Pd@COF-QA: A phase transfer composite catalyst for aqueous Suzuki-Miyaura coupling reaction

Article abstract of DOI:10.1039/c9gc03718g

A Pd NP-loaded and paraffin-chain quaternary ammonium salt-decorated covalent organic framework, Pd@COF-QA, and its chitosan aerogel-based continuous flow-through reactor, which could be an excellent phase transfer catalyst to promote the aqueous Suzuki-Miyaura coupling reaction, is reported.

Full text of DOI:10.1039/c9gc03718g

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DOI: 10.1039/C9GC03718G
COMMUNICATION
Pd@COF-QA: A phase transfer composite catalyst for aqueous
Suzuki-Miyaura coupling reaction
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
a
a
Jian-Cheng Wang, ‡ Cong-Xue Liu, ‡ Xuan Kan, Xiao-Wei Wu, Jing-Lan Kan, Yu-Bin Dong *
DOI: 10.1039/x0xx00000x
A Pd NP loaded and paraffin-chain quaternary ammonium salt our group developed a series of MOF-based PTC catalytic
decorated covalent framework Pd@COF-QA and its chitosan systems which can well promote the organic transformations
2
0,21
aerogel-based continuous flow-through reactor, which can be an in aqueous phase.
As a promising alternative to MOFs, the
excellent phase transfer catalyst to promote aqueous Suzuki- covalent bond driven COFs should be more stable in aqueous
Miyaura coupling reaction, is reported.
phase, and their PTC behaviour is really worth pursuing.
Herein, we report a Pd NP loaded and N, N-dimethyldodecyl
ammonium bromide decorated COF. The obtained Pd@COF-
QA and its chitosan aerogel-based continuous flow-through
reactor can be an excellent phase transfer catalyst to promote
Suzuki-Miyaura coupling reaction in water under mild
conditions even at gram scale level.
As shown in Scheme 1, the quaternary ammonium salt
decorated dihydrazide (L-QA) was prepared from 2, 5-di-(4-
methoxycarbonylphenyl) toluene (A) via three steps. COF-QA
was synthesized as light-yellow crystalline solids through the
Schiff-base condensation between L-QA and 1,3,5-
triformylbenzene under solvothermal conditions (ESI†). The as-
synthesized COF-QA was characterized by FT-IR and solid-state
CP-MAS spectroscopies, and the formation of COF-QA from L-
QA and tribenzaldehyde was directly evidenced (ESI†).
Although covalent organic frameworks (COFs) being in their
1
early teens, as a typical class of organic crystalline porous
species, they have already been found to be the promising
2
3
functional materials in gas adsorption, separation, proton
4
5
6
conduction, optical devices, drug delivery, chemical
7
8
9
sensing, energy storage, and catalysis.
Taking their advantages of the tuneable and permanent
porosity and excellent chemical stability, a predestined ambit
for COFs could be the ideal carriers for loading active catalytic
species such as metal nanoparticles (M NPs) to fabricate
heterogeneous composite catalytic systems (M@COFs).
For example, palladium loaded COFs (Pd@COFs) have been
found to be highly efficient heterogeneous catalysts to
promote Suzuki−Miyaura coupling reaction,
of the most important class of C-C coupling reactions.
However, the most reported COF-catalysed coupling reactions
were performed at relatively high temperature and in organic
media such as toluene, p-xylene, methanol, ethanol, and DMF,
which did not meet the resource conservation and
1
0-12
1
3-17
which is one
1
8
As shown in Fig. 1, the collected PXRD data revealed that the
obtained COF-QA was crystalline and its structural modeling
was thus conducted with the software of Materials Studio (ver.
22
5
.0) (ESI†). The most probable structure of COF-QA was a
typical 2D layered hexagonal network with the space group of
. As shown in Fig. 1, COF-QA showed a main Bragg
environment-friendly
requirements.
