Poly(: O -aminothiophenol)-stabilized Pd nanoparticles as efficient heterogenous catalysts for Suzuki cross-coupling reactions

Article abstract of DOI:10.1039/c7ra09947a

Poly(o-aminothiophenol) (PATP)-stabilized Pd nanoparticles with Pd nanoparticles embedded in a polymer matrix have been obtained through a facile one-step route by mixing o-aminothiophenol monomer and Pd(NO₃)₂ in an acidic aqueous solution without additional template or surfactant. The redox reaction between o-aminothiophenol and Pd(NO₃)₂ leads to the simultaneous formation of a PATP polymer and Pd nanoparticles. The PATP-stabilized Pd nanoparticles have been characterized by TEM, FTIR, XRD, ICP-MS and XPS. Catalytic results showed that PATP-stabilized Pd nanoparticles were highly stable and active catalysts for Suzuki cross-coupling reactions, where high yields could be achieved with arylboronic acid and aryl halides bearing a variety of substituents.

Full text of DOI:10.1039/c7ra09947a

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Poly(o-aminothiophenol)-stabilized Pd
nanoparticles as efficient heterogenous catalysts
Cite this: RSC Adv., 2017, 7, 47104
for Suzuki cross-coupling reactions
Yuan Chen, Minggui Wang, Long Zhang, Yan Liu and Jie Han *b
ab
b
ab
b
Poly(o-aminothiophenol) (PATP)-stabilized Pd nanoparticles with Pd nanoparticles embedded in a polymer
matrix have been obtained through a facile one-step route by mixing o-aminothiophenol monomer and
Pd(NO
3
)
2
in an acidic aqueous solution without additional template or surfactant. The redox reaction
leads to the simultaneous formation of a PATP polymer and
between o-aminothiophenol and Pd(NO )
3 2
Received 6th September 2017
Accepted 29th September 2017
Pd nanoparticles. The PATP-stabilized Pd nanoparticles have been characterized by TEM, FTIR, XRD, ICP-
MS and XPS. Catalytic results showed that PATP-stabilized Pd nanoparticles were highly stable and active
catalysts for Suzuki cross-coupling reactions, where high yields could be achieved with arylboronic acid
and aryl halides bearing a variety of substituents.
DOI: 10.1039/c7ra09947a
rsc.li/rsc-advances
ideal raw material for Suzuki cross-coupling reactions
compared to bromobenzene and iodobenzene. However, it is
Introduction
Among the carbon–carbon bond formation reactions catalyzed greatly limited in practical production and applications due to
1
–3
by palladium (Pd) in organic synthesis, cross-coupling reac- the low reactivity of chlorobenzene. Therefore, it is highly
4–6
tions as simple and practical reactions include the reactions desirable to develop efficient catalysts for the Suzuki cross-
7
of halogenated hydrocarbons with organotin (Stille reactions),
coupling reaction of chlorobenzene. We have successfully
8
organoboron (Suzuki reactions), organosilicon (Hiyama reac- prepared the poly(o-aminothiophenol) (PATP)-stabilized gold
tions), alkenes (Heck reactions) and alkynes (Sonogashira nanoparticles as catalysts for the Suzuki cross-coupling reac-
9
10
11
19
reactions). The Suzuki cross-coupling reaction refers to the tions of aryl halides with arylboronic acids in water. In order to
reaction between a halogenated hydrocarbon and an organic further expand the research scope of substrates and improve
boron reagent catalyzed by Pd, and the reaction conditions are the yield of the products, PATP-stabilized Pd nanoparticles were
relatively mild, which is one of the important methods for chosen as catalysts for the Suzuki cross-coupling reactions of
preparing the asymmetric biphenyl compounds. Since the use aryl halides with arylboronic acids in water, especially aryl
of organic boron reagents with low toxicity, high stability and chlorides with low reactivity. The results showed that PATP-
easy preparation, the Suzuki cross-coupling reactions catalyzed stabilized Pd nanoparticles can effectively promote the Suzuki
by Pd are widely used and have attracted much attention due to cross-coupling reactions of aryl halides with arylboronic acids
the simple synthesis method and the easy recovery of the to obtain the series of diaryl compounds with high yields.
