Palladium immobilized on functionalized hypercrosslinked polymers: A highly active and recyclable catalyst for Suzuki-Miyaura coupling reactions in water

Article abstract of DOI:10.1039/c9nj02444a

Heterogeneous catalysts have shown advantages such as high stability, good recyclability and easy separation from reactants over homogeneous catalysts in recent years. In this paper, three pyridine-functionalized N-heterocyclic carbene-palladium complexes (HCP-Pd) were successfully synthesized via a simple external cross-linking reaction. In each catalyst (i.e., complex), palladium (Pd) was immobilized on the hypercrosslinked polymer (HCP) via formation of a six-membered ring by Pd²⁺ and the bidentate ligands of NHC and pyridine. The structure and composition of HCP-Pd were characterized by SEM, TEM, N₂ sorption, FT-IR, TGA and XPS. The catalytic performances of these catalysts in a Suzuki-Miyaura coupling reaction were also studied. The results prove that HCP-Pd is a very effective heterogeneous catalyst for the Suzuki-Miyaura coupling reaction of various aryl halides with aryl boronic acid in an aqueous medium under mild conditions.

Full text of DOI:10.1039/c9nj02444a

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DOI: 10.1039/C9NJ02444A
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Palladium immobilized on functionalized hypercrosslinked
polymers: A highly active and recyclable catalyst for Suzuki-
Miyaura coupling reactions in water
Received 00th January 20xx,
Accepted 00th January 20xx
Xi Liu, Wei Xu, Dexuan Xiang,* Zaixing Zhang, Dizhao Chen, Yangjian Hu, Yuanxiang Li, Yuejun
Ouyang, Hongwei Lin
DOI: 10.1039/x0xx00000x
www.rsc.org/
products.7 In addition, a variety of supported NHC-metal complexes
Heterogeneous catalysts have shown advantages such as high
stability, good recyclability and easy separation from reactants
over homogeneous catalysts in recent years. In this paper, three
have been prepared8 and include those supported on polymer,9
nanoparticle,10 carbon11 and silica material.12 Recently, a series of
NHC-metal complexes supported on hypercrosslinked polymers
(HCPs) by external cross-linking reaction were also reported.5b,13 With
high porosity and individual pore structures, the catalysts display
outstanding catalytic performance in a wide range of organic synthetic
reactions, such as Suzuki-Miyaura coupling, Ullmann C-N coupling,
and Glaser coupling reactions. In these cases, NHC-metal complexes
show higher thermal stability and catalytic activities than their
phosphine counterparts partially owing to their strong σ-electron-
donating ability that highly strengthens the NHC-metal bonds.14
Bidentate ligands containing both strong and weak donor groups are
propitious to produce vacant coordination sites that allow
complexation of substrates during the catalytic cycle, and at the same
time the strong donor moiety remains connected to the metal center.15
Pyridine-functionalised NHC (Py^NHC), as “classical” bidentate
ligands, have been frequently used as homogeneous catalysts in recent
years,16 but only few supported Py^NHC-metal complexes have been
prepared so far.17 Therefore, it is desirable to exploit the diversity of
immobilized Py^NHC-metal complexes and their application in
downstream catalytic reactors.
pyridine-functionalized
N-heterocyclic
carbene-palladium
complexes (HCP-Pd) were successfully synthesized through a
simple external cross-linking reaction. In each catalyst (i.e.,
complex), palladium (Pd) was immobilized on the
hypercrosslinked polymer (HCP) via formation of
a six-
membered ring by Pd2+ and the bidentate ligands of NHC and
pyridine. The structure and composition of HCP-Pd were
characterized by SEM, TEM, N2 sorption, FT-IR, TGA and XPS.
The catalytic performances of these catalysts in Suzuki-Miyaura
coupling reaction were also studied. The results prove that HCP-
Pd is a very effective heterogeneous catalyst for the Suzuki-
Miyaura coupling reaction of various aryl halides with aryl
boronic acid in aqueous medium under mild conditions.