Therefore,
the
P
3
development of COF-based green catalysts for Suzuki−Miyaura
coupling reaction is of great significance.
diffraction peak at 2.3°corresponding to the (100) plane, and
three weak peaks at 4.6°, 6.1° and 7.9°, and a broad peak
within the range of 17.5−26.2°. These observed peaks are
respectively associated with (200), (210), (220) and (002)
planes. The broad PXRD peaks, especially the (002) peak,
which should be caused by the long alkyl chains, which can
Phase-transfer catalysis (PTC) is a promising green technique
for organic transformation due to its simple operation,
1
9
aqueous medium and mild reaction conditions. Very recently,
2
3-25
disturb both the packing of layers and the size of unit cells.
a. College of Chemistry, Chemical Engineering and Materials Science, Collaborative
Innovation Center of Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education,
Shandong Normal University, Jinan 250014, P. R. China. Email:
yubindong@sdnu.edu.cn.
A Pawley refinement of COF-QA based on the experimental
PXRD and model PXRD patterns gave the fitting parameters of
Rwp = 1.88 and Rp = 1.46%, respectively. After Pawley
refinement, the unit cell parameters were determined as a = b
= 44.4, and c = 5.6 Å; α = β = 90°, and γ = 120° (ESI†).
b.
School of Chemical Engineering, Nanjing University of Science and Technology,
Nanjing, Jiangsu 210094, P. R. China.
†
These authors contributed equally.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C9GC03718G
COMMUNICATION
Scheme 1. Synthesis of ligand LA-QA, COF-Me and COF-QA. i) NBS, AIBN, CCl
dioxane/mesitylene/HOAc, 120C, 3 days. vii) and viii) Pd(OAc) /CH Cl
crystallographic c axis are shown. The sample photographs of COF-Me, COF-QA, Pd@COF-Me and Pd@COF-QA are inserted.
4
, 90C. ii) C14
H
31N, MeCN, 78C. iii) and iv) N
2
H
4
·H
2
O, MeOH, reflux. v) and vi) 1,4-
2
2
2
/24 h, TEA/50C/24h. Crystal packing patterns of COF-Me and COF-QA viewed down the
the in situ reduction processes but with the same crystal
structure based on their PXRD patterns (Fig. 2a-b, and ESI†). In
addition, the high-resolution transmission electron microscopy
(
HR-TEM) revealed that the loaded Pd NPs were well dispersed
in the COF-QA matrix with an average particle centred at ca.
.4 nm based on the statistic histogram for more than 100
2
randomly chosen particles and the atomic lattice fringes had
an interplanar spacing of 0.22 nm associated with the (111)
plane of the loaded Pd NPs (Figs. 2c-d). As indicated in Fig. 2e,
the oxidation state of the loaded Pd NPs in Pd@COF-QA were
found to be zero based on the Pd 3d binding energy at 335.05
Fig. 1 PXRD patterns of COF-QA (a) and COF-Me (b). The top and side views of
(
Pd-3d5/2) and 339.92 eV (Pd-3d3/2) in its measured X-ray
their structure are inserted.
1
0, 11
photoelectron spectroscopy (XPS),
implying that the in situ
reduction of palladium from Pd(II) to Pd(0) herein is successful.
The uniform texture of Pd@COF-QA was further confirmed by
SEM-EDX mapping, which showed a homogeneous distribution
of Pd, N, and C elements in the COF matrix (Fig. 2f). Inductively
coupled plasma (ICP) analysis indicated that the Pd loading
amount in Pd@COF-QA was 9.2 wt% (ESI†).
As indicated in Scheme 1, Pd@COF-QA was prepared as
deep brown crystalline solids by solution impregnating and in
situ reduction process, in which the unreacted free end
formamide groups on COF-QA acted as the reducing reagent
(ESI†).
