Stepwise post-modification immobilization of palladium Schiff-base complex on to the OMS-Cu (BDC) metal–organic framework for Mizoroki-Heck cross-coupling reaction

Article abstract of DOI:10.1002/aoc.4539

Palladium ions were successfully immobilized within the pores of open metal site (OMS) metal organic frameworks (MOFs) with Schiff-base (2-Py-SI) grafted in OMS-Cu (BDC) using the hydrothermal method. This Schiff-base complex on the Cu (BDC) greatly increased catalytic activity and acted as an efficient stabilizer of Pd ions. The hydrothermal method was a more efficient method for generating small metal ions in the MOF structures. The results revealed that the Pd^II@Cu (BDC)/2-Py-SI is a promising catalyst for the Mizoroki-Heck coupling reaction. The proposed catalyst has better recyclability and can be reused several times without apparent loss of activity.

Full text of DOI:10.1002/aoc.4539

Received: 25 May 2018
DOI: 10.1002/aoc.4539
Revised: 8 July 2018
Accepted: 9 July 2018
F U L L P A P E R
Stepwise post‐modification immobilization of palladium
Schiff‐base complex on to the OMS‐Cu (BDC) metal–organic
framework for Mizoroki‐Heck cross‐coupling reaction
Hassan Alamgholiloo1,2 | Sadegh Rostamnia1
| Asadollah Hassankhani3 | Jabbar Khalafy2 |
Mehdi M. Baradarani2 | Ghodrat Mahmoudi4 | Xiao Liu5
1 Organic and Nano Group (ONG),
Palladium ions were successfully immobilized within the pores of open metal
Department of Chemistry, Faculty of
Science, University of Maragheh, PO Box
55181‐83111, Maragheh, Iran
site (OMS) metal organic frameworks (MOFs) with Schiff‐base (2‐Py‐SI) grafted
in OMS‐Cu (BDC) using the hydrothermal method. This Schiff‐base complex
on the Cu (BDC) greatly increased catalytic activity and acted as an efficient
stabilizer of Pd ions. The hydrothermal method was a more efficient method
for generating small metal ions in the MOF structures. The results revealed
that the PdII@Cu (BDC)/2‐Py‐SI is a promising catalyst for the Mizoroki‐Heck
coupling reaction. The proposed catalyst has better recyclability and can be
reused several times without apparent loss of activity.
2 Faculty of Chemistry, University of
Urmia, Urmia 57153‐165, Iran
3 Department of New Materials, Institute
of Science and High Technology and
Environmental Sciences, Graduate
University of Advanced Technology,
Kerman, Iran
4 Department of Chemistry, Faculty of
Science, University of Maragheh, PO Box
55181‐83111, Maragheh, Iran
KEYWORDS
5 Key Laboratory of Pesticide & Chemical
Biology of the Ministry of Education,
College of Chemistry, Central China
Normal University, Wuhan 430079, P. R.
China
metal organic frameworks, Mizoroki‐Heck reaction, open metal site MOF, PdII@Cu (BDC)/2‐Py‐SI
Correspondence
Sadegh Rostamnia, Organic and Nano
Group (ONG), Department of Chemistry,
Faculty of Science, University of
Maragheh, PO Box 55181‐83111,
Maragheh, Iran.
Email: rostamnia.sadegh@nims.go.jp;
srostamnia@gmail.com;
rostamnia@maragheh.ac.ir
Xiao Liu, Key Laboratory of Pesticide &
Chemical Biology of the Ministry of
Education, College of Chemistry, Central
China Normal University, Wuhan 430079,
P. R. China.
Email: liuxiao71@tju.edu.cn
1 | INTRODUCTION
surface area and tenability.[1] Compared with convention-
ally used micro−/meso‐porous inorganic metal oxides,
Hybrid porous coordination polymers as metal organic
frameworks (MOFs) have emerged as an important class
of nanoporous solid material owing to their high porosity,
MOFs have the potential for flexible rational and
functionalization of the pores.[2] MOFs are also the ideal
platform for post‐synthetic modification chemistry to
Appl Organometal Chem. 2018;e4539.
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© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4539

