L-lysine-Pd Complex Supported on Fe3O4 MNPs: a novel recoverable magnetic nanocatalyst for Suzuki C-C Cross-Coupling reaction

Article abstract of DOI:10.1002/aoc.5668

In this work, L-lysine-Pd Complex, immobilized onto the surface of Fe₃O₄ MNPs, was successfully prepared via simple and inexpensive procedure. The prepared nanocatalyst was considered as a robust and clean nano-reactor catalyst for the Suzuki and Heck C-C Cross-Coupling reactions in water as the green condition. This eco-friendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray Diffractometer (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP), X-ray mapping, BET, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) techniques. The use of a green medium, easy separation and workup, excellent reusability of the nanocatalyst and short reaction time are some outstanding advantages of this method.

Full text of DOI:10.1002/aoc.5668

Received: 1 January 2020
DOI: 10.1002/aoc.5668
Revised: 3 March 2020
Accepted: 8 March 2020
F U L L P A P E R
L-lysine-Pd Complex Supported on Fe O MNPs: a novel
3
4
recoverable magnetic nanocatalyst for Suzuki C-C Cross-
Coupling reaction
1,2
3
1
Muhammad Aqeel Ashraf
| Zhenling Liu | Dangquan Zhang
|
4,5
Ashkan Alimoradi
1
School of Forestry, Henan Agricultural
University, Zhengzhou, 450002, China
In this work, L-lysine-Pd Complex, immobilized onto the surface of Fe O
3
4
2
Department of Geology Faculty of
MNPs, was successfully prepared via simple and inexpensive procedure. The
prepared nanocatalyst was considered as a robust and clean nano-reactor cata-
lyst for the Suzuki and Heck C-C Cross-Coupling reactions in water as the
green condition. This eco-friendly heterogeneous catalyst was characterized by
Fourier transform infrared spectroscopy (FT-IR), X-Ray Diffractometer (XRD),
energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma
atomic emission spectroscopy (ICP), X-ray mapping, BET, thermogravimetric
analysis (TGA), vibrating sample magnetometer (VSM), scanning electron
microscopy (SEM) and Transmission electron microscopy (TEM) techniques.
The use of a green medium, easy separation and workup, excellent reusability
of the nanocatalyst and short reaction time are some outstanding advantages
of this method.
Science, University of Malaya, Kuala
Lumpur, 50603, Malaysia
3
School of Management, Henan
University of Technology, Zhengzhou,
4
50001, China
4
Department for Management of Science
and Technology Development, Ton Duc
Thang University, Ho Chi Minh City,
Vietnam
5
Faculty of Applied Sciences, Ton Duc
Thang University, Ho Chi Minh City,
Vietnam
Correspondence
Dangquan Zhang, School of Forestry,
Henan Agricultural University,
Zhengzhou 450002, China.
Email: zhangdangquan@163.com
K E Y W O R D S
C-C coupling, Fe
3
O
4
@L-lysine-Pd, Nanocatalyst, reusable catalyst, Suzuki reaction
Ashkan Alimoradi, Faculty of Applied
Sciences, Ton Duc Thang University, Ho
Chi Minh City, Vietnam.
Email: ashkanalimoradi@tdtu.edu.vn
1
| INTRODUCTION
which can be regarded as the two valuable keys attached
to the catalytic reactions for the definition of sustainabil-
ity indicate that a catalytic process follows the “Green
There are two types of catalysts in which homogeneous
catalyst is in a similar phase with the reactants, But het-
erogeneous is in the solid phase while the reaction occurs
on the surface.
erogeneous catalysts over homogeneous processes in view
of the ease of handling and simple work-up and separa-
[
23–32]
Chemistry” principles.
But, in practical applica-
tions, using homogeneous catalysts in a real catalytic sys-
tem has some basic problems: having a high cost, time
consuming and boring procedure for the catalyst separa-
[1–7]
Industry favors the application of het-
[
7,31,33,34]
tion and recovery.
One way to solve these prob-
[8–15]
tions.
Because of the importance of environmental
lems is the heterogenization of the homogeneous
[
20,35–38]
and economic issues, global scientific and industrial dis-
coveries in the field of catalysts should use the principles
of “Green Chemistry”.
catalysts on solid supports.
One of the best
methods for the preparation of nanocatalysts is the syn-
thesis of heterogeneous catalysts by suitable supports
[16–23]
Recovery and reusability
Appl Organometal Chem. 2020;e5668.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 18
https://doi.org/10.1002/aoc.5668

