Palladium Immobilized on 2,2′-Dipyridyl-Based Hypercrosslinked Polymers as a Heterogeneous Catalyst for Suzuki–Miyaura Reaction and Heck Reaction

Article abstract of DOI:10.1007/s10562-020-03165-4

Abstract: 2,2′-Bipyridine was successfully integrated into the skeleton of hypercrosslinked polymers networks (HCPs-bipy) via Friedel–Crafts reaction and Scholl coupling reaction, and PdCl₂ was locked in this network polymers by coordination with pyridine motif. The preparation of HCPs-bipy has the advantages of low cost, mild conditions, easy separation and high yield. FT-IR, TGA, N₂ sorption, ICP, XPS, SEM, EDX and TEM was employed to characterize the structure and composition of the heterogeneous catalysts. The result indicates that HCPs-bipy-Pd possess high specific surface areas, large microporous volume, thermal stability, and highly dispersion of palladium species. HCPs-bipy-Pd can be applied in Suzuki–Miyaura reactions and Heck reactions as robust heterogeneous catalyst to afford high yield. The reusability test demonstrates that HCPs-bipy-Pd could be recovered and reused for at least five times without losing catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-020-03165-4

Catalysis Letters
https://doi.org/10.1007/s10562-020-03165-4
Palladium Immobilized on 2,2′‑Dipyridyl‑Based Hypercrosslinked
Polymers as a Heterogeneous Catalyst for Suzuki–Miyaura Reaction
and Heck Reaction
1
1
1
1
1
1
1
1
Cijie Liu · Wei Xu · Dexuan Xiang · Qionglin Luo · Shunqin Zeng · Lijuan Zheng · Yujie Tan · Yuejun Ouyang ·
Hongwei Lin1
Received: 27 November 2019 / Accepted: 1 March 2020
©
Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
2
,2′-Bipyridine was successfully integrated into the skeleton of hypercrosslinked polymers networks (HCPs-bipy) via Frie-
del–Crafts reaction and Scholl coupling reaction, and PdCl was locked in this network polymers by coordination with pyri-
2
dine motif. The preparation of HCPs-bipy has the advantages of low cost, mild conditions, easy separation and high yield.
FT-IR, TGA, N sorption, ICP, XPS, SEM, EDX and TEM was employed to characterize the structure and composition of
2
the heterogeneous catalysts. The result indicates that HCPs-bipy-Pd possess high speciꢀc surface areas, large microporous
volume, thermal stability, and highly dispersion of palladium species. HCPs-bipy-Pd can be applied in Suzuki–Miyaura
reactions and Heck reactions as robust heterogeneous catalyst to aꢁord high yield. The reusability test demonstrates that
HCPs-bipy-Pd could be recovered and reused for at least ꢀve times without losing catalytic activity.
Graphic Abstract
Keywords 2,2′-dipyridyl · Hypercrosslinked polymers · Heterogeneous catalyst · Suzuki–miyaura reaction · Heck reaction
1
Introduction
Palladium plays an important role in coupling reaction due
to their strong electrical and chemical properties [1–4]. Over
the past decades, numerous homogeneous catalytic systems
have been developed in the presence of a variety of auxil-
iary ligands, including amine-based [5], phosphine-based
Cijie Liu and Wei Xu have contributed equally to this work.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-020-03165-4) contains
supplementary material, which is available to authorized users.
[
6], N-heterocyclic carbenes [7], bipyridine-based [8] and
Extended author information available on the last page of the article
Vol.:(0
1
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3

C. Liu et al.
oxime-based [9] ligands. However, they also suꢁered from
the diꢂcult in separation, metal leaching, recovery and
recyclability [10, 11] which restricted their applications in
some extent. Heterogeneous catalysts have been developed
in recent decades to address these issues due to their excel-
lent performance in reactivity, stability, separation, puriꢀ-
cation and recyclability. Now palladium species have been
immobilized on various supporting materials, such as gra-
phene oxide [12], zeolites [13], activated carbon [14], ionic
liquids [15], metal–organic framework [16], mesoporous
silica [17], and microporous organic polymers [18]. How-
ever, these catalysts always accomplished with a substantial
decrease in activity attribute to the metal leaching [19]. In
addition, the metal agglomeration and supporting materials
collapse usually occurred in the process of catalyst recovery
and utilization [20, 21]. This shortcoming could be improved
by using appropriate supporting materials which have strong
coordination ability and rigid structure [22].