Scanning Electronic Microscopy (SEM) measurement showed
Thermogravimetric analysis (TGA) trace indicated that
Pd@COF-QA remained intact till temperature over 200°C,
that most of the larger particles of COF-QA were broken into
smaller pieces in Pd@COF-QA after the palladium loading and
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suggesting its good thermal stability (ESI†). As we know, the Table 1. Optimization of reaction conditions for the model Suzuki-VMieiwyaAurrtaiclceoOupnlliinneg
common molecular quaternary ammonium salts are generally reaction in water a
DOI: 10.1039/C9GC03718G
2
0
stable up to ca. 100ºC. Notably, after covalently grafting on
COF framework, their thermal stability was largely enhanced,
which would effectively expand their application temperature
range, and make them more suitable to catalyse organic
reactions at relative higher temperature.
b
entry
catalyst
base
TEA
TEA
TEA
TEA
TEA
T (C)/t (h)
25/1
Yield (%)
1
2
Pd@COF-QA
Pd@COF-QA
Pd@COF-QA
Pd@COF-QA
Pd@COF-QA
Pd@COF-QA
Pd@COF-QA
Pd/C
32
61
81
88
>99
58
66
13
79
82
The porosity difference before and after Pd NP loading was
35/1
demonstrated
measurement.
by
the
gas
adsorption-desorption
3
50/1
N
2
absorption amount of COF-QA and
3
−1
Pd@COF-QA at 77 K is 61.9 and 47.0 cm g , respectively.
4
50/3
Their corresponding surface areas calculated on basis of the
5
50/6
50/6
2
−1
BET model are 59.0 (COF-QA), 26.0 (Pd@COF-QA) m g ,
respectively. The decreased N adsorption and the reduced
6
2 3
K CO
2
surface area in Pd@COF-QA were obviously caused by the Pd
NP loading. The pore sizes distribution curves, generated from
Barrett-Joyner-Halenda analysis, showed that COF-QA and
Pd@COF-QA having the major contribution of the pore widths
at ca. 3.8 and 3.4 nm, respectively, which is well consistent
with their simulated structure.
7
2
Na CO
50/6
3
8
TEA
50/6
9
Pd@COF-Me
Pd@COF-Et
TEA
TEA
50/6
10c
50/6
a
Reaction condition: I-Ph (0.2 mmol), phenylboronic acid (0.24 mmol), base (0.4
b
mmol), catalyst (1.7 mol % Pd equiv), H
2
O (2.0 mL), in air. Determined by GC
c
(
ESI†). Reaction condition: I-Ph (0.2 mmol), phenylboronic acid (0.24 mmol),
2
base (0.4 mmol), catalyst (3.4 mol % Pd equiv), H O (2.0 mL), in air.
As shown in Table 1, the influence of different temperature,
time and base were examined for the model coupling reaction
in water. When triethylamine (TEA) was employed, the
coupling yield increased along with the reaction temperature
(Table 1, entries 1–3) and time (Table 1, entries 3–5) increase.
The best results were observed when the reaction was
conducted at 50 C for 6h in water, giving the desired diphenyl
in 99% yield (Table 1, entry 5). In addition, when the reaction
2 3 2 3
was carried out with inorganic base such as K CO or Na CO ,
the coupled product was obtained in much lower yields under
the given conditions (Table 1, entries 6 and 7). Worth
mentioning, when the reaction was carried out with
commercialized Pd/C under the optimal conditions, the
desired product was obtained in only 13% yield (Table 1, entry
8
).
The heterogeneous nature of Pd@COF-QA was well
demonstrated by the leaching test (ESI†), and no further
reaction took place without Pd@COF-QA after triggering of
the coupling reaction at 1.5 h. In addition, Pd@COF-QA could
be easily recovered by centrifugation and directly reused in the
next catalytic run under the same PTC conditions. As shown in
Fig. 3a, still 90% yield was observed after ten runs. The
structural integrity and morphology of Pd@COF-QA were well
preserved after multiple catalytic runs, which was well
Fig. 2 a) and b) SEM images of COF-QA and Pd@COF-QA. c) HRTEM image of
Pd@COF-QA. d) Pd NP size distribution in Pd@COF-QA. e) XPS spectrum of the supported by its PXRD pattern and SEM image (ESI†). HR-TEM
Pd 3d in COF-QA. f) SEM-EDX spectrum of Pd@COF-QA.
