Suzuki–Miyaura reaction by heterogeneously supported Pd nanoparticles on thio-modified multi walled carbon nanotubes as efficient nanocatalyst

Article abstract of DOI:10.1016/j.poly.2019.01.070

The palladium (Pd) supported on thio-modified multi walled carbon nanotubes (MWCNTs/CC-SH/Pd) was utilized as a useful and reusable nanocatalyst in Suzuki–Miyaura coupling reactions. The catalyst was really efficient for the Suzuki–Miyaura reaction of aryl halides (Ar–I, Ar–Br, Ar–Cl) with phenylboronic acid and conversion was good in most cases. The aryl iodides and aryl bromides reactions take place at room temperature, while reaction of aryl chlorides occurs at temperature of 80 °C. The products yields ranged between70% and 96%. The catalyst indicated excellent constancy and could be recycled and reused up to four cycles with no considerable change in its catalytic behavior.

Full text of DOI:10.1016/j.poly.2019.01.070

Accepted Manuscript
Suzuki–Miyaura reaction by heterogeneously supported Pd nanoparticles on
thio-modified multi walled carbon nanotubes as efficient nanocatalyst
Hojat Veisi, Ahmad Nikseresht, Nasim Ahmadi, Kaveh Khosravi, Fatemeh
Saeidifar
PII:
S0277-5387(19)30092-0
https://doi.org/10.1016/j.poly.2019.01.070
POLY 13743
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
22 November 2018
27 January 2019
31 January 2019
Please cite this article as: H. Veisi, A. Nikseresht, N. Ahmadi, K. Khosravi, F. Saeidifar, Suzuki–Miyaura reaction
by heterogeneously supported Pd nanoparticles on thio-modified multi walled carbon nanotubes as efficient
nanocatalyst, Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.01.070
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Suzuki–Miyaura reaction by heterogeneously supported Pd nanoparticles
on thio-modified multi walled carbon nanotubes as efficient nanocatalyst
Hojat Veisi,a,* Ahmad Nikseresht,a Nasim Ahmadi,a Kaveh Khosravi,b Fatemeh Saeidifara
aDepartment of Chemistry, Payame Noor University, Tehran, Iran
aDepartment of Chemistry, Faculty of Science, Arak University, Arak, 38156-8-8349, Iran
E-mail: hojatveisi@yahoo.com
Abstract. The palladium (Pd) supported on thio-modified multi walled carbon nanotubes
(MWCNTs/CC-SH/Pd) was utilized as a useful and reusable nanocatalyst in Suzuki-Miyaura
coupling reactions. The catalyst was really efficient for the Suzuki-Miyaura reaction of aryl
halides (Ar–I, Ar–Br, Ar–Cl) with phenylboronic acid and conversion was good in most cases.
The aryl iodides and aryl bromides reactions take place at room temperature, while reaction of
aryl chlorides occurs at temperature of 80 ºC. The products yields ranged between70% and
96%. The catalyst indicated excellent constancy and could be recycled and reused up to four
cycles with no considerable change in its catalytic behavior.
Keywords: Multi-walled carbon nanotubes, Thiol, Palladium, Nanocatalyst, Suzuki
1. Introduction
Over the last decade, modified carbon nanotubes (CNTs) have been greatly investigated in
terms of separation, features and catalytic behavior. This subject has been attentive owing to
the particular catalytic application comparing with homogenous complexes of CNTs. Besides
metal nanoparticles, diverse transition metal complexes such as polymers and porphyrins have
been used to functionalize CNTs [1-5]. Accordingly, CNTs can probably be utilized as an
effective solid support for cross coupling reactions [6-10]
Reactions containing carbon-carbon bond-formation in the presence of a palladium catalyst
play a key role in synthetic organic chemistry [11]. These kind of reactions have been improved
as a general technique for synthesizing modified biphenyls with biological activity, which have
extremely influenced on pharmaceuticals, and are key yields in drug discovery and agricultural
compounds [12-16]. Though, cross-coupling reactions are usually performed under
homogeneous conditions, in which a ligand is used to enhance the performance and specificity
of the catalyst, problems remain regarding the lack of recoverability and possible
contamination owing to remaining metal by-products [17,18]. Although, several promising
solutions have been obtainable for solving this issue, this remains a concern for
pharmacological uses. Solid-supported metal nanocatalysts have been used as optimal catalysts
that maximize the reactivity and stability of the compounds and increase the efficiency of
separation and recoverability level in more reactions. Therefore, many efforts have been
recently carried out to improve novel metal nanocatalysts for such cross-coupling reactions in
which the metal is immobilized on a group of compact supports such as activated carbon
[19,20], zeolites [21,22], polymers [23,24], mesoporous silica [25,26], inorganic oxides [27,
28], or nanoparticles [29-33]. CNTs owing to their thermal stability, large specific surface area,
and good structural and electronic features are used as support systems for immobilization of
the metal nanoparticles. Though, heterogeneous supports are chosen as they can be recycled
efficiently, stabilized catalysts tend to experience a decrease in their activity [34,35].
Consequently, further investigations are required to develop heterogeneous Pd nanocatalysts
1

