Palladium supported terpyridine modified magnetic nanoparticles as an efficient catalyst for carbon-carbon bond formation

Article abstract of DOI:10.1016/j.jorganchem.2021.121682

In this paper, a novel catalyst is designed, synthesized and characterized based on the functionalization of magnetic iron oxide nanoparticles by terpyridine as a ligand for the immobilization of palladium. The catalyst is fully characterized by several c

Full text of DOI:10.1016/j.jorganchem.2021.121682

Journal of Organometallic Chemistry 935 (2021) 121682
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Palladium supported terpyridine modified magnetic nanoparticles as
an efficient catalyst for carbon-carbon bond formation
a
a,b,∗
a,∗
Bahram Ahmadi Baloutaki , Mohammad Hosein Sayahi
Hassan Kefayati
, Mohammad Nikpassand ,
a
a
Department of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran
b
Department of Chemistry, Payame Noor University (PNU), 19395–3697, Tehran, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
In this paper, a novel catalyst is designed, synthesized and characterized based on the functionalization
of magnetic iron oxide nanoparticles by terpyridine as a ligand for the immobilization of palladium. The
catalyst is fully characterized by several characterization methods, including SEM, FTIR, DLS, VSM, EDS
and XRD analysis. The results of the characterization techniques proved the successful synthesis of the
desired catalyst. The applicability of the catalyst was evaluated in Heck and Suzuki reaction. The catalyst
showed very good activity through the mentioned carbon-carbon bond formation reactions. The catalyst
is magnetically recoverable and could be separated simply from the reaction media by an external mag-
net. The use of the catalyst in 10 sequential reactions did not show any significant loss in the activity of
the catalyst.
Received 3 November 2020
Revised 30 December 2020
Accepted 3 January 2021
Available online 6 January 2021
Keywords:
Palladium catalyst
SPION
Mizoroki-Heck reaction
Suzuki reaction
Immobilized catalyst
© 2021 Published by Elsevier B.V.
1. Introduction
semiconductors [20,21], medical imaging and therapy [22,23], drug
delivery [24,25] and the synthesis of polymer composites with im-
Carbon-carbon bond formation is a key reaction in organic
chemistry. Several efforts have focused on extending methods for
these reaction with higher efficiency in milder reaction condi-
tions. Palladium catalyzed cross coupling reaction of aryl halides
with alkenes (known as Mizoroki-Heck reaction), or with phenyl
boronic acids (known as Suzuki reaction) are of high interest
among carbon-carbon bond formation reactions [1–4]. Palladium is
the most popular catalyst for the mentioned reactions using vari-
ous ligands, such as bis pyrimidines [5,6], thiourea [7], β-diimines
proved properties [26–28].
Regarding the significance of Mizoroki-Heck and Suzuki reac-
tion in carbon-carbon bond formation reactions and the versatility
of superparamagnetic iron oxide nanoparticles in catalysis, in this
paper modified iron oxide nanoparticles are used as a support for
immobilization of palladium catalyst. Superparamagnetic iron ox-
ide nanoparticles are modified by terpyridine as a ligand for the
immobilization of palladium catalyst (denoted Pd@terPy@SPION).
The catalyst is applied in Mizoroki-Heck and Suzuki carbon-carbon
bond formation reactions.
[
8] and etc. For increasing the activity and reusability of palladium
catalyst in Mizoroki-Heck and Suzuki reaction, an approach is to
immobilize this metallic catalyst onto the modified solid supports
2. Results and discussion
[
9–14]. Among several materials, which have been used as support
In continuation of our work concerning the synthesis of hetero-
for the immobilization of palladium, magnetic iron oxide nanopar-
ticles are common candidates, due to their unique properties, in-
cluding chemical and thermal stability, ease of separation from the
reaction mixture and recovery, ease of functionalization and facil-
ity of the synthesis and fabrication [15–19]. Apart from applica-
tions in catalysis, superparamagnetic nanoparticles are of magnetic
materials, which have wide applications in several areas, including
cyclic and pharmaceutical compounds under mild and green pro-
tocols [29–37] we herein report a green procedures for Mizoroki-
Heck and Suzuki reaction using of Pd@terPy@SPION nanopar-
ticle as a novel nano-catalyst. In this paper, Pd@terPy@SPION
is designed and synthesized by the immobilization of palla-
dium onto terpyridine functionalized Superparamagnetic iron ox-
ide nanoparticles. For the fabrication of Pd@terPy@SPION cat-
alyst, 1-(pyridin-2-yl)ethan-1-one (1), 4-nitrobenzaldehyde (2)
ꢀ
∗
and ammonium acetate (3) were reacted together to form 4 -
Corresponding authors.
ꢀ
ꢀ ꢀ
(
4-nitrophenyl)-2,2 :6 ,2 ’-terpyridine (4). The reduction of nitro
E-mail addresses: sayahymh@pnu.ac.ir (M.H. Sayahi), Nikpassand@iaurasht.ac.ir
ꢀ
ꢀ ꢀ
(
M. Nikpassand).
group in compound (4) leads to the formation of 4-([2,2 :6 ,2 ’-
https://doi.org/10.1016/j.jorganchem.2021.121682
022-328X/© 2021 Published by Elsevier B.V.
0