12
13–16
catalysts.
It is important to make use of inexpensive, safe
and pollution-free reaction media in current organic synthesis.
17
Experimental
Early Beletskaya reported the Suzuki coupling reactions of
water-soluble iodobenzene and bromobenzene catalyzed by Materials
Pd(OAc) and PdCl respectively, which were carried out under
the protection of inert gas and at room temperature. Later,
2
2
o-Aminothiophenol (ABCR GmbH & Co. KG) was distilled under
reduced pressure before use. All other reagents were of analyt-
ical grade and purchased from Alfa Aesar. The water used in this
study was deionized by milli-Q Plus system (Millipore, France),
having 18.2 MU electrical resistivity.
18
Davydov studied the reduction coupling reactions of water-
insoluble aryl halides catalyzed by PdCl and water-soluble tri-
2
phenylphosphine in the emulsion, where the conversion of the
aryl halides is still lower, less than 50%, and only the aryl iodide
and bromide can be used as substrates. Chlorobenzene is an
Preparation of PATP-stabilized Pd nanoparticles
In a typical synthesis, o-aminothiophenol (100.0 mg) was
dispersed in HCl aqueous solution (1.0 mol L , 20 mL) with
a
School of Animal Pharmaceuticals, Jiangsu Agri-animal Husbandry Vocational
À1
College, Taizhou 225300, Jiangsu, People's Republic of China
b
magnetic stirring at room temperature to obtain a uniform
solution. Then 4 mL palladium nitrate aqueous solution
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou
2
25002, Jiangsu, People's Republic of China. E-mail: hanjie@yzu.edu.cn
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À1
(
0.1 mol L ) was added to the above mixture, stirring at room polymerized polymer PATP can act as effective capping agent for
temperature for 6 h. Finally, the mixture was washed with Pd nanoparticles as conjugated p electrons of benzene rings
deionized water and sodium hydroxide aqueous solution for and thiol groups coexist in PATP chains which can signicantly
23
several times and the resulting products were diluted by control and stabilize Pd nanoparticles. As a consequence, in
deionized water to a certain concentration, and then placed at the obtained PATP-stabilized Pd nanoparticles, Pd nano-
room temperature and under normal pressure for further use. particles are always embedded in polymer matrix.
In order to reveal the effect of molar ratio between o-amino-
thiophenol monomer and palladium nitrate, the amount of o-
aminothiophenol was decreased to 50 mg and 25 mg while
maintaining other conditions unchanged.
(1)
Catalysis for Suzuki cross-coupling reactions
The prepared PATP-stabilized Pd nanoparticles was centri-
fuged and then the Pd content of the supernatant solution was
measured to be 0.0084% of the total Pd content through ICP-MS
analysis, indicating that Pd ions were almost completely
reduced in the process. As a result, the amount of Pd in the
product was considered to be equal to that in initial addition of
Aryl halide (2.0 mmol), phenylboronic acid (2.4 mmol) and
NaOH (8.0 mmol) were added to 40 mL deionized water, which
ꢀ
were stirred at 80 C until the above-mentioned substances were
completely dissolved. Then a certain amount of Pd catalysts
(0.08 mol%) was added to the mixed solution, and the reaction
mixture was stirred for 4 h. Aer the mixture was cooled to room
temperature, the product was extracted three times with diethyl
ether (3 Â 20 mL), then the organic layer was dried with
3 2
Pd(NO ) . Fig. 1 shows the TEM images of PATP-stabilized Pd
nanoparticles, where the dark dots as ascribed to Pd nano-
particles are well dispersed in PATP polymer matrix. Fig. 1A is
the freshly prepared PATP-stabilized Pd nanoparticles, where
Pd nanoparticles are about 1 nm in diameter without aggrega-
tion (Fig. 1B). The clear lattice fringes 0.223 nm as shown in
insert in Fig. 1B that attributed to the (111) plane of face-
2 4
excessive Na SO . Aer ltration, volatile substances were
removed under reduced pressure. The crude material was
puried by ash chromatography on silica gel.