carbene by external cross-linking reaction and applied it in
Suzuki–Miyaura coupling reactions [42]. Then we prepared
two kinds HCPs networks by Friedel–Crafts reaction and
Scholl coupling reaction using readily available phenanth-
roline, and applied it in coupling reactions [43].
2,2′-Bipyridine (bipy), a nitrogen donor-based chelat-
ing ligand, has been widely employed as ligand in metal
catalyzed reaction [44–49]. In this paper, we describe the
polymerization of two kinds HCPs-bipy (Fig. 2) based on
2,2′-bipyridine by the knitting strategy and Scholl reaction,
respectively. After PdCl immobilized on HCPs-bipy by
2
coordination with pyridine motif, the HCPs-bipy-Pd could
play as a recyclable catalyst for Suzuki–Miyaura reactions
and Heck reactions with high yield. The nature of low cost,
simple preparation, high activity, stability, easy separation
and recyclability make it useful for the Suzuki–Miyaura
reactions and Heck reactions.
Hypercrosslinked polymers (HCPs), as a new kind of
porous material, have recently emerged as versatile plat-
forms for the heterogeneous catalysis [23–27]. The structure
of HCPs has a large number of permanent pores formed
by extensive chemical cross-linkage to provide a huge spe-
ciꢀc surface area. Compared to the traditional preparation
of other porous organic polymers (e.g. COFs, PIMs, and
CMPs) by noble metal catalysts [28–32], the preparation of
HCPs networks is much more economical by Friedel–Crafts
alkylation reactions which is usually catalyzed by Lewis acid
2 Experimental
2.1 Synthesis of HCPs‑bipy
FeCl (anhydrous, 0.09 mol) was added to a solution of ben-
3
zene (0.05 mol), 2,2′-bipyridine (0.02 mol), and formalde-
hyde dimethyl acetal (FDA, 0.10 mol) in 50 mL 1,2-dichlo-
roethane (DCE). The resulting mixture was stirred at 0 ℃ for
good mixing, and stirred at 45 ℃ for 5 h to form original net-
work, and then heated at 80 ℃ for 48 h to react completely.
The resulting precipitate was washed with water (20 mL) for
3 times, then washed with methanol in a Soxhlet for 50 h,
and ꢀnally dried under reduced pressure at 60 ℃ for 24 h to
give HCPs-bipy-I.
[
22, 33–35]. More importantly, Tan’s group independently
reported a breakthrough approach known as the knitting
strategy [36]. It utilizes formaldehyde dimethyl acetal (FDA)
as an external crosslinker to combine simple aromatic com-
pounds through rigid methylene bridges via Friedel–Crafts
reaction catalyzed by anhydrous FeCl (Fig. 1). The plau-
3
sible mechanism means that there is no need to introduce
2.2 Synthesis of HCPs‑bipy‑II
special polymerizable functional groups (e.g. –X, –NH ,
2
–
C=CH , –OH, –CHO, and –B(OH) ) on the monomers.
AlCl (anhydrous, 0.25 mol) was added to a solution of ben-
2
2
3
The HCPs formed by knitting strategy exhibit excellent prop-
erties, such as large surface areas, low cost, superior chemi-
cal and thermal stability, and widely applied in gas storage,
catalyst, luminescence, sensor, separation, and semiconduc-
tor materials [37–41]. Recently, our group also synthesized
three HCPs based on pyridine-functionalized N-heterocyclic
zene (0.04 mol) and 2,2′-bipyridine (0.020 mol) in 70 mL
chloroform. The resulting mixture was stirred at 0 ℃ for
good mixing, and stirred at 50 ℃ for 3 h to form original net-
work, and then heated at 80 ℃ for 40 h to react completely.