B.A. Baloutaki, M.H. Sayahi, M. Nikpassand et al.
Journal of Organometallic Chemistry 935 (2021) 121682
Fig. 1. (a) SEM, (b) DLS, (c) FTIR, and (d) VSM results of Pd@terPy@SPION catalyst.
ꢀ
terpyridin]-4 -yl)aniline (5), which then reacts to triethoxy(3-
spectrum. Surface hydroxyl groups of silica encapsulated magnetic
ꢀ
ꢀ
ꢀ
−1
isocyanatopropyl)silane (6) and gives 1-(4-([2,2 :6 ,2 ’-terpyridin]-
iron oxide nanoparticles are observed at 3230 cm . Vibrations of
ꢀ
−1
4
-yl)phenyl)-3-(4,4,4-triethoxybutyl)urea (7). SPION capsulated
CH2 bonds are observed at 2891 cm . Vibration bands at 577
and 1100 cm 1could be correlated to Fe-O-Fe and Si-O-Si vibra-
−
SiO2 nanoparticles were separately synthesized in two steps.
The first step involved the reaction of Fe2 and Fe
+
3+
in ba-
tions, respectively. The bands belonging to terpyridine vibrations
−
are observed at 766 and 1424 cm 1. The carbonyl group of the
sic medium to give SPION nanoparticles. Tetraethyl orthosili-
cate (TEOS) was used for the encapsulation of SPION by SiO2
urethane is observed at 1724 cm 1. Comparing the FT-IR spectra of
−
ꢀ
ꢀ
ꢀ
ꢀ
moieties to form (9). 1-(4-([2,2 :6 ,2 ’-Terpyridin]-4 -yl)phenyl)-3-
4,4,4-triethoxybutyl)urea (7) reacted with SPION capsulated SiO2
Pd@terPy@SPION catalyst and SiO @SPION clearly proves the func-
2
(
tionalization of SiO @SPION and successful synthesis of the cata-
2
nanoparticles (9) to form terpyridinmodified magnetic nanopar-
ticles (10), which was used as a ligand for palladium catalyst.
Pd@terPy@SPION (11) was synthesized by the reaction of (10) with
palladium acetate. The preparation steps of Pd@terPy@SPION cata-
lyst is presented in Scheme 1.
lyst. In addition, the presence of palladium in the structure of the
catalyst was confirmed by ICP analysis. ICP results showed the pal-
ladium content of the catalyst to be 0.19 wt% of Pd@terPy@SPION
catalyst. Finally, the magnetic properties of Pd@terPy@SPION cata-
lyst was compared to SPIO nanoparticles. The VSM results of SPION
and Pd@terPy@SPION catalyst are presented in Fig.1d. According to
the VSM results both SPION and Pd@terPy@SPION catalyst showed
superparamagnetic behavior. It was observed that after the encap-
The synthesis of Pd@terPy@SPION catalyst was studied by sev-
eral characterization methods, including SEM, IR spectroscopy, DLS,
ICP and VSM method. The microstructure and the morphology
of Pd@terPy@SPION catalyst was studied by SEM microscopy. The
SEM image of Pd@terPy@SPION catalyst is presented in Fig. 1a. It
could be observed that the catalyst particles are spherical with
the average size of 30 nm. The size of Pd@terPy@SPION cata-
lyst particles were confirmed by DLS analysis. DLS result is pre-
sented in Fig. 2b. According to the DLS result, the particles of
Pd@terPy@SPION catalyst is about 30 nm. The successful synthesis
of Pd@terPy@SPION catalyst was studied by FTIR spectroscopy. The
sulation of SPION by SiO , followed by functionalization by terpyri-
2
dine moieties and the synthesis of Pd@terPy@SPION catalyst, the
magnetization of the catalyst is decreased. However, it is still su-
perparamagnetic and the magnetization in the presence of external
magnetic field is sharp enough to be separated by a magnet from
the reaction mixture.
Further structural analysis of Pd@terPy@SPION catalyst was per-
formed by XRD analysis. The XRD pattern of Pd@terPy@SPION cat-
alyst is presented in Fig. 2a. It could be observed that, the diffrac-
tion pattern is in agreement with the desired structure of the cat-
alyst. The presence of palladium in the structure of the catalyst
FTIR spectrum of Pd@terPy@SPION catalyst and SiO @SPION are
2
presented in Fig. 1c. The characteristic peaks related to the desired
bonds in the structure of the catalysts could be observed in FTIR
2