with high activity, constancy and recoverability for the future of chemical and pharmacological
industries.
We previously immobilized palladium nanoparticles on thio modified-multi walled carbon
nanotubes (MWCNTs/CC-SH/Pd) as heterogeneous and reusable nanocatalyst for Buchwald–
Hartwig C–N cross coupling reactions [36]. Following our interest on the synthetic application
of metal supported nanocatalysts [37], we tried to utilize MWCNTs/CC-SH/Pd as a catalyst in
Suzuki-Miyaura coupling reaction under mild conditions.
2. Experimental
2.1. Preparation of the MWCNTs/CC-SH/Pd
The MWCNTs/CC-SH nanocatalyst is synthesized according to our earlier report [36]. Briefly,
MWCNTs-COOH (1 g) was added to 50 mL of ethylenediamine (EDA) and stirring for
5 minute. Next, (dicyclohexylcarbodiimide) DCC was poured into the solution and
refluxed for 48 h. Finally, the synthesized MWCNTS-EDA was isolated trough
centrifugation, rinsed with ethanol and dried in an oven at temperature of 80 ºC for 8 h.
Next phase, 100 mL of anhydrous THF, 0.5 g of MWCNTs-EDA and 0.2 ml of
diisopropylethylamine (DIPEA) were poured into a 250 mL of round-bottom flask. Then, 0.23
g (1.5 mmol) of cyanoric chloride (CC) was added in temperature of 0 °C. Following 3 hours
of agitation, the solution was decanted and rinsed with 2×25 of fresh THF and next decanted.
Then, acetonitrile (100 ml) and diisopropylethylamine (0.5 ml) were added to residue. 0.31 g
of 2-mercaptoethanol (4 mmol) was poured into the mixture and agitated for 3 hours in ambient
temperature and refluxed for 12 hours. At the end of the reaction, the solid products were
filtered, rinsed with deionized water and next acetone and dried at temperature of 50 °C for 12
h. The clung 2-mercaptoethanol on triazine modified MWCNTs (MWCNTs/CC-SH) was
achieved via this simple process.
500 mg of MWCNTs/CC-SH was dispersed in CH3CN (100 mL) in an ultrasonic bath for 30
min. Then, a yellow solution of PdCl2 (30 mg) in 30 mL acetonitrile was poured into dispersion
of MWCNTs/CC-SH and the resulted mixture was agitated for 10 hours at temperature of 25
ºC. Next, the MWCNTs/CC-SH/Pd(II) was isolated through centrifugation and rinsed with
CH3CN, H2O and acetone respectively to eliminate the unreacted substrates. The
MWCNTs/CC-SH/Pd(II) was reduced by hydrazine hydrate as following: MWCNTs/CC-
SH/Pd(II) (50 mg) was dispersed in of water (60 mL), and next 100 μL of hydrazine hydrate
(80%) was added. The pH of the mixture was set at 10 using 25% ammonium hydroxide and
the reaction was performed at temperature of 95 °C for 2 h. The final product MWCNTs/CC-
SH/Pd(0) was rinsed with water and dried in a vacuum at temperature of 40 °C.
2.2. General procedure for the Suzuki–Miyaura reaction
1 mmol of Aryl halide, 1.1 mmol of phenylboronic acid, 2 mmol of K2CO3, 10 mg of catalyst
(contained 0.2 mol% Pd) and 2 mL of water/ethanol (1:1) were poured into a 5 mL flask, and
mixed using a magnetic stirrer at RT or temperature of 80 ºC (depending on the aryl halide).
The development of the reactions was controlled using TLC. At the end of the reaction, the
reaction mixture was centrifuged to separate the catalyst and ethyl acetate was used to
extract the crude product. The pure products were achieved using column chromatography on
silica with the hexane and ethyl acetate as eluent.
2

