Supported Pd nanoparticles on Mn-based metal-organic coordination polymer: Efficient and recyclable heterogeneous catalyst for Mizoroki-Heck cross coupling reaction of terminal alkenes

Article abstract of DOI:10.1016/j.inoche.2014.02.045

Supported palladium nanoparticles on Mn-carboxylate coordination polymer (Pd/MnBDC) were prepared using solution impregnation method. This new catalyst was characterized by XRD, SEM, TEM, EDX, XPS, FTIR and TGA analysis. The Pd/MnBDC exhibits efficient catalytic activity for the Mizoroki-Heck coupling reaction between iodobenzene and either aromatic or aliphatic terminal alkenes and reuses up to four runs without significant loss of activities.

Full text of DOI:10.1016/j.inoche.2014.02.045

Inorganic Chemistry Communications 44 (2014) 10–14
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Supported Pd nanoparticles on Mn-based metal–organic coordination
polymer: Efficient and recyclable heterogeneous catalyst for Mizoroki–
Heck cross coupling reaction of terminal alkenes
a,
a
b
b
Mojtaba Bagherzadeh ⁎, Fatemeh Ashouri , Lida Hashemi , Ali Morsali
a
Department of Chemistry, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155-4838, Tehran, Iran
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Supported palladium nanoparticles on Mn-carboxylate coordination polymer (Pd/MnBDC) were prepared using
solution impregnation method. This new catalyst was characterized by XRD, SEM, TEM, EDX, XPS, FTIR and TGA
analysis. The Pd/MnBDC exhibits efficient catalytic activity for the Mizoroki–Heck coupling reaction between
iodobenzene and either aromatic or aliphatic terminal alkenes and reuses up to four runs without significant
loss of activities.
Received 21 January 2014
Accepted 25 February 2014
Available online 12 March 2014
Keywords:
©
2014 Elsevier B.V. All rights reserved.
Palladium nanoparticles
Heterogeneous catalyst
Mizoroki–Heck coupling reaction
Manganese coordination polymer
Organic reactions using heterogeneous catalysts are exceptionally
crucial for the development of sustainable chemical processes. Among
them, the Mizoroki–Heck reactions for formation of carbon–carbon
bonds play significant roles in modern synthetic chemistry. The Heck
reaction is broadly used for coupling of an aryl, vinyl halide or sulfonate
with an alkene and is found to be very versatile and applicable to a
wide range of species [1]. Aryl–aryl bond formation is one of the initial re-
actions including a transition metal [2]. One of the best strategies to in-
crease the activity of these heterogeneous catalysts is to keep the size of
the particles in the catalyst as small as possible. Due to the large surface
area of the particles, transition-metal nanoparticles have attracted a
great deal of attention as catalytic systems with considerable potential
ionic liquids, mesoporous silica, zeolite, SBA-15, metal oxides and poly-
mers have broadly been investigated for immobilization of palladium
[7].
Many attempts have been focused on the development of new
ligand-derived polymeric supports for the attachment of metals and
the design of new approaches to increase the catalytic activity [8]. An
important material within this group is 3D coordination polymer of
Zn
4 3
O(bdc) (MOF-5, bdc = 1,4-benzenedicarboxylate) that has
been loaded with catalytically active material such as palladium,
gold, copper and ruthenium [3,9]. Pd-NPs supported on MOF-5 have
been used as a highly active catalyst for a ligand- and copper-free
Sonogashira coupling reaction [10]. Therefore, coordination polymers
have emerged as a new class of attractive functional materials that
can be used for the stabilization of metal nanoparticles with adjustable
sizes. Although there have been several approaches to load Pd-NPs onto
different supports, such as chemical vapor deposition, impregnation,
co-precipitation and solution infiltration, development of a general
and facile method to obtain supported Pd-NPs remains challenging
due to leach without protecting groups [11]. This paper sheds light on
the preparation of supported Pd-NPs on Mn-carboxylate metal–organic
[3]. The application of transition-metal nanoparticles to the formation of
carbon–carbon bonds and the development of highly active and easily re-
usable immobilized catalysts are still challenging for scientists [4]. Among
catalytically active nanoparticles, palladium nanoparticles (Pd-NPs) have
extensively been utilized for the formation of C\C bonds [5].