B.A. Baloutaki, M.H. Sayahi, M. Nikpassand et al.
Journal of Organometallic Chemistry 935 (2021) 121682
Fig. 2. (a) XRD, (b) EDS, (c) TGA results, and (d) TEM image of Pd@terPy@SPION catalyst.
could be confirmed in the XRD pattern. In addition, the presence of
palladium in the structure of Pd@terPy@SPION catalyst was studied
by EDS method. The EDS result is presented in Fig. 2b. The pres-
ence of palladium can clearly be observed in the elemental anal-
ysis of the catalyst. In addition, the thermal behavior of the cata-
lyst was studied by TGA analysis. The results are presented in Fig.
Table 2. It could be observed that all the substrate has given
the product in good isolated yields. The catalyst has been active
through both Mizoroki-Heck and Suzuki reaction with different
substrates. All electron donating and electron withdrawing reac-
tants have participated in the reaction and have given the prod-
ucts in high isolated yields. It should be noted that this catalyst is
prominent due to the efficient recoverability, high turnover num-
ber (TON), and turnover frequency (TOF). The catalyst showed a cu-
mulative TONs of about 12000 over 10 successive runs. In addition,
the TOF for every run is approximately 1225. Moreover, the cumu-
lative TON is obtained by the sum of the values for the TONs for
2
c. It could be observed that, the catalyst is thermally stable up
to 300°C. A weight loss in 100°C could be correlated to the wa-
ter, which is adsorbed by the catalyst nanoparticles. TEM image in
Fig. 2d confirm the particle size and structures of Pd@terPy@SPION
catalyst.
The activity of Pd@terPy@SPION catalyst was evaluated in
Mizoroki-Heck and Suzuki reaction. For finding the optimal reac-
tion conditions, the reaction of bromobenzene and styrene were
selected as a model reaction. The reaction was performed in differ-
ent reaction conditions, including different bases, solvents and var-
ious amounts of the catalyst. The results are presented in Table 1.
It could be observed that, the best results are observed in water as
solvent by using sodium acetate as base. It should be noted that
the best results were obtained when 1.5 equivalent of the base
were used. The amount of the base was optimized in the reaction
of bromobenzene and styrene. The best result was observed when
all examined runs. Additionally, TOFs are calculated using TON.h 1.
The reusability of Pd@terPy@SPION catalyst was evaluated in
five sequential runs. For this purpose, after the reaction of styrene
and bromobenzene was completed, the catalyst was separated
from the reaction by an external magnet and Pd@terPy@SPION cat-
alyst was used in the next reaction. The progress was repeated for
five sequential runs. The results are presented in Fig. 3. It could
be observed in Fig. 2 that the activity of the catalyst has not been
decreased during the reactions. In addition, the stability of the cat-
alyst was evaluated by hot filtration studies [38–41]. The hot fil-
tration results clearly confirmed the stability of the catalyst. Also,
this test confirmed the critical role of the catalyst in the reaction
performance.
−
5
mg of the catalyst was used for each mole of the reactants. A
blank rub was performed in the absence of Pd@terPy@SPION cata-
lyst and the results proved that the presence of the catalyst is crit-
ical for the reaction performance. In the absence of the catalyst,
no product was observed. In addition, hot filtration test was per-
formed. This observation confirmed the necessity of the presence
of the catalyst for the reaction performance. It should be noted
that no product was observed without Pd@terPy@SPION catalyst
for the reaction performance.
For studying the stability of Pd@terPy@SPION catalyst, the cat-
alyst was isolated after 5th cycle and characterized by SEM mi-
croscopy. The SEM result of the recovered catalyst is presented in
Fig. 4. It could be observed that the catalyst is highly stable under
the reaction conditions.
In order to show the efficiency of Pd@terPy@SPION catalyst, its
activity in Heck coupling reaction of styrene and bromobenzene
was compared with various palladium catalysts based on the reac-
tion time and yield. The results are presented in Table 3. According
to the Table 3, Pd@terPy@SPION catalyst is the most effective cat-
alyst for this purpose in comparison to previously reported cata-
The generality of the catalyst for the mentioned carbon-
carbon bond formation reactions was evaluated by the reaction
of various aryl halides and olefins including electron-withdrawing
or electron-donating substituents. The results are presented in
3