image indicated that the loaded Pd species was still equally
distributed (ESI†), and the XPS spectrum showed that less than
We expected that the Pd@COF-QA with PTC functionality
2
3
0% of Pd(0) changed to Pd(II) after ten catalytic cycles (Fig.
b). Notably, the average size of Pd NPs was ca. 2.50 nm in
herein could bypass those adverse issues such as organic
solvents or relatively high temperature in the reported Suzuki-
Miyaura coupling reaction. For this, its catalytic activity was
diameter based on more than 100 randomly chosen particles,
indicating that basically no Pd NPs aggregation occurred over
multiple recycles (Fig. 3c). In addition, ICP analysis showed the
encapsulated Pd species amount was ca. 8.7 wt%, indicating
preliminarily examined by the PhI and PhB(OH)
water.
2
coupling in
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only ca. 5% Pd loss after ten catalytic runs. Therefore, COF-QA
herein is an ideal support to load Pd NP for heterogeneous
catalysis.
6
7
8
9
R
1
= 4-CO
2
CH
3
, X = I
R
2
= H
f: 90
8.8
View Article Online
DOI: 10.1039/C9GC03718G
R1 = 4-CN, X= I
R1 = H, X = I
R1 = H, X = I
R1 = H, X = Br
R2 = H
R2 = 3-OH
R2 = 4-CN
R2 = H
g: 98
h: 83
g: 92
a: 99
i: 97
9.6
8.1
9.0
9.7
9.5
8.4
9.4
9.1
9.0
9.0
9.4
9.3
9.4
9.7
9.0
9.6
9.7
9.3
6.1
6.2
4.1
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
1
1
1
1
1
1
1
1
1
2
2
2
2
R1 = 2-CN, X = Br
R = 2-OCH , X = Br
R2 = H
1
3
R2 = H
b: 86
j: 96
R = 2-NO , X= Br
1
2
R2 = H
R = 3-OCH , X = Br
1
3
R2 = H
k: 93
l: 92
R = 3-NH , X = Br
1
2
R2 = H
R1 = 3-OH, X = Br
R1 = 3-COOH, X = Br
R = 4-NO , X = Br
R2 = H
h: 92
m: 96
e: 95
n: 96
f: 99
o: 92
g: 98
a: 99
d: 95
p: 62
n: 63
g: 42
R2 = H
1
2
R2 = H
R1 = H, X = Br
R2 = 4-CHO
R = 4-CO CH
3
R1 = H, X= Br
R1 = H, X = Br
R1 = H, X = Br
R1 = H, X = Cl
2
2
R2 = 4-OH
R2 = 4-CN
R2 = H
Fig. 3 a) Catalytic cycle. b) XPS spectrum for Pd species in Pd@COF-QA after ten
catalytic runs, and trace amount of Pd(0) was oxidized to Pd(II) during the
multiple catalytic cycles. c) Pd NP size distribution in Pd@COF-QA after ten
catalytic runs.
24
R
= 3-NO
2
, X = Cl
2
R = H
1
2
2
2
5
6
7
R = 4-OCH , X = Cl
R2 = H
R2= H
R2 = H
1
3
With the optimized conditions in hand, we then investigated
the scope of the Pd@-COF-QA-catalyzed Suzuki-Miyaura
coupling utilizing various substituted halobenzene and
phenylboronic acids (Table 2, entries 1-27). Under the
optimized PTC conditions, the excellent catalytic activity of
R1 = 4-CHO, X = Cl
R1 = 4-CN, X = Cl
a
Reaction condition: PhX (0.2 mmol), PhB(OH)
Pd@COF-QA (1.7 mol % Pd equiv), H
Pd@COF-QA was observed for the various substituted GC (ESI†). TOF = conversion (mmol of substrate/mmol of cat., h).
