PdII Immobilized on Ferromagnetic Multi-Walled Carbon Nanotubes Functionalized by Aminated 2-Chloroethylphosphonic Acid with S -Methylisothiourea (FMMWCNTs@CPA@SMTU@PdII NPs) Applied as a Highly Efficient and Recyclable Nanostructured Catalyst for Suzuki-Miyaura and Mizoroki-Heck Cross-Coupling Reactions in Solvent-Free Conditions

Article abstract of DOI:10.1071/CH19117

The new ferromagnetic nanostructured FMMWCNTs@CPA@SMTU@Pd^II NPs (IV) as an eco-friendly heterogeneous nanocatalyst with a particle size of ～20-30 nm reported earlier by our group has been found to be very effective for Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions at ambient temperature. The procedure has been applied for a wide range of aryl halides, arylboronic acids, and alkenes. The magnetic separation by an external magnetic field, mild reaction conditions, and catalyst reusability up to four times without significant decrease in catalytic activity (reduced catalytic activity from 11 to 18 % in the fifth, sixth, and seventh cycles) made the present method sustainable and economically viable for C-C cross-coupling reactions.

Full text of DOI:10.1071/CH19117

CSIRO PUBLISHING
Aust. J. Chem.
Full Paper
https://doi.org/10.1071/CH19117
PdII Immobilized on Ferromagnetic Multi-Walled
Carbon Nanotubes Functionalized by Aminated
2-Chloroethylphosphonic Acid with S-Methylisothiourea
(FMMWCNTs@CPA@SMTU@PdII NPs) Applied as a Highly
Efficient and Recyclable Nanostructured Catalyst for
Suzuki–Miyaura and Mizoroki–Heck Cross-Coupling
Reactions in Solvent-Free Conditions
A
A B
,
Maryam Sadat Ghasemzadeh and Batool Akhlaghinia
A
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,
Mashhad 9177948974, Iran.
B
Corresponding author. Email: akhlaghinia@um.ac.ir
The new ferromagnetic nanostructured FMMWCNTs@CPA@SMTU@PdII NPs (IV) as an eco-friendly heterogeneous
nanocatalyst with a particle size of ,20–30 nm reported earlier by our group has been found to be very effective for
Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions at ambient temperature. The procedure has been applied for
a wide range of aryl halides, arylboronic acids, and alkenes. The magnetic separation by an external magnetic field, mild
reaction conditions, and catalyst reusability up to four times without significant decrease in catalytic activity (reduced
catalytic activity from 11 to 18 % in the fifth, sixth, and seventh cycles) made the present method sustainable and
economically viable for C–C cross-coupling reactions.
Manuscript received: 9 March 2019.
Manuscript accepted: 18 May 2019.
Published online: 2 July 2019.
Introduction
catalytic species with the anchorage of Pd nanoparticles on
different kinds of supports, such as amorphous, or ordered sili-
cates, clays, zeolites, or even carbon nanomaterials, i.e. carbon
nanotubes and graphene, for C–C coupling reactions is reported
each year.[21–28]
In the last 30 years, the formation of C–C bonds which is well
documented in the literature has gained increasing interest from
both academic and industrial points of view.[1–3] Due to their
versatility and efficiency, the C–C cross-coupling reactions via
Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions
are extremely useful tools in the preparation of natural products,
organic synthesis, preparation of advanced materials, biologi-
cally active compounds, UV screens, herbicides, preparation of
hydrocarbons, polymers, liquid crystal materials, and predom-
inantly for pharmaceutical and agrochemical purposes.[4–6]
Typically, the Suzuki–Miyaura and Mizoroki–Heck cross-