B.A. Baloutaki, M.H. Sayahi, M. Nikpassand et al.
Journal of Organometallic Chemistry 935 (2021) 121682
Table 1
Optimization of the reaction conditions for Pd@terPy@SPION catalyzed reaction.
Entry
Solvent
Base
Amount of base (mmol)
Amount of catalyst (mg)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
EtOH
MeOH
DMF
DMSO
CH3CN
DCM
H2O
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
TEA
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1
5
5
5
5
5
5
5
5
5
5
5
3
7
10
5
-
4
4
4
4
4
4
4
4
4
4
2
4
4
4
4
6
4
6
77
72
69
70
56
62
66
H2O
58
H2O
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
K2CO3
No base
70
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
H2O
1.2
1.5
1.5
1.5
1.5
2
81
H2O
96
H2O
51
H2O
96
H2O
96
H2O
96
H2O
1.5
1.5
-
trace
40
H2O
5
5
H2O
trace
Table 2
Pd@terPy@SPION catalyzed carbon-carbon bond formation reaction with various substrates.
Entry
R
X
substrate
product
Isolated yield
1
2
3
4
5
6
7
8
9
H
Br
Cl
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
14
14
14
14
14
14
15a
15a
15b
15c
15c
15d
15d
15e
15f
91
87
93
92
88
90
85
95
95
97
96
90
95
93
93
91
94
96
93
90
95
H
4-Me
4-MeO
4-MeO
4-NO2
4-NO2
4-CN
3,5-Cl2
H
Br
Br
Cl
Br
Cl
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
16a
16b
16c
16d
16e
16f
4-Me
4-OMe
4-NO2
4-CN
3,5-Cl2
H
17a
17b
17c
17d
17e
17f
4-Me
4-OMe
4-NO2
4-CN
3,5-Cl2
lysts. Also, this catalyst shows the highest catalytic activity in very
small amounts compared to other catalysts mentioned as indicated
in Table 3.
was recorded by a VEGATESCAN-LMU instrument. The parti-
cle size of the samples was analyzed by Nanotrac Wave from
Microtrac DLS instrument. FT-IR spectra were recorded on
a
Bruker Tensor 27 FTIR spectrophotometer. Nuclear magnetic res-
onance spectra were recorded on a Bruker FT- 250 spectrom-
eters using tetramethyl silane (TMS) as internal standard in
pure deuterated solvents. Chemical shifts are given in the δ
scale in parts per million (ppm) and singlet (s), doublet (d),
triplet (t), multiplet (m) and doublets of doublet (dd) are
recorded.
3
. Experimental section
3
.1. General remarks
All the chemicals, reagents and solvents were purchased
from Merck, Across, and Scharlau. SEM image of the catalyst
4

