Bipyridyl palladium embedded porous organic polymer as highly efficient and reusable heterogeneous catalyst for Suzuki-Miyaura coupling reaction

Article abstract of DOI:10.1039/c6ra03331h

Two robust porous organic polymers embedded with bipyridyl ligand (Bpy-POP) were obtained via a bottom-up strategy. After a simple post-treatment, a Pd(ii)-containing POP (Bpy-Pd-POP) was used as highly efficient and reusable heterogeneous catalyst for the Suzuki-Miyaura coupling reaction. It could be reused at least 15 times without significant loss of the catalytic activity (97-99% yield).

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Bipyridyl Palladium Embedded Porous Organic Polymer as Highly
Efficient and Reusable Heterogeneous Catalyst for Suzuki-Miyaura
Coupling Reaction
Received 00th January 20xx,
Accepted 00th January 20xx
Chang-An Wang*, Yin-Feng Han, Yan-Wei Li, Kun Nie, Xue-Li Cheng, and Jian-Ping Zhang
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract: Two robust porous organic polymers embedded with efficient photocatalysis.11 Cooper and co-workers elaborated
bipyridyl ligand (Bpy-POP) were obtained via bottom-up the synthesis of a series of the bipyridine metal-functionalized
a
strategy. After a simple post-treatment, a Pd(II)-containing POP conjugated microporous polymers as an efficient
(Bpy-Pd-POP) was used as highly efficient and reusable heterogeneous catalyst for reductive amination.12 However, to
heterogeneous catalyst for the Suzuki-Miyaura coupling reaction. the best of our knowledge, the recyclable and reusable (<5
It could be reused at least 15 times without significant loss of the times) of these bipyridine metal-functionalized POPs are not
catalytic activity (97-99% yield).
satisfactory. Therefore, towards the practical applications of
POP catalysts, the following criteria should be considered: i)
The synthesis of POP catalysts should be concise and based on
inexpensive chemicals; ii) The POP catalysts should be robust
and has high activity and selectivity; iii) The POP catalysts
should possess persistent recycling and reusing.
Chelating ligands containing pyridyl moieties are extensively
used ligand frameworks in coordination chemistry1 and
homogeneous catalysis2. As one of the most important
chelating ligands, the bipyridines has offered an interesting
alternative in developing catalytic systems for organic
synthesis due to its robust redox stability, coordinating ability
With these considerations in mind, herein, we report the
synthesis of two robust porous organic polymers embedded
with bipyridyl ligand (Bpy-POP) via a bottom-up strategy. After
being post-modified with palladium ions, these polymers (Bpy-
Pd-POP, Scheme 1) could be utilized as highly efficient and
recyclable heterogeneous catalysts for carbon-carbon coupling
reaction. Inspired by the pioneering work of Cooper and co-
workers, where the surface area and the pore size of CMPs
could be tuned by varying the molecular length of the rigid
building blocks (alkynes).13 Accordingly, we could synthesize
two robust bipyridyl-functionalized POPs with tunable surface
areas and pore size distributions, and preliminary investigate
the influence of the properties on the catalytic activity.
with
a
wide range of metal ions and ease of
functionalization.2a-b,2e However, many noble metals used in
homogeneous catalysis are quite expensive and it is difficult to
separate the ligand-metal catalysts from the reaction system,
which restricted their practical application on a large scale.
Accordingly, immobilization of homogeneous catalysts using a
solid support provide an interesting approach to solve these
vital problems.3
In this context, Porous organic Polymers (POPs),4 due to
their large surface area, low skeletal density and high chemical
stability, have attracted particular attention as a new class of
porous materials for various potential applications.5-9 In
particular, POPs have provided a highly tunable platform for
designing heterogeneous catalysts via the embeddedness of
rigid catalytic active monomers into the frameworks.10
Importantly, the bipyridine ligand coordinated with metal ions
embedded POPs framework was shown high catalytic activity
for heterogeneous catalysis. For example, Lin and co-workers
developed the synthesis of phosphorescent [Ru(bpy)3]2+ and
[Ir(ppy)2(bpy)]+-incorporating porous cross-linked polymers for
The polymer networks were constructed by palladium-
catalyzed Songashira-Hagihara cross-coupling reaction of 4,4'-
dibromo-2,2'-bipyridine (
with tetra(4-ethynylphenyl)methane
triethynylbenzene ( ) as the structural building blocks(see the
1) as the functional building blocks
(2)
or 1,3,5-
3
Supporting Information for experimental details). The general
synthetic routes for the Bpy-POP networks are shown in
scheme 1. Both of the obtained polymers Bpy-POP-1 and Bpy-
POP-2 are a dark brown powder, and are insoluble in all of the
o
solvents tested. The polymer is thermally stable up to 400 C
under nitrogen atmosphere (TGA result for Bpy-POP shown in
Figure S1 and S2 in the Supporting Information). Powder X-ray
diffraction measurements indicated that the Bpy-POP network
is amorphous in nature (Figure S3, SI).
a.College of Chemistry and Chemical Engineering, Taishan University, Tai'an
Shandong 271000 (P. R. China)
E-mail: wangcha_chem@163.com.