2.3. Procedure for reusing the catalyst
After completion of the reaction, 5 mL of ethyl acetate was poured into the mixture and agitated
for 5 min. Then, the catalyst was isolated through centrifugation. In the following phase, the
recovered catalyst was rinsed using EtOH and dried under vacuum. Next, the recovered catalyst
was utilized for another cycle.
3. Results and discussion
The Suzuki-Miyaura reaction, which is a C-C bond formation reaction of aryl halides with
phenyl boronic acid, was used to assess the MWCNTs/CC-SH/Pd heterogeneous nanocatalyst
[37] (Scheme 1). Firstly, 4-bromotoluene and phenyl boronic acid at room temperature were
utilized to carry out the Suzuki coupling reaction as a model for the further development in
other reaction factors containing the solvent, base and the concentration of catalyst utilized.
Table 1 presents the list of research performed on optimization of conditions. As expected, no
target product was produced with no use of the catalyst, while, the yield and formation of the
target product was quickly increased via addition of the catalyst to the mixture. A 1:1 ratio of
H2O/EtOH solvent was applied in the reaction, and K2CO3 was the most effective bases
amongst tested ones. The effectiveness of catalysts was assessed using diverse amounts of the
catalyst ranging between 0.1 and 0.3 mol%, with 0.010 g (0.2 mol%) of the catalyst resulting
in the highest yield.
SH
HS
SH
HS
Pd
Pd
O
O
N
O
N
O
N
N
N
N
Pd
NH
NH
HN
HN
Pd
Pd
O
O
O
HN
N
O
H
R
R
B(OH)2
MWCNTs/CC-SH/Pd
K2CO3, H2O-EtOH
+
X
X = I, Br, Cl
Scheme 1. Synthesis of biaryls through the Suzuki cross-coupling reaction
.
3

Table 1. The optimization of reaction parameters for the Suzuki reaction of 4-bromotoluene
with phenyl boronic acid.a
B(OH)2
Br
various conditions
CH3
+
H3C
Entry Pd (mol%)
Solvent
Base
Time (h) Yield (%)b
1
2
3
4
5
6
7
8
9
0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.2
0.3
0.2
0.0
DMF
Toluene
EtOH
H2O
K2CO3
K2CO3
K2CO3
K2CO3
3
3
3
5
3
4
2
1
1
65
50
75
45
75
65
80
98
96
EtOH/H2Oc NaOAc
EtOH/H2Oc
Et3N
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc No base
EtOH/H2Oc K2CO3
10
11
12
12
Trace
0.0
aReaction conditions: 4-bromotoluene (1.0 mmol), phenylboronic acid (1.0 mmol), catalyst, base (2 mmol) and
solvent (3 mL) at room temperature.
bIsolated yield.
c3 mL (1:1)
However, subject to the optimum conditions for reaction and in the presence of a catalyst, the
reactions of structurally diverse aryl iodides, bromides and chlorides with phenylboronic acid
were studied (Table 2). The outcomes clarify that aryl iodides and aryl bromides containing
electron-donating and electron withdrawing parts with phenylboronic acid fittingly progressed
and the equivalent coupling products was produced in plentiful (good to excellent) efficacies
(Table 1, entries 4, 5, 7, 8, 10-15). Furthermore, the reactions between the unsubstituted
iodobenzene and bromobenzene improve optimally and result in the associated products (Table
1, entries 1, 2). The reaction of 2-iodothiphene and 2-bromothiophene as heterocyclic aryl
halides combining with phenylboronic acid resulted in the coupling product by 95% and 90%,
respectively (Table 2, entries 16 and 17). Substituted aryl chlorides are more economical
comparing with aryl iodides and bromides, and more accessible for Pd-catalyzed cross-
coupling reactions. Despite this, the aryl chlorides reactions subject to optimal reaction
conditions at room temperature were properly lethargic; and so, the reaction temperature was
increased to 80 ºC. According to these conditions, the Suzuki-Miyaura reaction was optimal,
and the predicted cross-coupling products were attained effectively (good to excellent
performance) (Table 1, entries 3, 6, 9).
Table 2. Scope of the Suzuki-Miyaura reaction.a
Entry RC6H4X
X
I
Br
Cl
I
Br
Cl
I
Br
Cl
I
Time (h) Yield (%)b
1
2
H
H
1.0
2.0
24
96
96
70c
96
96
65c
96
96
70c
96
92
3
H
4
5
6
7
8
9
10
11
4-CH3
4-CH3
4-CH3
4-COCH3
4-COCH3
4-COCH3
4-CH3O
4-CH3O
1.0
2.5
24
1.5
4.0
24
1.5
4.0
Br
4

