Nanoporous phenanthroline polymer locked Pd as highly efficient catalyst for Suzuki-Miyaura Coupling reaction at room temperature

Article abstract of DOI:10.1002/aoc.5310

Because of the intrinsic advantages, Suzuki coupling reactions have been one of the most popular coupling reactions in organic synthesis, however developing a high-performance heterogeneous catalyst for Suzuki coupling reactions in aqueous media at low temperature (e.g. room temperature) is still a challenge. Herein, a heterogeneous catalyst with coordinated Pd as active site and a designed conjugated phenanthroline based porous polymer (CPP) as support was fabricated. Systematically investigation on CPP support by Fourier transform infrared spectroscopy (FT-IR), Thermogravimetric analysis (TGA), Transmission electron microscopy (TEM), N₂ adsorption–desorption isotherm and Scanning electron microscopy (SEM) show that the derived CPP catalyst support owns a porous structure, moderately good surface area (141 m²/g) and an excellent thermal stability. As a heterogeneous catalyst for the synthesis of biphenyl derivatives via Suzuki coupling, Pd/CPP achieves an excellent catalytic performance and recycling ability towards Suzuki reaction of various reactants at room temperature in ethanol-water medium.

Full text of DOI:10.1002/aoc.5310

Received: 4 May 2019
DOI: 10.1002/aoc.5310
Revised: 13 September 2019
Accepted: 18 September 2019
F U L L P A P E R
Nanoporous phenanthroline polymer locked Pd as highly
efficient catalyst for Suzuki-Miyaura Coupling reaction at
room temperature
Jian Chen1
| Ju Zhang2 | Yan Zhang1 | Mingjiang Xie1
| Tao Li2
1Hubei Key Laboratory for Processing and
Application of Catalytic Materials,
Huanggang Normal University,
Huanggang, 438000, China
2Hubei Key Laboratory of Material
Chemistry and Service Failure, School of
Chemistry and Chemical Engineering,
Huazhong University of Science and
Technology, 1037 Luoyu Road, Wuhan,
430074, P. R. China
Because of the intrinsic advantages, Suzuki coupling reactions have been one
of the most popular coupling reactions in organic synthesis, however develop-
ing a high-performance heterogeneous catalyst for Suzuki coupling reactions
in aqueous media at low temperature (e.g. room temperature) is still a chal-
lenge. Herein, a heterogeneous catalyst with coordinated Pd as active site and
a designed conjugated phenanthroline based porous polymer (CPP) as support
was fabricated. Systematically investigation on CPP support by Fourier trans-
form infrared spectroscopy (FT-IR), Thermogravimetric analysis (TGA), Trans-
mission electron microscopy (TEM), N2 adsorption–desorption isotherm and
Scanning electron microscopy (SEM) show that the derived CPP catalyst sup-
port owns a porous structure, moderately good surface area (141 m2/g) and an
excellent thermal stability. As a heterogeneous catalyst for the synthesis of
biphenyl derivatives via Suzuki coupling, Pd/CPP achieves an excellent cata-
lytic performance and recycling ability towards Suzuki reaction of various
reactants at room temperature in ethanol-water medium.
Correspondence
Mingjiang Xie, Hubei Key Laboratory for
Processing and Application of Catalytic
Materials, Huanggang Normal University,
Huanggang 438000, China.
Email: xiemingjiang@smail.nju.edu.cn
Tao Li, Hubei Key Laboratory of Material
Chemistry and Service Failure, School of
Chemistry and Chemical Engineering,
Huazhong University of Science and
Technology, 1037 Luoyu Road, Wuhan,
430074, P. R. China.
