Green and sustainable palladium nanomagnetic catalyst stabilized by glucosamine-functionalized Fe3O4@SiO2 nanoparticles for Suzuki and Heck reactions

Article abstract of DOI:10.1002/aoc.6260

A novel magnetic and heterogeneous palladium-based catalyst stabilized by glucosamine-functionalized magnetic Fe₃O₄@SiO₂ nanoparticle was synthesized. The strategy relies on the covalently bonding of glucosamine to cyanuric chloride-functionalized magnetic nanoparticles followed by complexation with palladium. The structure of magnetic nanocatalyst was fully determined by FT-IR, XRD, DLS, FE-SEM, TEM, ICP, UV-Vis, TGA, VSM, and EDX. The obtained results confirmed that the palladium nanoparticles stabilized by glucosamine immobilized onto the magnetic support exhibited high activity in cross-coupling reactions of Suzuki-Miyaura and Mizoroki-Heck. Various aryl halides were coupled with arylboronic acid (Suzuki cross-coupling reaction) and olefins (Heck reactions) under the green conditions to provide corresponding products in high to excellent yields. Interestingly, the catalyst can be easily isolated from the reaction media by magnetic decantation and can subsequently be applied for consecutive reaction cycles (at least seven times) with no notable reduction in the catalytic activity.

Full text of DOI:10.1002/aoc.6260

Received: 9 October 2020
DOI: 10.1002/aoc.6260
Revised: 25 March 2021
Accepted: 27 March 2021
F U L L P A P E R
Green and sustainable palladium nanomagnetic catalyst
stabilized by glucosamine-functionalized Fe3O4@SiO2
nanoparticles for Suzuki and Heck reactions
Hassan Eslahi1
| Ali Reza Sardarian1
| Mohsen Esmaeilpour2
1Chemistry Department, College of
Sciences, Shiraz University, Shiraz, 71946
84795, Iran
2Chemistry and Process Engineering
Department, Niroo Research Institute,
Tehran, 1468617151, Iran
A novel magnetic and heterogeneous palladium-based catalyst stabilized by
glucosamine-functionalized magnetic Fe3O4@SiO2 nanoparticle was synthe-
sized. The strategy relies on the covalently bonding of glucosamine to cyanuric
chloride-functionalized magnetic nanoparticles followed by complexation with
palladium. The structure of magnetic nanocatalyst was fully determined by
FT-IR, XRD, DLS, FE-SEM, TEM, ICP, UV-Vis, TGA, VSM, and EDX. The
obtained results confirmed that the palladium nanoparticles stabilized by glu-
cosamine immobilized onto the magnetic support exhibited high activity in
cross-coupling reactions of Suzuki-Miyaura and Mizoroki-Heck. Various aryl
halides were coupled with arylboronic acid (Suzuki cross-coupling reaction)
and olefins (Heck reactions) under the green conditions to provide
corresponding products in high to excellent yields. Interestingly, the catalyst
can be easily isolated from the reaction media by magnetic decantation and
can subsequently be applied for consecutive reaction cycles (at least seven
times) with no notable reduction in the catalytic activity.
Correspondence
Ali Reza Sardarian, Chemistry
Department, College of Sciences, Shiraz
University. Shiraz 71946 84795, Iran.
Email: sardarian@shirazu.ac.ir
Funding information
Iran National Science Foundation; Shiraz
University
K E Y W O R D S
core shell, green synthesis, magnetic nanoparticles, Mizoroki-Heck reaction, Suzuki-Miyaura
reaction
1 | INTRODUCTION
magnetic resonance imaging, contrasting reagents, can-
cer treatment, targeted drug delivery, tissue repairing,
Nanostructures with controlled morphology and geome-
try, multiple compartments, and a variety of chemical
magnetic storage media, biosensing, magnetic inks for jet
printing, and catalysis.[18–21] However, having anisotropic
dipolar attraction, MNPs trend to be aggregated easily in
aqueous solutions.[22] In addition, they are unstable
under acidic conditions and susceptible to air oxidation,
which can alter magnetic properties, reduce the sorption
capacity, and restrict the application range.[23,24] To over-
come this limitation, the stabilization of MNPs should be
considered. Magnetic core shells, bearing both advan-
tages of cores and wide spectrum of shells, have absorbed
much attention in the intensive researches.[25–28] Meso-
porous silica is one of the best applicable reagents for
which bearing remarkable chemical compatibility,
functionalities
represent
microstructures
and
nanostructures to improve nanoscaffolds designing.[1,2]
Nanoparticles have been applied in many interesting fields
including bio-nanoscience,[3] optics,[4] electronics,[5,6]
drug delivery,[7] medicine,[8] solar cells,[9] and catalysts.[10]
Among all nanoparticle types, magnetite (Fe3O4) has
attracted more attentions because of its unique magnetic
properties,[11–13] low toxicity,[14] facile magnetically
removal,[15] chemically modifiable surface,[16] and bio-
compatibility.[17] Therefore, applications of these mag-
netic nanoparticles (MNPs) have been developed in
Appl Organomet Chem. 2021;e6260.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6260

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ESLAHI ET AL.
stability, and reactivity with various coupling
agents.[29,30] Additionally, the existence of hydroxyl func-
tional groups on silica shell surface supply suitable sites
for possible conjugation of varies function scaffolds.[31]
Therefore, the obtained Fe3O4@SiO2 nanostructures have
ideally both features of magnetic nanoparticles and meso-
porous silica layer.[32]
There are some reports in the literature which sup-
port high catalytic activity of homogeneous Pd-based cat-
alysts in organic chemistry,[33] but there are some
drawbacks associate to these catalysts including their
high price,[34] toxicity,[35] and difficult separating, purify-
ing, and recycling from reaction that restrict their utiliza-
tion.[36] To overcome such obstacles, immense endeavors
have been accomplished to heterogenized these homoge-
neous Pd-based catalysts by immobilization tech-
niques.[37,38] Several researches exhibited effective
loading of Pd particles by diverse carriers.[39–43]
The catalyzed establishment of carbon carbon bond
couplings is of the utmost interesting reactions in syn-
thetic organic chemistry.[44] In last decades, nanocatalysts
based on palladium particles have been found to be appli-
cable in wide spectrum of C C bond formations.[45]
Among all palladium catalyzed reactions, the Mizoroki-
Heck and Suzuki-Miyaura reactions have been powerful
means for the formation of C C bond in numerous
organic transformations leading to the synthesis of natu-
ral products, pharmaceuticals, and biologically active
molecules due to significant properties of palladium in
these reactions.[46] Although many impressive modifica-
tion methodologies in such reactions have intensively
been published in the literature,[47,48] they suffer com-
monly from some disadvantages such as tedious workup
procedures, consuming notably large quantities of Pd-
based catalyst, toxic and expensive ligands as worrying
costly factors, long reaction times, low yields, high tem-
peratures, and using toxic solvents. Therefore, the design
and production of new catalytic alternates, which are not
only active and stable but also are easily separable and
reusable, are highly eligible and demanded to simplify
their applications and make them effective in C C bond
formations (Figure 1).
Therefore, relying on outstanding features of glucos-
amine (GA), economically and environmentally, as a
well-known carbohydrate involving biodegradability,[49]
catalytic activities,[50] bioactivity,[51] therapeutic proper-
ties, and its solubility in water,[52] we decided first to syn-
thesize
a
novel separable and heterogeneous
Fe3O4@SiO2-TCT-GA-Pd(0) magnetic nanocomposite
with hydrophilic head (Scheme 1) and then use it in
Suzuki and Heck coupling reactions to synthesis different
interesting organic compounds.
FIGURE 1 (A) Homogeneous and (B) magnetic heterogeneous catalysts in Mizoroki-Heck and Suzuki-Miyaura reactions