coupling reactions are catalysed by palladium as a valuable
transition-metal based on homogenous or heterogeneous sys-
tems.[7–12] With respect to global environmental concerns, every
catalytic approach is critically examined in terms of activity,
selectivity, and its environment friendly aspect as well.[13–17]
The search for cleaner, simpler, and greener approaches has led
to the advent of nanocatalysts which have fulfilled the need for
developing sustainable and environmentally benign strate-
gies.[14] The efficiency of nanocatalysts, which amalgamate the
superior selectivity of homogeneous catalysts with the recy-
clability of heterogeneous catalysts,[15–17] depends on their
nanostructure and composition.[18–20] A huge variety of these
Carbon nanotubes (CNTs) including single-walled carbon
nanotubes (SWNTs) and multi-walled carbon nanotubes
(MWNTs) have attracted a great deal of attention in fabricating
advanced functional materials due to their excellent mechani-
cal, structural, and electronic properties.[29–31] However, the
main drawback of CNTs which has had a negative effect on
their usage is their limited solubility. To tackle this issue, a kind
of functionalization must be developed. This is achieved by
introducing chemically active sites to the catalyst surface,
which also function as anchoring sites for the deposition of
metal nanoparticles (NPs). The two techniques used to recover
heterogeneous metallic-based catalysts (i.e. filtration or cen-
trifugation) are energy and time consuming and they also may
lead to the loss of the catalyst during the separation process. In
order to address these drawbacks, the designed nanocompo-
sites (as catalyst supports) should contain both MWCNTs and
magnetic materials. These nanocomposites lead to an increase
in contact area, improve the separation of MWCNTs, and
enhance thermal and chemical stability. The catalyst loss is
Journal compilation ꢀ CSIRO 2019
www.publish.csiro.au/journals/ajc

B
M. S. Ghasemzadeh and B. Akhlaghinia
OH
OH
OH
OH
OH
OH
OH
1) Deionized Water
Sonication 30 min
OH
OH
OH
FMMWCNTs (I)
Fe3O4
2) FeSO4·7H2O, H2SO4
Sonication 30 min
3) NaBH4
OH
OH
OH
OH
OH
OH
O
P
Cl
Cl
HO
HO
MWCNTs
O
Toluene, Reflux
20 h
P
Cl
O
Cl
P
P
O
O
P
P
O
Cl
Cl
FMMWCNTs@CPA (II)
NH
HN
HN
. 1/2 H2SO4
S
S
H2N
K2CO3
EtOH, Reflux, 24 h
O
H
NH
P
S
N
O
NH
S
P
NH
P
O
O
P
P
O
H
NH
N
S
NH
NH
S
FMMWCNTs@CPA@SMTU (III)
Pd(OAc)2
Acetone, r.t., 24 h
HN
S
HN
O
P
H
N
NH
S
O
NH
S
P
NH
P
O
O
P
P
O
H
N
NH
S
NH
NH
S
FMMWCNTs@CPA@SMTU@PdII NPs (IV)
Scheme 1. Preparation of PdII immobilized on ferromagnetic multi-walled carbon nanotubes functio-
nalized by aminated 2-chloroethylphosphonic acid with S-methylisothiourea (FMMWCNTs@-
CPA@SMTU@PdII NPs) (IV).
prevented by the use of magnetic separation which in turn
spares the researchers the difficulty of using traditional meth-
ods. This method of separation is both economical and practi-
cal. With this aim in view, we have recently been trying to
develop new nanostructured magnetic catalysts.[32–42] Follow-
ing these studies, the synthesis of PdII immobilized on ferro-
magnetic multi-walled carbon nanotubes functionalized by
aminated 2-chloroethylphosphonic acid (CPA) with S-methy-
lisothiourea (SMTU) (FMMWCNTs@CPA@SMTU@PdII
NPs (IV)) was reported previously as a new heterogeneous
nanocatalyst based on nanoparticles (see Scheme 1).[43] Sub-
sequently, the nanostructured catalyst was used in the Suzuki–
Miyaura and Mizoroki–Heck cross-coupling reactions in
solvent-free conditions at ambient temperature.