K E Y W O R D S
Phenanthroline polymer, room temperature, Suzuki polycondensation reaction
Email: taoli@hust.edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21473064
1 | INTRODUCTION
homogeneous ones in Suzuki reactions is particularly fas-
cinating as its improvement in reusability of the precious
The Suzuki-Miyaura coupling reaction is a widely used
method for the construction of biphenyl compounds
basic organic synthesis due to synthetic variations and
functional group tolerance.[1–3] Homogeneous catalysts
with excellent activity and products selectivity have been
widely used in organic synthesis because of its uniform
dispersion and small steric hindrance.[4–6] However, their
shortage associated with recovery and reusability limits
their industrial application.[1–6] To overcome these issues,
the use of heterogeneous catalysts rather than
metal catalysts component.[7–10]
Recently, environmental awareness pressed us to pro-
duce chemical products and prompt the reaction pro-
cesses in green reaction conditions and process.[11–14] It is
estimated that about 80% of the useless chemical waste
can be reduced from a reaction systems corresponds to
the green solvent or procedure.[11–14] From secure, eco-
nomic and ecological points of regard, the use of harm-
less water-based solvent in organic synthesis is a sensible
choice. However, organic synthesis with water-based
Appl Organometal Chem. 2019;e5310.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5310

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CHEN ET AL.
solveꢀnt usually needs high reaction temperature (usually
>80 C). In this regard, the design of a catalytic system
using harmless solvent and mild conditions (room tem-
perature and in air) would be a very promising and fasci-
nating direction for exploiting greener and more secure
Suzuki reactions.[14,15] Nowadays, many Suzuki-Miyaura
coupling reactions can be conducted under very mild
reaction conditions and in a short time,[15–21] among
which various reusable heterogeneous catalysts have
been exploited, including inorganic solid (silicate,
agarose-alumina composite, CeO2, iron oxide, TiO2) and
Merrifield resin supported catalysts.[15–34] But these inor-
ganic solid supported usually suffers from poor stability
due to the weak interaction between supports and active
components.
Recent studies have demonstrated the feasibility of
employing porous organic polymers (POPs) materials in
adsorption,[35–37] gas storage,[38,39] and especially in het-
erogeneous catalysis[10,40–44] due to their high surface
area, high stability and controllable skeletons. As in the
case of other heterogeneous catalysts, POPs materials
were designed and employed in catalysis mainly because
their excellent stability to thermal treatments, organic
and inorganic solvents and the incorporation of active
metal components.[35] Except boron-containing COFs
materials, the most well-known triazole,[45] imine[36,40,44]
and hydrazine[44] based POPs materials are stable in
water and organic solvents. Moreover, it has been well
demonstrated that the heteroatoms (N,[10,46] O[47] and
S[37]) in the skeletons of COFs, MOFs and other porous
materials are feasible in anchoring different active metal
ions.[46–48] The introduction of heteroatom is conducive
to the recycling of catalysts and their industrial
application.[46–48] However, there are only a very few
reports available on the synthesis of organic polymer sup-
port and applications in Suzuki-Miyaura coupling reac-
tion in water solvent at room temperature and in air
reaction of various reactants at room temperature in
ethanol-water medium.
2 | EXPERIMENTAL SECTION
2.1 | Synthesis
Porous phenanthroline based polymer catalyst was syn-
thesized through Suzuki reaction. Firstly, 0.35 g tetrakis
(triphenylphosphine) palladium (0.3 mmol), 0.51 g
3,8-dibromo-1,10-phenanthroline (1.5 mmol) and 0.46 g
1,3,5-phenyltriboronic acid tris-(pinacol) ester (1.0 mmol)
building monomer were uniformly dispersed in 32.0 ml
of 1,4-dioxane. Then, 8.0 ml 0.375 M solution of K2CO3
was added to the 1,4-dioxane dispersed solution for 5 min
under vigorously ultrasonic treatment. Finally, the
obtained homogeneous organic–inorganic mixture was
vacuumed to remove residual oxygen and heated at 95 ꢀC
for 24 hr under nitrogen atmosphere. The resulting black
precipitate was collected by filtration and thoroughly
washed with 500 ml water to remove water-soluble sub-
stances and then washed by 300 ml ethanol to remove
organic substances and then dried to obtain porous
phenanthroline polymer (denoted as CPP, yield
of 92.9%).