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ALAMGHOLILOO ET AL.
achieve multi‐purpose materials. A wide range of metal
groups can be incorporated into the ligand structure or
post‐synthetically constructed in the pores of the
MOF.[3] Among them, MOFs with open metal sites
(OMS‐MOFs) are promising candidates for adsorption/
storage, separation gases and catalysis purposes.[2]
In recent years, application of MOFs as heterogeneous
catalysts has attracted interest, especially in the use of
OMS‐MOFs as scaffolds for the grafting of metal (Pd,
Au, Pt and Ru) nanoparticles.[4] Indeed, metal@MOFs
have been used as catalysts in diverse reactions, such as
cross‐coupling,[5] C‐H activation[6] and nitro reduction.[7]
The treatment of MOFs supports after metal loading with
reducing agents such as NaBH4 and LiAlH4 has been
avoided in order to maintain the framework rigidity and
crystallinity of the support. Also, utilization of these
nanoparticles@MOFs as catalysts to be performed in
acidic–basic aqueous medium has been avoided.[8]
The Mizoroki‐Heck cross‐coupling reaction is one of
the most commonly employed transformations for C‐C
bond formation in modern organic synthesis[9] and,
because of the availability of reagents and the broad func-
tional group tolerance of this transformation, it has found
extensive use in synthetic organic chemistry.[10] Several
Pd supports on MOFs are currently reported for the catal-
ysis of the Mizoroki‐Heck cross‐coupling reaction.[11–14]
A number of solid materials as supports have broadly
been investigated for the immobilization of palladium,
such as carbon nanotube,[15] carbon nanofibers,[16]
N‐doped carbon,[17] grapheme,[18] PMO,[19] MCM‐41,[20]
SBA‐15,[21] magnetic Fe3O4,[22] metal oxides[23] and poly-
mers.[14,24] Among the nanoporous and high‐surface‐area
solid supports, MOFs can also be considered as suitable
hybrid material for immobilization of Pd ions.[25]
Recently, we have reported on the catalytic applica-
tion of OMS‐MOFs of copper coordinated to carboxylate
acids belonging to terephthalic acid (BDC = benzene
1,4‐dicarboxylate) and 1,3,5‐benzene tricarboxylate.[26]
Herein, we have demonstrated Cu (BDC) as an efficient
OMS MOF toward the direct grafting of Schiff‐base
[pyridyl salicylimine (2‐Py‐SI)] and complexation of that
with Pd ions. The synthesized PdII@Cu (BDC)/2‐Py‐SI
MOF was then applied to the Mizoroki‐Heck reaction as
a heterogeneous and recyclable green catalyst.
copper (II) cubic clusters of Cu (BDC) possess terminal
DMF molecules, and their lability allows their replace-
ment by other groups after vacuum treatment at 393 K,
without changes in the structure. Arnanz et al. have
recently reported synthesis of a pyridine‐coordinated
Cu‐BTC MOF to immobilization of the Pd catalyst for
the Sonoghashira/click reaction.[27] Ferey's group pre-
pared a Pd@MIL‐101 pre‐catalyst for the Heck coupling
reaction.[28] Herein, in our current method, the Cu
(BDC)·nDMF was prepared by using copper nitrate and
terephthalic acid as organic linkers in solvothermal con-
ditions, which was then activated at 393 K under vacuum
to obtain OMS Cu (BDC) solid [OMS‐Cu (BDC)]. This
OMS‐MOF reacted with as‐synthesized 2‐pyridyl‐
salicylimine (2‐Py‐SI) moiety in ultra‐dried toluene for
coordination of 2‐Py‐SI Schiff‐base to unsaturated
metal/cluster site of activated Cu (BDC). Then, PdCl2
was added to the Cu (BDC)/2‐Py‐SI to produce PdII@Cu
(BDC)/2‐Py‐SI (Scheme 1).
The crystallinity and purity of as‐synthesized Cu
(BDC) in DMF and PdII@Cu (BDC)/2‐Py‐SI were
checked by powder X‐ray diffraction (PXRD) measure-
ment (Figure 1). The results demonstrate that the peak
positions were well matched with those of the simulated
diffraction pattern.[29] A comparison of the PXRD pat-
terns of PdII@Cu (BDC)/2‐Py‐SI with Cu (BDC) revealed
a shift for the main peak (220) to smaller 2θ angles,
although other main diffraction peaks are in agreement
with the pristine Cu (BDC)·nDMF.
Figure
2 shows the Fourier‐transform infrared
(FT‐IR) spectra of synthesized Cu (BDC)·nDMF, Cu
(BDC)/2‐Py‐SI and PdII@Cu (BDC)/2‐Py‐SI. The FT‐IR
spectrum of the Cu (BDC)·nDMF compared with the
samples after Schiff‐base ligand and Pd grafting. As for
Cu (BDC)·nDMF, the strong peaks at 1396 cm−1 symmet-
ric and 1623 cm−1 asymmetric vibration correspond to
carboxylate presence in the MOF.[26,27,30] The bonds at
1507 cm−1 and 2971 cm−1 are assigned to C=C in the aro-
matic ring of BDC, and the aliphatic C‐H of coordinated
DMF and C‐H of aromatic rings of BDC. A new peak that
appears at 3357 cm−1 in Cu (BDC)/2‐Py‐SI and PdII@Cu
(BDC)/2‐Py‐SI shows the frequencies of the O‐H group
of the 2‐Py‐SI ligand in MOFs, and also demonstrates
the grafting of the 2‐Py‐SI ligand onto copper (II) CUSs
in the cages of the Cu (BDC). The FT‐IR of PdII@Cu
(BDC)/2‐Py‐SI demonstrate that the structure did not
change considerably after attachment of the Pd (II) ions
onto the Cu (BDC) pore cage.
2 | RESULTS AND DISCUSSION
The structure of Cu (BDC) is constituted of a cluster of
two copper (II) atoms with a paddle‐wheel shape that
has a square planar coordination,[27] in which the BDC
linker acts as a planar ligand connecting the diatomic
copper cluster that defines the nanocage.[11] Dimeric
Scanning electron microscopic (SEM) images of the
Cu (BDC)·nDMF and PdII@Cu (BDC)/2‐Py‐SI are shown
in Figure 3. The SEM images of Cu (BDC) and the mod-
ified MOFs sample with the Pd/Py‐SI complex revealed
the presence of cubic assembled layered microcrystals