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
C
200
and 69.688 are indexed to the (1 1 1), (2 0 0), and (2 2 0)
reflections of the cubic structure of Pd, respectively in the
XRD pattern of FMMWCNTs@CPA@SMTU@PdII NPs (IV)
(ref. code: 00-001-1201). Correspondingly, the diffraction peak
at 2y ¼ 288 demonstrates the (0 0 2) plane of the hexagonal
graphite structure (ref. code: 41-1487). The Debye–Scherrer
equation (d ¼ Kl/(bcosy)) was used to calculate the average
crystalline size of the FMMWCNTs@CPA@SMTU@PdII NPs
(IV) which was estimated to be 22 nm (Fig. S2, Supplementary
Material).[43]
150
(b)
100
(a)
50
The morphology and mean diameter of the nanoparticles
immobilized on the surface of FMMWCNTs (I) were investi-
gated by TEM (Fig. S3, Supplementary Material). The TEM
image of the FMMWCNTs@CPA@SMTU@PdII NPs (IV)
proves that the nanocatalyst is decorated with well dispersed
nanoparticles. In addition, TEM observation further indicates
that the nanoparticles on the surface of the FMMWCNTs (I)
are spherical in shape and the average size is found to be around
20–30 nm (Fig. S3, Supplementary Material).[43]
0
–50
200
250
300
350
400
450
500
550
Wavelength [nm]
Fig. 1. UV-Vis DRS of FMMWCNTs@CPA@SMTU@PdII NPs (IV) in
(a) Suzuki–Miyaura and (b) Mizoroki–Heck cross-coupling reactions.
FE-SEM was carried out to show the surface morphology of
the FMMWCNTs@CPA@SMTU@PdII NPs (IV) (Fig. S4,
Supplementary Material). The corresponding FE-SEM image
illustrates a uniform rod-like morphology. In addition, the
existence of Pd nanoparticles deposited on the nanostructured
catalyst is clearly visible as bright spots in Fig. S4 (Supplemen-
tary Material).[43]
The EDX spectrum was obtained to record the type of
elements in the FMMWCNTs@CPA@SMTU@PdII NPs (IV)
(Fig. S5, Supplementary Material). The presence of Fe, Pd, S, P,
N, and O in the EDX spectrum confirms the composition of the
FMMWCNTs@CPA@SMTU@PdII NPs (IV) (Fig. S5, Sup-
plementary Material).[43] The uniformly dispersed Fe, Pd, P, S,
C, N, and O on the surface of the FMMWCNTs@CPA@-
SMTU@PdII NPs (IV) was recorded by an EDS map (Fig. S6,
Supplementary Material).[43]
Results and Discussion
Characterization of FMMWCNTs@CPA@SMTU@PdII
NPs (IV)
The nanocatalyst was characterized by the following techni-
ques: FT-IR spectroscopy, X-ray diffraction (XRD) analysis,
transmission electron microscopy (TEM), field emission scan-
ning electron microscopy (FE-SEM), energy-dispersive X-ray
spectroscopy (EDX), EDS mapping, thermogravimetric analy-
sis (TGA), vibrating sample magnetometry (VSM), inductively
coupled plasma–atomic emission spectroscopy (ICP-OES),
X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse
reflectance spectroscopy (DRS).
FT-IR spectroscopy confirmed the presence of corresponding
functional groups at different steps involved in the preparation of
the catalyst (Scheme 1). Fig. 1 demonstrates the FT-IR spectra
of MWCNTs, FMMWCNTs (I), FMMWCNTs@CPA (II),
FMMWCNTs@CPA@SMTU (III), and FMMWCNTs@-
CPA@SMTU@PdII NPs (IV). Fig. S1a (Supplementary Mate-
rial) shows the broad absorption band around 3442 cmꢀ1 that can
be ascribed to the hydroxy groups (nOH) of the raw MWCNTs.
Meanwhile, the vibrational frequencies of C=C bonds due to
graphite sheets appear around 1612–1322 cmꢀ1. The stretching
vibration mode of the Fe–O bond appears in the region 600–
400 cmꢀ1 (Fig. S1b, Supplementary Material). The presence of
the strong band at 1078 cmꢀ1 due to a P=O stretching vibration
confirms the successful chemical attachment of CPA on the
FMMWCNTs (I) surface (Fig. S1c, Supplementary Material).