2
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ASHRAF ET AL.
[
39]
[24,38,40–46]
[53–55]
the polymeric structure.[31,103–105] In this regard, Glaser,
Sonogashira, Ullmann, Stille, and Buchwald–Hartwig
such as silica nanoparticles,
SBA-15,
[47]
[44,48–51]
[52]
SBA-16,
alumina,
MCM-41,
heteropoly acids,
MCM-48,
FSM-16,
[56]
[57]
[58,59]
graphene oxide,
(MWCNTs),
which are among the predominantly used reactions are
[
60]
[23,31,106–108]
Multiwall
Boehmite,
carbon
nanotubes
peptide nanofibers,
or ferrites nanoparticles.
catalyzed by metals.
More specifically, palla-
[
31]
[61]
[62]
polymers,
dium-catalyzed cross-coupling reactions have attracted
much interest over the last 30 years, because they
unlocked valuable organic coupling pathways, not solely
[
63]
[7,5,20–23,32,37,64]
Fe O @SiO
2,
3
4
Among various supports, iron oxide magnetic
nanoparticles (Fe O -MNPs) have attracted more atten-
[109–112]
in academia but also for industrial applications.
3
4
tion due to their significant advantages i.e. high magnetic
permeability, large specific surface area, small size, low
The opportunity for a tolerable functionalization of aryl
halides with boronic acids, acetylenes or tin compounds
is the practical advantage for the use of Suzuki,
Mizoroki-Heck, Sonogashira, Stille and many other
[65–69]
cost and good stability.
The development of hybrid
inorganic–organic nanocomposite catalyst has gained
considerable attention due to its process ability, multi-
functionality, and the potential large-scale produc-
[
113]
cross-coupling reactions.
Compared to other cou-
pling reactions, the Suzuki-coupling reaction catalyst by
Pd nanoparticles has the advantages of low toxicity of
organic boron reagents, mild reaction conditions, good
[70–72]
tion.
Immobilization of the homogeneous catalysts
on these nanocomposites as a solid support will aid the
recovery of the catalyst and minimizing the pollution via
stability, wide application range of substrates and so
[73–79]
[113]
simple magnetic decantation.
In this sense, the
on.
Previously, these reactions were typically per-
combination of the magnetic property of the magnetic
nanoparticles (MNPs) and the molecular recognition of a
specific organic structure exposed their distinct advan-
formed under homogeneous conditions using palladium
[
114]
and (phosphine) ligands as a catalytic system.
days, more innovative catalyst systems are used.
Nowa-
Due
[
115]
[80–86]
tages.
The magnetic nanoparticles can be well dis-
to the fact that the separation of noble metal Pd(0) nano-
particle catalysts is difficult and the noble metal Pd(0)
nanoparticle catalysts are hard to recycle, the economic
costs will be increased and also it is not conducive to
persed in the reaction mixtures in the absence of
magnetic field providing large surface area for a readily
[7,23]
access of the substrate molecules.
On the other hand,
[
112,115]
the organic coat, owing catalytic sites along with struc-
tural approach, improves the catalytic activity of such
practical application and promotion.
In this report, a novel Pd Complex supported on
Fe O MNPs (Fe O @L-lysine-Pd MNPs) was introduced
[31,87]
nanocomposite.
In addition, the supported catalysts
3
4
3 4
on magnetic nanoparticles can be quickly separated from
the reaction mixture by inducing a magnetic field and be
reused for the next time.
as a new and efficient reusable catalyst for Suzuki cross-
coupling reaction under green reaction conditions. The
results of this study differ from the previously-reported
researches due to the natural origin of ligand, stable
complex of ligand with Pd and support, high yields of
the products and excellent selectivity, and recoverability
and reusability of the catalyst. In addition, water was
[88]
Palladium-catalyzed coupling reactions comprise a
family of cross-coupling reactions which employ palla-
[89–91]
dium complexes or nanoparticles as catalysts.
Car-
bon–carbon (C–C) bonds coupling reactions play an
important role in organic synthesis for a long time. In
addition, this technique has become a truly fundamental
route in organic, medicinal and supramolecular chemis-
try, natural product synthesis, materials and polymer sci-
used as
a green solvent under aerobic reaction
conditions.
[23,31,92]
ence, and also in catalysis.
The existence of
2 | EXPERIMENTAL
various books and review articles in recent years are a
testimony to the outstanding contribution of cross-cou-
2.1 | General procedure for the
[89,91,93–97]
pling reactions.
Since professor Akira Suzuki
preparation of the Fe O @L-lysine-Pd
3
4
of Hokkaido University in Japan first reported the
MNPs
[98]
Suzuki coupling reaction in 1981,
a lot of achieve-
ments have been made about palladium-catalyzed cross-
coupling which enabled Heck, Negishi, and Suzuki win
The Fe O magnetic nanoparticles were prepared by the
3 4
coprecipitation technique as it was previously
[
99–101]
[116]
the 2010 Nobel Prize in Chemistry for the work.
The cross-coupling of haloarenes and phenylboronic
reported.
2.5 mmol of L-lysine amino acid was
grafted on 1 g of the obtained Fe O MNPs in water
3
4
[96,97,102]
acids can form biaryl compounds.
Another well-
under N atmosphere at reflux conditions for 24 hr. In
2
known coupling is Mizoroki-Heck reaction, which con-
stitutes the interaction of unsaturated halides and
alkenes to form the substituted alkenes and also even
the next step, the reaction mixture was cooled down
and, then, Fe O @L-lysine MNPs were separated by
magnetic decantation. Finally, in order to prepare
3
4

