Porphyrin-based polymer-supported palladium as an excellent and recyclable catalyst for Suzuki–Miyaura coupling reaction in water

Article abstract of DOI:10.1002/aoc.3996

A porphyrin-based polymer with high surface area was synthesized using 5,10,15,20-tetraphenylporphyrin through a one-pot Friedel–Crafts alkylation reaction. Pd(II) was successfully supported on this polymer. This strategy provides an easy approach to produce highly stable Pd–porphyrin-based polymer. The resulting Pd catalyst was characterized using Fourier transform infrared and X-ray photoelectron spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and N₂ adsorption–desorption measurements. This porphyrin-based polymer-supported Pd was used as a heterogeneous catalyst for Suzuki–Miyaura coupling reaction in water. The results demonstrated that this Pd catalyst indeed exhibited excellent catalytic activity and recycling performance in water, even for inactive aryl chloride substrate. A new heterogeneous strategy for catalyzing the Suzuki–Miyaura reaction in water is provided.

Full text of DOI:10.1002/aoc.3996

Received: 16 May 2017
DOI: 10.1002/aoc.3996
Revised: 27 June 2017
Accepted: 27 June 2017
F U L L P A P E R
Porphyrin‐based polymer‐supported palladium as an
excellent and recyclable catalyst for Suzuki–Miyaura
coupling reaction in water
Jian Chen1 | Ju Zhang1 | Dajian Zhu1,2
| Tao Li1
1 Hubei Key Laboratory of Material
A porphyrin‐based polymer with high surface area was synthesized using
5,10,15,20‐tetraphenylporphyrin through a one‐pot Friedel–Crafts alkylation
reaction. Pd(II) was successfully supported on this polymer. This strategy
provides an easy approach to produce highly stable Pd–porphyrin‐based
polymer. The resulting Pd catalyst was characterized using Fourier transform
infrared and X‐ray photoelectron spectroscopies, thermogravimetric analysis,
scanning and transmission electron microscopies and N2 adsorption–desorption
measurements. This porphyrin‐based polymer‐supported Pd was used as a
heterogeneous catalyst for Suzuki–Miyaura coupling reaction in water. The
results demonstrated that this Pd catalyst indeed exhibited excellent catalytic
activity and recycling performance in water, even for inactive aryl chloride
substrate. A new heterogeneous strategy for catalyzing the Suzuki–Miyaura
reaction in water is provided.
Chemistry and Service Failure, Key
Laboratory of Material Chemistry for
Energy Conversion and Storage, Ministry
of Education, School of Chemistry and
Chemical Engineering, Huazhong
University of Science and Technology,
Wuhan 430074, China
2 Shenzhen Research Institute of
Huazhong University of Science and
Technology, 9 Yuexing Third Avenue,
Shenzhen 518057, China
Correspondence
Dajian Zhu and Tao Li, School of
Chemistry and Chemical Engineering,
Huazhong University of Science and
Technology, Wuhan 430074, China.
Email: zhudj@hust.edu.cn;
taoli@hust.edu.cn
KEYWORDS
Pd catalyst, polymer‐supported catalyst, Suzuki–Miyaura coupling reaction, tetraphenylporphyrin
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21473064;
Shenzhen Science and Technology
Innovation Program, China, Grant/Award
Number: JCYJ20150630155150201;
Natural Science Foundation of Hubei
Province, Grant/Award Number:
2016CFB537
1 | INTRODUCTION
easy recovery and separation from reaction systems.[1]
Consequently, immobilization of Pd catalysts on supports
Nowadays, the Pd‐catalyzed Suzuki–Miyaura coupling
reaction is one of the most efficient methods for the con-
struction of biaryls or substituted aromatic moieties.[1]
Many homogeneous Pd complexes with various ligands
have been developed for this reaction.[2] However, their
industrial applications have been limited due to the diffi-
culty in the separation of catalysts from products. From
this point of view, heterogeneous Pd catalytic systems
are preferred for industrial applications because of their
such as polymers,[3–10] silica,[11–15] carbon[16–18] and metal
oxides[19,20] has been extensively investigated in Suzuki–
Miyaura reactions. However, some of these heteroge-
neous Pd catalysts have a lower activity in comparison
with their counterpart homogeneous systems.[12,13]
Water is an eco‐friendly alternative to conventional
organic solvents because it is cheap, non‐toxic and non‐
flammable. Therefore, water has attracted great interest
for potential applications in catalysis.[21] Organic solvents
Appl Organometal Chem. 2018;32:e3996.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3996