B.A. Baloutaki, M.H. Sayahi, M. Nikpassand et al.
Journal of Organometallic Chemistry 935 (2021) 121682
Table 3
added and the product was extracted from the reaction mixture.
The product was added to a flask containing water and methanol
mixture (1:1, 20 mL) and zinc powder (20 equivalent) was added
portion wise during 1h. The reaction mixture was stirred at room
temperature, monitored by TLC. After the reaction completion, the
mixture was filtered and the filtrated was collected. The solvent
was evaporated and the product was purified by recrystallization
from ethanol.
A catalytic activity comparison of Pd@terPy@SPION with the previously reported
catalysts for the Heck coupling reaction of styrene and bromobenzene.
Entry
Catalyst (mol%)
Conditions
Time (h)
Yields (%)ref.
93[42]
1
2
3
9
TiO2@Pd NPs (1)
HMMS-NH2-Pd (4)
Fe3O4-NH2–Pd (5)
Pd@terPy@SPION
DMF, Et3N, 140°C
NMP, K2CO3, 130°C
NMP, K2CO3, 130°C
Current work
10
20
24
96[43]
96[44]
97
The
product
(2
mmol,
648
mg),
triethoxy(3-
isocyanatopropyl)silane (2 mmol, 494 mg) and triethylamine
(
(
3 mmol, 303 mg) were added to a flask containing dry toluene
25 mL) and stirred at room temperature for 24 h. After 24
3
.2. Synthesis of the catalyst
-(Pyridin-2-yl)ethan-1-one (5 mmol, 605 mg) and 4-
h, the solvent was evaporated and the product was washed
1
three times with n-hexane, and then recrystallized from EtOH at
nitrobenzaldehyde (2.5 mmol, 378 mg) were added to a flask
containing acetic acid (10 mL) and stirred under reflux conditions.
The reaction completion was monitored by TLC. After the reaction
was completed, water (50 mL) and ethyl acetate (50 mL) were
ꢀ
ꢀ
ꢀ
ꢀ
0
°C to obtain 1-(4-([2,2 :6 ,2 ’-terpyridin]-4 -yl)phenyl)-3-(4,4,4-
triethoxybutyl)urea.
Scheme 1. Synthesis steps of Pd@terPy@SPION catalyst.
5

B.A. Baloutaki, M.H. Sayahi, M. Nikpassand et al.
Journal of Organometallic Chemistry 935 (2021) 121682
5. Conclusion
In this paper, a novel catalyst is designed and synthesized
based on the immobilization of palladium on magnetic iron ox-
ide nanoparticles. For this purpose, superparamagnetic iron oxide
nanoparticles were prepared by the co-precipitation of Fe2 and
+
Fe3 in basic medial the synthesized SPION were then encapsu-
+
lated by SiO . The nanoparticles were functionalized by terpyri-
2
dine moieties, which were used a ligand for palladium. The cata-
lyst is characterized by several methods, including SEM, DLS, FTIR,
ICP and VSM. The activity of the catalyst was evaluated toward
Mizoroki-Heck and Suzuki reaction. The results were advantageous
and showed that various substrates with different functionalities
were successfully participated in the reaction and have gave the
desired products in high isolated yields. The catalyst showed very
good reusability and its activity did not decrease after five sequen-
tial reactions.
Fig. 3. Reusability of Pd@terPy@SPION catalyst.
Declaration of Competing Interest
We declare that none of the authors of this manuscript are offi-
cial representatives or on behalf of the government. So, we confirm
that the research presented in the submitted paper is not funded
by, or on behalf of, the State or Government of Iran.
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
The authors are not any Conflict of Interest.
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7