ASHRAF ET AL.
3 of 18
0
Fe O @L-lysine-Pd
organometallic
complex,
the
2.3.3 | 2-Methoxy-1,1 -biphenyl (Table 2
entry 14)
3
4
obtained Fe O @L-lysine MNPs (0.1 g) was dispersed in
3
4
2
5 ml ethanol by sonication for 30 min. and, then, Palla-
1
dium (II) acetate (0.5 g) was added to the reaction mix-
ture which was stirred under the N2 atmosphere at
reflux conditions (80 C) for 24 hr. Afterwards, 6 mmol
M.p. oil. H NMR (400 MHz, CDCl , δ, ppm): 7.53 (2H, d,
J = 5.2 Hz), 7.40 (2H, t, J = 7.2 Hz), 7.28–7.33 (3H, m), 7.02
(1H, t, J = 8.8 Hz), 6.98 (1H, d, J = 8.8 Hz), 3.78 (3H, s).
3
ꢀ
of NaBH was added to the mixture and stirred for 8
4
more hours. Subsequently, the reaction mixture was
cooled to room temperature and, then, the final
Fe O @L-lysine-Pd MNPs were isolated, using an exter-
0
2.3.4 | 1,1 -biphenyl (Table 2 entry 15)
3
4
ꢀ
1
nal magnet, from the reaction mixture, washed by etha-
nol to remove the remaining impurities and, finally,
M.p. 68–69 C. H NMR (400 MHz, CDCl , δ, ppm): 7.61
3
(4H, d, J = 8 Hz), 7.45 (4H, t, J = 7.2 Hz), 7.33–7.38
ꢀ
dried in an oven at 70 C for 8 hr.
(2H, m).
0
2.2 | General procedure for Suzuki
2.3.5 | 4-Nitro-1,1 -biphenyl (Table 2
reaction
entry 19)
ꢀ
1
A mixture of phenylboronic acid (1 mmol), aryl halide
M.p. 107–109 C. H NMR (400 MHz, CDCl , δ, ppm):
3
(
1 mmol), and Na CO (1.5 mmol) in the perecence of
8.31 (2H, d, J = 6.8 Hz), 7.75 (2H, d, J = 8.8 Hz), 7.64
2
3
Fe O @L-lysine-Pd MNPs (0.08 mol%) was dissolved in
(2H, d, J = 6.8 Hz), 7.46–7.53 (3H, m),
3
4
water (3 ml) and, then, stirred at reflux conditions. The
progress of the reaction was monitored by TLC. After
completion of the reaction, the mixture was cooled
down, Fe O @L-lysine-Pd MNPs were separated using
2.3.6 | 2-Hydroxy-5-phenylbenzaldehyde
(Table 2 entry 22)
3
4
an external magnet and washed with EtOAc. The
ꢀ
1
remaining reaction mixture was extracted with H O
M.p. 96–99 C. H NMR (400 MHz, CDCl , δ, ppm):
2
3
and EtOAc. The organic layer was dried over anhy-
10.96 (1H, s), 8.29 (1H, d, J = 1.2 Hz), 8.26 (1H, d,
J = 1.2 Hz), 7.70 (1H, d, J = 2.8 Hz), 7.63 (2H, m), 7.54
(2H, t, J = 7.6 Hz), 6.94 (1H, d, J = 8.8 Hz).
drous Na SO4 (1.5 g). Afterwards, ethyl acetate was
2
evaporated and pure biphenyl derivatives were obtained
in excellent yields.
2
.3.7 | 1,4-Diphenylbenzene (Table 2
2.3 | Selected spectral data
entry 24)
ꢀ
1
The copies of spectral data 1H NMR for some of prepared
compounds can be found in the Supporting information.
M.p. 189–192 C. H NMR (400 MHz, CDCl , δ, ppm):
3
7.61 (4H, s), 7.57 (4H, d, J = 7.2 Hz), 7.39 (4H, t,
J = 7.6 Hz), 7.27–7.31 (2H, m).
0
2
.3.1 | 4-Methoxy-1,1 -biphenyl (Table 2
entry 3)
2.3.8 | 5-Phenylnicotinic acid (Table 2
entry 26)
ꢀ
1
M.p. 87–89 C. H NMR (400 MHz, CDCl , δ, ppm): 7.55
3
ꢀ
1
(4H, t, J = 7.6 Hz), 7.42 (2H, t, J = 7.6 Hz), 7.30 (1H, t,
M.p. 252–254 C. H NMR (400 MHz, CDCl , δ, ppm):
3
J = 7.2 Hz), 6.98 (2H, d, J = 8.4 Hz), 3.85 (3H, s).
8.25 (1H, s), 8.23 (1H, s), 7.69 (1H, s), 7.59 (2H, t,
J = 7.6 Hz), 7.51 (3H, t, J = 7.6 Hz).
2
.3.2 | 4-Phenylphenol (Table 2 entry 4)
2
.3.9 | 3-Phenylbenzaldehyde (Table 2
ꢀ
1
M.p. 156–159 C. H NMR (400 MHz, CDCl , δ, ppm):
entry 30)
3
8
.28 (1H, d, J = 6.8 Hz), 7.56 (2H, t, J = 7.2 Hz), 7.51 (2H,
d, J = 8.4 Hz), 7.44 (2H, t, J = 7.6 Hz), 7.33 (1H, t,
J = 7.2 Hz), 6.93 (2H, d, J = 8.4 Hz).
M.p. oil. 1 H NMR (400 MHz, CDCl , δ, ppm): 10.11 (1H,
s), 8.13 (1H, s), 7.87–7.89 (2H, dd, J = 6.4 Hz), 7.66 (1H, t,
3