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CHEN ET AL.
or mixed media of organic solvents and water are most
commonly used in heterogeneous Pd‐catalyzed Suzuki–
Miyaura reactions,[1,2] while some of those heterogeneous
Pd catalysts have a low activity in neat water, especially
for aryl chloride substrates.[21] Therefore, heterogeneous
Pd catalysts with high catalytic performance in water are
highly desired for Suzuki–Miyaura reactions.
accelerating voltage of 200 kV. Pd content data were
obtained with a PerkinElmer AA‐800 (USA). Scanning
electron microscopy (SEM) images were obtained with a
FEI Sirion 200 microscope at 10.0 kV. X‐ray photoelectron
spectroscopy (XPS) was performed in a VG multilab 2000
spectrometer, using a MgAl Ka X‐ray source with a
passing energy flow of 100 eV. The samples were
degassed in a chamber at 5 × 10−10 mbar at room
temperature. C 1s transition was adjusted at 284.6 eV.
Porphyrins, methylene‐bridged four‐pyrrole derivative
molecules,
are
highly
conjugated
heterocyclic
macrocycles.[22] Pd–porphyrin systems have found appli-
cations in luminescent, oxygen sensor and gas sorption
fields.[23–26] However, there are very few reports of Pd–
porphyrin catalytic applications in Suzuki–Miyaura
reactions, especially in water. Kostas et al. reported the
first water‐soluble Pd complex with a porphyrin ligand
to catalyze the Suzuki–Miyaura reaction in water, but
the catalytic activity was low.[27] Röhlich and Köhler also
reported a Pd–porphyrin catalyst used in Suzuki–Miyaura
reactions with mixed media of N‐methyl‐2‐pyrrolidone
and water.[28] Moghadam and co‐workers reported
Pd–porphyrin supported on resins for C–C coupling
reactions.[29]
In our recent research, we reported that a kind
of porphyrin‐based polymer, synthesized from 5,10,15,
20‐tetraphenylporphyrin, showed large gas storage
capacity.[30] Herein, we report the synthesis of a porphy-
rin‐based polymer‐supported Pd catalyst via a one‐pot
method and its catalytic application in Suzuki–Miyaura
coupling reactions in water.
Thermogravimetric data were recorded with
a
PerkinElmer Diamond TG/DTA instrument. GC analyses
were performed using a Fuli GC9790, equipped with a
FFAP (30 m × 0.25 mm × 0.25 μm) capillary column
and a flame ionization detector.
2.3 | Synthesis of Pd/KAPs(DCM‐TPP)
catalyst
PdCl2 (0.18 g, 1 mmol) was added into a solution of
5,10,15,20‐tetraphenylporphyrin (2.00 g, 3.25 mmol) in
30 ml of dichloromethane (DCM). The resulting mixture
was stirred at 50 °C for 4 h. AlCl3 (anhydrous, 2.10 g,
15.7 mmol) was added to the solution and then heated
at 80 °C under N2 atmosphere for 48 h to react completely.
The resulting precipitate was washed three times with
ethanol, DCM, then washed with ethanol, tetrahydrofu-
ran and DCM in a Soxhlet for 24 h, and finally dried
under reduced pressure at 70 °C for 24 h. The catalyst
was denoted as Pd/KAPs(DCM‐TPP) (Scheme 1). The Pd
content of the catalyst was 3.45 wt% measured using
atomic absorption spectroscopy.
2 | EXPERIMENTAL
2.1 | Materials
2.4 | Typical procedure for Suzuki–
Miyaura coupling reaction
Aryl halides, arylboronic acids and 5,10,15,20‐
tetraphenylporphyrin were purchased from Alfa Aeser.
PdCl2, AlCl3, bases and solvents were obtained from
National Medicines Corporation Ltd of China. All
chemicals were of analytical grade and used without
further purification.
Suzuki–Miyaura coupling reactions were carried out at
80 °C in a 10 ml reactor under N2 atmosphere. In a typical
run, Pd/KAPs(DCM‐TPP) (20 mg), bromobenzene (79 mg,
0.5 mmol), phenylboronic acid (92 mg, 0.75 mmol),
K3PO4⋅3H2O (400 mg, 1.5 mmol) and water (2 ml) were
added in a 10 ml reactor and allowed to react for the
required time. Then the mixture was separated quickly
by centrifugation. The solid was extracted with copious
ethyl acetate and the liquid was concentrated. The prod-
uct was obtained by preparative TLC. Yields are based
on aryl halides.
2.2 | Measurements and characterizations
Polymer surface areas, N2 adsorption isotherms (77.3 K)
and pore size distributions were measured using a
Micromeritics ASAP 2020M surface area and porosity
analyzer. Before analysis, the samples were degassed at
200 °C for 8 h under vacuum (10−5 bar). Fourier trans-
form infrared (FT‐IR) spectra were recorded under ambi-
ent conditions in the range 400–4000 cm−1 using a Bruker
VERTEX 70 FT‐IR spectrometer. Transmission electron
microscopy (TEM) images were obtained with a Tecnai
G20 microscope (FEI Corp., USA) operated at an
2.5 | Reusability of catalyst
In order to determine the catalyst durability, the Pd/
KAPs(DCM‐TPP) catalyst was separated by centrifugation
after each run of reactions and the clear supernatant
liquid was analyzed using GC. After being washed with

