Immobilization of palladium(II)-containing bis(imidazolium) ligand on ion-exchange resins: Efficient and reusable catalysts for C-C coupling reactions

Article abstract of DOI:10.1002/aoc.3297

Suzuki reactions catalysed by a palladium(II) complex of a functionalized bis(imidazolium) ligand, Pd^II(BIM), immobilized on Dowex 50 WX8 and Amberlite IR-120 ion-exchange resins as heterogeneous, recyclable and active catalysts are reported. The catalysts, Pd^II(BIM)@Amberlite IR-120 and Pd^II(BIM)@Dowex 50 WX8, were characterized using Fourier transform infrared and diffuse-reflectance UV-visible spectroscopies and scanning electron microscopy. These heterogeneous catalysts are oxygen-insensitive and air- and moisture-stable in C-C coupling reactions, and are reusable several times without significant loss of their catalytic activity.

Full text of DOI:10.1002/aoc.3297

Full Paper
Received: 6 December 2014
Revised: 22 January 2015
Accepted: 22 January 2015
Published online in Wiley Online Library: 23 March 2015
(wileyonlinelibrary.com) DOI 10.1002/aoc.3297
Immobilization of palladium(II)-containing bis
imidazolium) ligand on ion-exchange resins:
(
efficient and reusable catalysts for C–C
coupling reactions
Zari Pahlevanneshan, Majid Moghadam*, Valiollah Mirkhani*,
Shahram Tangestaninejad, Iraj Mohammadpoor-Baltork
and Ahmad R. Khosropour
II
Suzuki reactions catalysed by a palladium(II) complex of a functionalized bis(imidazolium) ligand, Pd (BIM), immobilized on
Dowex 50 WX8 and Amberlite IR-120 ion-exchange resins as heterogeneous, recyclable and active catalysts are reported. The
II
II
catalysts, Pd (BIM)@Amberlite IR-120 and Pd (BIM)@Dowex 50 WX8, were characterized using Fourier transform infrared and
diffuse-reflectance UV–visible spectroscopies and scanning electron microscopy. These heterogeneous catalysts are oxygen-
insensitive and air- and moisture-stable in C–C coupling reactions, and are reusable several times without significant loss of their
catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.
Keywords: palladium(II) complex; heterogeneous catalyst; ion-exchange resins; C–C coupling reactions; aryl halides
and reuse of the catalyst are most important. A large number of ma-
terials including activated carbon, silica gel, polymers containing
Introduction
C–C cross-coupling reactions catalysed by palladium are the
most widely used carbon–carbon bond-forming tools for the
synthesis of various unsaturated structures, many of which are
important intermediates in natural product synthesis and in the
covalently bound ligands, metal oxides, porous aluminosilicates,
clays and other inorganic materials, and microporous and mesopo-
rous supports have been used for immobilization of Pd
[
35–43]
compounds.
[
1–7]
production of fine chemicals.
In these cross-coupling reac-
Ion-exchange resins are commercial products commonly
available in the form of small beads (16–400 mesh, 38–1180 μm in
diameter) or as membranes. Shape and size allow these materials
to be easily and quantitatively recovered by simple filtration or
decantation. This is not the case for other powdered materials often
used as catalyst supports (e.g. zeolites and carbon). When the
particle size is about 1 μm or less, they might not settle in the
solution within a short time, and it would be very difficult to collect
them for recycling. The separation of the catalyst thus requires
centrifugation or ultrafiltration.
tions, two molecules are assembled on the metal via the forma-
tion of a metal–carbon bond. The catalytic steps contain
[
8]
oxidative addition, transmetalation and reductive elimination. In
this way, the carbon atoms bound to palladium are brought very
close to one another. In the next step, they couple to one another
and this leads to the formation of a new carbon–carbon single
bond. Palladium is probably the most versatile metal in promoting
or catalysing reactions involving C–C, C–N and C–S bond formation
due to its excellent catalytic efficiency in these types of reactions.