The stabilized Pd-NPs exhibit suitable catalytic activity [6]. More-
over, the immobilization of catalysts has several important potential
advantages such as recycle and reuse ability, relatively safe handling,
reduced environmental impact upon work-up, good thermal and chem-
ical stabilities and good dispersion of the active catalytic site [6]. Thus,
search for suitable supports in order to immobilize Pd-NPs is still a
tempting challenge in the field of heterogeneous catalysis. A number
of solid materials as supports, like clay, carbon nanofiber, graphene,
coordination polymer, Pd/MnBDC, (MnBDC = [Mn
3 3 4 n
(BDC) DMF ] ,
H
2
BDC = 1,4-benzendicarboxylic acid) and their application in
Mizoroki–Heck coupling reactions of iodobenzene with terminal
alkenes.
The Mn-carboxylate coordination polymer (MnBDC) was prepared
by reaction MnCl
12]. The supported Pd-NPs on Mn-carboxylate coordination polymer,
Pd/MnBDC, were obtained as gray powder by the addition of prepared
2 2 2
·2H O and H BDC according to our previous report
[
⁎
Corresponding author. Tel.: +98 21 66165354; fax: +98 21 66012983.
E-mail address: bagherzadeh@sharif.edu (M. Bagherzadeh).
http://dx.doi.org/10.1016/j.inoche.2014.02.045
387-7003/© 2014 Elsevier B.V. All rights reserved.
1

M. Bagherzadeh et al. / Inorganic Chemistry Communications 44 (2014) 10–14
11
MnBDC to the orange solution of PdCl
2
and NaCl in DMF in the presence
of hydrazine hydrate. After stirring for 15 min, the solid was isolated by
centrifuge, washed with DMF and dried in oven 90 °C [12]. The Pd con-
tents (10 wt.%) in the samples were determined based on Inductively
Coupled Plasma (ICP).
The supported Pd-NPs have similar decomposition profile, com-
pared to MnBDC (Fig. 1). It can be observed that minor decomposition
of both samples occurs at range 160–190 °C (associated with weight
losses of 12% for MnBDC and 5% for Pd/MnBDC). Comparing with
MnBDC, the maximum weight loss temperature of Pd/MnBDC
decreased from 550 to 430 °C, and the observation may be caused by
the presence of active Pd-NPs that facilitated degradation of organic
moieties [13].
The XRD pattern compounds based on Mn-carboxylate coordination
polymer as support have been demonstrated that, after the loading of
palladium, there is no significant loss of crystallinity in X-ray diffraction
patterns, indicating that the integrity of the MnBDC framework was
maintained (Fig. 1S). Compared to the MnBDC, the diffraction peaks of
the Pd-supported were all intensified due to the presence of palladium.
The characteristic peaks at 2θ = 40.1 and 46.5°, assignable to the
Pd(111) and Pd(200) respectively, are distinguishable due to the high
Pd loading and small palladium nanoparticles which is in line with
earlier report [14].
In order to elucidate the electronic nature of supported Pd-NPs,
X-ray photoelectron spectroscopy (XPS) measurement study was
assumed for the Pd/MnBDC and demonstrated that the Pd species in
polymer are presented in the metallic state (Fig. 2). This is verified by
the two peaks with the binding energy 335.65 and 341.15 eV in
the 3d5/2 and 3d3/2 level for Pd(0), respectively. Photoelectrons
emitted from carboxyl groups, C 1s and O 1s core level in the 1,4-
benzenedicarboxylate linker, generated peaks centered at 290 and
Fig. 2. Wide scan XPS spectra of the Pd/MnBDC with Pd core level spectra.
