Highly dispersed pd catalyst locked in knitting aryl network polymers for suzuki-miyaura coupling reactions of aryl chlorides in aqueous media

Article abstract of DOI:10.1002/adma.201200804

Highly dispersed palladium chloride catalysts locked in triphenylphosphine-functionalized knitting aryl network polymers (KAPs) are developed and exhibit excellent activity under mild conditions in the Suzuki-Miyaura cross-coupling reactions of aryl chlorides in aqueous media. This work highlights that the microporous polymers not only play the role of support materials, but also protect the Pd species from aggregation and precipitation, hence, positively effect the catalysis activity.

Full text of DOI:10.1002/adma.201200804

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Highly Dispersed Pd Catalyst Locked in Knitting Aryl
Network Polymers for Suzuki–Miyaura Coupling Reactions
of Aryl Chlorides in Aqueous Media
Buyi Li, Zhenhong Guan, Wei Wang, Xinjia Yang, Jianglin Hu, Bien Tan,* and Tao Li*
The porous materials with high surface area have attracted sig-
nificant scientific attention due to their diverse potential appli-
cations in separation,[1,2] heterogeneous catalysis,[3] and gas
storage.[4–8] During the last few decades, the surge to develop
such useful materials has led scientists to prepare a number
of novel porous materials such as metal organic frameworks
(MOFs),[9] porous organic cages,[10] and microporous organic
polymers (MOPs),[11] in addition to traditional porous mate-
rials such as zeolites and activated carbon. Among these porous
materials, MOPs have attracted particular attention due to
their unique properties such as large surface area, low skel-
etal density, and high chemical stability. One particular advan-
tage of MOPs is to introduce a broad range of useful chemical
functionalities within the porous framework. The introduc-
tion of Tröger’s base into conjugated microporous polymers
(CMPs) for heterogeneous catalysis is an early example in this
regard.[12] The use of metal-organic CMPs has been demon-
strated for heterogeneous catalysis,[13] and highly stable and
porous cross-linked polymers are reported as efficient photo-
catalysts.[14] In addition, microporous phthalocyanine polymer
with metal ions[15–17] and covalent organic frameworks (COFs)
with palladium catalysts[18] have also been studied for hetero-
geneous catalysis reactions. However, the application of MOPs
as heterogeneous catalysts is relatively limited due to high-cost,
for instance, noble metals catalysts are themselves consumed
in preparation of such materials.[13,15] Hence, economical mass
production of MOPs as heterogeneous catalysts remains a for-
midable challenge.
Nowadays, palladium-catalyzed Suzuki–Miyaura coupling reac-
tion[19,20] of aryl halides is one of the most efficient methods for the
construction of biaryls or substituted aromatic moieties in organic
synthesis. Although homogeneous palladium catalysts have
been extensively investigated,[21–26] their industrial applications
remained limited due to the difficulty in their separation from
the products for recycling.[21–27] Heterogenization of the existing
homogeneous palladium catalysts offers an attractive solution to
this problem.[28–31] From a practical point of view, the use of aryl
chlorides is highly desirable compared with the more expensive
aryl iodides, aryl bromides and aryl triflates. However, the activa-
tion of aryl chlorides is particularly challenging and successful
examples using unactivated aryl chlorides are quite rare.[32–34]
Since triphenylphosphine (PPh3) was employed as a ligand for
Pd-catalyzed Suzuki–Miyaura coupling reactions in the 1980s,[35]
it has become an indispensable class of ligands for the coupling
of aryl chlorides,[36,37] mainly due to its low cost and the high effi-
ciency of the catalyst formed.[38,39] However, the high air-sensitivity
of the complex makes the catalyst recycling/recovery difficult, and
thus an excess amount of PPh3 is usually required to achieve a
reasonable catalytic activity.[40] This limitation increases the appli-
cation cost of the heterogeneous catalytic system, and the benefits
related to the easier separation and the reuse of the catalyst are
further offset by its moderate activity. Thus there is an increasing
demand to develop new protocols for C-C couplings of aryl chlo-
rides, which should fulfill the following requirements: i) a low
loading of expensive catalyst, especially noble metals; ii) high
activity and selectivity; iii) recycling of catalysts without losing
their activity during prolonged reaction times.