Suzuki cross-coupling represents a powerful method for C–C bond
In continuation of our interest in the application of palladium-
[9–22]
[44,45]
formation.
Construction of biaryl compounds via palladium-
based catalysts,
here we report the preparation and characteri-
catalysed Suzuki reactions is an interesting area in organic synthe-
sis. The products of Suzuki reactions (biaryl units) are important mo-
lecular components in pharmaceuticals, herbicides and natural
products, as well as in engineering materials such as conducting
zation of an oxygen-insensitive, air- and moisture-stable palladium(II)
complex of a functionalized bis(imidazolium) ligand, Pd (BIM),
immobilized on Dowex 50 WX8 and Amberlite IR-120 ion-exchange
resins. The catalytic activities of these heterogeneous and recyclable
catalysts were investigated in Suzuki C–C coupling reactions
(Scheme 1).
II
[
23–32]
polymers, molecular wires and liquid crystals.
Homogenous
palladium catalysts used in Suzuki reactions cannot be recovered
from reaction media. The use of heterogeneous catalysts in organic
synthesis has now become a common practice, especially following
[33,34]
the rapid development of combinatorial chemistry.
Solid-
* Correspondence to: Majid Moghadam and Valiollah Mirkhani, Department of
Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441, Iran.
E-mail: moghadamm@sci.ui.ac.ir; mirkhani@sci.ui.ac.ir
supported palladium complexes having high activity and selectivity
offer several significant practical advantages in synthetic and
industrial chemistry, among which the ease of separation of the cat-
alyst from the desired reaction products and the ease of recovery
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan
81746-73441, Iran
Appl. Organometal. Chem. 2015, 29, 346–352
Copyright © 2015 John Wiley & Sons, Ltd.

Suzuki-miyaura reaction catalyzed by supported Pd catalysts
Scheme 1. Suzuki–Miyaura cross-coupling reaction catalysed by supported
II
Pd (BIM).
Experimental
General Remarks
All reagents were of analytical grade and used without further
purification. The chemicals used in this work were purchased from
Merck, Fluka and Sigma-Aldrich. FT-IR spectra were recorded with a
1
Jasco 6300 spectrophotometer. H NMR (400 MHz) spectra were
recorded with a Bruker-Avance 400 MHz spectrometer using
II
II
Figure 1. FT-IR spectra of (a) Dowex 50 WX8, (b) Pd (BIM) and (c) Pd (BIM)
@Dowex 50 WX8.
DMSO-d as solvent. The morphological features were investigated
6
using a Hitachi S-4700 field emission scanning electron microscopy
(SEM) instrument. The Pd content of the catalysts was determined
using a PerkinElmer inductively coupled plasma (ICP) analyser. Sub-
stances were identified and quantified using gas chromatography
(GC) with an Agilent GC 6890 equipped with a 19096C006 80/100
WHP packed column and a flame ionization detector. Diffuse
reflectance UV–visible (DR UV-Vis) spectra were recorded with a
II
Jasco V-670 spectrophotometer. Pd (BIM)was prepared according
[
38]
to a literature method.
II
Immobilization of Pd (BIM) on Amberlite IR-120 and Dowex 50
WX8
The commercial cation-exchange resin Dowex 50 WX8 (5g) was
first washed with aqueous Na CO (5%, w/v) and then sequentially
2 3
with water, methanol and acetone, and dried under vacuum.
II
Pd (BIM) (500 mg) was dissolved in a minimum volume of DMSO
and was added to an acetone–water (1:1, 50ml) solution. The reac-
II
II
Figure 2. FT-IR spectra of (a) Amberlite IR-120, (b) Pd (BIM) and (c) Pd (BIM)
Amberlite IR-120.
@
tion mixture was stirred at 80 °C for 24h. At the end of the reaction,
II
the catalyst, Pd (BIM)@Dowex 50 WX8, was filtered, washed with
DMSO, acetone and water, and dried under vacuum. The same
II
method was used for the preparation of Pd (BIM)@Amberlite
IR-120. The prepared catalysts were characterized using ICP, SEM
and DR UV-Vis and FT-IR spectroscopies.