such as solvent, base and reaction temperature have a dramatic influ-
ence on the yield of the Mizoroki–Heck reaction [16]. In order to opti-
mize these parameters, the Mizoroki–Heck cross-coupling reaction of
styrene with iodobenzene using Pd/MnBDC as catalyst under various
reaction conditions was initially examined (Table 1). Apparently, the
efficiency of the C\C coupling reaction is very solvent-dependent
(entries 1–5). Dimethylacetamide (DMA) was found to be the solvent
of choice with excellent conversion even at a lower temperature
(entry 14). A variety of inorganic and organic bases were examined as
HI neutralizer and remover. The reaction yield was found to be strongly
dependent on the base employed and a remarkable increase in the
product formation was observed in the presence of bases like
triethylamine (Et N) or NaCH CO (entries 1–3 and 10, 11). Nonethe-
3
3
2
less, Et N being slightly more basic than NaCH CO gave a higher con-
3
3
2
5
38 eV binding energy respectively. The peak in 641 eV was assigned
version. In the case of organic bases such as pyridine or pyrrolidine,
the yield of the coupled products was notably decreased (entries 12,
13). A controlled experiment indicated that no cross-coupling product
was observed in the absence of the catalyst or base (entries 15, 16). As
to Mn (2p3/2) in Mn–O environment [15].
6
The scanning electron microscope (SEM) images of supported
Pd-NPs on MnBDC (Fig. 3) demonstrate that MnBDC is present at
rod shape morphology and Pd uniform spherical nanoparticles are
aggregated on its rods. The transmission electron microscope
(
TEM) images obviously show that the highly aggregated Pd-NPs
are attached on the surface of the support polymer (Fig. 4). The energy
dispersive X-ray (EDX) spectroscopy confirmed the presence of aggre-
gated Pd-NPs on the external surface of MnBDC coordination polymer
(
H
Fig. 2S). This aggregation was predictable due to unfunctionalized
BDC linker as observed in Pd/MIL-53(Al) [5a]. Using the Debye–
Scherer equation, the average diameter of Pd-NPs was estimated to be
.3 nm, which matched very well with TEM data as estimated by size
2
6
distribution (Fig. 3S).
The supported Pd-NP catalyst described above was applied to the
Mizoroki–Heck coupling reaction. A meticulous view into the C\C
cross coupling reaction process indicates that the reaction conditions
Fig. 1. TGA curves of MnBDC coordination polymer (a) and Pd/MnBDC (b).
Fig. 3. SEM images of Pd/MnBDC (a, b).

12
M. Bagherzadeh et al. / Inorganic Chemistry Communications 44 (2014) 10–14
that the formation of the cross-coupled products initially increased
along with the progress of the reaction time, reached a maximum
after 9 h and then remained intact (Fig. 4S).
Since, high catalyst loading inhibits the catalytic reaction and low
palladium catalyst loading is required in some cases [17], using small
amounts of catalyst in order to achieve high conversions in the Heck
cross-coupling reactions is preferred. To ascertain the efficiency of the
catalyst, different catalyst to substrate ratios were tested in the coupling
reaction of styrene with iodobenzene in the presence of Pd/MnBDC as
catalyst and the results were summarized in Table 2. It was found that
a decrease in the amount of catalyst does not affect the yields of the re-
action and the use of 0.12 mol% Pd of catalyst still gives high conversion
and simultaneously, increased the Turnover number (TON). Achieving
high TON is one of the merits of this Pd supported catalyst.
The Heck coupling reaction of iodobenzene with various olefinic
substrates including either aromatic or aliphatic terminal alkenes with
electron-donating or electron-withdrawing substitution was also inves-
tigated using Pd/MnBDC catalyst (Table 3, entries 1–11). It was
observed that supported Pd-NPs on MnBDC function as an active cata-
lyst for the coupling reaction of iodobenzene with terminal alkenes
and show the desired E-isomeric products as the major product with
good to excellent yields. Comparing with styrene, 4-methylstyrene
and 4-methoxystyrene, electron-rich substituted, exhibited the lowest
activity in the process of coupling with iodobenzene (entries 1–3).
The α-methylstyrene gave a much lower conversion than unsubstituted
ones which is probably due to steric effect (entry 4). It is note worthy
that increase in hydrocarbon chain length of aliphatic alkenes has
no significant influence on yield of coupling products (entries 6–8).
In the case of methyl-2-hydroxyacrylate, electron-withdrawing
β-substituted processed lower coupling than electron-rich ones, ethyl
methacrylate (entries 9, 10).