ESLAHI ET AL.
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SCHEME 1 Preparation
process of glucosamine-
functionalized magnetic
Fe3O4@SiO2 catalysis based on
Pd(0)
2 | EXPERIMENTAL SECTION
2.1 | Materials and methods
spectra using KBr pellet. The X-ray diffraction (XRD) of
the samples was also studied by the Bruker AXS
D8-advance X-ray diffractometer using CuKα radiation.
It was also investigated transmission electron microscopy
(TEM) on a Philips EM208 microscope and was operated
at 100 kV. Field emission scanning electron microscopy
(FE-SEM) was performed by HITACHI S-4160. Dynamic
light scatterings (DLSs) were done on a HORIBA-LB550.
The constructing elements of samples were probed by
energy-dispersive X-ray (EDX) spectroscopy accessory to
the Philips scanning electron microscopy (SEM).
PerkinElmer device was considered to get thermal gravi-
metric analysis (TGA) data. Vibrating sample magnetom-
eter (VSM) measurements were determined by using an
instrument model BHV-55 VSM. The loading amount of
Pd was recorded by inductively coupled plasma (ICP;
Varian, Vista-pro). The elemental analyses (C, H, and N)
were performed from a Thermo Finnigan Flash EA-1112
CHNSO rapid elemental analyzer. An Electrothermal
9100 apparatus was applied to get melting points of
2.1.1 | Chemicals and instrumentation
All chemicals were obtained from Merck and Sigma-
Aldrich companies and were employed without any fur-
ther purification. The progress of reaction was pursued
by thin-layer chromatography (TLC) analysis. The puri-
fied products were isolated from the reaction mixture by
silica gel impregnated with a fluorescent initiator on
glass plates, and all outcomes were investigated on a
PerkinElmer Lambda 25 UV/Vis spectrometer by
ultraviolet-visible (UV) spectroscopy. A Bruker advanced
DPX-250 spectrometer was obtained to take NMR spectra
1
in CDCl3 for 13C at 62.9 MHz and for H at 250 MHz.
UV-Vis spectra were checked out on a PerkinElmer
Lambda 25 UV/Vis spectrometer. The spectrometer
model Shimadzu FT-IR 8300 was applied to get FTIR

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ESLAHI ET AL.
synthesized products, and all 1H NMR and 13C NMR
spectra, which have been displayed in Data S1, were pre-
cisely compared with literature reports.
external magnet, washed several times with H2O/EtOH
(1:1) to eliminate intact precursors and unpleasant
byproducts, and dried eventually at 60ꢀC
2.2 | Materials synthesis
2.2.4 | Production of Fe3O4@SiO2-N
(OH)2 NPs
2.2.1 | Preparation of Fe3O4
nanoparticles
The solution of 3-(3-hydroxy-propylamino)-propan-1-ol
(3 mmol, 0.4 ml) and triethylamine (3 mmol, 0.4 ml) in
EtOH/H2O (20 ml,1:1) was stirred mechanically at ambi-
ent temperature for 2 h. In the next, Fe3O4@SiO2-Cl (1 g)
was carefully poured into the solution with vigorous stir-
ring for 12 h at 70ꢀC. The produced Fe3O4@SiO2-N (OH)2
magnetic nanoparticles were taken out with an external
magnet from the reaction mixture, washed up several
times with distilled H2O/EtOH (1:1), and dried at 70ꢀC.
According to the previous modified chemical co-
precipitation approach,[53] the solution of FeCl2 (0.9 g,
4.5 mmol), FeCl3.6H2O (1.3 g, 4.8 mmol), and 1 g of poly-
vinyl alcohol (PVA, Mw = 15,000) in 30 ml deionized
H2O was mixed for 0.5 h with mechanical stirrer at 80ꢀC.
Hexamethylenetetramine (HMTA) (1.0 mol/L) was grad-
ually added drop by drop to the solution while it was
being stirred vigorously. The pH was adjusted to
pH = 10, and then, a black solid was appeared with con-
tinued stirring, and then, the mixture was allowed to be
warmed up on water bath at 60ꢀC for 2 h to obtain Fe3O4
nanoparticles. These dry pure nanoparticles were pro-
vided after magnetically removing from reaction vessel,
washing frequently with EtOH and deionized water to
get away any impurity and vacuum drying at 50ꢀC for
10 h.
2.2.5 | Production of Fe3O4@SiO2-
TCT NPs
To the dispersed solution of Fe3O4@SiO2-N (OH)2 (1 g)
synthesized
in
THF
(15 ml)
was
added
diisopropylethylamine (DIPEA) (6 mmol, 1.0 ml), and
the solution was gently stirred for 2 h. Next, 1.1 g of
2,4,6-trichloro-1,3,5-triazine (TCT) (1.1 gr, 6 mmol) was
poured into the previous mixture and stirred at room
temperature for 16 h. After that, the synthesized
Fe3O4@SiO2-TCT NPs were brought out from the reac-
tion solution by an external magnetic field, washed up
several times with H2O/EtOH (1:1, 30 ml), and dried at
70ꢀC for 4 h.
2.2.2 | Production of Fe3O4@SiO2 core
shell
In this step, the dispersed solution of Fe3O4 (0.5 g)
nanoparticles in deionized water (5 ml) was mixed with
the solution of NaOH (5 ml, 10 wt%) in EtOH using ambi-
ent temperature. Then, tetraethoxysilane (TEOS, 0.2 ml)
was added slowly and the solution stirred for 30 min. The
magnetic core shell produced, Fe3O4@SiO2 nanospheres,
were taken out magnetically from the reaction media,
washed up three times with deionized H2O and EtOH,
and finally dried completely at 80ꢀC for 10 h.[10,15]
2.2.6 | Production of Fe3O4@SiO2-TCT-
GA-Pd(0) NPs
Glucosamine (0.75 g) was completely dissolved in 1 g of
Fe3O4@SiO2-TCT nanoparticles (1 g) dispersed in THF
(20 ml) when the reaction temperature had been tuned
on 80ꢀC. After 6 h stirring, Fe3O4@SiO2-TCT-GA
nanocomposite was obtained. The nanocomposite was
magnetically segregated, washed with hot EtOH in a
Soxhlet apparatus to dispel the unreacted starting mate-
rials, and dried at 70ꢀC for 4 h. Then, Fe3O4@SiO2-TCT-
GA (1 g) and 0.09 g of Pd (OAc)2 (0.4 mmol) were mixed
in to THF (15 ml) and stirred mechanically under reflux
condition for 3 h to provide the title heterogeneous Pd-
based nanocatalyst. This dark precipitate was detached
magnetically from the reaction solution and washed up
several times with EtOH/H2O. At the end, it was dried at
60ꢀC for 3 h.
2.2.3 | Production of Fe3O4@SiO2
functionalized with
3-chlorotrimethoxypropyl silane
(Fe3O4@SiO2-Cl)
A total of 1.0 g of Fe3O4@SiO2 interspersed in ethanol
(20 ml) using an ultrasonicate instrument was treated
with 3-chloromethoxypropylsilane (3 mmol) under the
reflux conditions for 12 h. The resulting magnetic core
shells grafted with 3-chlorotriethoxypropyl silane
(Fe3O4@SiO2-Cl) were magnetically collected by an