4
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ASHRAF ET AL.
J = 1.6 Hz), 7.63 (2H, d, J = 7.2 Hz), 7.48–7.52 (2H, m),
.41–7.45 (1H, m).
characterized by FT-IR, XRD, EDS, ICP, X-ray mapping,
SEM, TEM, TGA, and VSM techniques.
7
2
3
3
.3.10 | 2-Hydroxy-
,5-diphenylbenzaldehyde (Table 2 entry
7)
3.2 | Catalyst characterizations
The as-prepared Fe O @Schiff-base-Cu catalyst was also
3
4
characterized by FT-IR, XRD, EDS, ICP, X-ray mapping,
BET, TGA, VSM, SEM and TEM techniques.
ꢀ
1
M.p. 114–116 C. H NMR (400 MHz, CDCl , δ, ppm):
3
1
(
7
1.52 (1H, s), 10.05 (1H, s), 7.88 (1H, d, J = 2.4 Hz), 7.78
1H, d, J = 2.4 Hz), 7.59–7.67 (4H, m), 7.46–7.50 (4H, m),
.38–7.44 (2H, m).
0
2
3
.3.11 | (4-Hydroxy-[1,1 -biphenyl]-
,5-diyl)dimethanol (Table 2 entry 38)
ꢀ
M.p. 90–93 C. 1H NMR (400 MHz, CDCl , δ, ppm): 7.95
3
(
7
(
1H, s), 7.93 (1H, s), 7.54 (2H, t, J = 7.6 Hz), 7.49 (1H, s),
.44 (2H, t, J = 7.2 Hz), 7.13 (1H, s), 5.23 (2H, s), 4.90
2H, s).
3
3
| RESULTS AND DISCUSSION
.1 | Catalyst preparation
In this work, a novel L-lysine-Pd Complex supported on
Fe O4 was prepared and described as an efficient
3
nanocatalyst for C-C cross coupling reactions. Initially,
the Fe O nanoparticles have been prepared according to
3
4
[116]
the reported procedure.
In order to prepare Fe O @
3 4
L-lysine MNPs, L-lysine has been grafted on Fe O MNPs
3
4
via the covalent bonding of R-COOH groups with OH
groups under surface of Fe O MNPs. Finally, the catalyst
3
4
was synthesized by the reaction of Fe O @L-lysine MNPs
FIGURE 1 FT-IR spectra of Fe O MNPs (a), L-lysine (b),
3
4
3 4
with Pd (OAc)2 (Scheme 1). This catalyst has been
3 4 3 4
Fe O @L-lysine (c) and Fe O @L-lysine-Pd (d)
SCHEME 1 Stepwise preparation of
Fe @L-lysine-Pd catalyst
3 4
O

