1H), 7.33ꢀ7.31 (d, J= 8 Hz, 2H), 2.47 (s, 3H) ppm;
The solutions of NaOH (6.490 g) in 50 mL of distilled water was
added to solutions of Al(NO ) .9H O (20 g) in 30 mL distilled water
13
C
3
3
2
NMR (400 MHz, CDCl ) δ= 141.2, 138.4, 137.1, 129.6, 128.8,
3
as drop to drop under vigorous stirring. The resulting milky mixture
was subjected to mixing in the ultrasonic bath for 3h at 25 ºC. The
resulted nano boehmite was filtered and washed by distilled water
and were kept in the oven at 220 ºC for 4 h. The obtained boehmite
nanoparticles (1.5 g) was dispersed in 50 mL toluene by sonication
for 30 min, and then 2.5 mL of (3ꢀcholoropropyl)triethoxysilane
1
[
7
27.1, 127.0, 21.2 ppm.
1,1'ꢀBiphenyl]ꢀ4ꢀcarbonitrile: H NMR (400 MHz, CDCl ): δ =
1
3
H
.78ꢀ7.75 (m, 2H), 7.73ꢀ7.70 (m, 2H), 7.64ꢀ7.61 (m, 2H), 7.54ꢀ7.50
13
(m, 2H), 7.48ꢀ7.44 (m, 1H) ppm; C NMR (400 MHz, CDCl ) δ=
3
1
4
7
6
1
45.7, 139.2, 132.7, 129.2, 128.7, 127.8, 127.3, 119.0, 110.1 ppm.
1
ꢀChloroꢀ1,1'ꢀbiphenyl: H NMR (400 MHz, CDCl ): δ = 7.60ꢀ
3
H
(CPTES) was added to mixture. The reaction mixture was stirred at
.58 (m, 2H), 7.57ꢀ7.54 (m, 2H), 7.50ꢀ7.43 (m, 4H), 7.42ꢀ7.38 (tt, J=
4
0 ºC for 8 h. Then, the prepared nanoparticles (nPrꢀClꢀboehmite)
13
, 1.6 Hz, 1H) ppm; C NMR (400 MHz, CDCl ) δ= 140.0, 139.7,
3
was filtered, washed with ethanol and dried at room temperature.
The obtained Clꢀboehmite (1g) were dispersed in 50 mL ethanol for
33.5, 129.0, 128.9, 128.5, 127.7, 127.1 ppm.
1
Butyl cinnamate: H NMR (400 MHz, CDCl ): δ = 7.74ꢀ7.70 (d,
J= 16 Hz, 1H), 7.57ꢀ7.55 (m, 2H), 7.43ꢀ7.40 (m, 3H), 6.50ꢀ6.46 (d,
3
H
2
0 min, and then Sꢀmethylisothiourea hemisulfate salt (2.5 mmol)
and potassium carbonate (2.5 mmol) were added to the reaction
mixture and stirred for 18 h at 80 ºC. Then, the resulting
nanoparticles (SMTUꢀboehmite) was filtered, washed with ethanol
and dried at room temperature. The TGA was used to determine the
percentage of chemisorbed organic functional groups onto the
boehmite nanoparticles. The obtained SMTUꢀboehmite (0.5 g) was
dispersed in 25 mL ethanol by sonication for 20 min, and then
palladium acetate (0.25 g) was added to the reaction mixture. The
J= 16 Hz, 1H), 4.26ꢀ4.23 (t, J= 6.4 Hz, 2H), 1.76ꢀ1.70 (m, 2H),
13
1
.50ꢀ1.45 (m, 2H), 1.02ꢀ0.98 (t, J= 7.6 Hz, 3H) ppm; C NMR (400
MHz, CDCl ) δ= 167.1, 144.6, 134.5, 130.2, 128.9, 128.1, 118.3,
3
6
4.5, 30.9, 19.2, 13.8 ppm. 1
Butyl 3ꢀ(pꢀtolyl)acrylate: H NMR (400 MHz, CDCl ): δ = 7.71ꢀ
3
H
7
8
2
.67 (d, J= 16 Hz, 1H), 7.47ꢀ7.45 (d, J= 8 Hz, 2H), 7.23ꢀ7.21 (d, J=
Hz, 2H), 6.45ꢀ6.41 (d, J= 16 Hz, 1H), 4.25ꢀ4.22 (t, J= 13.2 Hz,
H), 2.41 (s, 3H), 1.76ꢀ1.69 (quint, J= 6.4 Hz, 2H), 1.50ꢀ1.44 (sixt,
reaction mixture was stirred at 80 ºC for 20 h. Then, the NaBH (0.3
13
4
J= 7.6 Hz, 2H), 1.02ꢀ0.98 (t, J= 7.6 Hz, 3H) ppm; C NMR (400
mmol) was added to the reaction mixture and stirred for 2 hours. The
final product (Pd(0)ꢀSMTUꢀboehmite) was filtered, washed by
ethanol and dried at room temperature. The amount of palladium
determined by EDS and ICPꢀOES analysis.