12
13
14
15
16
17
4-NH2
4-NH2
4-OH
4-OH
2-Thienyl
2-Thienyl
I
Br
I
Br
I
Br
2.0
3.0
3.0
6.0
3.5
5.0
90
85
96
90
95
90
aReactions were carried out under aerobic conditions in 3 mL of H2O/EtOH (1:1), 1.0 mmol arylhalide,1.0 mmol
phenylboronic acid and 2 mmol K2CO3 in the presence of catalyst (0.010 g, 0.2 mol% Pd) at room temperature.
bIsolated yield.
cat 80 ºC.
It was found that the MWCNTs/CC-SH/Pd catalyst could be isolated easily through
centrifugation and could be reused at least 3 cycles with the performances of 96%, 96%, 95%
and 90% for the Suzuki coupling reaction between phenylboronic acid and 4-bromotoluene
subject to K2CO3 (Fig. 1). At the end of the reaction, the catalyst was separated via
centrifugation of the reaction mixture and rinsed several times by deionized water and ethanol.
Next, it was dried in an oven at temperature of 50 °C and the recycled catalyst was stored to
utilize in following reactions.
Fig. 1. Recyclability of catalyst in the Suzuki-Miyaura reaction
ICP was utilized to assess, the leaching of Pd into the reaction solution following 3 runs that
was achieved 1.58% and showed the stability of the catalysts under the reaction. The SEM
(scanning electron microscope), EDS (energy-dispersive X-ray spectroscopy) and TEM
(transmission electron microscopy) analysis (Fig. 2) corresponding to the catalyst following
the 3 runs indicated that the nanostructure of the catalyst was well-maintained. Based on the
TEM image resulted from recycled catalyst, the Pd NPs were still well dispersed and Pd NPs
were not accumulated. The heterogeneity of catalyst was measured via a hot filtration test
performed for the Suzuki reaction between 4-bromotoluene and phenylboronic acid with
MWCNTs/CC-SH/Pd under the same conditions. The performance of reaction was 70%
following proceeding for 60 minutes, and then, the catalyst was separated to reuse. The reaction
was continued for another 1 hour following separating the catalyst and no increase was found
in the product yield that shows the heterogeneity of the catalyst. Based on these outcomes and
literature [38], a reaction mechanism was suggested for Suzuki coupling with the synthesized
nanocatalyst (Scheme 2).
5

Fig. 2. a) SEM, b) TEM and EDS data for reused catalyst after the 3 runs.
Ar1
X
Reductive elimination
Ar1 Ar2
Oxidative addition
MWCNTs
Ar2
Ar1
Ar1
X
Ar2
X
Suzuki Reaction
Ar1
Ar1
Transmetalation
Ar2 B(OH)2
K2CO3
XB(OH)2
K2CO3
Scheme 2. Possible mechanism of Suzuki reaction catalyzed by MWCNTs/CC-SH/Pd.
6