ESLAHI ET AL.
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2.2.7 | General method for Suzuki
couplings
Typically, 1 mmol of aryl halide, 1.1 mmol of arylboronic
acid, 2 mmol of K2CO3, and 4 mg of Fe3O4@SiO2-GA-Pd
(0) (equal to 0.12 mol% Pd) catalyst were allowed to stir
at 50ꢀC in EtOH/H2O (1:1, 4 ml). After completion of the
reaction, the catalyst was magnetically detached, washed
up with ethyl acetate, dried in an oven, and reused
directly for successive runs. The solvent was evaporated,
and resulted precipitate was extra purified by chromatog-
raphy on silica gel (n-hexane: EtOAc).
2.2.8 | General procedure for the Heck
reaction
A mixture of aryl halide (1.0 mmol), n-butyl acrylate or
styrene (1.2 mmol), Fe3O4@SiO2-TCT-GA-Pd(0) (5 mg,
0.15 mol%
Pd),
K2CO3
(2.0
mmol),
and
2-Methoxyethanol/H2O (1:1, 4 ml) was stirred at 100ꢀC
for appropriate time. The reaction was cooled down to
room temperature, and the catalyst was isolated from the
reaction solution by an external magnetic field. The
related products were extracted from the residue solution
with ethyl acetate (2 × 10 ml). The organic phase was
extracted with H2O (2 × 10 ml), dried over anhydrous
Na2SO4, and evaporated in vacuum. The residue was
then purified by silica gel column chromatography and
n-hexane/ethyl acetate as eluent to yield the desired pure
product.
FIGURE 2 FT-IR spectra: (a) Fe3O4, (b) Fe3O4@SiO2,
(c) Fe3O4@SiO2-Cl, (d) Fe3O4@SiO2-N (OH)2, (e) Fe3O4@SiO2-
TCT, (f) Fe3O4@SiO2-TCT-GA, and (g) Fe3O4@SiO2-TCT-GA-Pd
(0) NPs
3 | RESULTS AND DISCUSSION
3.1 | Catalyst identification
3.1.1 | FT-IR analysis
bending vibration, respectively, provide two evidences for
modifying of the surface of Fe3O4 nanoparticles
with 3-chloromethoxypropylsilane (Fe3O4@SiO2-Cl;
Figure 2c). The presence of three distinguishable charac-
teristic absorption peaks such as C O (stretching), CH2
(bending), and C H (stretching) are shown at 1,354,
1,461, and 2,785–2,978 cm−1, respectively, and disappear-
ance of C Cl peak in Figure 2d via the reaction of
The FT-IR spectrum of each step was obtained to confirm
the functionalization of the magnetic particles. The
strong adsorption peak at about 570 cm−1 is cor-
responded to the Fe O bond (Figure 2a–g). The other
peaks around 3,400 and 1,620 cm−1 are related to
stretching vibrations of O H bonds depicted to the
adsorbed water in the samples.[54] The broad band
3-(3-hydroxy-propylamino)-propan-1-ol
with
Fe3O4@SiO2-Cl confirm successful synthesis of
Fe3O4@SiO2-N (OH)2 MNPs. In spite of overlapping the
peak of C Cl (normally a strong IR absorption band at
1,100 cm−1) with Si O bands, the existence of peaks at
1,512, 1,542 and 1,724 cm−1 in Figure 2e, which are allo-
cated to C N stretching absorptions of cyanuric chloride
(TCT), are indicative peaks for confirmation of
Fe3O4@SiO2-TCT nanoparticles. The presence of
around 1,100 cm−1
(asymmetric vibration), and the band around 790 cm−1
, which is relevant to Si-O-Si
,
which corresponds to the stretching vibrations of
Si-O-Si,[54] reflect the coating of silica on the magnetite
surface (Figure 2b–g).
The appearance of new peaks at 702 and 1,444 cm−1
,
which correspond to C Cl stretching vibration and CH2

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ESLAHI ET AL.
specified stretching vibration bands of Fe O at
species have been highly and uniformly dispersed on the
nanocatalyst surface (Figure 3c).[55]
570 cm−1; Si O Si at 1,100 cm−1; C O at 1,170 cm−1
;
C N at 1,510, 1,540, and 1,720 cm−1; and C H at 2,760–
3,050 cm−1 in Figure 2f,g provide sufficient indications
for formation of Fe3O4@SiO2-TCT-GA and Fe3O4@SiO2-
TCT-GA-Pd(0) nanostructures (Figure 2f and g). Ulti-
mately, the presence of the peak at 540 cm−1 is assigned
to the stretching vibration of Pd O demonstrates the
existence of Pd nanoparticles on the Fe3O4@SiO2-TCT-
GA surface.[22]
Using the Scherrer's equation, which has described as
follows, the mean diameter of nanoparticles was calcu-
lated in which K is a constant (K = 0.9 for CuKα), λ is the
wavelength of X-ray, β is the full width at half maximum
(FWHM), and ϴ is the diffraction angle.[56]
D = Kλ=βcosϴðScherrer equtionÞ
K is a constant (K = 0.9 for CuKα), λ is the wave-
length of X-ray, β is the full width at half maximum
(FWHM), and ϴ is the diffraction angle.
3.1.2 | XRD analysis
The crystalline forms of the superparamagnetic Fe3O4,
Fe3O4@SiO2 and Fe3O4@SiO2-GA-Pd(0) NPs were speci-
fied by powder XRD. As Figure 3a demonstrates all dif-
fraction peaks at 2ϴ = 30.1ꢀ, 35.4ꢀ, 43.1ꢀ, 53.4ꢀ, 57ꢀ and
62.6ꢀ corresponding to 220, 311, 400, 422, 511 and
440 reflection intensities of crystalline Fe3O4 NPs, respec-
tively, with cubic spinal structure (Reference JCPDS card
no. 19-629).
The intensity of Fe3O4 phase after coating was
detracted and the presence of amorphous SiO2 appears
between 15 and 25 of 2ϴ as a wide diffraction peak
(Figure 3b). Also, the coating process is not led to any
phase change of Fe3O4. This broad peak was demised to
lower angles in the case of Fe3O4@SiO2-GA-Pd(0) NPs
owing to the synergetic effect of attached organics and
amorphous silica layer (Figure 3c). The absence of peaks
of palladium nanoparticles implied that the palladium
3.1.3 | FE-SEM, TEM, and DLS analyses
Nanostructure size and morphology of Fe3O4,
Fe3O4@SiO2, and Fe3O4@SiO2-TCT-GA-Pd(0) composites
are investigated by FE-SEM and TEM techniques
(Figure 4). Typical FE-SEM picture of the Fe3O4
nanoparticles is shown in Figure 4a. The morphology of
these particles is spherical in shape, and their sizes are
ranging between 8 and 20 nm. Fe3O4@SiO2 composites,
which are prepared by coating Fe3O4 with dense silica,
show spherical morphology as shown as the FE-SEM pic-
ture (Figure 4b). The FE-SEM picture (Figure 4c) shows
that the Fe3O4@SiO2-TCT-GA-Pd(0) nanospheres still
keep the morphological properties of Fe3O4@SiO2 core
shell. As exhibited in Figure 4d, Fe3O4 possesses a mean
diameter of 12 nm. After the surface modification of
Fe3O4 particles with silica layer, the average diameter
size of obtained nanomagnetic Fe3O4@SiO2 particles
increased to 20 nm, but they still keep spherical shape of
Fe3O4 nanoparticles. According to TEM picture of
Fe3O4@SiO2 core shell in Figure 4e, it could be clearly
observed that the dark Fe3O4 nanoparticles have been
embedded in the light-gray matrix and the typical thick-
ness of silica layer has been approximately 8 nm
(Figure 4e). It can be seen from the TEM picture of
Fe3O4@SiO2-TCT-GA-Pd(0) NPs in Figure 4f that
Fe3O4@SiO2-TCT-GA-Pd(0) nanospheres synthesized
with a mean size of 35 nm have been well dispersed. The
average hydrodynamic size of Fe3O4, Fe3O4@SiO2, and
Fe3O4@SiO2-TCT-GA-Pd(0) NPs was measured by DLS
to be 12, 20, and 36 nm, respectively (Figure 4g–i).
3.1.4 | UV-Vis, EDX, and XPS analyses
UV-Vis spectrometer is an applicable technique to
recognize the oxidation state of loaded catalytic metal
species (Figure 5a). The UV-Vis patterns of Pd (OAc)2,
FIGURE 3 XRD patterns of (a) Fe3O4, (b) Fe3O4@SiO2, and
(c) Fe3O4@SiO2-TCT-GA-Pd(0) NPs