The resulting precipitate was washed with methanol (20 mL)
N
N
N
N
HCPs-bipy-I
HCPs-bipy-II
Fig. 1 The external crosslinking routes
Fig. 2 The structure of HCPs-bipy
1
3

Palladium Immobilized on 2,2′-Dipyridyl-Based Hypercrosslinked Polymers as a Heterogeneous…
for three times, then washed with methanol in a Soxhlet for
5
2
0 h, and ꢀnally dried under reduced pressure at 60 ℃ for
4 h to give HCPs-bipy-II.
2.3 Synthesis of HCPs‑Pd
HCPs-bipy (2.0 g), PdCl (0.060 g) and 50 mL of DMF were
2
placed in a three-necked ꢃask. Then, the reaction mixture
was stirred at 80 ℃ for 24 h. Finally, the solid was ꢀltered
and washed with methanol for three times (3×20 mL), then
washed with acetone in a Soxhlet for 40 h, and dried under
reduced pressure at 60 ℃ for 24 h to give HCPs-bipy-Pd.
Fig. 3 XPS spectra of the HCPs-bipy-Pd
3
Results and Discussion
3
.1 Characterization
The surface area and pore properties of the networks were
investigated by nitrogen adsorption analyses at 77.3 K. All
of the networks have the type I nitrogen gas adsorption–des-
orption isotherms (Fig. 4). It is easy to see a steep nitro-
The structure of HCPs-bipy and HCPs-bipy-Pd were con-
rmed by Fourier transform infrared (FT-IR) spectroscopy,
ꢀ
and the FT-IR spectra was shown in ESI (Section III). The
gen gas adsorption at low relative pressure (P/P < 0.001)
0
−
1
peaks around 2800–3000 cm could be assigned to the
C–H stretching band and in-of-plane bending vibrations
from the isotherms, reꢃecting abundant micropore struc-
ture existed in the networks. A slight hysteresis loop indi-
cates some mesopore in the networks and a sharp rise at
−
1
in the aryl rings. The peaks between 1550–1750 cm in
HCPs-bipy-I and HCPs-bipy-Pd-I were corresponded to
the –C=N– stretching band in pyridine rings, while the
corresponding peaks in HCPs-bipy-II and HCPs-bipy-Pd-
II appeared in the same range as wide peaks. The band in
high pressure regions (P/P = 0.9–1.0) implies a spot of
0
macropores in these materials. The experiment of appar-
ent Brunauer–Emmett–Teller surface areas (S ) demon-
BET
strate that the S
of HCPs-bipy is small larger than the
BET
1
420–1480 is attributed to the ring skeleton stretching vibra-
HCPs-bipy-Pd (Table 1), which can be attributed to par-
tial of the pore ꢀlled with palladium species. In addition,
these materials were further analyzed by pore-size distri-
bution analysis. No remarkable change was found after
Pd was immobilized on the HCPs-bipy. The Pd content
in HCPs-bipy-Pd was also detected by ICP-AES analysis
(Table 1), and the result indicated the Pd content is 1.21%
and 1.36% in HCPs-bipy-Pd-I and II, respectively.
tions of benzene and pyridine. The absorption between 650
−
1
and 850 cm was attributed to the C–H out-of-plane bend-
−
1
ing vibrations of the aryl rings. The peak around 1490 cm
in HCP-bipy-I and HCPs-bipy-Pd-I is assigned to in-of-plane
bending vibrations of CH , while no peak appeared in this
2
area in HCP-bipy-II and HCPs-bipy-Pd-II. The result indi-
cates that bipy and benzene were linked by CH as bridges
2
in HCP-bipy-I and HCPs-bipy-Pd-I.