CHEN ET AL.
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SCHEME 1 One‐pot synthesis of Pd/
KAPs(DCM‐TPP) catalyst
ethanol as well as water, and drying under vacuum
at 50 °C for 12 h, the catalyst was re‐used with fresh
charge of solvent and reactant for a subsequent reaction
under the same conditions. We performed five runs using
the catalyst.
stretching mode of the starting material almost disap-
peared after polymerization. Bands attributed to methy-
lene C―H stretching modes at 2930 and 2853 cm−1 are
also found, indicating the presence of methylene
―CH2― in the network polymer. In addition, the bands
at 1593, 1600 and 1500 cm−1 are associated with C―H
stretch in phenyls, C═C stretch in phenyls and C═C
stretch in porphyrin, respectively. The relative intensity
of the absorption band associated with ═C―H plane
bending vibration decreased, indicating the ―CH2―
binds the benzene ring successfully.[30] The peak at
3400 cm−1 may be attributed to the O―H stretch of
physisorbed water in the sample.
The crystal structure of the Pd/KAPs(DCM‐TPP)
catalyst was investigated using powder X‐ray diffraction
(XRD). The result is shown in Figure 2. The XRD pattern
confirmed the amorphous character of Pd/KAPs(DCM‐
TPP). Nearly no Pd characteristic diffraction peak could
be observed obviously.
3 | RESULTS AND DISCUSSION
3.1 | Synthesis and characterization of Pd/
KAPs(DCM‐TPP) catalyst
Metalloporphyrins possess chemical, material, biological
and catalytic multiple functionalities.[22] It is of great
interest to develop a method which combines the
synthesis of the porphyrin‐based polymer and the
loading of active metal. The porphyrin‐based porous
hypercrosslinked polymer‐supported Pd catalyst was syn-
thesized by a simple one‐pot Friedel–Crafts alkylation
method (Scheme 1). The success of the formation of the
aryl metalloporphyrin network polymer was confirmed
by FT‐IR measurements. Figure 1 shows spectra of Pd/
KAPs(DCM‐TPP) and the starting material. Compared
with the 5,10,15,20‐tetraphenylporphyrin monomer, the
peak at 3022 cm−1 for C―H bond of benzene ring
XPS was employed to investigate the coordination
state of the active species. XPS spectra of Pd for fresh
and used Pd/KAPs(DCM‐TPP) catalysts displayed in
Figure 3 revealed that the Pd species in the fresh Pd/
FIGURE 1 FT‐IR spectra of starting material and catalyst
FIGURE 2 XRD pattern of Pd/KAPs(DCM‐TPP) catalyst