ESLAHI ET AL.
7 of 21
FIGURE 4 FE-SEM images of (a) Fe3O4, (b) Fe3O4@SiO2, and (c) Fe3O4@SiO2-TCT-GA-Pd(0) NPs; TEM images of the (d) Fe3O4,
(e) Fe3O4@SiO2, and (f) Fe3O4@SiO2-TCT-GA-Pd(0) NPs and DLS images of (g) Fe3O4, (h) Fe3O4@SiO2, and (i) Fe3O4@SiO2-TCT-GA-Pd
(0) NPs
Fe3O4, Fe3O4@SiO2-TCT-GA, and Fe3O4@SiO2-TCT-GA-
Pd(0) NPs are displayed in Figure 5a. This evaluation pro-
vides an evidence for existence of palladium with zero
oxidation state in the desired magnetic nanocatalyst and
confirms complete conversion of Pd (II) to Pd(0) by
vanishing of the broad peak between 420 and 430 nm,
which belongs to Pd (II) species.[37]
spectrum of Fe3O4@SiO2-TCT-GA-Pd(0) nanocatalyst
was studied. The presence of two peaks at 335.11 and
340.32 eV, which are assigning to 3d5/2 and 3d3/2 of palla-
dium (0), confirmed strongly the presence of palladium
with zero oxidation state in the catalyst (Figure 6).[10]
As illustrated in Figure 5b, the existence of elements
of carbon, iron, silica, nitrogen, and palladium has been
proven in the structure of Fe3O4@SiO2-TCT-GA-Pd
(0) particles by occurring the related peaks in EDX
spectrum.
3.1.5 | TGA, VSM, and ICP analyses
TGA study of the synthesized nanocomposites were also
taken to evaluate the stability of nanocatalyst and con-
structing organic functional groups (Figure 7A). The cur-
ves are noticed by two main weight losing regions. The
first step is attributed to a weight loss up to 150ꢀC giving
For determination of the oxidation state of palladium
included in the catalyst, the X-ray photoelectron

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ESLAHI ET AL.
FIGURE 5 (a) UV-Vis spectra of Fe3O4, Fe3O4@SiO2-TCT-GA, Pd (OAc)2, and Fe3O4@SiO2-TCT-GA-Pd(0) NPs; (b) EDX spectra of
Fe3O4@SiO2-TCT-GA-Pd(0) NPs
magnetic properties of all Fe3O4, Fe3O4@SiO2 and
Fe3O4@SiO2-TCT-GA-Pd(0) samples with the magnetiza-
tion values of 64.8, 40.3, and 27.1 emu/g, respectively.
This information reveals supermagnetic property of these
nanoparticles. It means they do not have magnetic mem-
ory and, although loss their magnetic moments in the
absence of any external magnetic field, they respond to
an external magnetic field.
Compared with Fe3O4 NPs, Fe3O4@SiO2 NPs and
Fe3O4@SiO2-TCT-GA-Pd(0) NPs represent smaller mag-
netization values ascribed to an enhancement in the size
and mass caused by the depositing silica gel and organic
compounds on Fe3O4 and Fe3O4@SiO2 NPs surfaces,
respectively (Figure 7B [b] and B [c]). Although the sur-
charge of nonmagnetic parts leads to a reduction in satu-
ration magnetizations, the Fe3O4@SiO2-TCT-GA-Pd
(0) NPs will still present prompt response against external
magnet and make them speedy separable from the
suspended reaction mixture in less than 0.5 min
(Figure 7C). Furthermore, the amount of 0.31 mmol/g of
palladium nanoparticles was determined for the palla-
dium incorporated in the catalyst, by ICP analysis
technique.
FIGURE 6 XPS spectrum of Fe3O4@SiO2-TCT-GA-Pd
(0) nanocatalyst
to desorption and vaporization of adsorbed water on the
surface.[21] Whereas in the second region, the weight loss
observed in range of 150–700ꢀC is ascribed to disintegra-
tion of organic compounds. For Fe3O4@SiO2-TCT-GA-Pd
(0) NPs, weight loss at temperatures below 150ꢀC can be
imputed to desorption of water (3.1%) from Fe3O4@SiO2
NPs surfaces, while weight loss at higher than 150ꢀC
(38.4%), resulting from the elimination of glucosamine
and organic part anchored on to the surface of
Fe3O4@SiO2 (Figure 7A [c]).
4 | CATALYTIC ACTIVITY OF
Fe3O4@SiO2-TCT-GA-CU
(II) NANOCATALYST
After investigation and characterization of Fe3O4@SiO2-
TCT-GA-Pd(0) heterogeneous nanocatalyst, it was found
that this nanocomposite can be employed as a magneti-
cally separable nanocatalyst in the cross-coupling reac-
tions of Suzuki and Heck.
Figure 7B, as a magnetization curve, gives the mag-
netic properties of NPs in exerted field of 6 kOe at 300 K.
These curves show no hysteresis or saturation in the

ESLAHI ET AL.
9 of 21
FIGURE 7 (A) Thermogravimetric analysis of (a) Fe3O4@SiO2, (b) Fe3O4@SiO2-Cl, and (c) Fe3O4@SiO2-TCT-GA-Pd(0) NPs;
(B) Magnetization curves for (a) Fe3O4, (b) Fe3O4@SiO2, and (c) Fe3O4@SiO2-TCT-GA-Pd(0) NPs
4.1 | Suzuki-Miyaura cross-coupling
reaction
bromobenzene, 1.1 mmol of phenyl boronic acid, 4 mg of
the Fe3O4@SiO2-GA-Pd(0) catalyst (0.12 mol% Pd), and
2 mmol of K2CO3 in EtOH/H2O (4 ml, 1:1) at 50ꢀC.
With having the optimized reaction parameters, the
catalyzed cross-coupling reaction of Suzuki-Miyaura
between aryl halides (I, Br, and Cl) and large library of
arylboronic acids was checked out by Fe3O4@SiO2-GA-
Pd(0) (4 mg, 0.12 mol% Pd) as a catalyst (Table 2). Almost
all of the expected products were achieved in outstanding
yields and TOFs. Treatment of arylboronic acids bearing
various electron-withdrawing and electron-releasing sub-
stitutions with aryl halides containing electron-releasing
and electron-withdrawing substitutions was led to the
related products in high to excellent yields. Although
electron-withdrawing substitutions on the same aryl
halide derivatives increased the reactivity (Table 2,
entries 3h, 3i, and 3o) and electron-releasing substitu-
tions reduced the reactivity (Table 2, entries 3b–3g), both
substitution types on the arylboronic acid showed the
similar effect and no significant difference was observed
in their reactivity (Table 2). According to the data in
Table 2, aryl chlorides react somehow slower than aryl
iodide and bromide derivatives. But because of lower
price of aryl chlorides and their facile availability, they
are ideal substrates compared with their bromide or
iodide counterparts. Therefore, their reactivity was
checked in the presence of higher amount of the catalyst
and at higher temperature (Table 2, entries 3a–3s). In
continues, the behavior of diiodo and dibromo pyridines
was explored in the Suzuki-miyaura reaction and gave
good yields of the related diarylated pyridines (Table 2,
entries 3v and 3w).
The catalytic reactivity of Fe3O4@SiO2-GA-Pd(0)
nanocatalyst was explored in the construction of variety
of biaryls using cross-coupling reaction of Suzuki-
Miyaura. The optimized conditions were initially deter-
mined for the model reaction between phenylboronic
acid and bromobenzene (Table 1). As it can be figured
out clearly, the solvent has remarkable effect on the effi-
ciency of the model coupling reaction of Suzuki. Various
solvents have been screened in the optimization process
(Table 1, entries 1–6). The nanocatalyst behaves its
highest activity in EtOH/H2O (1:1) and produces biphe-
nyl in the highest yield, 96% (Table 1, entry 6). In con-
tinue, it was found that increasing amount of the catalyst
up to 4 mg (0.12 mol% Pd) raises the efficacy of model
reaction and gives highest yields (Table 1, entries 6–9).
However, using higher amounts of the catalyst reduce
the efficiency of model reaction (Table 1, entry 10).
Therefore, 4 mg (0.12 mol% Pd) of the palladium-based
catalyst is selected as the best choice of catalyst amount
(Table 1, entry 6). Then, several bases including K2CO3,
Na2CO3, K3PO4, NaOAc, and Et3N were employed in the
presence
of
Fe3O4@SiO2-GA-Pd(0)
magnetic
nanoparticles (4 mg, 0.12 mol% Pd) in EtOH/H2O (4 ml,
1:1) at 50ꢀC (Table 1, entries 6 and 12–15). According to
this information (Table 1), K2CO3 shows the highest
activity (Table 1, entry 6).
In addition, we checked out diverse temperatures
(entries 6, 16, and 17), and it was identified that the tem-
perature has a substantial role on the isolated yield and
the best efficiency is achieved at 50ꢀC (Table 1, entry 6).
According to above-mentioned screening, the optimum
conditions are chosen briefly to be 1.0 mmol of
For comparing of our achievements with those of
recoverable Pd-based nanocatalysts reported in the
organic chemistry sources, the cross-coupling reaction of