ALAMGHOLILOO ET AL.
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SCHEME 1 Post‐modification immobilization of Pd ions onto the OMS‐Cu (BDC)
150 mm (~0.15 μm) thick (layered thickness; Figure 3c
is extracted from Figure 3a by Digimizer image
zooming and scale calculator). The SEM micrograph
of the PdII@Cu (BDC)/2‐Py‐SI shows its stability of
structure and even morphology after multi‐step post‐
modifications.
Elemental EDX analysis was performed for the MOFs
solids. Figure 4 shows the SEM–EDX spectra of synthe-
sized OMS‐Cu (BDC), Cu (BDC)/2‐Py‐SI and PdII@Cu
(BDC)/2‐Py‐SI. Based on this analysis, copper, carbon
and oxygen atoms exist in the structure of OMS‐Cu
(BDC), which indicate purity and perfect activation of
Cu‐MOF solids. C, Pd, Cl and N atoms in PdII@Cu
(BDC)/2‐Py‐SI demonstrate that palladium ions were
successfully coordinated onto the Schiff‐base (2‐Py‐SI)
decorated OMS‐Cu (BDC) pore cage. The wt% of Pd in
the PdII@Cu (BDC)/2‐Py‐SI structure was calculated
using atomic absorption spectroscopy (AAS), and accord-
ing to this the wt% of Pd was 0.78%.
The thermal stability of Cu (BDC)·nDMF and
PdII@Cu (BDC)/2‐Py‐SI was evaluated by thermogravi-
metric analysis (TGA). In Cu (BDC)·nDMF, the initial
weight loss at 200 °C can be attributed to loss of mois-
ture, remained coordinated DMF that continues up to
260 °C. For PdII@Cu (BDC)/2‐Py‐SI, a sharp decrease
in weight was observed from 280 °C onward, which
could be attributed to loss of loosely bound ligand. The
weight loss from 260 °C to 400 °C may be due to decom-
position of organic BDC linker and collapsing of MOF
structure (Figure 5).
After sufficient characterization of the PdII@Cu
(BDC)/2‐Py‐SI, the catalytic activity of this bifunctional
Pd/Cu‐MOF was examined for C‐C coupling reaction,
namely the Mizoroki‐Heck reaction. The Mizoroki‐Heck
coupling reaction of aryl halides and alkenes was exam-
ined using different amounts of catalyst, base and solvent
at a temperature range of 25–120 °C (Table 1).
To optimize the reaction conditions, when the reac-
tion was carried out in the absence of catalyst there
was no product even after 24 hr (Table 1, entry 1).
The best yield and selectivity was obtained when the
reaction was carried out in the presence of 0.25 mol%
of catalyst in solvent DMF and bases K2CO3 at reflux
conditions (Table 1, entry 3). In the next step, the effect
of polar and nonpolar solvent, such as DMF, DMF/H2O,
MeOH, DCM and toluene, on the reaction progress was
FIGURE 1 Powder X‐ray diffraction (PXRD) patterns of as‐
synthesized Cu (BDC)·nDMF and PdII@Cu (BDC)/2‐Py‐SI