Characterization
24
centered cubic (fcc) Pd indicates the signal crystal of each
Pd nanoparticles. Further investigations revealed that the molar
ratio between o-aminothiophenol monomer and palladium
nitrate has negligible effect on the size of Pd nanoparticles,
which should be ascribed to the effective capping ability of
polymerized polymer PATP for Pd nanoparticles. Compared to
The morphologies of products were characterized by a trans-
mission electron microscopy (TEM, Tecnai-12 Philip Apparatus
Co., USA) and a high-resolution transmission electron micros-
copy (HR-TEM, JEOL, JEM-2010, Japan). FTIR spectra of prod-
À1
ucts were recorded in the range of 400–4000 cm using FTIR
spectroscopy (Nicolet-740, USA) and the samples were prepared
in pellet form with spectroscopic grade KBr. X-ray diffraction
(XRD) patterns were recorded by an X-ray diffractometer (XRD,
MO3XHF22, MacScience, Japan) and X-ray photoelectron spec-
troscopy (XPS) data were recorded by a X-ray photoelectron
spectrometer (Thermo Escalab 250, USA). The content of Pd was
measured by inductively coupled plasma mass spectrometry
(
(
ICP-MS, ELAN DRC-e, PE, USA) analysis. Gas chromatography
GC) analysis (6890N, Agilent, USA) was performed on an Agi-
lent DB-1 GC-FID system equipped with a 100% dimethyl pol-
ysiloxane capillary column (length, 30 m; internal diameter,
0.25 mm; lm thickness, 0.25 mm). The GC yield was obtained
from the calibration curve.
Results and discussion
Morphology and structure of PATP-stabilized Pd
nanoparticles
The chemical oxidation polymerization of o-aminothiophenol
monomers to PATP polymer is induced by the reduction of Pd(II)
to Pd(0), where PATP polymer and Pd nanoparticles are gener-
ated simultaneously (eqn (1)), resulting in the formation of
20–22
PATP-stabilized Pd nanoparticles.
The PATP polymer oligo-
mers prefer to locate on surfaces of newly formed Pd nuclei to
lower down the surface energy. The choice of o-amino-
Fig. 1 TEM images of PATP-stabilized Pd nanoparticles: (A and C)
freshly prepared sample, (C and D) after aging 6 months. Scale bar: (A
thiophenol as the reductant is based on the fact that its and C) 20 nm, (B and D) 5 nm.
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the freshly prepared Pd nanoparticles, the size of Pd nano- Table 2 Suzuki cross-coupling of chlorobenzene and phenylboronic
a
acid catalyzed by PATP-stabilized Pd nanoparticles
particles aer aging 6 months at room temperature does not
change (Fig. 1C and D), which shows that PATP polymer plays
the role of protective agent to prevent the aggregation of Pd
nanoparticles.
As shown in Fig. 2A, the strong absorption band at 3150–
À1
3
500 cm can be ascribed to the N–H stretching vibrations, the
No.
Storage time (day)
Yield (%)
À1
weak absorption band at 2615 cm is attributed to the S–H
1
2
3
4
1
96
96
95
95
stretching vibrations. The strong characteristic peaks at
À1
À1
10
30
180
1
609 cm and 1475 cm come from the C]C stretching
deformation of quinone and benzene, respectively, where the
relative intensity of the former is weaker than that of the latter,
a
Chlorobenzene (2 mmol), phenylboronic acid (2.4 mmol), Pd catalyst
0.08%), NaOH (8 mmol).
(
Table 3 Recovery and reuse of PATP-stabilized Pd nanoparticles as
catalysts for Suzuki cross-coupling of chlorobenzene and phenyl-
a
boronic acid
Use
Yield (%)
1st
96
2nd
96
3rd
96
4th
95
5th
95
6th
96
a
Chlorobenzene (2 mmol), phenylboronic acid (2.4 mmol), Pd catalyst
0.08%), NaOH (8 mmol).