10 of 21
ESLAHI ET AL.
TABLE 1 Evaluation of the reaction parameters on the Suzuki-Miyaura reaction for the preparation biphenyla
Entry
1
Catalyst (mol% Pd)
Solvent
Base
Temp. (ꢀC)
Time (h)
Yield (%)b
0.12
0.12
0.12
0.12
0.12
0.12
0.04
0.08
0.1
EtOH
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
No base
Na2CO3
K3PO4
NaOAc
Et3N
50
50
2
88
79
91
83
57
96
72
87
91
94
Trace
75
84
86
91
82
93
2
H2O
2.5
2.5
2.5
3
3
DMF
50
4
DMSO
50
5
Toluene
50
6
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
EtOH/H2O (1:1)
50
1.5
4
7
50
8
50
2
9
50
1.5
1.5
5
10
11
12
13
14
15
16
17
0.14
0.12
0.12
0.12
0.12
0.12
0.12
0.12
50
Reflux
50
1.5
2.5
1.5
2.5
4
50
50
50
K2CO3
K2CO3
r.t
60
1.5
Note: Bold text means the optimized condition obtained for the model reaction studied.
aReaction conditions: 1.1 mmol of phenylboronic acid, 1 mmol of bromobenzene, 2 mmol of base, Fe3O4@SiO2-TCT-GA-Pd(0), and 4 ml of solvent.
bIsolated yield.
Suzuki-Miyaura of iodobenzene with phenylboronic was
considered as a model reaction. The results summarized
in Table 3 appear the advantages of Fe3O4@SiO2-TCT-
GA-Pd(0). It catalyzes quantitatively the model reaction
in the shortest time with highest TOF value at one of
lowest temperatures in nontoxic solvent instead of toxic
mediums like toluene, CH2Cl2, THF, NMP, or DMF.
critical and the model cross-coupling reaction was
occurred only in the presence of catalyst (Table 4, entry
10). In the catalyst loading point of view, 5 mg of
Fe3O4@SiO2-TCT-GA-Pd(0), which is equal to 0.15 mol%
Pd, was found to be optimal value (Table 4, entry 5).
When 1.3–3.3 mg of Fe3O4@SiO2-TCT-GA-Pd(0) (equal
to 0.04–0.1 mol% Pd) were applied, the reaction did not
go to completion (Table 4, entries 11–14). However, an
ignorable improvement was observed on the reaction
time and the yield when the higher amount of
nanocatalyst was utilized (entry 15).
4.2 | Mizoroki-Heck reaction
Superb catalytic activity of Fe3O4@SiO2-TCT-GA-Pd
(0) nanocatalyst in the cross-coupling reaction of Suzuki-
Miyaura encouraged us to check its ability for catalyzing
Heck reaction. For finding out the most efficient condi-
tions, the effect of solvents, loading of catalyst, base, and
temperature were evaluated in the cross-coupling reac-
tion of bromobenzene (1 mmol) with n-butyl acrylate
(1.2 mmol) (Table 4). Initially, the effect of reaction sol-
vent was investigated. According to data given in Table 4,
2-methoxyethanol/H2O (4 ml, 1/1) was the most efficient
solvent for this reaction (entry 7). The role of catalyst was
Additionally, the efficiency of several organic and
inorganic bases was explored in the model reaction, and
the highest effect was obtained with K2CO3 (Table 4,
entries 5 and 16–20). The temperature effect was also
investigated on the activity of the synthesized catalyst
Fe3O4@SiO2-GA-Pd(0) (Table 4, entries 5 and 21–24).
Derived from optimized data, an increment in the tem-
perature promotes clearly the model reaction. When the
temperature was increased from room temperature to
100ꢀC, the isolated yield was substantially increased
(from 22% up to 96%). The raising temperature to 110ꢀC

ESLAHI ET AL.
11 of 21
TABLE 2 Catalyzed cross-coupling reaction of Suzuki-Miyaura of arylboronic acids with aryl halides by Fe3O4@SiO2-TCT-GA-Pd(0)
NPsa
(3b)
(3a)
X = I: 1.5 h, 90%b, TOF = 500 (h−1
)
X = I: 0.75 h, 97%b, TOF = 1,077 (h−1
)
X = Br: 3 h, 88%b, TOF = 244 (h−1)Xc = Cl: 10 h, 70%b, TOF = 39
(h−1
X = Br: 1.5 h, 95%b, TOF = 533 (h−1
Xc = Cl: 8 h, 76%b, TOF = 53 (h−1
)
)
)
(3d)
X = I: 1.5 h, 90%b, TOF = 500 (h−1
)
(3e)
X = I: 2 h, 88%b, TOF = 367 (h−1
X = Br: 5 h, 86%b, TOF = 143 (h−1)Xc = Cl: 11 h, 69%b, TOF = 35
(h−1
X = Br: 3 h, 87%b, TOF = 242 (h−1)Xc = Cl: 11 h, 71%b, TOF = 36
(h−1
)
)
)
(3f)
X = I: 1.5 h, 90%b, TOF = 500 (h−1
(3 g)
X = I: 1.7 h, 89%b, TOF = 436.3 (h−1
)
)
X = Br: 2.5 h, 87%b, TOF = 290 (h−1
)
X = Br: 3 h, 85%b, TOF = 236 (h−1
)
Xc = Cl: 10 h, 74%b, TOF = 41 (h−1
)
Xc = Cl: 10 h, 77%b, TOF = 43 (h−1
)
(3 h)
(3i)
X = I: 0.75 h, 92%b, TOF = 1,022 (h−1
)
X = I: 0.5 h, 95%b, TOF = 1,584 (h−1
)
X = Br: 1.5 h, 90%b, TOF = 500 (h−1
Xc = Cl: 8 h, 75%b, TOF = 52 (h−1
)
X = Br: 1.25 h, 94%b, TOF = 626 (h−1
)
Xc = Cl: 7 h, 89%b, TOF = 71 (h−1
)
)
(3j)
(3 k)
X = I: 1 h, 93%b, TOF = 775 (h−1
)
X = I: 1.2 h, 95%b, TOF = 660 (h−1
)
X = Br: 1.2 h, 89%b, TOF = 618 (h−1
Xc = Cl: 8 h, 77%b, TOF = 53 (h−1
)
X = Br: 1.5 h, 90%b, TOF = 500 (h−1
Xc = Cl: 8 h, 79%b, TOF = 55 (h−1
)
)
)
(Continues)