ASHRAF ET AL.
5 of 18
−
1
The FT-IR spectra for the Fe O MNPs (a), L-lysine
b), Fe O @L-lysine (c) and Fe O @L-lysine-Pd complex
3 4 3 4
The amine band was situated at 1629.17 cm . Moreover,
the characteristic adsorption band (FeO) of Fe O
3
4
(
(
3 4
−
1
d) are shown in Figure 1. The strong absorption at 590
appeared at 589.36 cm . Hence, these data clearly
proved the successful synthesis of L-lysine -modified
Fe O NPs (Figure 1c). The shift on the absorption peak
at approximately 1612 cm (amine stretching vibration)
in the Fe O @L-lysine-Pd (d) spectra is due to the com-
−
1
and 628 cm in the all spectrums was exhibited as it was
attributed to the presence of Fe–O stretching vibra-
3
4
[117]
−1
−1
tion.
In addition, the peak appearing at 1624 cm
was attributed to the bending vibration of OH band or
stretching vibrational mode of an adsorbed water
3
4
[
31]
plexion of Pd ions with Fe O @L-lysine-.
3
4
[118]
−1
layer.
Moreover, the broad band at around 3392 cm
The XRD patterns of Fe O @L-lysine-Pd complex
3 4
is attributed to asymmetric and symmetric stretching
nanoparticles are shown in Figure 2. The sharp peaks in
the XRD patterns verified good crystallinity of the pre-
pared samples. The crystalline peaks at diffraction angles
vibrations of –OH band of the surface of the Fe O
3
4
[119]
nanoparticles.
Moreover, The FT-IR spectra
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
(
Figure 1c) of the Fe O @L-lysine MNPs (c) differed from
2θ = 35.27 , 41.52 , 50.56 , 63.24 , 67.49 , and 74.47 cor-
respond to the (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1) and
(4 4 0) reflections, respectively, which are in agreement
with the standard patterns of inverse cubic spinel magne-
tite (Fe O ) crystal structure. This analysis clearly affi-
3
4
those of the Fe O NPs and pure L-lysine amino acid.
3
4
However, the characteristic bands of L-lysine were clearly
distinguished from those of the Fe O @L-lysine MNPs.
3
4
3
4
rmed that the surface modification and functionalization
of the Fe O nanoparticles did not lead to phase change.
3
4
ꢀ
ꢀ
ꢀ
Other peaks at 2θ values of 39.3 , 45.1 and 66.1 corre-
[
31]
spond to Pd(0) in Fe O @L-lysine-Pd MNPs.
The pres-
3
4
ence of these new peaks proves that new layers had been
loaded onto the surface of the Fe O NPs and affected the
3
4
XRD pattern because of the well-defined crystal
structures.
The element composition of the synthesized
Fe O @L-lysine-Pd nano-structure was studied using
3
4
energy-dispersive X-ray spectroscopy (EDX) which
showed the presence of Fe, O, C, N and Pd species in the
prepared nanocatalyst (Figure 3). The results confirmed
the
successfully
immobilization
L-lysine-Pd
3 4
FIGURE 2 XRD curve of Fe O @L-lysine-Pd catalyst
3 4
FIGURE 3 EDX pattern of Fe O @L-
lysine-Pd catalyst

6
of 18
ASHRAF ET AL.
organometallic complex on the surface of Fe O MNPs
Fe O @L-lysine-Pd (b) were shown in Figure 6. In the
3
4
3 4
(
Figure 3). Moreover, in order to extend the scope of cata-
TGA curves, the physically adsorbed water mass loss
ꢀ
lysts characterization, the exact amount of Pd in
Fe O @L-lysine-Pd was examined by ICP-OES tech-
nique. The Pd amount of the immobilized catalyst on
MNPs was found to be 1.16 × 10−3 mmol g .
occurred at temperatures below 250 C. Moreover, the
ꢀ
endothermic weight loss at 300 C is attributed to water
3
4
[16]
loss from structural hydroxyl groups in the precursor.
In TGA curve of the Fe O @L-lysine-Pd (b), the first
−1
3
4
ꢀ
X-Ray Mapping (WDX analysis) of Fe O @L-lysine-
weight loss stage (below 100 C) can be ascribed to the
evaporation of water molecules in the composition. The
3
4
Pd confirmed a homogeneous distribution of all elements
Iron, Oxygen, Carbon, Nitrogen and Palladium) in the
structure of the heterogenized catalytic complex
Figure 4).
The surface area of Fe O @L-lysine-Pd nano-
ꢀ
(
next weight loss stage (200–800 C) can be ascribed to
the decomposition of the L-lysine-Pd organometallic
(
complex on the surface of Fe O MNPs. These results
3
4
confirmed that L-lysine-Pd organometallic complex has
been successfully chemisorbed on the surface of Fe O
3
4
material was analyzed using a fully automated BET
surface area analyzer (Brunauer–Emmett–Teller, model:
Belsorp-miniII) by nitrogen multilayer dsorption mea-
sured as a function of relative pressure (P /P ). As can
3
4
[
120,121]
MNPs.
The vibration sample magnetometer (VSM) of the
Fe O @L-lysine-Pd was displayed in Figure 7 in which
s
0
3 4
be seen from Figure 5, the BET surface area of the
prepared nano structure is 109.8 m /g. The high sur-
face may endow the material stronger than the cata-
lytic properties.
the saturation magnetization of the catalyst is about
41 emu/g. This magnetization value is less than the
uncoated Fe O MNPs due to the coated shell.
3 4
2
[
122]
In order to evaluate the morphology and particle size
of the Fe O @L-lysine-Pd hybrid material, scanning elec-
The TGA was used to determine the percentage of
3
4
the chemisorbed L-lysine-Pd on the surface of Fe O4
tron microscopy (SEM) was used (Figure 8). On the basis
of SEM images, the catalytic particles in the Fe O @L-
3
MNPs. The TGA curves of Fe O4 MNPs (a) and
3
3 4
3 4
FIGURE 4 The X-ray map analysis Fe O @L-lysine-Pd catalyst