MHz, CDCl ) δ= 167.3, 144.6, 140.6, 131.8, 129.6, 128.1, 117.2,
3
6
4.4, 30.8, 21.5, 19.2, 13.8 ppm.
1
Butyl 3ꢀ(4ꢀmethoxyphenyl)acrylate: H NMR (400 MHz, CDCl ):
3
δH= 7.68ꢀ7.64 (d, J= 15.6 Hz, 1H), 7.51ꢀ7.49 (d, J= 6.8 Hz, 2H),
6
.93ꢀ6.92 (d, J= 7.2 Hz, 2H), 6.36ꢀ6.32 (d, J= 16 Hz, 1H), 4.24ꢀ4.21
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 11

RSC Advances
Page 12 of 13
View Article Online
RSC Advances
DOI: 10.1039/C6RA02967A
ARTICLE
(
1
t, J= 6.4 Hz, 2H), 3.85 (s, 3H), 1.73ꢀ1.67 (quint, J= 6.8 Hz, 2H),
.51ꢀ1.42 (sixt, J= 8 Hz, 2H), 1.01ꢀ0.97 (t, J= 7.6 Hz, 3H) ppm; C
23. W. Chen, L. X. Zhong, X. W. Peng, K. Wang, Z. F. Chen, R. C. Sun,
Catal. Sci. Technol. 2014, 4, 1426.
13
NMR (400 MHz, CDCl ) δ= 167.4, 161.3, 144.2, 129.7, 127.2,
24. M. Ma, Q. Zhang, D. Yin, J. Dou, H. Zhang, H. Xu, Catal. Commun.
3
2
012, 17, 168.
1
3
7
15.8, 114.3, 64.3, 55.3, 30.8, 19.2, 13.8 ppm.
1
25. M. Hajjami, B. Tahmasbi, RSC Adv. 2015, 5, 59194.
ꢀ(pꢀTolyl)acrylonitrile: H NMR (400 MHz, CDCl ): δ = 7.42ꢀ
3
H
2
2
2
2
6. F. Havasi, A. GhorbaniꢀChoghamarani, F. Nikpour, microporous
.37 (m, 3H), 7.29ꢀ7.23 (m, 2H), 5.88ꢀ5.84 (d, J= 16.4 Hz, 1H), 2.42
13
mesoporous mater. 2016, 224, 26.
(s, 3H); C NMR (400 MHz, CDCl ) δ= 150.5, 140.2, 130.2, 129.1,
3
7. A. GhorbaniꢀChoghamarani, Z. Darvishnejad, B. Tahmasbi, Inorg.
Chim. Acta. 2015, 435, 223.
8. S. Rostamnia, E. Doustkhah, B. Zeynizadeh, Microporous
Mesoporous Mater. 2016, 222, 87.
9. H. B. Wang, Y. H. Zhang, H. L Yang, Z. Y. Ma, F. W. Zhang, J. Sun,
J. T. Ma, Microporous Mesoporous Mater. 2013, 168, 65.
0. T. Chen, J. Gao, M. Shi, Tetrahedron, 2006, 62, 6289.
1. M. Nasrollahzadeh, S. M. Sajadi, M. Maham, J. Mol. Catal. A: Chem.
2015, 396, 297.
1
3
7
2
1
1
1
3
28.5, 118.4, 95.1, 21.3 ppm.
1
,4ꢀDifluoroꢀ1,1'ꢀbiphenyl: H NMR (400 MHz, CDCl ): δ = 7.80ꢀ
3
H
.74 (m, 1H), 7.70ꢀ7.68 (m, 2H), 7.56ꢀ7.52 (m, 2H), 7.50ꢀ7.45 (m,
1
3
H), 7.42ꢀ7.38 (m, 1H); C NMR (400 MHz, CDCl ) δ= 151.5,
3
51.3, 150.8, 150.7, 149.1, 148.9, 148.4, 148.3, 138.4, 138.3, 138.3,
38.2, 138.2, 129.5, 128.4, 127.2, 123.9, 123.9, 123.8, 124.8, 118.4,
3
3
18.3, 116.3, 116.1 ppm.
,4ꢀDifluoroꢀ4'ꢀnitroꢀ1,1'ꢀbiphenyl: H NMR (400 MHz, CDCl ):
1
3
δ = 8.33ꢀ8.29 (m, 2H), 8.02ꢀ7.99 (m, 2H), 7.97ꢀ7.94 (m,1H), 7.71ꢀ
32. V.W. Faria, D.G. M. Oliveira, M. H. S. Kurz, F. F. Goncalves, C. W.
Scheeren, G.R. Rosa, RSC Adv. 2014, 4, 13446.
H
1
3
7
.68 (m,1H), 7.65ꢀ7.58 (m, 1H) ppm; C NMR (400 MHz, CDCl3)
δ= 151.8, 151.7, 151.6, 151.5, 149.3, 149.2, 149.2, 149.0, 147.4,
33. S. J. Sabounchei, A. Hashemi, Inorg. Chem. Commun. 2014, 47, 123.
34. M. Nasrollahzadeh, A. Azarian, M. Maham, A. Ehsani, J. Ind. Eng.
Chem. 2015, 21, 746.