2
(0.24 mmol), TEA (0.4 mmol),
O (2.0 mL), 50 C, 6h, in air. b Determined by
2
C
iodobenzene and bromobenzene with substituted phenylbonic
acids regardless of electron-withdrawing or electron-donating
groups at different substituted positions (Table 2, entries 1, 3- based coupling reactions, the chlorobenzene-based coupling
, 9-11, 13–22, 90–99%) except -OMe substituted iodobenzene reaction is more significant due to its much lower production
Table 2, entry 2, 85%), bromobenzene (Table 2, entry 12, 86%) cost. Up to now, some attractive Pd loaded and COFs or MOFs
and -OH substituted phenylboronic acid (Table, entry 8, 83%). or POPs based heterogeneous catalysts for the PhCl-PhB(OH)
In comparison with the iodobenzene or bromobenzene-
7
(
2
It is noteworthy to point out that the Pd@COF-QA herein aqueous Suzuki-Miyaura coupling reaction has been reported.
exhibited excellent catalytic behavior for the chlorobenzene- As indicated in Table 3, only a handful catalysts exhibited high
(
Table 2, entry 23, 99%) and 3-nitrochlorobenzene- catalytic activity for PhCl-PhB(OH)
2
coupling but at higher
, -OMe, -CHO temperature or with prolonged reaction time.2
6-30
Therefore,
phenylboronic acid coupling in water. For -NO
2
and -CN substituted chlorobenzenes, it showed less catalytic Pd@COF-QA herein could be a valuable alternative to the
activity and provided the coupling yields in the range of 42-63% heterogeneous catalysts for the aqueous chlorobenzene-based
(
Table 2, entries 25-27).
Suzuki-Miyaura coupling reaction. The catalytic performance
of Pd@COF-QA herein in water is even comparable to those
reported MOF- and COF-based catalysts in organic media
Table 2. Substrate scope for Pd@-COF-QA-catalyzed Suzuki-Miyaura coupling reaction a
(ESI†).
Table 3. Summary of the reported Pd loaded COFs, MOFs and POPs-based catalysts for
PhCl-PhB(OH) Suzuki-Miyaura coupling reaction in water
2
-1 c
Entry
PhX
PhB(OH)
2
Yield b (%)
a: 99
TOF[h ]
catalyst
base
T (C)
t (h)
yield (%)
Ref.
1
2
3
4
5
R
1
=H, X=I
R
2
R
2
R
2
R
2
= H
= H
= H
= H
9.7
Pd/MIL-101
Pd/Y-MOF
NaOMe
K2CO3
80
80
80
20
8
99
22
99
26
27
28
R
1
= 2-OCH
= 2-CF , X = I
= 3-NO , X = I
R = 4-NO , X = I
3
, X = I
b: 85
8.3
R
1
3
c: 93
9.1
Pd@MIL-101Cr-NH
2
K
K
K
2
CO
2
CO
2
CO
3
3
3
6
R
1
2
d: 99
9.7
Pd/TATAE
Ru-CP-Pd
75
90
50
5
8
6
65
23
99
29
30
R2 = H
e: 98
9.6
1
2
Pd@COF-QA
TEA
This work
4
| J. Name., 2012, 00, 1-3
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mmol), phenylboronic acid (1.3 g, 10.6 VmiewmAortilc)le Oanlninde
For better demonstrating the PTC functionality of Pd@COF- triethylamine (1.8 g, 17.8 mmol) was pu
D
m
O
p
I:
e
1
d
0.1
t
0
h
3
r
9
o
/
u
C
g
9
h
GC
a
0
p
37ie18
ce
G
QA in this Pd-catalyzed aqueous coupling reaction, the COF- of Pd@COF-QA@chitosan aerogel monolith (150 mg, 60 wt%
Me COF without quaternary ammonium salt and its Pd NP of Pd@COF-QA, 1.7 mol % Pd equiv) using a peristaltic pump
loaded Pd@COF-Me were prepared under the same at a flow rate of 1.0 mL/min. The desired biphenyl product was
solvothermal conditions (Scheme 1, ESI†). The different obtained in 88 % yield within ca. 8h. The Pd@COF-
functional decoration on COF-Me resulted in a different Pd QA@chitosan aerogel monolith herein is very stable toward
loading amount and particle size. Only 3.3 wt% of Pd NPs with water and common polar organic solvent, and it can be reused
ca. 3 nm in diameter were found in Pd@COF-Me (ESI†). As three times with almost no yield drop (ESI†).