(
indicating the amount of quinone ring is less than that of
benzene ring. From the XRD pattern of PATP-stabilized Pd
nanoparticles (Fig. 2B), it can be seen that the crystal structure
of Pd nanoparticles is face-centered cubic, which is consistent
Fig. 2 (A) FTIR, (B) XRD, and (C and D) XPS spectra of PATP-stabilized
Pd nanoparticles.
25
with the previous report. The main diffraction peaks of PATP-
ꢀ
ꢀ
ꢀ
stabilized Pd nanoparticles appearing at 40.1 , 46.4 , 68.1 and
Table 1 Effect of catalyst amount, alkali and solvent on the yield of
ꢀ
8
2.1 that corresponding to (111), (200), (220) and (311) Bragg
planes of Pd, can be observed. The broad diffraction peaks
between 15–35 indicate the amorphous structure of PATP
a
Suzuki cross-coupling of chlorobenzene and benzoboric acid
26
ꢀ
polymer.
The XPS spectrum shows clearly the signatures of C, N and S
for PATP, and Pd for Pd nanoparticles (Fig. 2C). Fig. 2D repre-
sents the XPS signature of the Pd 3d, with the splitting of 5.6 eV
Pd amount
(n mol%)
Entry
Solvent
Alkali
Yield (%)
1
2
3
4
5
6
7
8
9
0.06
0.08
0.10
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
H
H
H
H
H
H
2
2
2
2
2
2
O
O
O
O
O
O
NaOH
NaOH
NaOH
94
96
96
96
95
98
96
95
96
96
10
6
K
2
CO
3
Na
Et
3
PO
3
N
3
DMF/H
THF/H
2
O (1 : 1)
O (1 : 1)
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
2
C
C
2
H
H
5
OH/H
OH
2
O (1 : 1)
10
11
12
13
2
5
DMF
THF
TX-100/H
b
2
O (2%, w/w)
97
a
b
ꢀ
Fig. 3 Dependence of biphenyl yield on reaction time for the Suzuki
cross-coupling of chlorobenzene and phenylboronic acid catalyzed
by PATP-stabilized Pd nanoparticles under different runs.
Chlorobenzene (2 mmol), benzoboric acid (2.4 mmol), 80 C, 4 h.
Reaction temperature was maintained at 50 C.
ꢀ
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Table 4 Suzuki cross-coupling of aryl halides and phenylboronic loss of partial electrons, leading to the decrease of the electronic
a
acids
cloud density of the valence electrons and the shielding effect of
the electrons in the inner shell layer, nally resulting in the
increase of the binding energy of the inner shell layer. Results
indicate compact interactions between PATP polymer and Pd
nanoparticles.
Entry
X
R
Yield (%)
Catalysis in Suzuki cross-coupling reactions
1
2
3
4
5
6
Br
I
Cl
Cl
Cl
Cl
H
H
2-OCH
4-OCH
4-CHO
99
100
95
95
97
97
The Suzuki cross-coupling reaction of aryl halides with aryl-
boronic acids is one of the most powerful and convenient
synthetic protocols for the generation of biaryl in organic
3
3
27
chemistry. Pd nanoparticles usually show enhanced reactivity
under mild conditions because of their large surface area.
Herein, the Suzuki cross-coupling reactions were then chosen
as the target model reactions to test the catalytic performances
of PATP-stabilized Pd nanoparticles.
4-COOH
a
Aryl halides (2 mmol), phenylboronic acid (2.4 mmol), Pd catalyst
0.08%), NaOH (8 mmol).