12 of 21
ESLAHI ET AL.
TABLE 2 (Continued)
(3 L)
(3 m)
X = I: 1.1 h, 93%b, TOF = 704.5 (h−1
)
X = I: 1.1 h, 95%b, TOF = 720 (h−1
)
X = Br: 1.5 h, 90%b, TOF = 500 (h−1
Xc = Cl: 9 h, 74%b, TOF = 46 (h−1
)
X = Br: 1.4 h, 90%b, TOF = 535 (h−1
Xc = Cl: 9 h, 72%b, TOF = 44 (h−1
)
)
)
)
)
(3n)
(3o)
X = I: 1.5 h, 92%b, TOF = 511 (h−1
)
X = I: 1.2 h, 94%b, TOF = 653 (h−1
)
X = Br: 1.8 h, 87%b, TOF = 403 (h−1
Xc = Cl: 9 h, 70%b, TOF = 43 (h−1
)
X = Br: 1.6 h, 91%b, TOF = 474 (h−1
Xc = Cl: 8 h, 78%b, TOF = 54 (h−1
)
)
(3p)
(3q)
X = I: 2 h, 90%b, TOF = 375 (h−1
)
X = I: 2.5 h, 87%b, TOF = 288 (h−1
)
X = Br: 2.5 h, 88%b, TOF = 293 (h−1
)
X = Br: 3.5 h, 83%b, TOF = 198 (h−1
Xc = Cl: 10 h, 68%b, TOF = 38 (h−1
)
Xc = Cl: 11 h, 73%b, TOF = 37 (h−1
)
(3r)
(3 s)
X = I: 2 h, 91%b, TOF = 379 (h−1
)
X = I: 2.1 h, 92%b, TOF = 365 (h−1
)
X = Br: 2 h, 89%b, TOF = 371 (h−1
Xc = Cl: 9 h, 75%b, TOF = 46 (h−1
)
)
X = Br: 2.2 h, 90%b, TOF = 341 (h−1
Xc = Cl: 9 h, 73%b, TOF = 45 (h−1
)
)
(3u)
(3 t)
X = I: 4 h, 90%b, TOF = 188 (h−1
)
X = I: 3.5 h, 90%b, TOF = 214 (h−1
)
X = Br: 4.8 h, 87%b, TOF = 151 (h−1
)
X = Br: 4.2 h, 87%b, TOF = 173 (h−1
)

ESLAHI ET AL.
13 of 21
TABLE 2 (Continued)
(3v)
(3w)
Xd = I: 3 h, 83%b, TOF = 115 (h−1
)
)
Xd = I: 2.5 h, 87%b, TOF = 115 (h−1
)
Xd = Br: 4 h, 77%b, TOF = 80 (h−1
Xd = Br: 3.6 h, 80%b, TOF = 371 (h−1
)
aReaction conditions: 1 mmol of aryl halide, 1.1 mmol of arylboronic acid, 2 mmol of K2CO3, Fe3O4@SiO2-TCT-GA-Pd(0) (4 mg, 0.12 mol% Pd), EtOH/H2O
(4 ml, 1:1), and 50ꢀC.
bIsolated yield.
cReaction conditions: 1 mmol of aryl chloride, 1.2 mmol of arylboronic acid, 2 mmol of K2CO3, Fe3O4@SiO2-TCT-GA-Pd(0) (6 mg, 0.18 mol% Pd), EtOH/H2O
(4 ml, 1:1), and 70ꢀC.
dReaction conditions: 1 mmol of aryl halide, 2.2 mmol of arylboronic acid, 4 mmol of K2CO3, Fe3O4@SiO2-TCT-GA-Pd(0) (8 mg, 0.24 mol% Pd), EtOH/H2O
(10 ml, 1:1), and 60ꢀC.
TABLE 3 Catalytic activity of the different Pd-based catalysts on the Suzuki-Miyaura coupling reaction of phenylboronic acid with
iodobenzene
Time
(h)
Yield
(%)
TOF
Entry Catalyst
Condition
(h−1
250
19.2
2.1
)
1
2
3
Pd/NiFe2O4 (0.1 mol%)[57]
Pd-Fe3O4 (0.1 mol%)[58]
C/Co@PNIPAM-PPh2-Pd (3 mol%)[59]
DMF/Na2CO3/90ꢀC
DME/H2O(3:1)/K2CO3/reflux
2
50
92
99
48
16
Toluene/H2O(2:1)/
K2CO3/85ꢀC
4
5
Fe3O4-Bpy-Pd (OAc)2 (0.5 mol%)[60]
Toluene/K2CO3/80ꢀC
6
2
99
96
33
44
Co/C-ROMPgel immobilized Pd-complex (1.1 mol
%)[61]
THF/H2O(1:2)/Na2CO3/65ꢀC
6
Fe@FexOy/Pd (0.5 mol%)[62]
Xerogel g1-MNPs (1 mol%)[63]
Pd@Mag-MSN (1 mol%)[64]
Pd(0)-ZnFe2O4 (4.62 mol%)[65]
Pd-MWCNT (0.3 mol%)[66]
Fe@NC@Pd (1.25 mol%)[67]
Fe3O4/SiO2-DTZ-Pd (0.33 mol%)[68]
Fe3O4@SiO2/Schiff base/Pd(П) (0.3 mol%[69]
EtOH/H2O(1:1)/K2CO3/r.t
CH3OH/Na2CO3/60ꢀC
CH2Cl2/K2CO3/80ꢀC
EtOH/K2CO3/Reflux
MeOH, NaOAc/Reflux
EtOH/K2CO3/reflux
2
98
99
85
92
95
99.9
94
96
97
98
7
2
49.5
14
8
6
9
4
5
10
11
12
13
14
2
158
52.7
131.4
427
1,077
1.5
2.16
0.75
0.75
PEG/Na2CO3/60ꢀC
NMP/K2CO3/100ꢀC
Fe3O4@SiO2-TCT-GA-Pd(0) (0.12 mol% Pd) (this
Work)
EtOH/H2O (1:1)/K2CO3/50ꢀC
presented no enhancement in yield, and consequently,
the appropriate temperature was determined to be 100ꢀC
(Table 4, entry 5). Thus, the suitable conditions for this
coupling reaction are Fe3O4@SiO2-TCT-GA-Pd(0) (4 mg,
0.12 mol% Pd) in 4 ml of 2-methoxyethanol/H2O (1/1)
using K2CO3 (0.28 gr, 2.0 mmol) as base at 100ꢀC
(Table 4, entry 7).
After optimizing of the reaction factors, diverse aryl
halides and styrene or t-butyl acrylate were subjected to
the optimized reaction conditions to define the