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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2
Pd(PPh3
)2Cl2/CuI
PdCl2, CH3CN
reflux
DMF/Et3N, N2, 80 o
C
N
N
Pd
Cl
Cl
N
N
Bpy-Pd-POP-1
Br
Br
Bpy-POP-1
N
N
1
Pd(PPh3
)
2Cl2/CuI
N
N
PdCl2, CH3CN
reflux
DMF/Et3N, N2, 80 o
C
N
N
N
N
N
N
Pd
Cl
Cl
Bpy-POP-2
3
Bpy-Pd-POP-2
Scheme 1. Synthesis of bipyridyl palladium catalyst-embedded porous organic polymers
The permanent porosity of Bpy-POP was investigated by
nitrogen sorption measurements at 77 K, and the obtained
results are listed in Table S1. The application of the Brunauer-
Emmett-Teller (BET) modal resulted in the surface areas of 506
and 443 m2g-1 for Bpy-POP-1 (Figure S4, SI) and Bpy-POP-2
(Figure S5, SI), respectively. By comparing Bpy-POP-1
(monomer 2) and Bpy-POP-2 (monomer 3), we found that the
polymer networks with long-lengthed building block had a
IUPAC classification, POP-1 displays a Type-IV gas sorption
isotherm with H2 hysteresis loops, indicating that this polymer
consist of mesoporous and POP-2 displays a Type-I gas
sorption isotherm reflecting the presence of abundant
micropores structure. From t-plot analysis, the Bpy-POP-1
ploymer displays both a microporous contribution of 206 m2g-1
(40.7%) and a mesoporous contribution of 300 m2g-1 (59.3%).
As calculated by non-local density functional theory (NLDFT),
the pore size distribution (PSD) of Bpy-POP-1 and Bpy-POP-2
mainly distributed around 0.7 and 1.3 nm, respectively (Figure
1(c) and (d)). However, the broad PSD curves of POP-1 also
suggest the co-existence of micro- and mesopores in the
polymer networks. Specifically, the constructed mesopores
greatly facilitate the mass transport process. After being post-
modified with PdCl2, the BET surface area of Bpy-POP-1
decreases to 394 m2g-1 due to the PdCl2 hanging in the pore
volume.
The chemical composition of Bpy-POP were characterized
by solid-state 13C cross-polarization magic-angle spinning
(CP/MAS) NMR spectroscopy. Figure 2 shows the 13C CP/MAS
NMR spectra recorded for Bpy-POP-1. The signals at
δ = 121,
149 and 155 ppm confirmed that the bipyridyl monomer
skeleton has well been embedded into the polymer networks,
while the peak at approximately 88 and 93 ppm represent the
alkynyl groups in the polymers. The peak at about 65, 131 and
149 ppm also confirm that the tetra(4-ethynylphenyl)methane
skeleton has been successful embedded into the frameworks.
Additionally, elemental analysis of Bpy-POP polymer
identified the content of nitrogen (6.59% and 8.00%), based on
Figure 1. Nitrogen sorption isotherm of Bpy-POP-1 (a) and Bpy-POP-2 (b). Pore size
distribution (PSD) for Bpy-POP-1 (c) and Bpy-POP-2 (d), calculated with non-local
density functional theory (NLDFT).
higher BET surface area (506 m2g-1 vs 443 m2g-1). In Figure 1(a)
and (b) are shown the N2 volume adsorbed, Vads, vs. relative
pressure P/Po, for Bpy-POP-1 and Bpy-POP-2. According to the
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which the molar loading of bipyridyl ligand moieties could be has attracted extensive attention in recent years.15 To evaluate
calculated. All of the results proved the successful synthesis of the catalytic activity of Bpy-Pd-POP as a robust heterogeneous
the polymer networks.
catalyst, we accordingly chose the Suzuki-Miyaura coupling
reaction of phenylboronic acid with bromobenzene as a model
reaction (Table 1). Using Bpy-Pd-POP-1 polymer as the
catalyst, the reaction occurred smoothly in EtOH at 80 oC to
give the desired product with high yield (Table 1, entry 1).