The MWCNTs/CC-SH/Pd was compared with numerous previously reported Pd catalysts in
terms of catalytic behavior in the Suzuki coupling reaction (Table 3). Based on the outcomes
of this comparison in Table 3, the catalyst offered in current research shows more adaptations
and performance competing with other offered systems. Furthermore, in the current method,
the relevant products were obtained completely with excellent turnover frequencies (TOF) in
milder conditions (for entry 6, the reaction conditions are hard).
Table 3. Catalytic performance of different catalysts in the coupling reaction of iodobenzene
and bromobenzene with phenylbronic acid.
Entry Catalyst (mol%)
Conditions
X
Time (h) Yield (%)
TOF (h-1)a (TON)b Refs.
1
2
3
Bis(oxamato)palladate(II)
I
Br
I
Br
I
Br
Br
I
I
Br
I
Br
2.0
2.0
5.0
6.0
5.0
5.5
24
78
65
98
90
95
88
77.7
100
96
96
95
90
7.8 (15.6)
6.5 (13)
[39]
[40]
[41]
Et3N, n‐Bu4NBr,
120 °C
K3PO4.3H2O, H2O,
TBAB, 40 °C
complex (5)
NHC‐Pd(II) complex
(0.2)
SiO2‐pA‐Cyan‐Cys‐Pd
(0.5)
Pd3(dba) (1)
Pd–BOX (2)
γ ‐Fe2O3‐acetamidine‐Pd
(0.12)
Pd‐isatin Schiff base‐γ‐
Fe2O3 (0.5, 1.5)
98 (490)
75 (450)
38 (190)
32 (176)
3.24 (77.7)
K2CO3, H2O, 100 °C
4
5
6
K3PO4, THF, 80 °C
K2CO3, DMF, 70 °C
Et3N, DMF, 100 °C
[42]
[43]
[44]
6.0
8.3 (50)
0.5
0.5
0.5
0.7
1600 (800)
1600 (800)
380 (190)
85.7 (60)
7
8
[45]
Et3N, Solvent‐free,
100 °C
MWCNTs/CC-SH/Pd
(0.2)
K2CO3, H2O/EtOH,
r.t.
I
Br
1.0
2.0
96
96
480 (480)
240 (480)
this
work
aTOF, turnover frequencies.
bTON, turnover number, moles of aryl halides converted per mole of Pd.
4. Conclusions
In current research, we have introduced a novel, effective procedure using MWCNTs/CC-
SH/Pd as heterogeneous and recoverable nanocatalyst for the Suzuki-Miyaura cross-coupling
reactions. This catalyst can be easily recycled without significant decrease in its catalytic
performance and the suggested procedure can be a substitute technique for synthesis of
biphenyl compounds.
Acknowledgments. We are thankful to Payame Noor University and Arak University for
partial support of this work.
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9

Graphical Abstract
Suzuki–Miyaura reaction by heterogeneously supported Pd nanoparticles
on thio-modified multi walled carbon nanotubes as efficient nanocatalyst
Hojat Veisi,* Ahmad Nikseresht, Nasim Ahmadi, Kaveh Khosravi, Fatemeh Saeidifar
SH
HS
SH
HS
N
Pd
Pd
O
O
N
O
N
O
N
N
N
Pd
NH
NH
HN
HN
Pd
Pd
O
O
O
HN
N
O
H
R
R
B(OH)2
MWCNTs/CC-SH/Pd
K2CO3, H2O-EtOH
+
X
X = I, Br, Cl
10

Graphical Abstract
SH
HS
SH
HS
Pd
Pd
O
O
N
O
N
O
N
N
N
N
Pd
NH
NH
HN
HN
Pd
Pd
O
O
O
HN
N
O
H
R
R
B(OH)2
MWCNTs/CC-SH/Pd
K2CO3, H2O-EtOH
+
X
X = I, Br, Cl
The Pd supported on thio-modified multi walled carbon nanotubes (MWCNTs/CC-SH/Pd)
was used as an effective and recyclable nanocatalyst in Suzuki-Miyaura coupling reactions.
11