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ALAMGHOLILOO ET AL.
FIGURE 2 Fourier‐transform infrared (FT‐IR) spectrum of Cu (BDC)·nDMF (black), Cu‐BDC/2‐Py‐SI (green) and PdII@Cu (BDC)/2‐Py‐SI
(red)
FIGURE 3 (a–c) Scanning electron microscopy (SEM) images of Cu (BDC)·nDMF, and (d) PdII@Cu (BDC)/2‐Py‐SI
also monitored (Table 1, entries 3, 5–9). The best results
were obtained in solvent DMF. We then investigated
the effects of the base on the progress reaction in the
optimized condition. Different bases, including NaOAc,
Na2CO3, Et3N, KOH and K2CO3, were studied on the
reaction progress, among them K2CO3 was suitable from
the viewpoint of yield and selectivity (Table 1, entries 3,
10–13).

ALAMGHOLILOO ET AL.
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FIGURE 4 EDAX image of OMS‐Cu (BDC), Cu (BDC)/2‐Py‐SI and PdII@Cu (BDC)/2‐Py‐SI
FIGURE 5 Thermogravimetric analysis
(TGA) of Cu (BDC)·nDMF (brown) and
PdII@Cu (BDC)/2‐Py‐SI (green)
After examination of various conditions on the reac-
tion progress, we explored the general applicability of
the catalyst with aryl halides and alkenes containing elec-
tron‐withdrawing or ‐donating substituents, and the
results are presented in Table 2. Indeed, aryl iodides com-
pared with aryl bromides show a high activity and short
reaction time in the Heck coupling reaction. As shown in
Table 2, all the derivatives, electron withdrawing or
donating, were in good to excellent yields. This may be
due to the higher activity of the catalyst the reaction prog-
ress of each derivative.
A comparison of the efficiency and catalytic perfor-
mance of PdII@Cu (BDC)/2‐Py‐SI with several hetero-
geneous catalysts and composite materials for the
Heck coupling reaction is presented in Table 3. It
turned out that Pd/Cu‐MOF gave better results than
the other material catalysts listed in Table 3 in terms
of selectivity and yield. The advantages of our method