The mechanism for the reaction of iodobenzene with terminal
alkynes catalyzed by Pd/MnBDC is proposed on the basis of the mecha-
nism of previous reports [18] and our results, as shown in Scheme 1. The
catalytic cycle begins with the oxidative addition of iodobenzene to
supported Pd-NPs to form σ-arylpalladium intermediate A. The syn-
migratory insertion of alkyne to A leads to the formation of B intermedi-
ate followed by an internal rotation case which creates C intermediate.
The comparison between the results of α-methylstyrene and styrene
coupling reactions with iodobenzene (Table 3, entries 1, 4) further con-
firms the B intermediate formation. The large energy barrier to internal
rotation favors the production of E-isomeric products (note to % selec-
tivity in Table 3). The hydridopalladium halide D is formed by syn-β
hydride elimination of C or B. In the last step, the catalytic cycle is
completed by reductive elimination of H–Pd–I intermediate (D) in the
Fig. 4. TEM images of supported Pd-NPs on MnBDC.
3
a conclusion, Et N as base in DMA solvent at 90 °C is the optimized con-
dition for the coupling reaction in current catalytic system. Although
aryl iodides react readily, aryl bromides and chlorides are considerably
less reactive (conversion of 60% and 35% respectively) due to the
stronger carbon–halogen bond.
The formation of trans-stilbene from the cross-coupling reaction of
styrene with iodobenzene as a function of time displayed indicates
Table 1
Optimization of the reaction conditions in cross coupling reaction of iodobenzene and
a
styrene in the presence of Pd/MnBDC.
% conversionb
% selectivityc
presence of Et
3
N as base to remove HI from the D and palladium (0) is
Entry
Solvent
Base
reformed. The ultimate outcome of this catalytic cycle is C\C coupled
products.
1
2
3
4
5
6
7
8
9
DMSO
DMF
DMA
Et
Et
Et
Et
Et
3
N
N
N
N
N
CO
CO
CO
85
92
97
89
90
92
85
70
88
88
85
85
90
91
87
89
88
–
3
We conducted the control experiments to confirm that the reaction
was indeed catalyzed by Pd/MnBDC instead of free Pd-NPs, since some
of active sites in solid catalyst could dissolve into the solution during
the course of the reaction. In several cases, these leached species from
the solid catalyst could contribute dramatically to the total conversion
of the reaction [19]. So, the catalytic coupling reaction iodobenzene
with styrene was carried out in DMA for 9 h at 90 °C using 0.16 mol%
catalyst. After the reaction, the catalyst was simply separated from the
reaction mixture by centrifugation. The reaction solution was trans-
ferred to a new vessel, and fresh reagents were then added to the
solution. The resulting mixture was stirred at 90 °C. Only less than 8%
conversion was observed after 24 h. These results confirmed that the
coupling reaction could only proceed in the presence of the solid cata-
lyst, and there was no contribution from leached active species in the
liquid phase.
3
d
3
CH CN
3
65
p-Xylene
DMSO
DMF
DMA
DMSO
DMF
DMA
DMA
DMA
DMA
DMA
DMA
3
21
70
78
80
76
90
92
15
13
K
K
K
2
3
2
2
3
3
NaCH
NaCH
NaCH
Pyridine
Pyrrolidine
3
3
3
CO
CO
CO
2
10
11
12
13
14
15
16
2
2
e
Et
Et
3
N
N
70
f
3
1
–
1
–
a
Reaction condition: 13 mg Pd/MnBDC (0.12 mol% Pd), styrene 1.1 mmol,
iodobenzene 1 mmol, base 1.5 mmol, temperature 90 °C, after 9 h.
b
Determined by GC, based on iodobenzene; average of two runs.
Selectivity to trans-stilbene.
Solvent boiling point.
Temperature 70 °C.
c
d
The recycling of the catalyst is one of the significant aspects for prac-
tical applications. Therefore, the recyclability of the Pd-NPs supported
catalyst was investigated in reaction of styrene with iodobenzene in
e
f
Reaction without catalyst.

M. Bagherzadeh et al. / Inorganic Chemistry Communications 44 (2014) 10–14
13
Table 2
The effect of catalyst amount on conversion and TON of coupling reaction iodobenzene
a
and styrene.