The thermal stability was also assessed by thermo gravi-
metric analyzer (TGA). The measurement was carried out
in the temperature range of 50–800 ℃ with a heating rate
The chemical state of HCPs-bipy-Pd was investigated by
X-ray photoelectron spectroscopy (XPS). As described in
Fig. 3, the binding energy of HCPs-bipy-Pd-I at 337.4 eV
and 342.7 eV was corresponded to Pd 3d and 3d orbit-
−
1
of 20 ℃ min in nitrogen. The TGA traces obtained from
HCPs-bipy and HCPs-bipy-Pd are shown in Fig. 5. The T
5
/2
3/2
10%
als. Compared with the homogeneous counterpart, PdCl
of these materials are also described in Fig. 5. The materials
exhibit excellent thermal stability in nitrogen below 300 ℃,
and a slight decomposition was occurred when the tempera-
ture is higher than 300 ℃. It also can be observed that the
thermal stability of HCPs-bipy is better than HCPs-bipy-Pd
at a high temperature.
2
2
+
(
337.9 eV and 343.1 eV), the Pd binding energy shifts
negatively by 0.5 eV in 3d and 0.4 eV in 3d , the slight
5
/2
3/2
diꢁerence between them may come from the change of
chemical environments. This result conꢀrms that the Pd
species is present in the +2 oxidation state rather than the
2
+
metallic state. Furthermore, it demonstrates that Pd can
be locked in the HCPs-bipy networks by coordination rather
than by physical adsorption. The XPS spectra reꢃects that
the state of Pd in HCPs-bipy-Pd-II is consistent with that in
HCPs-bipy-Pd-I.
The surface morphology of the networks was investigated
by scanning electron microscopy (SEM), and the results are
shown in Fig. 6. It is obvious to see abundant micropores and
some mesopores irregular distribution in the entire networks
surface. No obvious change was observed on HCPs-bipy-Pd
1
3

C. Liu et al.
Fig. 4 N adsorption–desorp-
2
tion isotherms and correspond-
ing pore size distributions of
HCPs-bipy and HCPs-bipy-Pd
Table 1 Physical properties of HCPs-bipy and HCPs-bipy-Pd
HCPs-bipy-Pd. The results imply that the major elements
in HCPs-bipy-Pd are C, N, Pd and Cl, and the distribution
of Pd is highly dispersed in the materials (ESI, Section IV).
These materials were also subjected to transmission elec-
tron microscopy (TEM) and the TEM images are shown in
ESI (Section V). The agglomerated palladium was not found
from the TEM images, indicating that palladium was highly
dispersed in HCPs-bipy.
a
b
c
[Pd] d
(wt%)
Sample
S
(
S
V
Micro
BET
Micro
m g−1)
2
(m g−1)
2
(m g−1)
3
HCPs-bipy-I
564
1027
517
902
254
655
285
617
0.1245
0.2915
0.1390
0.2772
HCPs-bipy-II
HCPs-bipy-Pd-I
HCPs-bipy-Pd-II
1.21
1.36
a
Surface area calculated from the nitrogen adsorption isothermusing
the BET method
The micropore volume derived using a t-plot method based on the
3.2 Application
b
Halsey thickness equation
To evaluate the catalytic activity of this heterogeneous, the
HCPs-bipy-Pd was used as a robust heterogeneous catalyst
in Suzuki–Miyaura coupling reaction with iodobenzene 1a
and phenylboric acid 2a as a model substrate. The reaction
c
Total pore volume at P/P =0.99
0
d
Data were obtained by inductively coupled plasma mass spectrom-
etry (ICP-AES)
ꢀ
rst attempted at 80 ℃ in water in the present of K PO and
3 4
HCPs-bipy-Pd-I (0.5 mol%). The resulting mixture quickly
gathered together and turned into a brown viscous solid.