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ALAMGHOLILOO ET AL.
TABLE 1 Optimization of reaction conditions in the Heck coupling reaction in the presence of PdII@Cu (BDC)/2‐Py‐SIa
Entry
Catalyst (mol%)
Solvent
Base
T (°C)
t (hr)
Conversion (%)b
Selectivity (%)c
1
–
DMF
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
NaOAc
Na2CO3
Et3N
120
120
120
120
120
120
120
120
120
120
120
120
120
100
25
24
18
16
16
16
16
16
16
16
16
16
16
16
18
24
–
–
2
0.2
DMF
70
98
97
80
57
40
90
45
60
50
60
90
85
35
90
99
99
90
88
98
98
97
80
85
90
98
98
97
3
0.25
0.3
DMF
DMF
4
5
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
H2O
6
MeOH
EtOH
DMF/H2O
Toluene
DMF
7
8
9
10
11
12
13
14
15
DMF
DMF
DMF
KOH
DMF
K2CO3
K2CO3
DMF
aReaction conditions: 4‐bromoacetophenone (1 mmol), methyl acrylate (1.2 mmol), K2CO3 (2 mmol).
bIsolated yield.
cSelectivity to trans‐alkene.
are high selectivity, mild conditions, and good to excel-
lent yields.
solution phase. Thin‐layer chromatography (mesh 60)
was used to monitor the reaction completion.
We investigated the recyclability and recovery of the
PdII@Cu (BDC)/2‐Py‐SI in the Heck reaction between 4‐
bromoacetophenone and ethyl acrylate in the optimized
condition. After completion of the reaction, the catalyst
was easily and rapidly separated from the mixture reaction
by simply centrifuging, and then reused for the next runs.
As shown in Figure 6, this catalyst could be recycled over
six runs without any significant loss of its catalytic activity,
but after the seventh run the yields decreased to 44%, and
in this case the XRD pattern fully changed and showed that
the MOF structure was destroyed.
3.2 | Synthesis of Cu (BDC)·nDMF and its
activation [OMS‐Cu (BDC)]
The MOFs of Cu (BDC)·nDMF were synthesized under
hydrothermal conditions according to the reported litera-
ture.[27,30] In a typical preparation, equimolar quantities
of Cu (NO3)2·3H2O (7.5 mmol, 1.812 g) and terephthalic
acid (7.5 mmol, 1.245 g) in 150 ml DMF were used. This
solution was placed in a Teflon‐lined autoclave in an
oven at 110 °C for 36 hr. Then, the Teflon‐lined autoclave
cooled slowly at a rate of 1 °C min−1 to room tempera-
ture. The blue precipitate was collected by centrifugation
and washed once with DMF. To remove residual
unreacted ions and H2BDC, the as‐synthesized Cu
(BDC)·nDMF was purified with hot methanol and DCM
for 4 hr, and then it was filtered and dried at 60 °C over-
night. The Cu (BDC)·nDMF was activated at 393 K under
vacuum to obtain the OMS‐Cu (BDC) solid. The Cu
(BDC) MOF was then characterized using a variety of dif-
ferent techniques.
3 | EXPERIMENTAL
3.1 | Chemicals and apparatus
All reagents were obtained commercially from Sigma‐
Aldrich, Merck (Germany) and Fluka (Switzerland), and
were used without further purification. The crystalline
phases of the MOF material were recognized by XRD
measurements (Philips‐PW 1800 diffractometer). The pal-
ladium content of the MOFs was measured by AAS of the