Further investigation on the effect of reaction media was
conducted (Table 1, entries 2-6) and mixture solvent of EtOH
and H2O with a ratio of 1/1 gave the best result (Table 1, entry
6, 99% yield). The effect of temperature on this reaction was
also examined (Table 1, entries 7-8), when the temperature
was lower to 60 oC, the reaction proceeded much slower in
EtOH/H2O (1:1, v/v) and a product yield of 95% could be
achieved in more than 2 h (Table 1, entry 7). We hoped to
investigate the influence of the properties on the catalytic
activity, unfortunately, the Bpy-Pd-POP-2 polymer showed
similar reactivity to Bpy-Pd-POP-1 under this system (Table 1,
entry 9). Finally, the optimized condition for the Suzuki-
Miyaura coupling reaction was chosen as: EtOH/H2O (1:1, v/v)
as the co-solvent, 0.8 mol% Bpy-Pd-POP-1 as the
heterogeneous catalyst, in the presence of potassium
Figure 2. Solid-state 13C CP/MAS NMR spectra for Bpy-POP-1. The assignments for the
13C MAS NMR signals are indicated (top). 13C CP/MAS NMR spectra for Bpy-POP-2 are
shown in Figure S6.
carbonate, and at 80 oC.
Next, through a simple post-treatment of Bpy-POP with
palladium chloride (Scheme 1), the porous organic catalyst
Bpy-Pd-POP was facilely prepared (see SI for details). We then
performed X-ray photoelectron spectroscopy (XPS)
measurements to investigate the incorporation of palladium
within Bpy-Pd-POP-1. As shown in Figure 3 (red), the binding
energy (BE) at 336.88 eV correspond to Pd3d5/2 orbitsal in Bpy-
Pd-POP-1, which indicated that the Pd species is present in +2
state.14 The BE of 336.88 eV for the Pd species in Bpy-Pd-POP-
Table 1. Screening conditions for the Suzuki-Miyaura coupling reaction.a
catalyst (0.8 mol%)
Br
+
B(OH)2
solvent, Temp.,
K2CO3 (2.0 eq),
Entry
Catalyst
Solvent
Temp.
Time
(h)
1
Yield
(%)b
95
TONc
119
106
75
(oC)
1
2
Bpy-Pd-
POP-1
EtOH
H2O
80
Bpy-Pd-
POP-1
80
80
80
80
80
60
100
80
80
1
3
85
60
52
60
99
95
99
98
n.d.
1
shifted negatively 0.75 eV in comparison with that of 337.63
eV for free PdCl2 (Figure 3, black), which indicates the strong
coordination of PdCl2 with the bipyridyl ligand of Bpy-POP-1
polymer. In addition, the slight difference in the FT-IR spectra
of Bpy-POP and Bpy-Pd-POP also indicates that the
coordinated palladium chloride in the polymer (Figure S7 and
S8, SI).
3
Bpy-Pd-
POP-1
Toluene
CH2Cl2
DMF
4
Bpy-Pd-
POP-1
3
65
5
Bpy-Pd-
POP-1
3
75
6
Bpy-Pd-
POP-1
EtOH/H2O
(1:1)
0.5
2
124
119
124
123
0
7
Bpy-Pd-
POP-1
EtOH/H2O
(1:1)
8
Bpy-Pd-
POP-1
EtOH/H2O
(1:1)
0.5
0.5
3
9
Bpy-Pd-
POP-2
EtOH/H2O
(1:1)
10
------
EtOH/H2O
(1:1)
a
General condition: phenylboronic acid (0.5 mmol), bromobenzene (1.0 mmol),
b
K2CO3 (1.0 mmol), and catalyst (0.8 mol%), solvent (1.0 mL), temperature.
Isolated yield after silica gel column chromatography.
c
TON =(moles of
product)/(moles of metal in the catalyst), unless otherwise noted.
Having established the optimized reaction conditions, we
tested a variety of substituted aryl halides to probe the
versatility of our catalytic system (Table 2). As shown in Table
2, good to excellent isolated yields (93-99%) were obtained for
all of the Suzuki-Miyaura coupling reaction of a variety of
Figure 3. XPS spectra for free PdCl2 (black) and Bpy-Pd-POP-1 (red).
The Suzuki-Miyaura coupling reaction is one of the most
versatile methods for the facile formation of C-C bonds, which
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bromo and iodo derivatives with phenyboronic acid catalyzed
by the
Next, we examined the recyclability of this porous organic
catalyst Bpy-Pd-POP-1 (see Supporting Information, Table S2).