ASHRAF ET AL.
7 of 18
FIGURE 5 Nitrogen
adsorption– desorption
isotherms of the Fe
lysine-Pd catalyst
3 4
O @L-
FIGURE 6 TGA curves of Fe
3
O
4
MNPs (a), and Fe
3
O
4
@L-
3 4
FIGURE 7 Magnetization curves of Fe O @L-lysine-Pd
lysine-Pd (b)
catalyst

8
of 18
ASHRAF ET AL.
3 4
FIGURE 8 SEM images of Fe O @L-lysine-Pd catalyst
lysine-Pd sample has a spherical shape. It is worth men-
tioning that the obtained morphology resulted in maxi-
mizing the simultaneous increasing of the catalyst
efficiency and frequency of molecular interactions or
decreasing activation energy of the rate determining step.
Morphology of the synthesized Fe O @L-lysine-Pd
different experimental parameters; including, the amount
of the catalyst, solvent, base and the effect of temperature
on the selected model substrate were investigated
(Scheme 2). The results are summarized in Table 1. In
the first step, the influence of different amounts of the
catalyst on the outcome of the reaction was studied, and
it was revealed that the best yield was obtained in the
presence of 0.08 mol% of Fe O @L-lysine-Pd MNPs.
3
4
was evaluated by Transmission electron microscopy
Figure 9). Particle size measurements gave a distribution
of nanoparticle dimensions across a range from 4 to
3 nm, with an average size of 7.8 nm.
(
3
4
Meanwhile, in the absence of the catalyst, the reaction
didn't proceed at all even after 48 hours (Table 1, entry
1
1). In the next step, the effects of the solvent, base and
the reaction temperature were screened, and the best C-C
coupling product was obtained in water in the presence
of Na CO as the most effective base under reflux condi-
3.3 | Catalytic study
2
3
After the successful synthesis and characterization of
Fe O @L-lysine-Pd MNPs, their catalytic properties were
examined in Suzuki reaction.
tions with the highest yield of the biphenyl product.
According to the observed results, the optimal conditions
for this reaction are: Fe O @L-lysine-Pd catalyst
3
4
3
4
In order to find the best conditions for Suzuki reac-
tion, the coupling of iodobenzene (1 mmol) with phe-
nylboronic acid (1 mmol) under different conditions was
selected as the model reaction. Then, the effect of the
(0.080 mol%), Na CO (1.5 mmol) as base in water at
2 3
reflux conditions (Table 1, entry 6).
After optimizing the reaction conditions, the catalytic
effectiveness of Fe O @L-lysine-Pd MNPs was
3
4

ASHRAF ET AL.
9 of 18
3 4
FIGURE 9 TEM images of Fe O @L-lysine-Pd catalyst
donating groups. Moreover, the Suzuki C-C cross-cou-
pling of phenylboronic acid with aryl iodide, aryl bro-
mides, was easier than those with aryl chlorides as the
less reactive aryl source. Because the order of reactivity of
the electrophilic partners in Suzuki coupling based on
their leaving groups is: I > > Br > OTf > > Cl > F, the
chloride electrophiles are the most nonreactive ones as
they are reluctant to participate in oxidative addition.
Furthermore, in this work, aryl chlorides electrophiles
have been established using L-lysine as an electron-
donating (electron rich) ligand on the Pd catalyst and
K CO base in order to encourage dissociation of Cl. In
order to show the chemoselectivity of this new catalytic
system, the reaction of 1-bromo-4-chloro benzene was
also investigated in which the bromide group showed
more reactivity (Tables 2 entry 23). This selectivity allows
the product to remain an active halide site for further
functionalization.
SCHEME 2 Optimization of the reaction conditions for the
Suzuki C-C cross coupling of iodobenzene with phenylboronic acid
investigated in the Suzuki C-C cross-coupling reactions of
a wide range of commercially available aryl halides with
phenylboronic acid as phenylating source (Scheme 3).
The results are listed in (Table 2) in which the target
products were afforded in moderate to excellent yields.
The experimental results show that various ortho-, meta-,
and para-substituted aryl halides; including, aryl iodide,
aryl bromides and aryl chlorides having both electron-
withdrawing and electron-donating groups, produced
their corresponding biphenyl derivatives in good to excel-
lent yields. However, it is worth mentioning that the reac-
tion time of the aryl halides with electron-donating
groups on the aromatic ring was longer than aryl halides
with electron-withdrawing groups. Due to the fact that
the aryl halides electrophilic partners in Suzuki coupling
are activated by electron-withdrawing (EWD) groups in
the ortho or para positions, their reactivity in oxidative
addition is increased as compared to those with electron-
2
3
In summary, the results show that the catalytic sys-
tem is very efficient for Suzuki cross coupling catalytic
systems and affords the corresponding products in high
to excellent yields in green media.
The catalytic cyclic mechanism for Suzuki reaction in
the presence of Fe O @L-lysine-Pd is shown in the
3
4
Scheme 4 based on the previously reported mecha-
[
23]
nism.
The general catalytic cycle for Suzuki cross