II
Figure 3. DR UV-Vis spectrum of Pd (BIM).
General Procedure for Suzuki–Miyaura Cross-Coupling Reac-
tion of Aryl Halides With Phenylboronic Acid in the Presence of
II
II
Pd (BIM)@Amberlite IR-120 and Pd (BIM)@Dowex 50 WX8
Catalysts
2 3
A mixture of aryl halide (1mmol), arylboronic acid (1.5 mmol), K CO
II
Scheme 2. Preparation route for the catalysts.
(207 mg, 1.5 mmol) and catalyst (0.46 mol% for Pd (BIM)@Dowex 50
Appl. Organometal. Chem. 2015, 29, 346–352
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Z. Pahlevanneshan et al.
II
Figure 5. DR UV-Vis spectra of (A) Amberlite IR-120 and (B) Pd (BIM)
@Amberlite IR-120.
negatively charged ligands at the Pd(II) centre balanced by the
[46]
positive charges on the pendant imidazolium groups. Therefore,
this complex can be immobilized on negatively charged Amberlite
IR-120 and Dowex 50 WX8 ion-exchange resins. The prepared
catalysts were characterized using FT-IR and DR UV-Vis spectros-
copies, elemental analysis and SEM.
II
Figure 4. DR UV-Vis spectra of (A) Dowex 50 WX8 and (B) Pd (BIM)@Dowex
0 WX8.
5
II
II
The parent Pd (BIM) shows the characteristic CO vibrational
WX8 and 0.55 mol% for Pd (BIM)@Amberlite IR-120) in 3 ml of
DMF–H O (2:1) was stirred at 100 °C under air atmosphere. The
progress of the reaction was monitored using GC. After comple-
tion of the reaction, ethyl acetate (15 ml) was added and the cat-
alysts were filtered. The organic phase was washed with H
2 × 10 ml), dried over anhydrous MgSO and evaporated. The
À1
bands at 1585 and 1564 cm . These bands appear in the FT-IR
2
II
II
spectra of Pd (BIM)@Dowex 50 WX8 and Pd (BIM)@Amberlite
II
IR-120 which proves the supporting of Pd (BIM) on the resins
(Figs. 1 and 2).
2
O
The homogeneous catalyst shows four absorption bands at 385,
(
4
341, 269 and 217 nm (Fig. 3). Dowex 50 WX8 has two absorption
residue was recrystallized from ethyl acetate and ether (1:3) to
afford the pure product.
bands at 321 and 269 nm (Fig. 4(A)) while for Amberlite IR-120 these
two absorption bands appear at 328 and 264 nm (Fig. 5(A)). Both
catalysts show the characteristic bands of homogeneous catalyst
Catalyst Recovery
II
and also the support. In the DR UV-Vis spectrum of Pd (BIM)@Dowex
The Suzuki reaction of 4-iodoanisole (1mmol) with phenylboronic
acid was chosen as model reaction. At the end of each reaction,
the catalysts were filtered and the filtrates were used for determina-
tion of Pd leached. The amount of Pd leached was measured using
ICP optical emission spectrometry (detection limit of 2 ppb).
50 WX8,the absorption bands appear at 394, 333, 259 and 220 nm
(Fig. 4(B)) while for Pd (BIM)@Amberlite IR-120, these bands appear
II
at 382, 327, 267 and 220 nm (Fig. 5(B)). These observations clearly
II
confirm the presence of Pd (BIM) complex on Amberlite IR-120
and Dowex 50 WX8.