Previously we have proposed a low-cost strategy to synthesize
high surface area microporous knitting aryl network polymers
(KAPs) via one-step ‘knitting’ of rigid aromatic compounds
blocks with an external crosslinker.[41] We herein report the
synthesis of an inexpensive, stable, highly active, and recover-
able palladium–phosphine heterogeneous catalyst following
a similar strategy, i.e., knitting PPh3 with benzene to produce
functionalized KAPs(Ph-PPh3), and then binding Pd with PPh3
groups to form KAPs(Ph-PPh3)-Pd (Scheme 1a, see Supporting
Information (SI) for experimental details). This catalyst enables
fast Suzuki–Miyaura coupling reaction in an aqueous ethanol
solution under mild conditions (80 °C). Biaryl products were
obtained consistently in excellent yields using various aryl chlo-
rides and benzoboric acid. Moreover, this work demonstrates
that the microporous polymer backbone knitting with phos-
phine ligand can efficiently disperse Pd to promote the catalytic
activity, which is much higher than that of homogeneous cata-
lysts under the similar conditions.
B. Li,[+] X. Yang, Prof. B. Tan
Institute of Polymer Science and Engineering
School of Chemistry and Chemical Engineering
Huazhong University of Science and Technology
Luoyu Road No. 1037, Wuhan, 430074, China
E-mail: bien.tan@mail.hust.edu.cn
Z. Guan,[+] J. Hu, Prof. T. Li
Key Laboratory for Large-Format Battery Materials and System
Ministry of Education, School of Chemistry and Chemical Engineering
Huazhong University of Science and Technology
Luoyu Road No. 1037, Wuhan, 430074, China
E-mail: taoli@mail.hust.edu.cn
Prof. W. Wang
State Key Laboratory of Applied Organic Chemistry
Lanzhou University
College of Chemistry and Chemical Engineering
Lanzhou 730000, China
[+] B. Li and Z. Guan contributed equally to this work
DOI: 10.1002/adma.201200804
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identical and both show resonance peaks
near 137 and 130 ppm due to substituted
aromatic carbon and non-substituted aro-
matic carbon respectively, and the resonance
peaks near 37 ppm are due to carbon in the
methylene linker formed from Friedel–Crafts
reaction.[41] Compared with KAPs(Ph-PPh3),
the 31P HPDEC/MAS NMR resonance peaks
of KAPs(Ph-PPh3)-Pd (Figure 1b) became
slightly broader and shifted from 18 ppm to
21 ppm, which indicate the successful coordi-
nation of PdII with the phosphorous atom.[43]
XPS spectroscopy was employed to investigate
the elemental compositions of the surface and
coordination states of Pd species. In Figure S2
of the SI, an XPS study of KAPs(Ph-PPh3)-Pd
derived from PdCl2 reveals that C, P, Cl, and
Pd elements are present in the solid mate-
rial. The XPS spectra in Figure 1c, 1d revealed
that Pd species in the KAPs(Ph-PPh3)-Pd were
Scheme 1. Synthetic route of: a) KAPs(Ph-PPh3)-Pd, b) PS-PPh2-Pd and, c) KAPs(Ph)-PPh3-Pd. present in +2 oxidation state rather than in
Big balls represent PPh3 or PPh2 functional groups. Small balls represent PdCl2. Solid line
represents boundary of material particles. Dashed lines represent inner network of material
particles.
metallic state, corresponding to the binding
energy (B.E.) of 337.6 eV and 342.8 eV in
the Pd 3d5/2 and 3d3/2 levels respectively.[44]
In comparison with the PdCl2 (337.9 and
343.1 eV), the PdII binding energy in the KAPs(Ph-PPh3)-Pd
shifted negatively by 0.3 eV, which can be attributed to the strong
electron-donation of the Ph-PPh3 network. These results confirm
that the PdII is successfully immobilized on the KAPs(Ph-PPh3)
by coordination to PPh3 functional groups rather than by phys-
ical adsorption of PdCl2 on the surface.