2.2 | Preparation of porous
phenanthroline based polymer supported
Pd catalyst
Phenanthroline based polymer supported Pd catalyst was
prepared by simple loading method.[48] Briefly, CPP
(1.5 g) material and palladium acetate (0.77 g) were
refluxed in 40.0 ml acetonitrile at 55 ꢀC for 4 hr. The solid
was firstly filtered and washed repeatedly with about
100 ml acetonitrile to eliminate uncoordinated palladium
(II) species by phenanthroline units in the support, then
washed by dichloromethane in Soxhlet extractor for 24 hr
to remove residual physisorbed Pd (II) ions. The washed
product was dried in vacuum to give the tawny powders
and the final obtained catalyst was denoted as Pd/CPP.
The Pd content in Pd/CPP was measured to be 2.94% by
flame atomic absorption spectrometry.
atmosphere.
Among
all
the
polymer
units,
1,10-phenanthroline has considerably strong coordinat-
ing ability toward metals ions, presumably due to its fixed
and conjugated cis-chelating structure, which makes it an
attractive ligand.[49] Consequently, 1,10-phenanthroline
derivatives have widely synthesized into heterogeneous
catalysts systems by immobilization,[50] loading[51] and
integrated[46,52–54] method. To date, there are very few
reports on phenanthroline based porous catalysts with
covalently linked catalytic metal sites for heterogeneous
catalysis.[46,55]
2.3 | Catalytic performance test of Pd/
Herein, a heterogeneous catalyst with coordinated Pd
as active site and a designed conjugated phenanthroline
based porous polymer (CPP) as support was fabricated
and the obtained Pd/CPP achieves an excellent catalytic
performance and recycling ability towards Suzuki
CPP catalyst for Suzuki reaction
Typically, aryl halides (0.5 mmol), phenylboronic acid or
its derivatives (0.75 mmol), base (1.0 mmol) and Pd/CPP
catalyst (10.0 mg, 0.55 mol % Pd) were added to 3.0 ml

ROOM TEMPERATURE SUZUKI-MIYAURA COUPLING REACTION
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solvent. The reaction mixture was stirred at room temper-
ature (25 ꢀC) in air. After the reaction completely proceed
(monitored by TLC), the mother solution was collected
by centrifugation and the centrifuged deposit was washed
and centrifuged with dichloromethane (5 ml) for third
times. The organic solution was combined and washed
with 15 ml water (3 times) to remove the remaining base.
The organic crude products were then gathered under
vacuum and further purified by column chromatography.
The recycle use performance test of the catalyst was
conducted with bromobenzene and phenylboronic acid
as the model substrate for the C-C coupling reaction.
Concrete procedures are as follows: 0.5 mmol
bromobenzene, 10 mg Pd catalyst (0.55 mol % Pd),
0.75 mmol phenylboronic acid and 1.0 mmol K2CO3 were
dispersed in 3.0 ml ethanol/water mixed solvent and
reacted for a certain of time. After each cycle procedure,
the catalyst was recycled by centrifugation and washed
by dichloromethane solvent and then reused directly
without any other treatment. For characterization, the
recycled catalyst was purified with 300 ml water initially
and 300 ml dichloromethane subsequently, and dried at
80 ꢀC under vacuum.
degassed in a chamber at 5 × 10−10 mbar at room temper-
ature. C1s transition was adjusted at 284.6 eV. Ther-
mogravimetric (TGA) data were recorded on
PerkinElmer Diamond TG/DTA instrument.
a
3 | RESULTS AND DISCUSSION
3.1 | Catalyst characterization
As the Scheme 1 shown, phenanthroline based polymer
CPP was synthesized by a simple Suzuki-Miyaura cou-
pling reaction from 1,3,5-phenyltriboronic acid tris-
(pinacol) ester and 3,8-dibromo-1,10-phenanthroline. The
resulted CPP material is stable in common solvents such
as water, ethanol, methanol, THF, dichloromethane,
DMF, DMSO, acetone and trichloromethane, etc, which
favors its application in heterogeneous catalysis as cata-
lyst
support.