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CHEN ET AL.
high‐magnification SEM images showed that the mono-
liths consist of ca 300–700 nm elementary spheres, while
their surfaces were quite rough (Figure 4). High‐resolu-
tion TEM images revealed the presence of nanometer‐
scale cavities, and no Pd nanoparticle was found in fresh
Pd/KAPs(DCM‐TPP) catalyst (Figure 5a). However, in
the used catalyst, relatively uniform Pd nanoparticles
were clearly observed (Figure 5b). This means that Pd(II)
was reduced to Pd(0) during the coupling reaction, which
is consistent with the results of XPS analysis. The particle
size distribution ranged from 3 to 7 nm with an average
size of about 4.5 nm. Few larger agglomerates of Pd parti-
cles were found. The porphyrin scaffold may stabilize the
Pd nanoparticles and inhibit agglomeration.
FIGURE 3 XPS spectra of fresh and used Pd/KAPs(DCM‐TPP)
N2 adsorption–desorption isotherm of Pd/KAPs(DCM‐
TPP) at 77 K displayed a typical type І curve along with a
large adsorption at low pressure (P/P0 < 0.1), which are
suggestive of the coexistence of micropores and
mesopores in the framework (Figure 6).[32] The
Brunauer–Emmett–Teller surface area was found to be
1357 m2 g−1. The results of N2 adsorption–desorption iso-
therms confirmed the presence of such a porous structure.
The porosity of the knitting aryl metalloporphyrin net-
work polymers is beneficial for the mass transfer of reac-
tants and products, the lipophilic property of the
catalysts (Pd 3d)
KAPs(DCM‐TPP) catalyst was present in the +2 oxidation
state rather than in the metallic state, corresponding to a
binding energy of 337.9 eV of PdCl2 in the Pd 3d5/2
level.[31] Also, in comparison with PdCl2, the binding
energy for the Pd(II) species in the catalysts was shifted
in the positive direction, this positive shift clearly indicat-
ing the strong coordination of Pd(II) with the nitrogen of
the porphyrin‐based polymer.[31] In comparison with
fresh Pd/KAPs(DCM‐TPP) catalyst, the binding energy
of Pd 3d5/2 in the spectrum of the used Pd/KAPs(DCM‐
TPP) is 334.9 eV, which is characteristic of Pd 3d5/2 of
metallic Pd and agrees well with the TEM result, indicat-
ing that Pd(II) was reduced to Pd(0) nanoparticles during
Suzuki–Miyaura coupling reaction, similarly as observed
for other Pd catalysts supported on polymers.[3]
The morphology of Pd/KAPs(DCM‐TPP) was investi-
gated using SEM and TEM. SEM images indicated that
fresh Pd/KAPs(DCM‐TPP) adopts spherical clusters of
several micrometers in size (Figure 4). A closer look at
FIGURE 5 TEM images of (a) fresh and (b) used Pd/KAPs(DCM‐
FIGURE 4 SEM image of fresh Pd/KAPs(DCM‐TPP) catalyst
TPP) catalysts

CHEN ET AL.
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at 100 °C for a reaction time of 1 h. A yield of 99% can
be obtained on increasing the reaction time to 3 h. Com-
pared with microwave heating condition, a biphenyl yield
of 82% can be achieved with resin‐encapsulated Pd nano-
particles within 8 min.[33] This means that microwave
heating was superior to thermal conditions.
With the optimized reaction conditions in hand, the
substrate scope of the Suzuki–Miyaura coupling reaction
was evaluated by employing different aryl halides and
arylboronic acids. The results are presented in Table 2.
The solid catalyst produced biphenyl from aryl chloride
in 96% yield at 100 °C within 6 h (Table 2, entry 1). This
result is better than that for polypyrrole with Pd nanopar-
ticles and Pd/Fe3O4/r‐GO nanohybrid for aryl chloride
with about 85% yield in water,[34,35] which means this
Pd catalyst is highly efficient for the coupling reaction of
inactive aryl halides. The porphyrin structure of the cata-
lyst may favor substrate molecules in making contact with
active species.
FIGURE 6 Nitrogen adsorption and desorption isotherm curves
of Pd/KAPs(DCM‐TPP) catalyst
skeleton is advantageous for the contact of reactants and
products with active centers, and the porphyrin structure
of the skeleton enhances the dispersion of active metal,
which our previous work has demonstrated.[30]
It is noteworthy that sterically hindered aryl chloride
with o‐substituted ―CH3 group was also easily converted
with 95% yield. While aryl chloride with p‐substituted
―CH3 group converted with 93% yield (Table 2, entries
3.2 | Catalytic performance of Pd/
KAPs(DCM‐TPP) in Suzuki–Miyaura
coupling reactions
2
and 3). Furthermore, under similar conditions,
bromobenzene and iodobenzene were almost completely
converted within 3 and 1 h, respectively (Table 2, entries
4 and 10). The catalytic activity towards the coupling of
benzyl chloride and phenylboronic acid gave complete
conversion, which demonstrates that Pd/KAPs(DCM‐
TPP) has high activity for the coupling of benzyl chloride
Several bases were tested for the reaction of phenyl
bromide with phenylboronic acid catalyzed by Pd/
KAPs(DCM‐TPP) in water. The results are summarized in
Table 1. Among the bases, K3PO4⋅3H2O was the optimal
base for this catalyst used in water. The yield can be 46%
TABLE 1 Effect of base on Suzuki–Miyaura coupling reaction catalyzed by Pd/KAPs(DCM‐TPP)a
Entry
Base
Solvent
Temperature (°C)
Time (h)
Yield (%)b
1
K2CO3
H2O
100
1
29
2
KOH
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
100
100
100
100
100
100
100
100
100
100
100
1
23
17
46
27
32
11
22
68
83
93
99
3
C2H5OK
1
4
K3PO4⋅3H2O
NaOH
1
5
1
6
Na2CO3
1
7
HCOONa⋅2H2O
Na3PO4⋅12H2O
K3PO4⋅3H2O
K3PO4⋅3H2O
K3PO4⋅3H2O
K3PO4⋅3H2O
1
8
1
9
1.5
2
10
11
12
2.5
3
aReaction conditions: bromobenzene (0.5 mmol), phenylboronic acid (0.75 mmol), Pd/KAPs(DCM‐TPP) (20 mg, 1.29 mol% with respect to bromobenzene), base
(1.5 mmol), water (2 ml), 100 °C, under N2 atmosphere.
bGC yield (n‐tetradecane as internal standard).