The SEM images of Dowex and Pd (BIM)@Dowex 50 WX8 show
II
that some microspheres are broken upon immobilization of the
Pd complex on Dowex 50 WX8 (Fig. 6). The same SEM results
are obtained for Pd (BIM)@Amberlite IR-120 catalyst but the
Results and Discussion
II
II
II
Characterization of Pd (BIM)@Amberlite IR-120 and Pd (BIM)
Dowex 50 WX8
particles preserve their microsphere nature (Fig. 7). The Pd
@
II
II
content of Pd (BIM)@Dowex 50 WX8 and Pd (BIM)@Amberlite
À1
The preparation route for the catalysts is shown in Scheme 2. As can
be seen, the palladium complex is a zwitterionic complex, with the
IR-120, determined using ICP analysis, is 0.234 and 0.156 mmol g
respectively.
,
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Appl. Organometal. Chem. 2015, 29, 346–352

Suzuki-miyaura reaction catalyzed by supported Pd catalysts
II
Figure 6. SEM images of (a) Dowex 50 WX8 and (b) Pd (BIM)@Dowex
50 WX8.
II
Figure 7. SEM images of (a) Amberlite IR-120 and (b) Pd (BIM)@Amberlite
IR-120.
II
The thermal stability of Pd (BIM)@Dowex 50 WX8 was also stud-
ied. As can be seen, the supported catalyst is stable up to 621 °C
Fig. 8).
(
Suzuki–Miyaura Cross-Coupling of Aryl Halides With
II
Phenylboronic Acid in the Presence of Pd (BIM)@Amberlite
II
IR-120 and Pd (BIM)@Dowex 50 WX8
The catalytic activity of both catalysts was investigated in the Suzuki
C–C coupling reaction of aryl halides with phenylboronic acid. In
this manner, the reaction parameters such as kind of base and
solvent, temperature and catalyst amount were optimized in the
coupling of 4-iodoanisole (1mmol) with phenylboronic acid
(1.5 mmol). The progress of the reaction was monitored using GC.
The results are summarized in Table 1. In the optimization of the
amount of catalyst, the best results are obtained using 0.0055 and
II
II
0
.0046 mmol of Pd (BIM)@Amberlite IR-120 and Pd (BIM)@Dowex
5
0 WX8, respectively (Table 1, entries 1–5). This coupling reaction
Figure 8. Thermogravimetry–differential themogravimetry curves of
Pd (BIM)@Dowex 50 WX8.
II
is found to be highly sensitive to the reaction temperature. A
Appl. Organometal. Chem. 2015, 29, 346–352
Copyright © 2015 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

Z. Pahlevanneshan et al.
II
a
Table 1. Optimization of conditions in the Suzuki reaction of 4-iodoanisole and phenylboronic acid catalysed by supported Pd (BIM)
b
Entry
Catalyst, mg (mol% Pd)
Pd (BIM)@Dowex Pd (BIM)@Amberlite Base
Temperature (°C)
Yield (%)
II
II
II
II
II
II
Solvent
Pd (BIM) Pd (BIM)
Pd (BIM)@Dowex Pd (BIM)@Amberlite
50 WX8 IR-120
@Dowex @Amberlite
50 WX8 after
90 min
IR-120 after 120 min
50 WX8
IR-120
1
2
3
4
5
6
7
8
9
0
0
K
K
K
K
K
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
DMF–H
2
2
2
2
2
2
2
2
2
O (2:1)
100
100
100
100
100
r.t.
100
0
25
70
96
96
15
58
70
96
50
72
64
45
47
75
30
5
0
32
64
98
98
19
33
55
98
66
74
60
43
52
72
28
4
4 (0.075)
15 (0.36)
20 (0.46)
30 (0.67)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
20 (0.46)
17 (0.26)
30 (0.47)
35 (0.55)
43 (0.67)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
35 (0.55)
3
DMF–H
DMF–H
DMF–H
DMF–H
DMF–H
DMF–H
DMF–H
DMF–H
O (2:1)
O (2:1)
O (2:1)
O (2:1)
O (2:1)
O (2:1)
O (2:1)
O (2:1)
100
100
100
100
3
3
3
3
r.t.