The
FT-IR
spectrum
of
1,3,5-phenyltriboronic
acid tris-(pinacol)
ester,
3,8-dibromo-1,10-phenanthroline and the derived CPP
polymer are shown in Figure 1. 1,3,5-phenyltriboronic
acid tris-(pinacol) ester monomer shows a strong stretch
at 2975–2845 cm−1 for methyl.[56] It can be seen that the
peak around 3037 cm−1 emerged in the FT-IR spectra for
both the raw material and the derived polymer, which
can be attributed to the aromatic C-H stretching vibra-
tions for all the compounds.[57] A broad absorption band
at 3500–3280 cm−1 was observed in the FT-IR spectrum
of resulting polymer, attributed to the existence of lattice
or coordinated water in the polymer.[58] Compared with
the adopted raw material of 1,3,5-phenyltriboronic acid
tris-(pinacol) ester, the strong stretching peaks at
2975–2845 cm−1 for methyl disappeared, suggesting that
2.4 | Hot filtration test
To monitor whether the heterogeneous or homogeneous
feature of Pd species were real effective species responsi-
ble for the catalytic performance, the heat filtration test
was conducted according to the former reported
method.[9]
2.5 | Characterization
the
success
of
the
polymerization
of
1,3,5-phenyltriboronic acid tris-(pinacol) ester and
3,8-dibromo-1,10-phenanthroline. As shown in Figure 1,
the peak at 1633 cm−1 is attributed to the stretching
vibration peak of the C=N bond. Moreover, the distinct
peak at 1401 belong to the deformation vibration of the
benzene ring in aromatic skeleton of the polymer. The
C=C and C=N bond infrared absorption peak confirmed
the success of polymer syntheisis. After the loading of
active metal, the stretching vibration peak of the C=N
bond moves to 1584 cm−1, which may be caused by the
formation of a coordination bond between the N atom
and the palladium ion. Furthermore, the solid state 13C
CP/MAS NMR was further used to confirm the successful
synthesis for phenanthroline based CPP polymer and its
result was shown in Figure 2. The resonance peaks at
162.3, 145.1, and 124.7 ppm could be assigned to unsatu-
rated aromatic carbons (C=N bond) in the
phenanthroline units,[59] clearly indicating that the
All reagents were commercially purchased and used
without any further purification. The surface areas, pore
size distributions of the support, pore volume and N2
adsorption isotherms (77.3 K) were measured using
Micromeritics ASAP 2020 M instrument. Before analysis,
the samples were dried in vacuum oven and then
ꢀ
degassed at 200 C for 8 hr. FT-IR spectra were recorded
on a Bruker VERTEX 70 FT-IR Spectrometer. TEM
images were taken on a Tecnai G20 microscope (FEI
Corp., Oregon, USA) instrument. Pd content data were
obtained on Perkin Elmer AA-800 (Massachusetts, Amer-
ica). XRD patterns were recorded on an X'Pert PRO X-ray
diffractometer with Cu Kα radiation. SEM images were
obtained on a FEI Sirion 200 scanning electron micro-
scope at 10.0 kV. XPS was performed in a VG multilab
2000 spectrometer, using an Mg-Al Ka X-ray source with
the passing energy flow of 100 eV. The samples were

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CHEN ET AL.