(
Table 1 shows the synthetic conditions of catalyst amount,
alkali and solvent on the biphenyl yield of Suzuki cross-coupling
reaction of chlorobenzene and benzoboric acid. The optimized
choice is using NaOH as the alkali (entries 2, 4–6, Table 1), H O
2
as the green solvent (entries 2, 7–13, Table 1), and 0.08 mol% Pd
indicating the metallic nature of Pd. However, the energy peak
of Pd (3d5/2) at 337.1 eV is 1.9 eV higher than that of the stan-
dard Pd (3d5/2) at 335.2 eV, indicating the change of the
chemical environment of Pd nanoparticles. The possible reason
is that Pd nanoparticles may coordinate with other atoms and
Table 6 Suzuki cross-coupling of 2-chloroanisole and arylboronic
a
acids
Table 5 Suzuki cross-coupling of chlorobenzene and arylboronic
a
acids
Entry
1
Arylboronic acid
Yield (%)
78
Entry
1
Arylboronic acid
Yield (%)
64
2
83
2
75
3
4
5
79
90
76
3
4
5
43
72
61
6
58
40
6
44
21
7
7
a
Chlorobenzene (2 mmol), arylboronic acids (2.4 mmol), Pd catalyst
0.08%), NaOH (8 mmol).
a
(
2-Chloroanisole (2 mmol), arylboronic acids (2.4 mmol), Pd catalyst
0.08%), NaOH (8 mmol).
(
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catalysts (entries 1–3, Table 1), the yield can reach as high as centrifuged, ltered and washed with water three times to
6%. It was found that when using pure organic solvents, such remove the by-products adsorbed on the surfaces of catalysts,
as THF and DMF, the yield is below 10% (entries 11, 12, Table and then were reused for the repeated catalytic reaction under
). As the PATP polymer shows high solubility in such solvents, the same reaction conditions. The results showed that the yield
9
1
the dissolution of PATP in organic solvents leads to aggregation of biphenyl almost unchanged (Table 3). The PATP-stabilized Pd
of supported Pd nanoparticles, which will eventually result in nanoparticles as catalysts remained the same size aer six
decreased catalytic activity. In addition, the introduction of cycles (Fig. 1), together with similar kinetic curves for each run
surfactant in the reaction system can lower down the reaction (Fig. 3), which provided high recyclability of the catalysts. In
ꢀ
temperature from 80 to 50 C with comparable yield (entry 13). addition, both the yield and recyclability of PATP-stabilized Pd
This is mainly related to the special property of surfactant, nanoparticles are better than those using commercial Pt/C
28
which can self-assembly into micelles that can increase the catalysts, revealing their high potentials in Suzuki cross-
solubility of reactants (chlorobenzene and benzoboric acid) in coupling reactions.
water. The concentration of reactants in micelles is favorable for
catalytic reactions, ensuring high yield even at low reaction aryl halides and phenylboronic acids at the same reaction
temperature. conditions were shown in Table 4. As for bromobenzene and
The yields of diaryl produced by the Suzuki cross-coupling of
The effect of the aging time of catalyst on the yield of iodobenzene, the yields of diaryl reached as high as 99% (entry
biphenyl was also investigated. As seen in Table 2, the yield of 1) and 100% (entry 2), respectively. It is reasonable as the
biphenyl which was produced by the Suzuki cross-coupling of reactivity of aryl halides is in the following order: iodobenzene >
chlorobenzene and phenylboronic acid catalyzed by the freshly bromobenzene > chlorobenzene. In addition, it can be seen that
prepared PATP-stabilized Pd nanoparticles was 96%. When the PATP-stabilized Pd nanoparticles can also be well suited for the
catalyst was aged for 6 months, the yield can also reach as high Suzuki cross-coupling of chlorobenzene with various substitu-
as 95%, which proved high stability and activity of the catalysts. ents and phenylboronic acids, where the yields were more than
The recyclability of PATP-stabilized Pd nanoparticles as 95% (entries 3–6). Besides, when activated aryl chloride was
catalysts was also studied, where the used catalysts were used, the yields were higher (entry 5, 6, Table 4) than those of
deactivated ones (entries 3, 4, Table 4).