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CHEN ET AL.
TABLE 2 Suzuki–Miyaura coupling reactions of various substrates catalyzed by Pd/KAPs(DCM‐TPP)a
Entry
X
R1
R2
Time (h)
Yield (%)b
1
Cl
H
H
6
96
2
Cl
2‐Me
4‐Me
H
H
10
10
3
95
93
98
97
96
98
97
96
97
96
97
3
Cl
H
4
Br
H
5
Br
H
4‐OMe
4‐OCF3
4‐CF3
2‐Me
4‐Me
H
6
6
Br
H
6
7
Br
H
6
8
Br
H
6
9
Br
H
6
10
11
12
I
H
1
―CH2Cl
H
H
6
Br
H
Ph
6
aReaction conditions: aryl halide (0.5 mmol), arylboronic acid (0.75 mmol), Pd/KAPs(DCM‐TPP) (20 mg, 1.29 mol% with respect to aryl halide), K3PO4⋅3H2O
(1.5 mmol), H2O (2 ml), 100 °C, under N2 atmosphere.
bIsolated yield.
were retained after five runs with very low Pd leaching,
which may account for this excellent reusability.
4 | CONCLUSIONS
In summary, we report a simple method for the synthesis
of a polymer‐supported Pd catalyst, Pd/KAPs(DCM‐TPP),
from 5,10,15,20‐tetraphenylporphyrin through a one‐pot
Friedel–Crafts alkylation reaction. No Pd nanoparticles
were found in the fresh Pd/KAPs(DCM‐TPP) catalyst. N2
adsorption–desorption isotherms confirmed the presence
of microporous and mesoporous structures. The obtained
Pd catalyst exhibited excellent activity and selectivity in
Suzuki–Miyaura coupling reactions in water. The porphy-
rin contained in the skeleton enhanced the dispersion of
the active metal and heterogeneous porous structure can
also improve the diffusion of reactants and products.
The Pd/KAPs(DCM‐TPP) catalyst can be recycled five
times without significant loss of catalytic activity. In
addition, during Suzuki–Miyaura reactions, Pd(II) was
reduced to Pd(0) nanoparticles. This work provides the
synthesis of a porphyrin‐based polymer‐supported Pd
catalyst with excellent catalytic performance in water.
FIGURE 7 Reuse of Pd/KAPs(DCM‐TPP) catalyst for Suzuki–
Miyaura reaction
and phenylboronic acid (Table 2, entry 11). The catalytic
performances for the couplings of various arylboronic
acids with bromobenzene were further tested and
superior yields were obtained in all cases (Table 2, entries
5–9 and 12).
We also evaluated the reusability of Pd/KAPs(DCM‐
TPP) in Suzuki–Miyaura coupling reactions in water. It
was successfully recycled five times without apparent loss
of catalytic activity (Figure 7). The Pd content of the
Pd/KAPs(DCM‐TPP) catalyst is 3.33 wt% after the fifth
Suzuki reaction cycle, a slight decrease in comparison
with the fresh catalyst. The uniform Pd nanoparticles
ACKNOWLEDGEMENTS
This work was supported by the National Natural
Science Foundation of China (21473064), Shenzhen
Science
and
Technology
Innovation
Program

CHEN ET AL.
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How to cite this article: Chen J, Zhang J, Zhu D,
Li T. Porphyrin‐based polymer‐supported
palladium as an excellent and recyclable catalyst for
Suzuki–Miyaura coupling reaction in water. Appl
Organometal Chem. 2018;32:e3996. https://doi.org/
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