SCHEME 1 Synthesis diagram towards the Pd-CPP catalyst for Suzuki-Miyaura Coupling Reaction
FIGURE 2 The 13C CP-MAS NMR spectroscopy of CPP
polymer
FIGURE 1 FT-IR spectra for the starting materials and the
derived CPP
and transmission electron microscope (TEM). SEM image
of CPP in Figure 3a shows a lump-like morphology with
honeycombed porous structure. The boundaries of the
TEM image in Figure 3b show the layered arrangement
of CPP polymer. Figure 3c shows the TEM image of
Pd/CPP, which displays an analogous morphology to the
original CPP, suggesting a good stability in organic sol-
vent. The thermal stability of the solid CPP materials was
studied by thermogravimetric analysis (TGA) under N2
phenanthroline monomers were integrated into the skel-
eton of the CPP polymer through the Pd catalyzed
Suzuki-Miyaura condensation reaction. Obviously, both
the 13C CP/MAS NMR and FT-IR results confirmed the
successfully integration of the phenanthroline into the
porous polymer.
The morphology and microstructure of CPP were
observed through scanning electron microscope (SEM)

ROOM TEMPERATURE SUZUKI-MIYAURA COUPLING REACTION
5 of 11
FIGURE 3 (a) FE-SEM image
of CPP; (b) TEM image of CPP;
(c) TEM image of Pd/CPP;
(d) nitrogen sorption isotherms and
the pore size distribution curve
(inset)
atmosphere. The obtained thermal plots for CPP polymer
material was as shown in Figure S1 in supporting infor-
mation (SI). The weight loss at 450 ꢀC was just 10%,
suggesting that the obtained porous polymer shows a
good thermal stability. Wide angle X-ray diffraction was
used to study the crystalline structure of CPP polymer.
XRD pattern for CPP material in Figure S2 exhibits a
board peak at 2θ value of 23.5o with no other characteris-
tic diffraction peak, implying the amorphous nature of
the phenanthroline based polymer. Compared with the
XRD of the CPP material, there is only one board charac-
teristic peak at 23.5o in the XRD spectrum, indicating
that the structure of the catalyst is also amorphous.
The textural properties of the derived CPP polymer
are very critical parameters for heterogeneous catalysts
and analyzed by N2 sorption analysis. The nitrogen sorp-
tion isotherms of CPP, as shown in Figure 3d, exhibit a
IV type isotherms with a sharp uptake of nitrogen gas
when relative pressure (P/P0) under 0.001, indicating the
existence of microporous structure. Additionally, an obvi-
ous rise from the middle to the high relative pressure
(P/P0 = 0.8–1.0) means the existence of macropores in
the polymer architecture. The pore size distribution
curve, as shown in Figure 3d inset, also verified the coex-
istence of primary micropore, meso- and macro-pore,
which may resulted from piled pore and the intrinsic
porosity.[60] The BET surface area of CPP was calculated
to be 141 m2/g.
state rather than in metallic state.[9,10] Moreover, the
binding energy for +2 state Pd in Pd/CPP catalyst shifted
0.6 eV to nether more value in contrast to that of
338.4 eV for Pd element in Pd (OAc)2. This negative shift
suggests the strong coordination interaction of active Pd
ions with the N atoms in the CPP polymer: electrons
gravitate toward Pd ions, which increases the electron
density of Pd ions and makes the +2 state Pd ions minor
electron-deficient, which is agrees well with XPS experi-
ment results of N species.[10]
3.2 | Catalytic performance for Suzuki-
Miyaura coupling reaction
The palladium-catalyzed Suzuki reaction is a powerful
means to construct C-C bond in organic synthesis. The
X-ray photoelectron spectroscopy (XPS) measurement
was performed to further analysis the state of Pd species
in Pd/CPP catalyst. As shown in Figure 4, the XPS spec-
tra of the fresh Pd/CPP exhibits two peaks around the
binding energy (B.E.) of 337.6 eV and 342.8 eV, revealing
that Pd species in the CPP were present in +2 oxidation
FIGURE 4 XPS spectra of fresh Pd/CPP and the used Pd/CPP
catalysts

6 of 11
CHEN ET AL.
catalytic performance of the Pd/CPP catalyst in heteroge-
neous Suzuki reaction was systematically investigated.