The porous properties of the samples were analyzed by
nitrogen sorption analysis. The BET surface area of KAPs(Ph-
PPh3) was found to be 1036 m2/g and that of KAPs(Ph-PPh3)-Pd
was 1025 m2/g. As shown in Figure 2a and 2b, the adsorption
and desorption isotherms of KAPs(Ph-PPh3) and KAPs(Ph-
PPh3)-Pd are also quite similar. The adsorption isotherms dis-
play a steep nitrogen gas uptake at low relative
The successful growth of microporous network with PPh3
functional groups and incorporation of Pd metal were confirmed
by Fourier transform infrared (FTIR) spectroscopy, solid-state 13
C
cross polarization (CP) and 31P high power decoupling (HPDEC)
magic angle spinning (MAS) spectra. FTIR spectroscopy of
KAPs(Ph-PPh3) and KAPs(Ph-PPh3)-Pd (Figure S1 of the SI)
display a series of bands around 1600–1450, 1250–950, and 900–
650 cm−1 which can be attributed to benzene skeleton stretching,
C–H out-of-plane bending and in-plane bending vibrations of the
benzene ring respectively.[42] The peaks at 1437 cm−1 correspond
to the vibrations of the P–CH2 bond.[43] The 13C CP/MAS NMR
of KAPs(Ph-PPh3) and KAPs(Ph-PPh3)-Pd (Figure 1a) are almost
pressure (P/P0 < 0.001) reflecting abundant
micropore structure, a slight hysteresis loop
implying a spot of mesopore and a sharp rise
at medium and high pressure regions (P/P0 =
0.8–1.0) indicating the presence of macropores
in these materials.[45] The pore size distribu-
tion of KAPs(Ph-PPh3) and KAPs(Ph-PPh3)-
Pd (Figure 2c and 2d) also confirm the pres-
ence of such heterogeneous porous structure.
Actually, the heterogeneous porous structure
is favorable for catalysis process. The macro-
porous structure accelerates the mass transfer
of reactants and products, and micropore of
suitable size is beneficial for anchoring metal
catalysts. According to the previous work,[41]
the pure benzene-based KAPs (KAPs(Ph))
possess the nice heterogeneous structure
and that is why the benzene is chosen as co-
monomer to form the porous framework.
Suzuki–Miyaura coupling reactions of
aryl chlorides were successfully catalyzed by
Figure 1. Solid-state 13C CP/MAS (a) and 31P HPDEC/MAS (b) natural abundance NMR spectra
of samples. Asterisks denote spinning sidebands. XPS spectra for Pd on pure PdCl2 compound
(c), fresh KAPs(Ph-PPh3)-Pd (d), and KAPs(Ph-PPh3)-Pd after 5 runs (e).
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by successfully preventing Pd aggregation and
precipitation. Hence, it seems that the excel-
lent catalytic performance of KAPs(Ph-PPh3)
as support materials can be attributed to its
special microporous structure and highly
dispersed PPh3 functional groups as seg-
ment of micropore backbone (the 3D model
shown in Figure S3 of the SI). To explore
the mechanism, similar heterogeneous cata-
lysts PS-PPh2-Pd (Table 1, entry 3, yield 63%)
and KAPs(Ph)-PPh3-Pd (Table 1, entry 4,
yield 99%) were employed in the reaction.
At the beginning of once control experiment
of PS-PPh2-Pd, the PS spheres turned black
rapidly, which indicated the formation of Pd
black and the deactivation of the catalyst. For
PS-PPh2-Pd (Scheme 1b), PPh2-Pd functional
groups were grafted on the walls of larger
inter-pore channels of the spheres (BJH pore
size is 413 Å shown in Table 1, the nitrogen
adsorption and desorption isotherms and pore
distribution shown in Figure S4 and S5 of the
SI) and the spacious meso-and macro-pores
are incapable of protecting Pd0 species[46]
generated during the reaction from aggrega-
tion and precipitation. As a result, low activity
was obtained with this catalyst and the cata-
lyst can not be reused (Figure S6 of the SI).