Heterogeneous catalysts have been extensively used for the catalysis
of various organic reactions due to their unique properties such as high
reactivity, high stability, easy separation, easy purification and good
recyclability.1 However, their catalytic efficiency and selectivity are
normally lower than those of homogeneous systems because of their
long diffusion pathway to catalytic sites and the difference of electron
density on active sites.2 This shortcoming can be overcome by using
appropriate support materials that can provide a large reaction surface
with more active sites.3 Hypercrosslinked polymers (HCPs) with high
specific surface area and large pore volume have already been
regarded as superior supports for heterogeneous catalysts.4 One distinct
advantage of HCPs is that some electron-donating ligands can be
installed in the skeletal framework without any additional chemical
modification.5
N-heterocyclic carbenes (NHCs), also called “phosphine mimics” in
catalysis, have attracted increasing attention as they have been proven
to act as competent spectator ligands in coordination chemistry and
catalysis.6 There are numerous NHC-metal complexes acting as
homogeneous catalysts for cross-coupling reactions with high yields of
Scheme 1 HCP and HCP-Pd
In this work, we designed and synthesised three pyridine-
functionalized NHC-palladium complexes (HCP-Pd) by external
crosslinking (Scheme 1). In each catalyst (i.e., complex), palladium
was immobilized on the hypercrosslinked polymer via formation of a
six-membered ring by Pd2+ and the bidentate ligands of NHC and
Hunan Engineering Laboratory for Preparation Technology of Polyvinyl
Alcohol(PVA) Fiber Material, Institute of Organic Synthesis, Huaihua University,
Huaihua 418000, China. E-mail: dexuanxiang@126.com
Electronic Supplementary Information (ESI) available: Experimental details, spectral
characterization data and supplementary figures. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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pyridine. We then determined the catalytic properties of the catalysts essential because these structures enabled the frameworVkisewtoArbtieclehOignhlinlye
DOI: 10.1039/C9NJ02444A
in Suzuki-Miyaura coupling reactions under mild conditions in neat soaked in a certain solvent. As a result, the accessibility of the
water as a solvent. The simple preparation of this porous catalyst and catalytically active sites toward the substrates can be maximized. The
its high adaptability to various aryl halides and aryl boronic acid make ICP-AES analysis indicates that the Pd loading in HCP-Pd I, II and III
it perfect catalytic option for Suzuki-Miyaura coupling reactions in were 5.1, 6.6 and 5.5 wt% (Table 1), respectively.
water.
The supporting material HCP was prepared from N-(pyridin-2-
Table 1 Physical properties of HCP and HCP-Pd
a
b
c
Sample
SBET
SMicro
VMicro
[Pd]d
[wt%]
[m2g-1]
[m2g-1]
[m3g-1]
ylmethyl)benzimidazolium chloride (NHC), FDA and benzene with
FeCl3 as catalyst. The following treatment of HCP with PdCl2 in THF
resulted in three kinds of HCP-Pd catalysts. The FT-IR spectra of HCP
and HCP-Pd(Fig. 1) display a series of bands at around 1600-1700cm-1
which were assigned to the stretching of-C=N-in imidazolium ring.
The bands at around 1550-1400 and 850-650cm−1 were corresponded
to the benzene and pyridine skeleton stretching and the C-H out-of-
plane bending vibrations of the aryl rings, respectively.
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59
60
HCP-I
HCP-Pd-I
HCP-II
HCP-Pd-II
HCP-III
693
648
774
610
667
600
352
366
656
483
358
256
0.159
0.170
0.274
0.215
0.159
0.132
-
5.1
-
6.6
-
5.5
HCP-Pd-III
a
Surface area calculated from the nitrogen adsorption
isothermusing the BET method. b Micropore volume derived using a t-
c
plot methodbased on the Halsey thickness equation. Total pore
d
volume at P/P0=0.99. Data were obtained by inductively coupled
plasma mass spectrometry (ICP-AES).