14 of 21
ESLAHI ET AL.
TABLE 4 Screening of the reaction factors on the efficiency of Mizoroki-Heck model reactiona
Entry
1
Catalyst (mg/mol% Pd)
5/0.15
Solvent
Base
Temp. (ꢀC)
Reflux
Reflux
Reflux
100
Time (h)
Yield (%)b
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
NaOH
piperidine
NEt3
5
6
6
3
3
3
3
3
8
12
8
5
4
3
3
5
6
6
6
6
8
5
4
3
61
55
52
92
90
94
96
91
31
0
2
5/0.15
EtOH
3
5/0.15
H2O/EtOH (1:1)
4
5/0.15
DMF
5
5/0.15
DMF/H2O (1:1)
100
6
5/0.15
2-Methoxyethanol
100
7
5/0.15
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:2)
Toluene
100
8
5/0.15
100
9
5/0.15
Reflux
100
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
None
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
2-Methoxyethanol/H2O (1:1)
1.67/0.05
2.5/0. 075
3.33/0.1
4.17/0.125
5.83/0.175
5/0.15
100
47
72
84
87
91
74
45
67
35
41
22
79
86
92
100
100
100
100
100
5/0.15
100
5/0.15
100
5/0.15
100
5/0.15
DBU
100
5/0.15
K2CO3
K2CO3
K2CO3
K2CO3
r.t
5/0.15
80
5/0.15
90
5/0.15
110
Note: Bold text means the optimized condition obtained for the model reaction studied.
aReaction conditions: 1 mmol of bromobenzene, 1.2 mmol of n-butyl acrylate, Fe3O4@SiO2-TCT-GA-Pd(0) catalyst, and solvent (4 ml).
bIsolated yield.
application catalytic scopes of this reaction (Table 5).
This study revealed suitability of this the catalytic system
towards all kind of aryl halides (I, Br, Cl) with reactivity
order of ArI > ArBr > ArCl. As expected, in general, aryl
halides bearing EWG substituents underwent the reac-
tion smoothly but the precursors having ERG substitu-
ents showed less reactivity.
synthesized catalyst shows notably higher TON and TOF
in less toxic and mild reaction conditions.
5 | CATALYST RECOVERY AND
KINETIC STUDIES
To figure out the competency of novel Fe3O4@SiO2-
TCT-GA-Pd(0) heterogeneous catalyst, we compared the
performance of this proposed catalyst with the several
other catalysts which have already been reported
(Table 6). This comparison exhibited clearly that the
Giving to the importance of catalysts recoverability and
reusability, in respect of economy and environment,
these aspects were studied on the coupling reaction of
phenylboronic acid with bromobenzene (Suzuki reaction,
Figure 8A [a]) and n-butyl acrylate with bromobenzene

ESLAHI ET AL.
15 of 21
TABLE 5 Catalyzed Heck coupling reaction of various aryl halides with olefins by Fe3O4@SiO2-TCT-GA-Pd(0) NPsa
)5a(
(5b)
X = I: 2 h, 90%b, TOF = 300 (h−1
X = I: 0.5 h, 97%b, TOF = 1,293 (h−1
)
)
Br: 3 h, 96%b, TOF = 213 (h−1
Cl: 8 h, 86%b, TOF = 72 (h−1
)
Br: 4 h, 84%b, TOF = 140 (h−1
)
Cl: 10 h, 78%b, TOF = 52 (h−1
)
)
)5c(
(5d)
X = I: 2.5 h, 90%b, TOF = 240 (h−1
)
X = I: 1 h, 93%b, TOF = 620 (h−1
)
Br: 5 h, 87%b, TOF = 116 (h−1
Cl: 11 h, 79%b, TOF = 48 (h−1
)
)
Br: 3.5 h, 91%b, TOF = 173 (h−1
Cl: 9 h, 84%b, TOF = 62.2 (h−1
)
)
(5e)
(5f)
X = I: 3 h, 90%b, TOF = 200 (h−1
)
X = I: 4 h, 91%b, TOF = 152 (h−1
)
Br: 7 h, 85%b, TOF = 81 (h−1
Cl: 12 h, 78%b, TOF = 43.3 (h−1
)
Br: 8 h, 85%b, TOF = 71 (h−1
Cl: 13 h, 73%b, TOF = 37.5 (h−1
)
)
)
(5 g)
(5 h)
X = I: 0.6 h, 96%b, TOF = 1,066 (h−1
)
X = I: 0.7 h, 95%b, TOF = 905 (h−1
)
Br: 3 h, 95%b, TOF = 211 (h−1
Cl: 7 h, 84%b, TOF = 80 (h−1
)
Br: 3.5 h, 93%b, TOF = 177.2 (h−1
Cl: 8 h, 82%b, TOF = 68.3 (h−1
)
)
)
(Continues)

16 of 21
ESLAHI ET AL.
TABLE 5 (Continued)
(5j)
X = I: 2.5 h, 90%b, TOF = 240 (h−1
(5i)
X = I: 0.5 h, 94%b, TOF = 1,254 (h−1
)
)
Br: 6 h, 86%b, TOF = 95 (h−1
)
Br: 3.5 h, 92%b, TOF = 175 (h−1
Cl: 14 h, 83%b, TOF = 39 (h−1
)
Cl: 20 h, 76%b, TOF = 25 (h−1
)
)
(5 k)
(5 L)
X = I: 2.5 h, 90%b, TOF = 240 (h−1
)
X = I: 1.3 h, 96%b, TOF = 492.3 (h−1
)
Br: 5.5 h, 81%b, TOF = 98.2 (h−1
Cl: 14 h, 70%b, TOF = 33.3 (h−1
)
)
Br: 2.5 h, 94%b, TOF = 251 (h−1
Cl: 10 h, 86%b, TOF = 57 (h−1
)
)
(5 m)
X = I: 1 h, 96%b, TOF = 640 (h−1
)
(5n)
Br: 2 h, 95%b, TOF = 317 (h−1
)
X = I: 1.5 h, 93%b, TOF = 413.3 (h−1
)
Cl: 9 h, 87%b, TOF = 64.4 (h−1
)
Br: 2.8 h, 91%b, TOF = 217 (h−1
Cl: 11 h, 82%b, TOF = 50 (h−1
)
)
(5o)
X = I: 1.8 h, 93%b, TOF = 344.5 (h−1
)
Br: 3 h, 90%b, TOF = 200 (h−1
)
aReaction conditions: aryl halide (1 mmol), olefin (1.2 mmol), K2CO3 (2 mmol), Fe3O4@SiO2-TCT-GA-Pd (0) catalyst (5 mg, 0.15 mol% Pd), 100ꢀC, and
2-methoxyethanol/H2O (4 ml, 1/1).
bIsolated yield.

ESLAHI ET AL.
17 of 21
TABLE 6 Comparison between Fe3O4@SiO2-TCT-GA-Pd(0) catalyst efficiency and the other reports on the same model reaction
Entry
Catalyst
Condition
Time (h)
Yield (%)
TOF (h−1
)
1
TiO2@Pd NPs (1 mol%)[67]
Pd-PVP-Fe (3.7 mol%)[68]
DMF/NEt3/140ꢀC
24
4
90
95
83
85
86
95
94
60
92
96
3.75
78
2
DMF/K2CO3/100ꢀC
DMF/NEt3/80ꢀC
3
Pd-DABCO-γ-Fe2O3 (1 mol%)[69]
TRGO-NPy-Pd (0.3 mol%)[70]
Fe3O4@MCM-41@Pd-P2C (1 mol%)[71]
Pd-SMU-MNPs (1.2 mol%)[72]
Pd/Fe3O4 (5 mol%)[73]
7
11.85
0.95
58
4
DMF/Na2CO3/140ꢀC
PEG-400/K2CO3/120ꢀC
DMF/K2CO3/120ꢀC
NMP/K2CO3/130ꢀC
DMF/NEt3/120ꢀC
15
1.5
1.3
12
4
5
6
61
7
1.6
8
Fe3O4@CS-Schiff base-Pd (1 mol%)[74]
Fe3O4@SiO2-Polymer-imid-Pd (1 mol%)[75]
15
9
NMP/K2CO3/110ꢀC
2-Methoxyethanol/H2O/K2CO3/100ꢀC
2
46.5
213.3
10
Fe3O4@SiO2-TCT-GA-Pd(0)
(0.15 mol%) (This Work)
3
FIGURE 8 (A) Studies of recycling of the catalyst during the successive reaction cycles for a) Suzuki and b) Heck reactions; (B and C)
FE-SEM and DLS images of Fe3O4@SiO2-TCT-GA-Pd(0) nanoparticles after seven reaction cycles