Table 7 Suzuki cross-coupling of 4-chloroanisole and arylboronic
acid
a
Table 8 Suzuki cross-coupling of 4-chlorobenzaldehyde and aryl-
boronic acids
a
Entry
1
Arylboronic acid
Yield (%)
70
Entry
1
Arylboronic acid
Yield (%)
83
2
74
2
85
3
4
5
79
80
50
3
4
5
81
88
77
6
40
31
6
61
40
7
7
a
a
4
-Chloroanisole (2 mmol), arylboronic acids (2.4 mmol), Pd catalyst
4-Chlorobenzaldehyde (2 mmol), arylboronic acids (2.4 mmol), Pd
catalyst (0.08%), NaOH (8 mmol).
(0.08%), NaOH (8 mmol).
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Chlorobenzene is cheaper than bromobenzene and iodo- reactions than 2-chloroanisole (Tables 7 vs. 6) due to the steric
benzene, but the use of aryl chlorides is limited by their weak hindrance effect.
reactivity. Therefore, searching suitable catalysts and reaction
Further investigations demonstrated that high yields could
system for the Suzuki cross-coupling reactions of aryl chlorides also be obtained when using 4-chlorobenzaldehyde (Table 8)
have attracted increasing attention. As shown in Table 5, PATP- and 4-chlorobenzoic acid (Table 9), respectively, where the
stabilized Pd nanoparticles can catalyze the Suzuki cross- steric hindrance effect plays the determining role in their
coupling reactions of chlorobenzene and arylboronic acids activity. Therefore, the results indicate that the prepared PATP-
(
(
entries 1–5). The yields of para-substituted arylboronic acids stabilized Pd nanoparticles as catalysts are suitable for the
entry 4) were higher than those of meta-substituted arylboronic Suzuki cross-coupling of chlorobenzene with different substit-
acids (entries 1–3, 5). The lower yields of entries 6 and 7 were uents and arylboronic acids, and the moderate yields can be
5
8% and 40%, respectively, owing to the obvious steric obtained even for those substrates with larger steric hindrance
29
hindrance effect.
(entries 6, 7, Tables 8 and 9).
The yields of the Suzuki cross-coupling of 2-chloroanisole
and arylboronic acids are shown in Table 6. It can be seen that
the yields were relatively low, and the yield of the Suzuki cross-
coupling of 2-chloroanisole and phenylboronic acid even with
an electron-withdrawing group was only 75% (entry 2).
However, the yields were obviously affected by steric hindrances
when phenylboronic acid with the same electron-donating
group at different positions and the 4-substituted phenyl-
boronic acid were preferred (entry 5 vs. 4).
Conclusions
In summary, PATP-stabilized Pd nanoparticles with high
stability have been successfully fabricated by the oxidation-
reduction of o-aminothiophenol and Pd(NO ) , where the
PATP polymer can act as the stabilizer for Pd nanoparticles. The
method of synthesis is simple and green, which does not
require any external protective agent and additives. The
prepared PATP-stabilized Pd nanoparticles exhibit excellent
catalytic performance in Suzuki cross-coupling reactions of aryl
halides and arylboronic acid, which prove their potential in
catalysis.
3
2
The catalytic activity was further investigated to use 4-
chloroanisole (Table 7). The results indicate that 4-chlor-
oanisole is more suitable for the Suzuki cross-coupling
Table 9 Suzuki cross-coupling of 4-chlorobenzoic acid and aryl-
a
boronic acids
Conflicts of interest
There are no conicts to declare.
Acknowledgements
Entry
1
Arylboronic acid
Yield (%)
81
The authors gratefully acknowledge nancial support from the
National Natural Science Foundation of China (21673202), Qing
Lan Project, Priority Academic Program Development of Jiangsu
Higher Education Institutions, Jiangsu Overseas Research &
Training Program for University Prominent Young & Middle-
aged Teachers and Presidents, Jiangsu High-end Research &
Training Program for Professional Leaders of Higher Vocational
Colleges (2016GRFX023), and the Phoenix Scholars Program of
Jiangsu Agri-animal Husbandry Vocational College. We would
also like to acknowledgment the technical support received at
the Testing Center of Yangzhou University.
2
85
3
4
5
80
88
78
Notes and references
1
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