shown in Fig. 1, the obtained COF-Me featured the same 2D
In conclusion, we have developed the paraffin-chain
structure as that of COF-QA but with the different interlayer quaternary ammonium salt decorated and Pd NP loaded COF-
distance due to the different substituted groups on the COF based composite catalytic system via in situ reduction
2
framework. Correspondingly, the N adsorption absorption approach. The obtained Pd@COF-QA can be a highly active
amount at 77 K of COF-Me and Pd@COF-Me is 143.4 and phase transfer catalyst to promote aqueous Suzuki–Miyaura
3
2
1
33.4 cm /g with the surface area of 222.0 and 143.0 m /g, coupling reaction under mild reaction conditions, especially for
respectively. Their pore sizes, calculated from Barrett-Joyner- PhCl-PhB(OH)2 coupling. The concept of COF-based
Halenda analysis, respectively centred at 3.8 (COF-Me) and 3.7 multifunctional integration leads the carbon-carbon coupling
nm (Pd@COF-Me) (ESI†), which is well agreement with their synthesis to be economical, eco-friendly, and source saving.
crystal structures.
The PTC catalytic activity of Pd@COF-Me was examined for the fabrication of many more practical multifunctional
based on the PhI-PhB(OH) model coupling reaction under the composite catalytic materials for a variety of green chemical
optimized conditions (H O, 1.7 mol% Pd equiv, 50C, 6h, in air). transformations.
We believe this approach to be general, effective and viable
2
2
As shown in Table 1 (entry 9), the desired diphenyl product
was obtained in only 79% yield (ESI†), which is obviously lower
than that of Pd@COF-QA case. Therefore, the positive charged
Pd@COF-QA might be more suitable for Pd NPs loading and
distribution besides PTC function.
Acknowledgements
We are grateful for financial support from NSFC (Grants
21971153, 21671122 and 21802090), Shandong Provincial
It is well known that the phase transfer catalysts with longer Natural Science Foundation (Grant ZR2018BB006), a Project of
paraffin chains are more efficient due to their larger extraction the Shandong Province Higher Educational Science and
constant.31 To verify this, Pd@COF-Et with shorter chain Technology Program (J18KA066), and the Taishan Scholar’s
quaternary ammonium salt was synthesized and used to Construction Project.
2
catalyse the PhI-PhB(OH) model coupling reaction under the
given conditions (Table 1, entry 10). As expected, the coupling
product was gotten in relatively low 81% yield (ESI†), which
illustrated that the longer alkyl chains are necessary for PTC.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
2
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Fig. 4 Reaction time examination and schematic representation of Pd@COF-
QA@chitosan aerogel reactor based gram scale Suzuki-Miyaura coupling
2
reaction between PhCl and PhB(OH) in water.
8
355.
7
8
9
S. Dalapati, E. Jin, M. Addicoat, T. Heine and D. Jiang, J. Am.
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For practical application, the gram scale coupling reaction
between PhCl and PhB(OH) was carried out based on a
continuous flow-through reactor equipped with Pd@COF-
QA@chitosan aerogel catalyzing column (ESI†). As shown in Fig.
2
4
, an aqueous solution (80 mL) of chlorobenzene (1.0 g, 8.9
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View Article Online
DOI: 10.1039/C9GC03718G
A Pd NP loaded and N, N-dimethyldodecyl ammonium bromide decorated Pd@COF-QA and its continuous flow-through reactor was
prepared. The obtained COF-based catalyst can highly promote the Suzuki–Miyaura coupling reaction in water under mild conditions
even at gram scale level.
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