The absorption bands of N–H, C=NH, C–N, and C–S appear at
1649, 1551, 1404, and 619 cmꢀ1 respectively, upon the amination
ofFMMWCNTs@CPA (II)withSMTU(Fig. S1d). The decrease
in intensity of these bands then confirms the immobilization
of PdII on the surface of FMMWCNTs@CPA@SMTU (III)
(Fig. S1e, Supplementary Material).[43]
The XRD technique was used to investigate the crystallo-
graphic structure of FMMWCNTs@CPA@SMTU@PdII NPs
(IV). As can be seen in Fig. S2 (Supplementary Material), the
XRD pattern shows reflection peaks at 2y ¼ 31.28, 36.88, 38.58,
43.738, 55.68, 57.358, and 65.18 which can be related to the (2 2 0),
(3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) reflections of
the cubic structure of Fe3O4, respectively (ref. code: 04-014-
9664). Moreover, the reflection peaks at 2y ¼ 41.048, 48.468,
TGA was performed to determine the thermal stability and
the amount of grafted organic moieties on the surface of the
FMMWCNTs (I) (Fig. S7, Supplementary Material). The TGA
curve of the MWCNTs indicates that the MWCNTs are decom-
posed in the temperature range of 500–6008C (Fig. S7a). The
TGA curve of FMMWCNTs@CPA (II) shows three weight
losses (Fig. S7b). In the first step, water evaporation occurs with
a weight loss of 3 % from 105 to 2008C. During the second step,
the decomposition of the CPA linker happens with a weight loss
of 5 % from 210 to 4008C. In addition, the amount of organic
segments is calculated to be 0.35 mmol gꢀ1 and this result is in
good agreement with elemental analysis data (C¼ 14.49 %). The
third step is related to the combustion of MWCNT fragments
in the FMWCNTs (I) which happens from 410 to 5008C and
gives an 8 % weight loss. The TGA curve of FMMWCNTs@-
CPA@SMTU (III) demonstrates three steps of weight loss from
25 to 9008C (Fig. S7c). The extrusion of physically absorbed
water occurs at the first step (10 % from 190 to 2308C). The
removal of the organic moieties happens in the second step at
a temperature range of 240–5208C (11 %). Likewise, the
grafted organic segments on the surface of the FMMWCNTs
(I) is estimated to be 0.46mmol gꢀ1. The elemental analysis data
shows that the loading amount of organic segments supported on
the FMMWCNTs (I) was 0.4 mmolgꢀ1 based on carbon, nitro-
gen, and sulfur contents (C¼ 15.92, N ¼ 3.20, and S ¼ 3.57%).
The third weight loss in Fig. S7c demonstrates the combustion
of MWCNT fragments in the FMWCNTs (I) (9% from
520 to 6508C). In addition, the TGA curve of the

D
M. S. Ghasemzadeh and B. Akhlaghinia
O
O
R3
R3
O
O
R1
Catalyst: 0.35 mol-%
NEt3, s.f., r.t.
X
B(OH)2
R1
(b)
R2
R2
R1
Catalyst: 0.55 mol-%
NEt3, s.f., r.t.
(a)
Catalyst: FMMWCNTs@CPA@SMTU@PdII NPs (IV)
R1 = H, 4-NO2, 4-Me, 4-OMe, 4-CHO, 4-CN
R2 = H, 4-Cl, 4-OMe
R3 = Me, Et, Bun
X = I, Br, Cl
Scheme 2. (a) The Suzuki–Miyaura and (b) the Mizoroki–Heck cross-coupling reactions in the presence of
FMMWCNTs@CPA@SMTU@PdII NPs (IV).