For the KAPs(Ph)-PPh3-Pd, which has PPh3
grafted on pre-made microporous KAPs(Ph)
(Scheme 1c), the activity of the first run was
Figure 2. Nitrogen adsorption (solid) and desorption (open) isotherms of: a) KAPs(Ph-PPh3)
and, b) KAP(Ph-PPh3)-Pd. Pore size distributions calculated using density functional theory
(DFT) methods (slit pore models, differential pore volumes, pore width) of: c) KAPs(Ph-PPh3)
and, d) KAP(Ph-PPh3)-Pd.
as high as that of KAPs(Ph-PPh3)-Pd, but it
KAPs(Ph-PPh3)-Pd containing 1.9 wt% P and 0.7 wt% Pd (see
SI for experimental details). Aryl chlorides were used as the
major substrates under investigation because of their challenge,
especially for heterogeneous catalysts.[32–34] As shown in Table 1,
using 0.6 mol% Pd with respect to chlorobenzene, KAPs(Ph-
PPh3)-Pd gave a 99% conversion within 3 h at 80 °C (Table 1,
entry 4). Generally speaking, the homogeneous catalysts would
show higher activity than their heterogeneous counterparts, but
KAPs(Ph-PPh3)-Pd presented obvious advantage over homo-
geneous catalysts, i.e., PdCl2 and PdCl2(PPh3)2 in the control
experiments (Table 1, entry 1, yield 13% and entry 2, yield 9%),
deactivated quickly in the second and third cycles (50% and 18%,
respectively) (Figure S6 of the SI). As shown in Table 1, the BET
surface area and pore volume of KAPs(Ph)-PPh3-Pd (especially in
macropore section) is obviously smaller than those of KAPs(Ph-
PPh3)-Pd (The nitrogen adsorption and desorption isotherms,
and pore distribution of KAPs(Ph)-PPh3-Pd shown in Figure S7
and S8 of the SI). In comparison with KAPs(Ph-PPh3) knitted by
one-step method, KAPs(Ph)-PPh3 synthesized by post-modifica-
tion is grafted more with PPh3 on the surface thus reducing the
diffusion due to pore blocking. The micropore on superficial
section isolate Pd0 species (generated during the reaction),[46]
T a b le 1 . The catalytic activity comparison of different solid catalysts.a)
Entry
Catalyst
PdCl2
Pd [wt%]
SBETb) [m2/g]
DPc) [Å]
VPd) [m3/g]
Yielde) [%]
1
2
3
4
5
–
–
–
–
–
–
13
9
PdCl2(PPh3)2
PS-PPh2-Pd
–
–
1.2
0.7
0.7
33
413
71
86
0.30
1.18
1.50
63
99
99
KAPs(Ph)-PPh3-Pd
KAPs(Ph-PPh3)-Pd
916
1025
a)Reaction conditions: 0.6 mol% Pd, 0.5 mmol of chlorobenzene, 0.75 mmol of phenylboronic acid, 1 mmol of K3PO4·3H2O, 2 mL of EtOH:H2O (3:2 v/v), 80 °C, 3 h,
under N2 atmosphere; b)Surface area calculated from nitrogen adsorption isotherms at 77.3 K using BET equation; c)Pore size calculated by Barrett–Joyner–Halenda (BJH)
adsorption mode; d)Pore volume calculated from nitrogen isotherm at P/P0 = 0.995, 77.3 K; e)Isolated yield.
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which avoids Pd0 aggregation, hence, KAPs(Ph)-PPh3-Pd exhibit
excellent activity at first control experiment. However, the Pd
bonded on the grafted PPh3 located in superficial section is not
tightly locked inside materials, hence, the Pd loss is unavoid-
able and even Pd black emerged after first run. Comparing with
PS-PPh2-Pd and KAPs(Ph)-PPh3-Pd, KAPs(Ph-PPh3)-Pd pos-
sesses microporous structure and highly dispersed Pd0 species
(Figure 1e, the XPS spectrum of KAPs(Ph-PPh3)-Pd catalyst after
5 runs shows that the Pd species were present in 0 state). The
knitting aryl network confines Pd inside each micropore alone
which prevents the aggregation of Pd0, as well as loss of Pd.