ALAMGHOLILOO ET AL.
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TABLE 2 Heck reaction of different aryl halides with alkenes over PdII@Cu (BDC)/2‐Py‐SI catalyst
Entry
I/Br
R
R'
t (hr)
Conversion (%)a
Selectivity (%)b
1
Br
Br
Br
Br
Br
Br
Br
I
H
‐CO2Me
‐CO2Et
‐CO2Bt
‐CO2Me
‐CO2Et
‐CO2Bt
‐Ph
18
18
18
18
18
18
18
4
98
99
98
98
88
90
92
85
99
99
99
99
90
99
2
H
97
3
H
93
4
4‐COMe
4‐COMe
4‐COMe
H
92
5
90
6
83
7
95
8
3‐NO2
3‐NO2
4‐Me
4‐OMe
4‐Me
4‐OMe
‐CO2Et
‐CN
98
9
I
4
98
10
11
12
13
I
‐CO2Me
‐CN
3
> 99
> 99
> 99
> 99
I
3
I
‐Ph
3
I
‐Ph
3
aIsolated yield.
bSelectivity to trans‐alkene.
TABLE 3 Comparison of the effect of Pd/Cu‐MOF with other catalysts for the Heck coupling reaction
Entry
Catalyst
Reaction conditions
Yield (%)
Ref.
[31]
1
Fe3O4@SiO2/Schiff base/PdII
Pd‐isatin Schiff base‐γ‐Fe2O3
Fe3O4@MCM‐41@Pd(0)‐P2C
Pd (II) doped UiO‐67
SiO2@ Fe3O4‐Pd
K2CO3, DMF, 110 °C
Et3N, solvent‐free, 100 °C
K2CO3, PEG, 120 °C
K2CO3, DMF, TBAB, 100 °C
K2CO3, DMF,100 °C
Et3N, DMF, 120 °C
97
95
96
97
95
98
95
96
97
95
98
> 98
[32]
[20]
[11]
[33]
[13]
[8]
2
3
4
5
6
Pd/ED‐MIL‐101
7
Pd(0)@TpPa‐1
K2CO3,CuI, Ph3P, 105 °C
Et3N, DMF, 120 °C
[34]
[35]
[36]
[37]
8
Fe3O4/DAG/Pd
9
Pd (OAc)2@MNP
Et3N, DMF, 120 °C
10
11
12
(PdCl2/bpy)10 multilayers
Pd (II)‐NHC
PdII@Cu (BDC)/2‐Py‐SI
Na2CO3, DMF, 140 °C
DMAc, KF, 140 °C
K2CO3, DMF,120 °C
This work
separated by centrifugation, washed with CH2Cl2 and
dried at 373 K overnight.
3.3 | Preparation of Cu (BDC)/2‐Py‐SI
One gram of Cu (BDC)·nDMF was activated at 393 K
under vacuum to obtain a dark‐violet solid. A solution
of 2‐aminopyridine (1 mmol) or salicylaldehyde (1 mmol)
was reacted under solvent‐free conditions and added to a
suspension in dry toluene (15 ml), and the mixture was
heated at 90 °C for 12 hr. The Cu (BDC)/2‐Py‐SI was
3.4 | Preparation of PdII@Cu (BDC)/2‐Py‐
SI
A solution of PdCl2 (0.1 mmol) in a mixture with dry tol-
uene and DMF (1:1, 5 ml) was added to a suspension of

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ALAMGHOLILOO ET AL.
FIGURE 6 Recyclability of PdII@Cu
(BDC)/2‐Py‐SI in (a) the Heck reaction
and (b) its X‐ray diffraction (XRD) analysis
after the seventh run
400 mg of Cu‐BDC/Py‐SI in 20 ml CH2Cl2. The mixture
was heated at reflux for 6 hr, and then cooled to room
temperature. Then the PdII@Cu (BDC)/2‐Py‐SI was
filtered, washed with DMF and CH2Cl2, and dried at
60 °C under vacuum. The wt% of palladium ions in
PdII@Cu (BDC)/2‐Py‐SI was calculated using AAS,
which gave a value of 0.78%. The surface area of OMS‐
Cu (BDC) decreased from 340 cm3 g−1 to 210 cm3 g−1
after loading Pd.
to excellent activation for the Heck coupling reaction.
The PdII@Cu (BDC)/2‐Py‐SI catalyst was found to be
an efficient, selective, recyclable and heterogeneous
catalyst for the Heck reaction. This catalyst could be sep-
arated from the reaction mixture by common filtration,
and could be reused in the next run a without a signifi-
cant loss of catalytic activity.
ORCID
Sadegh Rostamnia http://orcid.org/0000-0001-6310-8754
3.5 | General procedure for Heck coupling
reaction
REFERENCES
For the catalyst test, Pd@Cu (BDC)/2‐Py‐SI (0.25 mol%)
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(2 mmol) in 3 ml of DMF. The mixture was then stirred
for a certain time at 120 °C. After completion of the
reaction, the product was extracted from the reaction
mixture with CHCl3 and DI water, then the solvent
evaporated and the residue purified by column chroma-
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How to cite this article: Alamgholiloo H,
Rostamnia S, Hassankhani A, et al. Stepwise post‐
modification immobilization of palladium Schiff‐
base complex on to the OMS‐Cu (BDC) metal–
organic framework for Mizoroki‐Heck cross‐
coupling reaction. Appl Organometal Chem. 2018;
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