Figure 1. FT-IR spectra of HCP and HCP-Pd
XPS was employed to investigate the coordination states of
palladium species, and the results are shown in ESI (Section V). The
Pd 3d XPS spectra of the HCP-Pd-I catalyst reveal that Pd was present
in the +2 oxidation state rather than in the metallic state, corresponding
to the binding energy (B.E.) of 336.9 eV and 342.2 eV in the Pd 3d5/2
and 3d3/2 levels, respectively. Compared with the case of PdCl2 (337.9
eV and 343.1eV), the Pd2+ binding energy in the HCP-Pd-I catalyst
shifted negatively by 0.8 eV and 0.9 eV, which may be attributed to
the strong coordination effect of the HCP network with bidentate
ligands of NHC and pyridine groups. The results show that Pd2+ can be
immobilized successfully on HCP by coordination to NHC and
pyridine groups via forming a six-membered ring rather than by
physical adsorption onto the surface of HCP. XPS graphs of HCP-Pd-
II and III also reveal that Pd2+ was successfully immobilized on HCP
materials.
Figure 2.N2 adsorption-desorption isotherms and corresponding pore
size distributions of HCP and HCP-Pd.
The thermostability of HCP and HCP-Pd were also examined by
thermogravimetric analysis (TGA). As shown in Fig. 3, these materials
can remain stable at least up to a temperature less than 300oC. It seems
that HCP-Pd was more stable than HCP when the temperature
exceeded than 500oC, which may be ascribed to the six-membered
ring formed by Pd2+ and the bidentate ligands of NHC and pyridine. It
is worth mentioning that HCP-Pd-I showed the best thermostability
and its loss of weight was less than 10% as the temperature reached
800oC.
The surface area and pore structure of HCP and HCP-Pd were
investigated by nitrogen adsorption analysis at 77.3 K. As shown in
Fig. 2, HCP-Pd exhibited type I adsorption-desorption isotherms,
which were similar to the isotherms exhibited by the parent HCP,
implying that these polymers contained both micropores and some
mesopores. The apparent Brunauer-Emmett-Teller surface areas (SBET
)
of HCP-Pd were smaller than those of the non-metallized parent
networks (Table 1), but the materials were still significantly
microporous. The decrease in specific surface area can be attributed to
both partial pore filling and simple increase in mass. In addition, the
pore size distribution of HCP remained almost unchanged after Pd was
immobilized on it. The abundant micropores with a suitable size
favored naturally the dispersion of the metal species. The presence of a
few mesopores and macropores in the heterogeneous catalyst was also
Figure 3. TGAcurves of HCP and HCP-Pd
2 | J. Name., 2012, 00, 1-3
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HCP and HCP-Pd were also subjected to SEM and TEM analyses Pd with monomer N,N'-dibenzylbenzimidazolium chloride based on
View Article Online
(See ESI, Section III and IV). No remarkable changes in the literature,4b and applied it in Suzuki-Miyaura reaction under the
DOI: 10.1039/C9NJ02444A
morphologies of materials were observed after the palladium species optimized condition to obtain a yield of 86% (Entry13). This result
were loaded. Then scanning electron microscopy elemental mapping shows that HCP-Pd-I is more efficient than Poly-Pd in water, and the
was employed to study the composition of HCP-Pd, and the obtained phenomenon maybe due to the fact that the pyridine group in HCP-Pd
results are shown in ESI (Section III and IV). Obviously, the metal Pd is more hydrophilic than the phenyl group in Poly-Pd.
With optimal conditions in hand, the reaction scope was examined.