The TEM micrograph of KAPs(Ph-PPh3)-Pd after 5 runs does
not exhibit observable change compared with that of a fresh one
(Figure S9 of the SI). The Pd content in the filtrate after the first
reaction cycle is determined to be ca. 1.8 ppm, indicating 99%
Pd species are still on the solid catalyst at the end of the reac-
tion. In summary, our catalyst shows persistent excellent activity
for the Suzuki–Miyaura coupling of aryl chlorides under rela-
tively mild conditions and can be recycled. In addition, the solid
catalysts are highly stable in air and no decrease in activity was
observed after the catalyst was exposed to air for several days.
To expand the scope of substrates, we further examined
the catalyst KAPs(Ph-PPh3)-Pd in Suzuki–Miyaura coupling
reaction of various aryl chlorides (Table 2). At a Pd loading of
T a b le 2 . Suzuki–Miyaura coupling reaction catalyzed by KAPs(Ph-PPh3)-Pd.a)
Entry
1
Substrate 1
Substrate 2
Time [h]
3
Yieldb) [%]
99
16
4
84
97
84
2
3
6
4
5
4
88
99
10
6
7
8
4
4
91
87
12
1
65
97
9
10
11
12
13
14
1
98
2
95c)
97
4
6
73
a)0.6 mol% Pd, 0.5 mmol of aryl halide, 0.75 mmol of arylboronic acid, 1.5 mmol of K3PO4·3H2O, 2 mL of EtOH:H2O (3:2 v/v), 80 °C, under a N2 atmosphere; b)Isolated
yield; c)0.5 mmol of benzyl chloride was used.
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0.6 mol%, the solid catalyst produced biphenyl in 99% yield at
80 °C within 3 h (Table 2, entry 1). For aryl chlorides bearing
an electron-withdrawing group, such as –COCH3, –NO2, –CN,
KAPs(Ph-PPh3)-Pd gave good yields within 4–16 h (Table 2,
entries 2–6). It is noteworthy that sterically hindered aryl chlo-
rides with o-substituted –NO2 and –CN groups, also easily
converted with 84-99% yields (Table 2, entry 4 and entry 6). To
our delight, deactivated aryl chlorides with electron-donating
groups, such as –CH3 and –OCH3, also gave excellent yields
(Table 2, entries 7–9). More impressively, in the case of steri-
cally hindered and deactivated aryl chloride, i.e., 2-methylchlo-
robenzene, an 87% yield was achieved within 4 h (Table 2, entry
8). Furthermore, under the similar conditions, bromobenzene
and iodobenzene were almost completely converted within
1 h. Encouraged by the impressive results of our catalyst in
Suzuki–Miyaura coupling reactions of aryl chlorides and phe-
nylboronic acid, the catalytic activity towards the coupling of
benzyl chloride and phenylboronic acid were also examined.
The catalyst gave complete conversion and 95% selectivity of
diphenylmethane within 2 h, though the coupling of benzyl
chloride and phenylboronic acid remains a challenge, espe-
cially using heterogeneous catalysts,[39,47,48] which demonstrates
that KAPs(Ph-PPh3)-Pd has high activity for the coupling of
benzyl chloride and phenylboronic acid. We further tested
the catalytic performances for the couplings of various arylbo-
ronic acids with chlorobenzene (Table 2, entry 13 and 14). For
arylboronic acids bearing electron-donating group –CH3 and
electron-withdrawing group –CF3, 97% and 73% yields were
obtained, respectively. To determine whether the heterogeneous
or the dissolved homogeneous Pd species were the real cata-
lysts responsible for the reaction between aryl halide and phe-
nylboronic acid, the following strategy was adopted. When the
chlorobenzene conversion reached 57%, the reaction mixture
was filtered to remove the solid catalyst and then the mother
liquor was allowed to react for another 3 h under the similar
conditions.[49] No significant change in either the conversion or
the yield was observed, indicating that the active phase was not
the dissolved Pd species leached from the supports. Therefore
it is fair to conclude that the observed catalysis is really hetero-
geneous in nature.