18 of 21
ESLAHI ET AL.
FIGURE 9 XPS spectrum of recovered
Fe3O4@SiO2-TCT-GA-Pd(0) nanocatalyst
TABLE 7 The study of effect of TCT and glucosamine linker on the efficiency of Fe3O4@SiO2-TCT-GA-Pd(0) NPs in progressing of
Suzuki and Heck model reactions
Suzuki
Heck
Pd
(mol%)
Temp.
(ꢀC)
Time
(h)
Yield
(%)
Temp.
(ꢀC)
Time
(h)
Yield
(%)
Entry
Catalyst
1
2
3
4
5
Fe3O4-Pd(0) (4 mg)
Fe3O4-Pd(0) (12 mg)
Fe3O4@SiO2-Pd(0) (4 mg)
Fe3O4@SiO2-Pd(0) (12 mg)
0.017
0.04
Reflux
Reflux
Reflux
Reflux
50
15
13.5
12
11
8
15
18
20
22
35
Reflux
Reflux
Reflux
Reflux
100
24
18
15.5
14
9
Trace
Trace
14
0.025
0.075
0.041
17
Fe3O4@SiO2-N (OH)2-Pd(0)
(4 mg)
33
6
Fe3O4@SiO2-N (OH)2-Pd(0)
(12 mg)
0.123
70
5
54
100
8
45
7
8
9
Fe3O4@SiO2-TCT-Pd(0) (4 mg)
Fe3O4@SiO2-TCT-Pd(0) (12 mg)
0.075
0.225
0.12
50
70
50
4
43
67
95
100
100
100
6
4
3
52
61
96
2.5
1.5
Fe3O4@SiO2-TCT-GA-Pd(0)
(4 mg)
(Heck reaction, Figure 8A [b]) under the optimized con-
ditions in the presence of Fe3O4@SiO2-TCT- GA-Pd
(0) nanocatalyst (Figure 8A). After reaction quenching,
Fe3O4@SiO2-TCT- GA-Pd(0) nanocatalyst was separated
magnetically, washed with deionized water and ethyl
acetate, and was directly reused after drying in the next
reaction cycles. The results show clearly the ability of cat-
alyst for seven times reusability without notable reduc-
tion in its reactivity (Figure 8A).
Figure 8B,C gives the information about FE-SEM and
DLS analyses of heterogeneous nanocatalyst after seventh
recycle. The FE-SEM image shows that the morphology
of catalyst has been preserved after seven times
(Figure 8B). Additionally, the hydrodynamic diameter of
heterogeneous catalyst was measured by DLS technique.
This analysis appears that the size distribution is centered
at a value of 41 nm (Figure 8C), which is slightly bigger
than the distribution size of fresh catalyst (Figure 4i).
The hot filtration analysis was performed to deter-
mine the responsible species for catalyzing Suzuki cou-
pling reaction using bromobenzene and phenylboronic
acid as model starting materials under optimized condi-
tions. The reaction was quenched by cooling down to
room temperature after 0.5 h. The catalyst was taken
away from the reaction media by a magnet. Analysis of
the residue solution showed the presence of 62% of the
product by GC. Then, the remaining solution was stirred
at 50ꢀC. GC analysis of the reaction after 2 h showed the
existence of 65% of biphenyl. It means the amount of
leaching of palladium should be low and, therefore,

ESLAHI ET AL.
19 of 21
To clarify the role of TCT and GA in catalytic
capability of synthesized Fe3O4@SiO2-TCT-GA-Pd(0)
nanocatalyst in both reactions, a comparison between
the reactivity of this catalyst and Fe3O4-Pd(0)
NPs, Fe3O4@SiO2-Pd(0) NPs, Fe3O4@SiO2-N (OH)2-Pd
(0) NPs, and Fe3O4@SiO2-TCT-Pd(0) NPs was
performed (Table 7). The data registered in Table 7
showed that the simultaneous presence of TCT and
GA increases drastically reactivity using lower mole%
of pd(0) at lower temperature and in shorter time
because of enhancement of palladium loading by
raising the coordination sites (Hydroxyl groups of
glucosamine and nitrogen atoms of TCT) on the
surface of catalyst and increasing of dispersity of the
catalyst in the solvent of reactions.
At the end, the kinetic aspects of both Heck and
Suzuki model reactions were considered in the presence
of Fe3O4@SiO2-TCT-GA-Pd(0) to demonstrate the effi-
ciency behavior of nanocatalyst among seven sequential
runs, Figure 10. These studies appear similar trend in the
catalyst reactivity and present capability of heterogeneous
catalyst in these model reactions.
6 | CONCLUSIONS
A novel and stable magnetic palladium(0) nanocatalyst
has been synthesized using inexpensive chemical mate-
rials through immobilization of palladium on the surface
of glucosamine-functionalized magnetic Fe3O4@SiO2
NPs and utilized in C C couplings in aqueous media.
Notably, it displayed highly catalytic acting towards
Suzuki-Miyaura and Mizoroki-Heck reactions. The other
advantages of this new heterogeneous catalyst are
(a) thermal stability; (b) facile isolation by a magnet;
(c) compatibility in aqueous media; and (d) reusability
for seven consecutive reactions with negligible loss in the
catalytic activity. In addition to the above-mentioned
highlights of the catalyst, both C C cross-coupling reac-
tions of Suzuki-Miyaura and Mizoroki-Heck employed
exhibit several special features including need to low cat-
alyst loading to complete the reactions, work in less toxic
media (green solvent in Suzuki-Miyaura reaction), short
reaction times, excellent yields, high turnover frequency
(TOF), and simplicity of operation.
FIGURE 10 The Kinetic plots of treatment of Heck (A) and
Suzuki (B) model reactions by Fe3O4@SiO2-TCT-GA-Pd
(0) nanocatalyst
principal and responsible catalyst for the both coupling
reactions is the heterogeneous nanomagnetic of
Fe3O4@SiO2-TCT-GA-Pd(0).
The leaching amount of palladium from the catalyst,
which is an indication about the catalyst stability, was
measured by ICP after seven cycles for both Heck and
Suzuki model reactions. In the Suzuki type coupling reac-
tion, the palladium leaching amount after seven runs was
0.25%, while it was 0.54% in the Heck reaction. These
results may partly explain slightly decreasing in the cata-
lyst efficiency.
In general, herein, we have been able to introduce
two cost effective with less environmental side effect
methods for C C cross-coupling reactions.
The XPS analysis of recovered catalyst showed intact
oxidative state of Pd(0) nanoparticles in synthesized
nanocatalyst (Figure 9). The intact oxidation state of
nanoparticles exhibits the successful progress of reductive
elimination step in both investigated reactions.
ACKNOWLEDGMENTS
Financial support of Iran National Science Foundation
and the Research Council of Shiraz University is grate-
fully acknowledged by the authors.

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ESLAHI ET AL.
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AUTHOR CONTRIBUTIONS
Hassan Eslahi: Data curation; resources; validation.
Ali Reza Sardarian: Conceptualization; funding
acquisition; methodology; project administration;
supervision. Mohssen Esmaeilpour: Investigation;
methodology.
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ORCID
Hassan Eslahi https://orcid.org/0000-0002-3852-0955
Ali Reza Sardarian https://orcid.org/0000-0003-4407-
2527
Mohsen Esmaeilpour https://orcid.org/0000-0002-5716-
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Eslahi H, Sardarian AR,
Esmaeilpour M. Green and sustainable palladium
nanomagnetic catalyst stabilized by glucosamine-
functionalized Fe3O4@SiO2 nanoparticles for
Suzuki and Heck reactions. Appl Organomet Chem.
2021;e6260. https://doi.org/10.1002/aoc.6260
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