10 of 18
ASHRAF ET AL.
TABLE 1
Optimization of the reaction conditions for the C-C cross coupling of iodobenzene with phenylboronic acid
ꢀ
a
Entry
Catalyst (mol%)
-
Solvent
Water
Water
Water
Water
Water
Water
DMSO
DMF
Base
Temperature ( C)
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
110
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
9
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
2
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
3
3
2 days
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
45
NR
45
73
87
91
99
96
91
95
89
92
83
89
81
91
77
49
89
NR
53
76
88
0.020
0.035
0.050
0.060
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
0.080
110
PEG-400
EtOH
110
10
11
12
13
14
15
16
17
18
19
20
21
22
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
25
EtOH:H
Dioxane
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
2
O (1:1)
KOH
NaOH
2 3
K CO
Et
t-BuOK
Cs CO
3
N
2
3
Na
Na
Na
Na
2
2
2
2
CO
CO
CO
CO
3
3
3
3
60
80
90
a
Isolated yield.
coupling involves three fundamental steps: oxidative
addition, transmetalation, and reductive elimination as
demonstrated in scheme 4, The oxidative addition of aryl
halides to Fe O @L-lysine-Pd(0) complex is the initial
desired product and regenerate the original Fe O @L-
3 4
lysine-Pd(0) species.
3
4
step to give intermediate 1, a Fe O @L-lysine-Pd (II) spe-
3.4 | Recyclability study
3
4
cies. Due to the fact that oxidative addition is the most
difficult step of the entire catalytic cycle, the presence of
amines as the electron-donating groups on the L-lysine
ligand can activate the Pd(0) catalyst such that the Ar-X
bond can be easily broken along with the formation of
Pd-Ar and Pd-X bond. In the next step under the partici-
pation of base, an organoborane compound reacts with
intermediate 1 in transmetalation to afford intermediate
Recyclability of heterogeneous catalysts is an important
advantage in industrial applications. Therefore, the
recoverability and reproducibility of Fe O @L-lysine-Pd
3
4
0
were explored in the synthesis of 1,1 -biphenyl. After the
completion of the reaction, the Fe O @L-lysine-Pd cata-
3
4
lyst was separated using an external magnet, washed
ꢀ
with EtOAc and water and dried at 80 C. Then, it was
2
. This is followed by reductive elimination to give the
reused for the next run. As shown in Figure 10, the
3 4
SCHEME 3 Fe O @L-lysine-Pd catalyzed the
Suzuki Cross coupling of various aryl halides with
phenylboronic acid for the synthesis of biphenyl
products

ASHRAF ET AL.
11 of 18
TABLE 2
Catalytic C-C cross coupling reaction of various aryl halides with Phenylboronic acid in the presence of catalytic amounts of
3 4
Fe O @L-lysine-Pd
a
TOF (min−1
)
Entry
Aryl halide
Product
Time (min)
Yield (%)
TON
1
45
99
12375
275
2
3
30
20
95
97
1187.5
1212.5
39.58
60.625
4
5
25
15
96
97
1200
48
1212.5
80.83
6
25
95
1187.5
47.5
7
8
9
45
35
25
97
95
98
1212.5
1187.5
1225
26.94
33.92
49
10
30
95
1187.5
39.58
1
1
1
2
45
60
97
94
1212.5
1175
26.94
19.58
1
1
3
4
60
45
95
92
1187.5
1150
19.79
25.55
(
Continues)

12 of 18
ASHRAF ET AL.
TABLE 2 (Continued)
a
TOF (min−1
)
Entry
Aryl halide
Product
Time (min)
Yield (%)
TON
15
60
95
1187.5
19.79
1
6
35
60
95
89
1187.5
1112.5
33.92
18.54
17
1
1
2
2
2
8
9
0
1
2
75
25
70
35
40
92
91
95
94
94
1150
15.33
45.5
1137.5
1187.5
1175
16.96
33.57
29.37
1175
2
2
3
4
75
30
92
91
1150
15.33
37.91
1137.5
25
80
89
1112.5
13.90
2
2
6
7
75
70
93
92
1162.5
1150
15.5
16.42
28
85
92
1150
13.52

ASHRAF ET AL.
13 of 18
TABLE 2 (Continued)
a
TOF (min−1
)
Entry
Aryl halide
Product
Time (min)
Yield (%)
TON
29
110
87
1087.5
9.88
30
120
89
1112.5
9.27
3
3
1
2
100
140
91
89
1137.5
1112.5
1.37
7.94
3
3
3
4
110
180
91
49
1137.5
612.5
10.34
3.40
35
85
94
1175
20.25
3
3
6
7
95
80
91
95
1137.5
1187.5
11.97
14.84
3
3
8
9
95
92
89
1150
12.10
220
1112.5
5.05
a
Isolated yield.