To summarize, we report a ‘knitting’ strategy to prepare
Pd(II) organometallic catalysts immobilized on the triphe-
nylphosphine-functionalized KAPs(Ph-PPh3). The micro-
porous structure ensured the high dispersion of Pd active
sites and heterogeneous porous structure also improved
the diffusion of organic reactant molecules. As a result, the
KAPs(Ph-PPh3)-Pd exhibited excellent activity and selectivity
combined with the mild conditions and aqueous reaction
media for the Suzuki–Miyaura cross-coupling reaction of aryl
chlorides. The non-toxic aqueous media, mild reaction condi-
tions (80 °C), stability of the catalyst, and the facile synthesis
approach may eventually be helpful to use KAPs(Ph-PPh3)-
Pd on an industrial scale. This work also highlights that the
microporous polymers can not only play the role of support
materials, but also protect the catalyst and positively affect
the catalytic activity. In addition, we expect that the ‘knitting’
strategy will find extensive application, via the use of func-
tional KAPs materials, in other fields of research as well as in
catalytic applications.
Experimental Section
Synthesis of KAPs(Ph-PPh3) : FeCl3 (anhydrous 9.75 g, 0.06 mol) was
added to a solution of benzene (1.56 g, 0.02 mol), triphenylphosphine
(5.25 g, 0.02 mol), and formaldehyde dimethyl acetal (FDA, 4.56 g,
0.06 mol) in 20 mL 1,2-dichloroethane (DCE). The resulting mixture was
stirred at room temperature for good mixing, and then was stirred at
45 °C for 5 h to form original network, and then heated at 80 °C for 67 h
to react completely. The resulting precipitate was washed three times
with methanol, then washed with methanol in a Soxhlet for 24 h, and
finally dried under reduced pressure at 60 °C for 24 h.
Preparation of KAPs(Ph-PPh3)-Pd Catalyst: The palladium(II)
organometallic catalyst immobilized on the KAPs(Ph-PPh3) support
was prepared by coordinating palladium(II) ions with the PPh3 ligand.
Briefly, KAPs(Ph-PPh3) (1.0 g) was added to acetonitrile solution
(20 mL) containing PdCl2 (0.10 g, 0.56 mmol) and stirred under reflux at
80 °C for 12 h. The solid was centrifugally separated, washed repeatedly
with acetone, followed by Soxlet-extraction with acetone to remove
palladium(II) species that physisorbed on the support. The final catalyst
was dried at 60 °C under vacuum and the as-prepared catalyst was
denoted as KAPs(Ph-PPh3)-Pd. For comparison, the KAPs (Ph)-PPh3-Pd
was prepared in the same way.
Typical Procedure for Suzuki–Miyaura Coupling Reaction: The Suzuki–
Miyaura coupling reactions were carried out at 80 °C in a 10 mL reactor
under nitrogen atmosphere. In a typical run, a catalyst containing
0.6 mol% Pd, arylchloride (0.5 mmol), arylboronic acid (0.75 mmol),
and base (1.5 mmol) were added to solvent (2 mL, H2O:EtOH (2:3 v/v))
and allowed to react for definite time. Then the mixture was separated
quickly by centrifugation. The solid was extracted with copious ethyl
acetate and the liquid was concentrated. The product was obtained by
preparative thin-layer chromatography (TLC) using petroleum ether as
eluting solvent. Particularly, for the 2-cyanbiphenyl, a mixed solution of
ethyl acetate and petroleum ether (1:10 v/v) was used. Purity of products
was checked by NMR and yields are based on arylchlorides.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
We thank the Analysis and Testing Center, Huazhong University of
Science and Technology for their assistance in characterization of
materials. This work was financially supported by the program for New
Century Excellent Talents in University (NCET-10-0389), the program of
Scholarship Award for Excellent Doctoral Student granted by Ministry
of Education, Shanghai Tongji Gao Tingyao Environmental Science &
Technology Development Foundation (STGEF), Program for Changjiang
Scholars and Innovative Research Team in University (PCSIRT) and
National Natural Science Foundation of China (No. 20873047/20973068/
50973037/51173058).
Received: February 24, 2012
Published online: June 4, 2012
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