As listed in Table 3, a range of aryl boronic acids 2 with electron-
donating group, such as 4-CH3 (Table 5, entry 2), and electron-
withdrawing group, such as 4-F (entry 6), were applied to these
conditions in parallel. Corresponding biphenyl products were
produced in high to excellent yields. It is worth noting that the cross-
coupling reactions can proceed smoothly when aryl chloride and
benzyl chloride were used in the reaction (entry 15-18).
species were distributed in the support with a high degree of dispersion.
Meanwhile, Pd, N and C were clearly observed from these images,
which indicate that they were the major elements to construct the
HCP-Pd catalyst.
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To evaluate the activity of HCP-Pd catalysts, we utilized them in
Suzuki-Miyaura coupling reaction under mild conditions. Our
preliminary screening of solvent reveals that the presence of alcohol
can efficiently promote the reaction (Table 2, Entry1-4). Some studies
have shown that the addition of water to the solvent could speed up the
conversion of substrate to some extent.18 Then a range of reactions
were carried out. Specifically, the feed volume ratio of EtOH to H2O
was changed from 3/1 to 1/3, and various bases like K3PO4, K2CO3
and Na2CO3 were tested. Some of the results are summarized in Table
2. Notably, there was nearly no obvious change in the yields of the
reactions when H2O content in solvent was increased. Since water is
an easily available, cheap, safe and environmentally benign solvent,
water was chosen here as solvent for the reaction and the reaction was
found to proceed smoothly to achieve 95% yield of biaryl products
(Entry10).
Table 3 Suzuki-Miyaura reaction catalysed by HCP-Pd-Ia
Entry
R1
X
R2
3
Yield(%)b
1
2
3
4
5
6
7
8
H
H
H
H
H
H
H
H
I
I
I
I
I
I
I
I
H
3a
3b
3c
3d
3e
3f
3g
3h
3d
3i
3a
3d
3g
3h
3a
3d
3h
3j
95
96
92
97
92
93
91
94
97
98
95
93
90
91
88
90
85
87
2-CH3
3-CH3
4-CH3
2-F
3-F
4-F
4-CN
H
H
H
4-CH3
4-F
4-CN
H
4-CH3
4-CN
H
Table 2 Optimization of Suzuki-Miyaurareactiona
9
4-CH3
4-CH3O
I
I
10
11
12
13
14
15
16
17
18
H
H
H
H
H
H
H
H
Br
Br
Br
Br
Cl
Cl
Cl
CH2Cl
Entry
HCP-Pd
Solvent
Base
Yield(%)b
1
2
3
4
5
6
7
8
I
I
I
I
I
I
I
I
I
I
II
III
EtOH
CH3CN
DMF
THF
EtOH/H2O(3:1)
EtOH/H2O(1:1)
EtOH/H2O(1:3)
EtOH/H2O(1:1)
EtOH/H2O(1:1)
H2O
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
Na2CO3
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
96
56
84
47
97
98
97
88
85
95
90
88
86
96
a Reaction conditions:1a (2.5 mmol), 2a (3.3mmol), HCP-Pd-I (40mg),
K3PO4(5.0 mmol), H2O (20mL), 80oC, 1.0h. b Isolated yields.
9
10
11
12
13
14
H2O
H2O
H2O
H2O
Poly-Pd
PdCl2/NHCc
a Reaction conditions:1a (2.5 mmol), 2a (3.3mmol), HCP-Pd (40mg,
0.0115mmol), 80oC, 1.0h.
Isolated yields.c PdCl2(0.5 mol%,
b
0.0125mmol), NHC-I(0.6 mol%, 0.015 mmol).