14 of 18
ASHRAF ET AL.
(
Figure 3), the EDS spectrum of the recycled Fe O @L-
3
4
lysine-Pd shows the presence of Fe, O, C, N and Pd spe-
cies in the recycled catalyst. Therefore, the element com-
position of the catalyst has not been changed after
recycling.
FT-IR spectrums of the recycled catalyst is shown in
Figure 12b. The results show that a good agreement was
observed for FT-IR of the fresh Fe O @L-lysine-Pd
3
4
(
Figure 12a) and the recycled catalyst (Figure 12b).
Therefore, Figure 12 indicates good stability of Fe O @L-
3
4
lysine-Pd after recycling.
FIGURE 10 Recyclability study
3.5 | Hot filtration test
recycling process was repeated for five times with a slight
decrease in the activity of the catalyst. The amount of Pd.
leached Pd using ICP analysis was found to be 0.57%.
Also, in order to examine the stability of the catalyst
after recycling, the spent catalyst has been characterized
by EDS and FT-IR techniques. These characterizations
confirmed that the spent catalyst is in good agreement
with the fresh catalyst. These characterizations are strong
evidences for the high stability of Fe O @L-lysine-Pd
The heterogeneity of Fe O @L-lysine-Pd MNPs in the
3 4
reaction mixture was studied using the hot filtration test
0
which was performed in the synthesis of 1,1 -biphenyl
under the optimal reaction conditions. After the half
reaction time, the reaction was terminated and the
corresponding product was obtained in 53% of yield.
Then, the reaction was repeated, and at the half time of
the reaction, the catalyst was separated by magnetic sepa-
ration from the reaction mixture, which was allowed to
react further. Accordingly, we found that only a trace
conversion (<2%) of the coupling reaction was observed
upon heating of the catalyst-free solution for another half
time of the reaction, which means that the described
nanocatalyst is completely heterogeneous in the reaction
media.
3
4
after recycling.
In order to indicate the stability of the elements of cat-
alyst, EDS analysis of the recycled Fe O @L-lysine-Pd
3
4
was conducted (Figure 11). As like to fresh catalyst
3.6 | Leaching study
In order to consider the leaching of palladium into
reaction media, ICP-AES analysis was performed in
which the palladium content in reaction media, in the
0
synthesis of 1,1 -biphenyl, was found to be 0.21%. The
results show that the leaching of Pd into reaction
media is negligible.
3.7 | Comparison
In order to investigate the efficiency of this new proce-
dure, in comparison to the reported procedures in the lit-
erature, the results for the C-C cross coupling of
iodobenzene with phenylboronic acid, as the representa-
tive example, was compared to the best of the well-
known data from the literature as outlined in the Table 3.
The comparison results show that the present catalytic
system modified the Suzuki reaction time, yields and
conditions.
SCHEME 4 Mechanism of the palladium-catalyzed Suzuki
reaction

ASHRAF ET AL.
15 of 18
FIGURE 11 EDS spectrum of recycled
Fe O @L-lysine-Pd
3 4
3 4 3 4
FIGURE 12 FT-IR spectrums of Fe O @L-lysine-Pd and recovered Fe O @L-lysine-Pd MNPs
TABLE 3
Comparing catalytic activity of Fe
3
O
4
@L-lysine-Pd with previously reported methods in the Suzuki reaction
a
Entry
Catalyst
Time (mine)
Yield (%)
Ref.
[
[
[
[
[
[
[
123]
124]
125]
87]
1
2
3
4
5
6
7
8
VO (IV)–MCM-41
Pd@DCA-SBA
720
120
15
100
95
91
95
94
74
98
99
Fe
3
3
O
4
4
@SiO
2
@L-arginine@Pd(0)
-CoII NPs
Fe
O
@Boehmite-NH
2
30
126]
127]
31]
Pd@DCA-MCM
MCM-Pd
120
1440
30
Boehmite@Tryptophan-Pd
Fe @L-lysine-Pd
3
O
4
45
This work
a
Isolated yield.

16 of 18
ASHRAF ET AL.
4
| CONCLUSIONS
[21] L. Chen, A. Noory Fajer, Z. Yessimbekov, M. Kazemi,
M. Mohammadi, J. Sulfur Chem. 2019, 40, 451.
[
[
[
22] Q. Pu, M. Kazemi, M. Mohammadi, Mini. Rev. Org. Chem.
We have synthesized a palladium nanocatalyst as a
robust and heterogeneous catalyst in the Suzuki coupling
reaction. Easy separation of the catalyst and control of
the release of palladium into the reaction mixture
because of the strong bonding between L-lysine and pal-
ladium are factors contributing to this catalyst being
reusable. In addition, the experimental results confirm
that a broad variety of the functional groups can be used
in this type of the catalytic reaction.
2019, 16, 5775.
23] A. Ghorbani-Choghamarani, M. Mohammadi, Z. Taherinia,
J. Iran. Chem. Soc. 2019, 16, 411.
24] A. Ghorbani-Choghamarani, M. Mohammadi, T. Tamoradi,
M. Ghadermazi, Polyhedron 2019, 158, 25.
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ORCID
Dangquan Zhang https://orcid.org/0000-0003-4234-
[
[
[
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