Firstly, bromobenzene was chosen as model substrate to
optimize the reaction conditions. The Suzuki reactions
were examined on Pd/CPP catalyst using K3PO4Á3H2O as
a base in air atmosphere and at room temperature
(25 ꢀC), and various solvents were used (Table S1, entries
1–12 in supporting information). Noticeably, Pd/CPPs
worked more efficiently when using a green solvent of
ethanol and water (Vethanol:Vwater = 1:1) than other com-
mon solvents, attributed to the presence of hydroxyl
group in alcohol molecule, which endows it a hydrogen
bond donor, and thus facilitates the C-Br bond dissocia-
tion of halides and boost the coupling reaction.[61] The
influence of the bases on the catalytic property of the pre-
sent heterogeneous reactive system was also investigated
with the ethanol and water (Vethanol:Vwater = 1:1) as sol-
vent. As shown in Table S1, it can be found that K2CO3
worked the best performance compared with
K3PO4Á3H2O, CH3COOK, KOH, Na2CO3, Na3PO4Á12H2O
and NaOH (Table S1, entries 13–18). To rule out the cata-
lytic action of the light, the Suzuki reaction also carried
out in the dark. It was found that there is no significant
difference in catalytic performance compared with the
catalytic reaction in the light with all other things being
equal (Table S1, entries 19). Without the component of
Pd, the pure CPP polymer showed no conversion of the
bromobenzene raw material, conforming that the cata-
lytic activity stems from the active component of Pd
(Table S1, entries 20). As showed in Table S1, the yield of
the target reaction product was very low catalyzed by Pd
(OAc)2 and 1,10-Phenanthroline coordinated Pd (OAc)2,
indicating that the CPP polymer as scaffold plays an
important role in catalytic process (Table S1, entries
21 and 22). The superior catalytic performance of Pd/CPP
to Pd (OAc)2 and 1,10-Phenanthroline coordinated Pd
(OAc)2 may be attributed to the strong coordinating abil-
ity of the CPP support toward metals ions and the rich
porosity, in which, the former enables a highly uniform
dispersion of Pd, while, the later provide a unique con-
fined space for the substrate molecule and the catalyti-
cally active sites. To judge whether the heterogeneous
Pd/CPP catalyst or the dissolved homogeneous Pd species
were the actual active component responsible for the
Suzuki reaction, the hot filtration experiment was
tested.[62] When 92.9% of bromobenzene is converted into
biphenyl in 20 mins at room temperature and in air, the
catalyst in the reaction system was filtered and then the
filtrate was heated to react continuously for another 2 hr
under the previous reaction conditions. After hot filtra-
tion, the yield of the target product is 92.7%, showing no
further conversion of the raw materials without the par-
ticipation of Pd/CPP. The hot filtration test indicates that
the heterogeneous Pd/CPP is the effective catalytic com-
ponent instead of homogeneous leaked Pd2+ ions
(Table S1, entries 23).
After acquiring the optimal reaction conditions, the
couplings of various other aryl bromides derivatives with
phenylboronic acid were then proceeded at room temper-
ꢀ
ature (25 C) in air with ethanol-water as solvent. The
reactions of bromobenzene with different arylboronic
acids derivatives were also conducted under the same
mild reaction conditions (shown in Table 1, entries 1–8).
As shown in Table 1, the electron-donating substituents
on the arylboronic acid can reacted smoothly and yield
their corresponding products with high conversion and
selectivity,
while
electron-withdrawing
groups
substituted arylboronic acid derivatives exhibited lower
yield than electron-donating groups substituted ones
under the same reaction conditions. Aryl bromides of
various electronic characters also reacted smoothlyꢀwith
unsubstituted phenylboronic acid substrates at 25 C in
air atmosphere within 1 h (Table 1, entries 9–13).
Electron-deficient aryl bromides generally exhibited bet-
ter catalytic performance than electron-rich ones.[9] To
extend the testing scope of substrates, the catalytic perfor-
mance of Pd/CPP catalyst in Suzuki reaction of
chlorlbenzene and 4-Chlorotoluene was further tested.