3
60
60
90
3
80
3
120
130
10
11
12
13
14
15
16
17
3
MeOH–H
EtOH–H O (2:1)
MeCN–H O (2:1)
Toluene–H O (2:1)
THF–H O (2:1)
2
O (2:1)
Reflux
Reflux
Reflux
Reflux
Reflux
100
Reflux
Reflux
Reflux
Reflux
Reflux
100
3
2
3
2
3
2
3
2
Na
NEt
3
PO
4
DMF–H
DMF–H
DMF–H
2
2
2
O (2:1)
O (2:1)
O (2:1)
3
100
100
No base
100
100
a
Reaction conditions: 4-iodoanisole (1 mmol), phenylboronic acid (1.5 mmol), base (1.5 mmol), solvent (3 ml) under air atmosphere.
b
Isolated yield.
II
II
a
Table 2. Suzuki cross-coupling reaction of aryl halides and phenylboronic acid catalysed by Pd (BIM)@Amberlite IR-120 and Pd (BIM)@Dowex 50 WX8
II
b
II
c
Entry
R
X
Pd (BIM)@Dowex 50 WX8
Pd (BIM)@Amberlite IR-120
d
d
Time (min)
Yield (%)
TON
Time (min)
Yield (%)
TON
180
1
2
3
4
5
6
7
8
9
H
I
I
I
I
85
86
98
96
96
93
96
86
89
88
87
80
81
79
213.04
208.69
208.69
202.17
208.69
186.90
193.47
191.3
110
118
120
108
135
140
132
128
147
140
151
145
99
97
98
97
95
96
95
97
89
89
83
85
4-Me
176.36
178.18
176.36
172.72
174.54
172.72
176.36
161.81
161.81
150.90
154.54
4-MeO
90
4-NO
H
2
82
Br
106
110
95
4-MeO
Br
Br
Br
Cl
Cl
Cl
Cl
4-NO
4-Ac
H
2
90
118
112
120
115
189.13
173.91
176.08
171.73
10
11
12
4-Ac
4-MeO
4-NO
2
a
Reaction conditions: aryl halide (1 mmol), phenylboronic acid (1.5 mmol), K
CO
2 3
2
(1.5 mmol), DMF–H O (2:1, 3 ml) under air.
b
100°C, catalyst (0.46 mol% Pd).
c
1
00°C, catalyst (0.55 mol% Pd).
d
Isolated yield.
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Suzuki-miyaura reaction catalyzed by supported Pd catalysts
II
Table 3. Recycling and reuse of Pd (BIM)@Amberlite IR-120 and
groups react efficiently with phenylboronic acid and the desired
cross-coupling products are obtained in high yields. The results
show that the electronic properties of the substituents on the
aromatic rings of starting materials have no significant influence
on the reaction. As expected, aryl iodides are found to be more
reactive than aryl bromides and chlorides.
II
Pd (BIM)@Dowex 50 WX8 in the Suzuki reaction of 4-iodoanisole
a
(1 mmol) with phenylboronic acid
II
The catalytic activity of homogeneous Pd (BIM) was also investi-
gated in the model reaction. The results show that in the reaction
involving 4-iodoanisole (1mmol), phenylboronic acid (1.5mmol),
II
K CO (1.5 mmol) and Pd (BIM) (0.32 mol% Pd) in DMF–H O (2:1,
2
3
2
3
ml) at 100 °C under air, the amount of desired product is 100% af-
II
ter 15 min. The main disadvantage of homogeneous Pd (BIM) is its
solubility in the reaction mixture meaning it cannot be recovered
and reused.
Entry
Catalyst
II
b
e
II
c
Pd (BIM)@Dowex 50 WX8
Pd (BIM)@Amberlite IR-120
d
d
e
Yield (%)
Pd leached (%)
Yield (%)
Pd leached (%)
Catalyst Recovery and Reuse
1
2
3
4
5
96
93
93
91
89
1.95
1.32
—
98
95
92
92
88
1.86
1.17
—
The reusability of both heterogeneous catalysts was investigated
in the reaction of 4-iodoanisole with phenylboronic acid in the
presence of K CO . At the end of each reaction, the catalyst
2 3
—
—
was filtered and washed thoroughly with acetone, diethyl ether
and water, successively, and reused with fresh 4-iodoanisole
and phenylboronic acid. The results are summarized in Table 3.