Catalyst
mg)
Pd
mol%
Styrene
(mmol)
Time
(h)
Conversionb
(%)
Selectivityc
(%)
TONd
(
5
5
2
1
1
1
1.28
0.46
0.23
0.12
0.06
0.03
0.5
1
1
1
2
12
12
12
9
9
7
80
96
96
97
96
96
91
92
90
92
91
90
32
208
417
808
1600
3200
.5
.3
.3
.3
4
a
3
Reaction condition: The reactions were run in the presence of Et N in DMA solvent at
9
0 °C.
b
c
Determined by GC, based on iodobenzene.
Selectivity to trans-stilbene.
Turnover number (TON): ratio of moles of product formed to moles of catalyst used.
d
Table 3
The coupling reaction of iodobenzene and terminal olefins catalyzed by Pd/MnBDC.
a
Entry
1
Olefin
% Conversionb
97
Productc
Scheme 1. Proposed mechanism for Heck coupling reaction of iodobenzene and terminal
alkenes catalyzed by supported Pd-NP catalyst.
9
9
2%
0
2
3
87
the presence of Pd/MnBDC (13 mg, 0.12 mol% Pd) using Et
3
N/DMA at
9
0 °C for 9 h. The catalytic activity was found to remain almost
unchanged even after the 4 cycles without significant degradation in ac-
tivity and selectivity to trans-stilbene (Fig. 5S). Also, leaching test after
each catalytic run in styrene coupling reaction by ICP analysis revealed
that the amount of metal leach from catalyst is negligible (less than
8
6
8
8
4
17
0
.2% of Pd content). This result confirms that there is no contribution
from homogeneous catalysis of active species leaching into reaction
solution (Table 1S). It has been reported that leaching of Pd occurs during
C\C coupling reactions with Pd-supported catalysts in polar solvents,
particularly in DMF, which has an impact on the final observed catalytic
results [20]. A noticeable advantage of Pd/MnBDC heterogeneous catalyt-
ic system is low leaching compared to abovementioned. After reaction,
the Pd/MnBDC catalyst still displayed the same diffraction profile and
relatively similar intensity. These indicated that the Pd/MnBDC catalyst
retained well-crystallized structure after reaction (Fig. 1S).
9
8
0
5
5
6
91
97
1
00
7
94
In summary, supported palladium nanoparticles (Pd-NPs) on
Mn-carboxylate coordination polymers (Pd/MnBDC) were prepared
using a solution impregnation method. The XRD and EDS analysis
were employed to identify supported Pd nanoparticles (Pd-NPs) on
MnBDC. The size (average diameter 7 nm) and morphology of Pd-NPs
in Pd/MnBDC were investigated through incorporating a TEM and the
results conclude that the Pd-NPs are attached on the surface of the sup-
port material. The XPS showed that Pd-NPs are present at Pd(0) elec-
tronic state. The supported Pd-NPs could catalyze coupling reaction of
iodobenzene with various aromatic or aliphatic terminal olefins. The
use of the Pd/MnBDC as a heterogeneous catalyst for the Mizoroki–
Heck cross coupling reaction can simultaneously provide high activity
and selectivity to E-internal olefins, easy separation of catalyst and
appropriate performance in the recycling reaction.
1
7
00
7
8
9
87
60
5
5
1
0
82
9
2
a
Acknowledgment
Reaction condition: The reactions were run in the presence of 13 mg Pd/MnBDC
N (1.5 mmol), iodobenzene (1 mmol) and olefin (1.1 mmol) in DMA
(
0.12 mol% Pd), Et
3
solvent (2 mL) at 90 °C for 9 h.
M.B. acknowledges research council of Sharif University of Technology
for the research funding of this project.
b
Determined by GC, based on iodobenzene.

14
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(0.16 g, 1 mmol) and MnCl ·6H O (0.2 g, 1 mmol) was stirred for 48 h
at 90 oC. The white precipitate was isolated by filtration, washed with
DMF (2 × 5 Ml) and dried under 80 oC temperature for 24 h. Anal. Cal:
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mixture turned to gray immediately. After stirring for 15 min, the solid
was isolated by centrifuge, washed with DMF and dried in oven 90 °C.
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