1
1
44.7, 135.9, 135.8, 135.8, 135.8, 128.5, 124.9, 124.9, 124.8, 124.8,
24.5, 118.8, 118.7, 117.2, 117.0 ppm.
3
5. A. Modak, J. Mondal, M. Sasidharan, A. Bhaumik, Green Chem.
011, 13, 1317.
6. S. Singha, M. Sahoo, K. M. Parida, Dalton Trans. 2011, 40, 7130.
2
3
Acknowledgements
37. H. A. Patel, A. L. Patel, A. V. Bedekar, Appl. Organometal. Chem.
2
015, 29, 1.
This work was supported by the research facilities of Ilam
University, Ilam, Iran.
38. F. Alonso, I. P. Beletskaya, M. Yus, Tetrahedron 2008, 64, 3047.
39. H. Veisi, R. GhorbaniꢀVaghei, S. Hemmati, M. Haji Aliani, T. Ozturk,
Appl. Organometal. Chem. 2015, 29, 26.
4
4
4
0. F. Alonso, I. P. Beletskaya, M. Yus, Tetrahedron 2005, 61, 11771.
1. S. J. Sabounchei, M. Ahmadi, Inorg. Chim. Acta 2013, 405, 15.
2. M. L. Kantam, P. V. Redddy, P. Srinivas, A. Venugopal, S.
Bhargava, Y. Nishina, Catal. Sci. Technol. 2013, 3, 2550.
References
1
.
A. Islama, E. S. Chanc, Y. H. TaufiqꢀYapa, S. H. Teoa, Md. A.
Hoque, Ceramics Int. 2014, 40, 3779.
2
3
.
.
B. Xu, J. Wang, H. Yu, H. Gao, J. Environ. Sci. 2011, 23, S49.
A. GhorbaniꢀChoghamarani, B. Tahmasbi, New J. Chem. 2016, 40,
1
205.
4
5
.
.
L. Rajabi, A. A. Derakhshan, Sci. Adv. Mater. 2010, 2, 163.
N. V. Garderen, F. J. Clemens, C. G. Aneziris, T. Graule, Ceram. Int.
2
012, 38, 5481.
F. GranadosꢀCorrea, J. JimenezꢀBecerril, J. Hazard. Mater. 2009, 162,
178.
6
7
.
.
1
M. B. Gholivanda, G. Malekzadehb, A. A. Derakhshan, Sensor.
Actuat. B. 2014, 201, 378.
8
9
1
.
.
Y. Zheng, S. Ji, H. Liu, M. Li, H. Yang, Particuology 2012, 10, 751.
X. Y. Chen, H. S. Huh, S. W. Lee. Nanotechnology 2007, 18, 285608.
0. S. M. Kim, Y. J. Lee, K. W. Jun, J. Y. Park, H. S. Potdar, Mater.
Chem. Phys. 2007, 104, 56.
1
1
1
1
1
1
1
1
1. M. Thiruchitrambalam, V. R. Palkar, V. Gopinathan, Mater. Lett.
2
004, 58, 3063.
2. A. GhorbaniꢀChoghamarani, B. Tahmasbi, F. Arghand, S. Faryadi,
RSC Adv. 2015, 5, 92174.
3. M. Mirzaee, B. Bahramian, A. Amoli, Appl. Organometal. Chem.
2
015, 29, 593.
4. K. Bahrami, M.M. Khodaei, M. Roostaei, New J. Chem. 2014, 38,
515.
5
5. S. M. Islam, A. S. Roy, P. Mondal, N. Salam, Appl. Organometal.
Chem. 2012, 26, 625.
6. S. Pasa, Y. S. Ocak, H. Temel, T. Kilicoglu, Inorg. Chim. Acta. 2013,
4
05, 493.
7. A. GhorbaniꢀChoghamarani, H. Rabiei, Tetrahedron Lett. 2016, 57,
59.
8. S. Nadri, M. Joshaghani, E. Rafiee, Appl. Catal. A: Gen. 2009, 362,
63.
1
1
1
2
2
9. A. R. Hajipour, · F. Rafiee, J. Iran. Chem. Soc. 2015, 12, 1177.
0. H. Liu, J. Deng, W. Li, Catal. Lett. 2010, 137, 261.
1. A. GhorbaniꢀChoghamarani, B. Tahmasbi, P. Moradi, Appl.
Organometal. Chem. (2016) In Press, DOI: 10.1002/aoc.3449.
2. N. Shang, S. Gao, C. Feng, H. Zhang, C. Wang, Z. Wang, RSC Adv.
2
2
013, 3, 21863.
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 12

Page 13 of 13
RSC Advances
View Article Online
DOI: 10.1039/C6RA02967A
Graphical Abstract
Synthesis of new Pd(0)-complex supported on boehmite nanoparticles
and study of its catalytic activity for Suzuki and Heck reactions in H2O
or PEG
Arash Ghorbani-Choghamarani,* Parisa Moradi, Bahman Tahmasbi
Pd(0)-SMTU-boehmite was prepared using commercially materials and was applied as moisture-and air-stable
nanocatalyst in C-C coupling in H O or PEG-400.
2