The heterogeneous catalyst produced their corresponding
biphenyls with excellent activity with halide/Pd ratio at
ꢀ
0.55 mol % at 80 C within 5 hr, (Table 1, entries 14–16).
Motivated by the exciting results of Pd/CPP catalyst in
Suzuki reactions of aryl bromides and phenylboronic
acids under mild reaction conditions, the catalytic reac-
tion towards the coupling of phenylboronic acid and ben-
zyl chloride were also examined. The catalyst acquired
71.2% yield of diphenylmethane within 5 hr, which dem-
onstrates that Pd/CPP catalyst has high activity (Table 1,
entries 17).[63,64]
The Pd based catalyst catalyzed Suzuki reaction has
been widely used in homogeneous media for the versatile
construction of C-C bouds.[65–71] However, their practical
application is still limited due to the difficulty in reusabil-
ity.[9] In addition, high reaction temperature, inert gas
protection and environment unfriendly solvent is usually
inevitable. Developing an efficient and recyclable Pd
based heterogeneous catalysts is thus a hopeful solution.
One of the main advantages of the heterogeneous catalyst
is the separation and the recycling of the catalyst.[5] To
study the recycling performance of the Pd/CPP catalyst
in the present Suzuki reaction, the reaction of phe-
nylboronic acid and bromobenzene at 25 ꢀC in air and in
ethanol-water mixed medium was selected. After recycled
for five runs, the result (Figure 5) shows that there is no
obvious change in catalytic activity in the first three runs.
However, the catalytic activity of the solid Pd/CPP

ROOM TEMPERATURE SUZUKI-MIYAURA COUPLING REACTION
7 of 11
TABLE 1 Effect of aryl halides and aryl boronic acid on Suzuki-Miyaura reaction over Pd/CPP a catalyst
Entry
Substrate 1
Substrate 2
Product
t (h)
Yield (%)b
1
1
99
2
3
1
2
93
98
4
5
2
1
97
99
6
7
8
9
1
1
1
1
95
99
99
98
(Continues)

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CHEN ET AL.
TABLE 1 (Continued)
Entry
Substrate 1
Substrate 2
Product
t (h)
Yield (%)b
10
1
97
11
1
93
99
94
98
82
93
12
1
13c
14c
15c
16c
5
5
5
1.0
a0.55 mol % Pd, 0.5 mmol of aryl halide, 0.75 mmol of arylboronic acid, 1.5 mmol of K3PO4.3H2O, 3 ml solvent (v (EtOH): v(H2O) = (3:2)), 25 ꢀC, In Air
bIsolated yield.
c80 ꢀC, In N2 atmosphere.
catalyst reduced slightly in the last two recycle test. To
ascertain the deactivation cause of catalyst, the content of
Pd in Pd/CPP catalyst after five runs was determined to
be 2.94% by atomic absorption spectroscopy (AAS) analy-
sis (vs 2.94% Pd in the fresh Pd/CPP catalyst), which indi-
cates an excellent stability of the Pd/CPP catalyst during
the coupling reaction. In addition, the TEM image (-
Figure S3) of the catalyst after the fifth run showed that
metallic Pd nanoparticles with uniform size of 5 nm (-
Figure S4) generated in reused catalyst, indicating that
partial Pd2+ ions were reduced into the metallic Pd
nanoparticles during the coupling reactions. The pore
parameter of used catalysts analyzed by N2 sorption anal-
ysis and the result was shown in Figure S5. The sharp
uptake of nitrogen gas at relative pressure (P/P0) under
0.001 disappeared after reuse, impling the micropores in
the Pd/CPP catalyst was disappeared. Furthermore, the
BET surface area of reused Pd/CPP catalyst decreased
from 141 m2/g (Pd/CPP) to 101 m2/g, which may be cau-
sed by the blockage of microporous by active metal. Part

ROOM TEMPERATURE SUZUKI-MIYAURA COUPLING REACTION
9 of 11
excellent catalytic properties for the coupling of
bromobenzene and phenylboronic acid.