After 1.0 h, the solid was puriꢀed by column chromatogra-
phy to aꢁord biphenyl 3a in 53% yield. Then, we screened
the solvent in the reaction, such as DMF, EtOH, MeOH,
CH CN, DMSO and THF. The results revealed that EtOH
3
can promote the reaction eꢂciently. After screening out the
solvent, a series of experiments were carried out to optimize
the reaction conditions, including base, catalysis, and reac-
tion temperature. Eventually, the experiments demonstrated
that the yield of biphenyl could reach 97% when the reac-
tion of 1a with 2a was performed at 80 ℃ in the present
of K CO with HCPs-bipy-Pd-I (0.23 mol%) in EtOH for
2
3
1
.0 h. Having established the optimal conditions, we car-
ried out a series of reactions to determine its scope with
respect to the compound 1 and 2. As described in Table 2, a
range of aryl halogen 1 and aryl boronic acids 2 with elec-
tron-donating group and electron-withdrawing group were
applied to the reaction in the optimized conditions. Corre-
sponding products were obtained in high to excellent yields
after puriꢀcation.
Fig. 5 TGA curves: a HCPs-bipy-I, b HCPs-bipy-Pd-I, c HCPs-bipy-
II, d HCPs-bipy-Pd-II
surface after palladium species immobilized on HCPs-bipy.
Then the scanning electron microscopy elemental map-
ping (EDX) was applied to investigating the composition of
1
3

Palladium Immobilized on 2,2′-Dipyridyl-Based Hypercrosslinked Polymers as a Heterogeneous…
Fig. 6 SEM imagine of HCPs-bipy and HCPs-bipy-Pd
To extend the utilization of HCPs-bipy-Pd, we further
attempted to expand this catalyst to Heck reaction using
iodobenzene 1a and ethyl acrylate 4a as substrates. The opti-
mization of the reaction conditions, including solvents, base,
reaction temperature, time and catalysis were investigated.
Unlike the previous reaction, HCPs-bipy-Pd-II works better
in Heck reaction. When 1a and 4a were subjected to DMF
condition as Table 2 (entry 1). The reactions were quenched
by ice water when it reacted for 15 min, then the heteroge-
neous catalyst was separated from the reaction mixture by
ꢀltration. One of the reactions furnished the product biphe-
nyl in 43% yield after workup and puriꢀcation by column
chromatography. The other reaction was put in oil bath for
another 45 min, the yield of this reaction was 44% after
puriꢀcation. No signiꢀcant diꢁerence in the yield of the two
parallel reactions implies no further conversion after the het-
erogeneous was separated. This result indicates that the real
catalyst for the reaction is the heterogeneous, rather than the
homogeneous leached from heterogeneous.
in the presence of Et N at 110 ℃ using HCPs-bipy-Pd-II
3
as catalyst, the yield of 5a could reach 95% after separa-
tion. Under the optimal conditions, a range of aryl halogen
1
were subjected to ethyl acrylate 4 at 110 ℃ in the present
of HCPs-bipy-Pd-II, and some of the results are summarized
in Table 3. It was observed that the reactions of aryl halogen
1
bearing variable groups could proceed eꢂciently to aꢁord
3.3 Reusability
the corresponding product 5 in good yields (Table 3, entries
2
–8). Other acrylic ester 2 were also subjected to aryl halo-
From the perspective of industry, economy and green
chemistry, the performance of recovery and reusability is
very important for heterogeneous catalyst. Therefore, the
recovery and reusability of the catalyst in Suzuki–Miyaura
reaction and Heck reaction was investigated. The result is
described in Fig. 7. Firstly, the HCPs-bipy-Pd-I and II were
gen in the identical condition, furnishing the corresponding
products 5i-l in high yields (entry 9–12).