As can be seen, both catalysts can be recovered and recycled five
consecutive times. The yield after the fifth run is 88 and 89% for
—
—
a
Reaction conditions: 4-iodoanisole (1 mmol), phenylboronic acid
1.5 mmol), K CO (1.5 mmol), DMF–H O (2:1, 3 ml) under air.
00°C, catalyst (0.46 mol% Pd), 90 min.
00°C, catalyst (0.55 mol% Pd), 120 min.
(
2
3
2
b
c
1
1
II
II
Pd (BIM)@Amberlite IR-120 and Pd (BIM)@Dowex 50 WX8, re-
spectively. The amount of Pd leached was determined using
ICP analysis. As can be seen, no Pd is detected in the filtrates
after the first two runs.
d
Isolated yield.
e
Determined by ICP.
reaction temperature of 100 °C is found to be optimal for the
model reaction (Table 1, entries 5–9). Then, the same reaction Conclusions
was carried out in various aqueous/organic media. The results
In summary, a palladium(II) complex of a functionalized bis
imidazolium) ligand supported on ion-exchange resins was used
show that, when the reaction is conducted in a solvent like
DMF, higher yields are produced. When tetrahydrofuran (THF),
MeOH, EtOH and MeCN are used as solvent, lower yields of the
desired cross-coupling products are produced while in a non-
polar solvent such as toluene the product yield is very low.
(
as air- and moisture-stable and recyclable catalysts in the in
Suzuki–Miyaura C–C coupling reaction. The preparation of the cata-
lysts from commercially available supports, high air and moisture
stability, good catalytic activity and high reusability are noteworthy
advantages of these catalysts in the C–C coupling reactions.
2
Among the solvents examined, DMF–H O (2:1) is found to be
the best reaction medium (Table 1, entries 9–14). This can be at-
tributed to the better solubility of reactants in this solvent. The
model reaction was carried out in the presence of different or-
Acknowledgments
ganic and inorganic bases such as NEt , Na PO and K CO .
3
3
4
2
3
The authors are grateful to the Research Council of the University of
Isfahan for financial support of this work.
Among them, K CO is found to be the most efficient base. Com-
2
3
parison of inorganic bases utilized shows that carbonate base is
more stable than the other one and an organic base like Et N is
3
not as efficient as K CO (Table 1, entries 14–17). On the other
2
3
References
À
hand, K CO facilitates the conversion of PhB(OH) to Phb(OH) .
3
2
3
2
Therefore, it is concluded that the optimum reaction conditions
involve 4-iodoanisole (1mmol), phenylboronic acid (1.5mmol),
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2] N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457.
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II
K CO (1.5mmol) and Pd (BIM)@Dowex 50 WX8 (0.46 mol% Pd) in
2
3
[
DMF–H O (2:1, 3 ml) at 100 °C under air (Table 1, entry 4). When
2
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102, 1359.
tion, the best results are obtained in DMF–H O (2:1, 3 ml) at
2
[
[
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Chem. Commun. 2001, 1388.
1
00 °C in the presence of 0.55 mol% Pd using K CO3 as base
2
(Table 1, entry 4).
The generality and applicability of this method were examined in
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[10] U. Christmann, R. Vilar, Angew. Chem. Int. Ed. 2005, 44, 366.
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acid. As can be seen from Table 2, under the optimized reaction
conditions, various aryl halides were reacted with phenylboronic
acid to produce the substituted biphenyls. Aryl iodides, bromides
and chlorides bearing electron-donating and electron-withdrawing
[
[
12] T. E. Barder, S. D. Walker, J. R. Martinelli, S. B. Buchwald, J. Am. Chem. Soc.
2
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Appl. Organometal. Chem. 2015, 29, 346–352
Copyright © 2015 John Wiley & Sons, Ltd.
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