4 | CONCLUSION
In summary, for the first time, a phenanthroline based
polymer materials (CPP) was synthesized by simple
Suzuki-Miyaura coupling reaction. After anchoring of
Pd (OAc)2 into CPP polymer skeleton, the derived
Pd/CPP catalyst exhibits a superior catalytic activity
towards Suzuki reaction, in which the Pd/CPP catalyst
can build C-C bonds by a board scope of the reactants
at room temperature, in ethanol-water medium and in
air with an excellent yield and recycling catalytic per-
formance due to the strong coordinating ability of the
CPP support toward metals ions and the rich porosity,
enabling a highly uniform dispersion of Pd and provid-
ing a unique confined space for the substrate molecule
and the catalytically active sites. It is believed that the
phenanthroline based CPP scaffold could act as a stable,
robust and versatile supports and host a variety of
metal ions or nanoparticles for catalyzing a wide scope
of reactions. Moreover, the presented strategy in design-
ing phenanthroline based polymer loaded Pd catalyst
for Suzuki reaction under very mild conditions may
provide an alternative route to develop new green, effi-
cient and recyclable catalytic systems for C-H activa-
tion, Buchwald-Hartwig amination and Hydrogen
Evolution.
FIGURE 5 Recycle use performance of Pd/CPP catalyst for
Suzuki-Miyaura reaction
Pd ions was reduced into Pd nanoparticles during the
Suzuki-couling reaction process. The resulted Pd
nanoparticles was highly dispersed in the structure of the
catalyst, which may blocked the micropores and reduced
the special surface area. The XPS results further verified
that about 23.9 at % Pd2+ ions were reduced into the
metallic Pd nanoparticles (Figure 4). Therefore, the loss
of active specie of Pd2+ into Pd nanoparticles maybe
account for the reduction in the catalytic activity during
recycling use. As the Table 2 shown, the TOF value in
the literatures were between 11 and 802 h−1 with similar
reaction conditions, however, the TOF of this work was
1037 h−1, indicating that the catalyst has exhibited very
TABLE 2 Activity comparison of Pd catalyst in the SM reaction of bromobenzene in our research and references
Entry
1[16]
2[17]
3[18]
4[19]
5[22]
6[25]
7[30]
8[32]
9[70]
10[26]
11[27]
12
Catalyst
Time(h)
Yield(%)
TOF(h−1
280
11
)
Pd@Al2O3-agarose
Pd/CeO2
2
95
89
98
95
96
98
96
96
94
98
96
95
3
Pd@Cdots@Fe3O4
Fe@FexOy/Pd
Fe3O4/Ethyl-CN/Pd
Fe3O4/Py/Pd (0.02)
Fe3O4@TA/Pd
L-arginine/PdCl2 (1)
PdNPs@[Bmim]Lac
SBA-15/1,3-DCG/Pd
Pd@PS-Met
2
223
48
4
1
124
132
320
112
24
0.66
3
1
4
1
802
240
1037
4
Pd/CPP
1

10 of 11
CHEN ET AL.
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ACKNOWLEDGEMENTS
This work was supported by the National Natural Science
Foundation of China (21473064). We are also grateful to
the Analytical and Testing Center of Huazhong Univer-
sity of Science and Technology, Wuhan, China.
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ORCID
Jian Chen https://orcid.org/0000-0002-2602-9878
Mingjiang Xie https://orcid.org/0000-0002-9966-1911
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
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How to cite this article: Chen J, Zhang J,
Zhang Y, Xie M, Li T. Nanoporous phenanthroline
polymer locked Pd as highly efficient catalyst for
Suzuki-Miyaura Coupling reaction at room
temperature. Appl Organometal Chem. 2019;e5310.
https://doi.org/10.1002/aoc.5310