To determine whether the Suzuki–Miyaura reaction cata-
lyzed by heterogeneous or homogeneous dissolved in sol-
vent, two parallel reactions were performed in the optimized
1
3

C. Liu et al.
Table 2 Suzuki–Miyaura reaction catalyzed by HCPs-bipy-Pd-I
Table 3 Heck reaction catalyzed by HCPs-bipy-Pd-II
I
O
O
R4
HCPs-bipy-Pd-II
R4
O
+
O
DMF, 110 o
C
R3
R3
R1
R1
1
4
5
Entry
R1
X
R2
H
2-CH3
3-CH3
4-CH3
2-F
3-F
4-F
4-CN
H
H
H
H
H
4-CH3
4-F
4-CN
3
Yield(%)a
Entry
R1
H
4-Me
4-MeO
4-Cl
4-NO2
4-CN
3-Me
3,5-(Me)2
H
H
H
R3
R4
5
Yield (%)a
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
H
I
I
I
I
I
I
I
I
I
I
I
I
Br
Br
Br
Br
3a
3b
3c
3d
3e
3f
97
96
95
98
93
92
93
91
96
97
95
93
95
97
94
90
1
2
3
4
5
6
7
8
9
10
H
H
H
H
H
H
H
H
H
H
H
Me
Et
Et
Et
Et
Et
Et
Et
Et
Me
Bu
H
5a
5b
5c
5d
5e
5f
5g
5h
5i
95
96
93
91
90
88
93
91
96
92
90
87
3g
3h
3d
3i
4-CH3
4-OCH3
3,5-( CH3)
4-CN
H
H
H
H
10
11
12
13
14
15
16
3j
2
5j
5k
5l
3h
3a
3d
3g
3h
1
1
1
2
4-MeO
Me
Reaction conditions: 1a (2.5 mmol), 4a (3.5 mmol), Et N (3.7 mmol),
3
HCPs-bipy-Pd-II (50 mg, 0.26 mol%), DMF (20 mL), 110 °C
a
Isolated yields
Reaction conditions: 1a (2.5 mmol), 2a (3.0 mmol), K CO
2
3
(
3.5 mmol), HCPs-bipy-Pd-I (50 mg, 0.23 mol%), EtOH (10 mL),
8
0 °C
a
Isolated yields
employed in Suzuki–Miyaura reaction and Heck reaction
under the optimized reaction conditions, respectively. After
the reaction completion, the catalyst was recovered by ꢀltra-
tion, washing with water and methanol for three times, and
drying in a vacuum oven for 3.0 h. The recovered catalyst
could be reused for ꢀve cycles with no remarkable decrease
in the yield of product. Then, the recovered catalyst was
analyzed by ICP, SEM and EDX. The ICP result revealed
that the Pd content is 1.14% in HCPs-bipy-Pd-I and 1.27%
in HCPs-bipy-Pd-II, implying only a slight leaching of Pd
after several cycles. From the SEM images (ESI, Section
VI), no obvious change was found in the morphology of
the recovered catalyst. The materials still have numerous
micropores and some mesopores in their surface. The EDX
images (ESI, Section VI) indicate that the main elements (C,
N, Pd and Cl) are still highly dispersed, and no remarkable
aggregation of Pd species was found.
Fig. 7 Recycle test of HCPs-bipy-Pd-I in Suzuki–Miyaura reaction
and HCPs-bipy-Pd-II in Heck reaction
1
3

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Science Foundation of Hunan Province (Grant No. 2018JJ3409), Scien-
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Compliance with Ethical Standards
3
4. Xu SJ, Luo YL, Tan BE (2013) Macromol Rapid Commun
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4:471–484
Conflict of interest There are no conꢃicts to declare.
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Tan BE (2011) Macromolecules 44:2410–2414
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Publisher’s Note Springer Nature remains neutral with regard to
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jurisdictional claims in published maps and institutional aꢂliations.
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C. Liu et al.
Aꢀliations
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Cijie Liu · Wei Xu · Dexuan Xiang · Qionglin Luo · Shunqin Zeng · Lijuan Zheng · Yujie Tan · Yuejun Ouyang ·
Hongwei Lin1
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*
*
Dexuan Xiang
Hunan Engineering Laboratory for Preparation Technology
of Polyvinyl Alcohol (PVA) Fiber Material, Key Laboratory
of Research and Utilization of Ethnomedicinal Plant
Resources of Hunan Province, Huaihua University,
Huaihua 418000, Hunan, China
dexuanxiang@126.com
Hongwei Lin
linhongwei1968@163.com
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