The recycling experiment was performed by using a simple
centrifugation method to recover the heterogeneous catalyst.
The recovered polymer was washed with EtOH and EtOAc to
remove the residual product, and simple dried in vacuum
overnight before reuse. As shown in Figure 4, Owing to the
built-in character of the covalently linked catalytic sites in the
polymer networks, the Bpy-Pd-POP-1 nanoporous catalyst can
be reused at least fifteen times without any significant loss of
the catalytic activity (97-99% yield).16 To determine that the
reaction between bromobenzene and phenylboronic acid was
indeed catalyzed by Bpy-Pd-POP-1 instead of the dissolved
homogeneous Pd species leached from the supports, the
following strategy was adopted. When the phenylboronic acid
conversion reached about 50%, the solid catalyst was removed
from the hot reaction mixture and then the mother liquor was
allowed to reaction another 2 h under the same conditions.10f,
Bpy-Pd-POP-1 catalyst (Table 2, entries 1-9). For aryl iodides,
the coupling reactions were rapidly completed within 0.5 h,
giving the corresponding products with high yield (Table 2,
entries 8-9). The phenyboronic acid substrate with an electron-
withdrawing substituent could also be converted into the
corresponding adduct in high yield (Table 2, entry 10). These
results identified that the Bpy-Pd-POP-1 nanoporous polymer
works as a highly efficient heterogeneous catalyst for the
Suzuki-Miyaura coupling reaction.
Table 2. Investigating the substrate scope of the Suzuki-Miyaura coupling
reaction catalyzed by Bpy-Pd-POP-1.a
X
R1
R2
Bpy-Pd-POP-1 (0.8 mol%)
(HO)2B
Ar-X
R1
+
EtOH/H2O(1:1), 80 oC,
K2CO3 (2.0 eq)
R2
Yield (%) b
99
Ar-B(OH)2
Entry
1
Time (h)
0.5
1.5
7
Br
(HO)2B
(HO)2B
(HO)2B
(HO)2B
(HO)2B
17
No significant change in conversion or yield could be
observed. This study identified that PdCl2 is strongly
coordinated within Bpy-POP polymer and the active phase was
not the dissolved Pd species leached from the polymer. In
addition, XPS characterization of Bpy-Pd-POP-1 after catalytic
runs showed the well-retained state of Bpy-Pd(II) catalytic
species (Figure S9, SI) and TEM images showed no Pd(0)
nanoparticles were appeared in the frameworks of the
recycled catalyst (Figure S10, SI).
2
3
4
5
93
99
98
98
O2N
Br
Br
2
OHC
Br
2
H3COC
MeO
Br
To summarize, we have reported a powerful strategy to
prepare Pd(II) organometallic catalyst immobilized on the
bipyridyl ligand-functionalized porous organic polymer (Bpy-
POP). Owing to the high BET surface area, covalently linked
catalytic sites, wide opening and interconnected pores, the
Bpy-Pd-POP displays high efficient activity and excellent
recyclability for the Suzuki-Miyaura coupling reaction. The
catalyst could be reused at least 15 times without significant
loss of the catalytic activity (97-99% yield). We believe that
Bpy-Pd-POP may act as a promising heterogeneous catalyst
applicable to a variety of carbon-carbon coupling reactions,
the topic of which is under further research in our laboratory.
6
7
Br
1
3
99
99
(HO)2B
(HO)2B
MeO
Br
8
9
0.5
0.5
2
99
94
99
I
(HO)2B
(HO)2B
MeO
I
10
Br
(HO)2B
CHO
a
General condition: phenylboronic acid (0.75 mmol), aryhalide (0.5 mmol),
K2CO3 (1.0 mmol), and Bpy-Pd-POP-1 (0.8 mol%), EtOH/H2O (1.0 mL), 80 oC. b
Isolated yield after silica gel column chromatography.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21502136, 21402138, 21201131),
the Promotive Research Fund for Excellent Young and Middle-
aged Scientists of Shandong Province (No. BS2014CL035) and
Higher Educational Science and Technology Program of
Shandong Province (No. J15LC18).
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DOI: 10.1039/C6RA03331H
COMMUNICATION
Journal Name
Bipyridyl-palladium catalyst embedded porous organic polymers (Bpy-Pd-POP) was synthesized and used as highly effective and
reusable heterogeneous catalyst for the Suzuki-Miyaura coupling reaction. This porous organic catalyst could be reused at least 15
times without significant loss of the catalytic activity (97-99% yield).
6 | J. Name., 2012, 00, 1-3
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