Furthermore, we also compared the ability of the three HCP-Pd
catalysts to catalyze the Suzuki-Miyaura coupling reaction (Entry10-
12). The results show that the highest yield of 95% can be obtained
when the reaction of iodobenzene 1a with phenyl boronic acid 2a was
conducted in the presence of K3PO4 in water with HCP-Pd-I as a
catalyst. The reason that HCP-Pd-II and III was lower efficiency
maybe attributed to their smaller pore size which caused the reactants
to have to go through a long diffusion pathway to the catalytic sites.2
To compare the catalytic properties between catalysts with
monodentate and bidentate ligands, we synthesized the catalyst Poly-
Figure 4. Recycle test of HCP-Pd in the Suzuki-Miyaura reaction
For supported catalysts, lifetime and recyclability are two important
features. Therefore, we investigated the recycling performance of the
HCP-Pd catalysts in Suzuki-Miyaura reaction, and the results are
shown in Fig. 4. After five consecutive coupling reactions, HCP-Pd-I
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and II were still capable of catalyzing the reaction with yields of 93%
and 84%, respectively, and the contents of Pd in HCP-Pd-I and II were
3.4% and 4.1%, respectively. In comparison, HCP-Pd-III was not as
efficient as HCP-Pd-I and II, only affording the corresponding product
in 25% yield, and the content of Pd containing in HCP-Pd-III
decreased dramatically from 5.5% to 3.0%. This phenomenon may be
attributed to the electronic effect of the substituent on the NHC and the
cross-linked density of HCP. The stronger electron-withdrawing
ability of the substituent resulted in more effective stabilization of the
coordination bond of NHC-Pd2+. Moreover, the catalysts HCP-Pd-I
and II with benzyl and phenyl on NHC have more crosslinking sites
which provide more efficient stabilization.
4
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Complexes with Pincer Ligands that Comprise N-Heterocyclic
Carbene Donor Sites. In Privileged Pincer-Metal Platform:
Coordination Chemistry & Applications, VanKoten, G.; Gossage,
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In sum, three pyridine-functionalized N-heterocyclic carbene-
palladium complexes (HCP-Pd) were successfully synthesized through
a simple external cross-linking reaction. In each catalyst (i.e.,
complex), palladium was immobilized on the hypercrosslinked
polymer via formation of a six-membered ring by Pd2+ and the
bidentate ligands of NHC and pyridine. The microporous structure of
the support ensures high dispersion of palladium active sites. The six-
membered ring formed by Pd2+ and the bidentate ligands of NHC and
pyridine makes Pd2+ presenthigh catalytic activity. As a result, the
HCP-Pd catalyst exhibits outstanding catalytic performance in the
Suzuki-Miyaura coupling reaction of various aryl halides with aryl
boronic acid. In all the reactions, the HCP-Pd-I catalyst was found to
be easily recovered and reused without significant loss of catalytic
activity as compared with the HCP-Pd-II and III catalysts. Overall, this
paper successfully prepared an effective and recyclable heterogeneous
catalyst for the Suzuki-Miyaura coupling reaction of various aryl
halides with aryl boronic acid in aqueous media under mild conditions.
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This research was financially supported by the Natural Science
Foundation of Hunan Province (No. 2018JJ3409), Scientific Research
Fund of Hunan Provincial Education Department (No. 17B207),
Hunan Provincial Key Research Plan (No. 2016GK2020) and the
Construct Program of the Key Discipline in Huaihua University.
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Conflicts of interest
The authors declare that there are no conflictsof interests.
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DOI: 10.1039/C9NJ02444A
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New Journal of Chemistry
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Palladium immobilized on functionalized hypercrosslinked polymers: A
highly active and recyclable catalyst for Suzuki-Miyaura coupling
reactions in water
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Xi Liu, Wei Xu, Dexuan Xiang,* Zaixing Zhang, Dizhao Chen, Yangjian Hu, Yuanxiang Li, Yuejun
Ouyang, Hongwei Lin
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Receipt/Acceptance Data [DO NOT ALTER/DELETE THIS TEXT]
Publication data [DO NOT ALTER/DELETE THIS TEXT]
DOI: 10.1039/b000000x [DO NOT ALTER/DELETE THIS TEXT]
Table of Contents
Three palladium complexes were synthesized through external cross-linking reaction and found to be effective heterogeneous catalysts
for the Suzuki-Miyaura reaction.
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