FMMWCNTs@CPA@SMTU@PdII NPs (IV) illustrates three
steps of weight loss from 25 to 9008C (Fig. S7d). The first weight
loss which happens from 120 to 2008C (11 %) is indexed to the
removal of adsorbed water molecules. The organic groups on the
surface of the FMMWCNTs (I) decompose during the second
step (16 %) from 210 to 3808C. Thus, the amount of organic
fragments is calculated to be 0.581 mmolgꢀ1. In addition, the
third weight loss which takes place at 400–7008C (15 %),
corresponds to the combustion of MWCNT fragments of
FMWCNTs (I) (Fig. S7, Supplementary Material).[43]
The magnetization curves of FMMWCNTs (I) and
FMMWCNTs@CPA@SMTU@PdII NPs (IV) are illustrated
in Fig. S8a, b (Supplementary Material), respectively. Based
on VSM analysis, an occurrence of a hysteresis loop at the
magnetic hysteresis curves shows that all samples are ferromag-
netic. The saturation magnetization values (Ms) of the
FMMWCNTs (I) and FMMWCNTs@CPA@SMTU@PdII
NPs (IV) are 31.98 and 26.95. The decrease in the saturation
magnetization value of FMMWCNTs@CPA@SMTU@PdII
NPs (IV) is related to the presence of non-magnetic materials
on the surface of FMMWCNTs (I). Moreover, Table S1 (Sup-
plementary Material) illustrates other magnetic properties of the
samples (coercivity (Hci) and remnant magnetization (Mr)).[43]
The oxidation state of the palladium immobilized on the
FMMWCNTs@CPA@SMTU@PdII NPs (IV) was determined
by XPS analysis (Fig. S9, Supplementary Material). Accord-
ingly, in the Pd 3d XPS spectrum, the binding energy of the
doublet peak at 339 eV (related to Pd 3d5/2) and 343.7 eV
(related to Pd 3d3/2) can be indexed to the PdII species
(Fig. S9a). Furthermore, the peaks related to carbon (C 1s),
nitrogen (N 1s), iron (Fe 2p), palladium (Pd 3d), sulfur (S 2p),
and oxygen (O 1s) are demonstrated in the XPS elemental
survey scan of the nanostructured catalyst (Fig. S9b).[43]
cross-coupling reactions, the reaction conditions were opti-
mized and the results are illustrated in Tables 1 and 2. Initial
studies were done on the reaction of iodobenzene with phenyl-
boronic acid or methyl acrylate as model reactions of Suzuki–
Miyaura or Mizoroki–Heck cross-coupling reactions, respec-
tively. Initially, the effect of different parameters such as
amount of catalyst loading, various molar ratios of iodoben-
zene/base, and type of base were studied on model reactions.
When a blank experiment in the absence of the nanocatalyst or
base (in solvent-free conditions at ambient temperature) was
conducted, only a trace amount of the products was acquired
even after prolonged times (Tables 1 and 2, entries 1–3). To
improve the yield of the coupled products, the cross-coupling
reactions were examined by applying a 1/2 molar ratio of
iodobenzene/base under the same reaction conditions. The opti-
mum amount of nanocatalyst loading on the reaction rates was
then obtained. Based on the results outlined in Tables 1 and 2, it is
obvious that the best results were achieved by carrying out the
reactions with 0.55 and 0.35mol-% of the catalyst in the Suzuki–
Miyaura and Mizoroki–Heck cross-coupling reactions, respec-
tively (Tables 1 and 2, entry 5). It is worth mentioning that a
higher amount of base did not increase the yields of products
noticeably while decreasing the amount of base resulted in lower
yields under the same conditions (Tables 1 and 2, entries 7–9).
Afterwards, to further improve the yields of the desired products,
the reactions were performed in H2O (Tables 1 and 2, entry 10).
As can be clearly seen, the same results were acquired in both
solvent-free conditions and in aqueous media. The effect of base
was also investigated using various bases, such as Et3N, N,N-
diisopropylethylamine (DIPEA), K2CO3, NaOAc, NaHCO3,
KOH, n-butylamine, pyridine, and K3PO4. It was found that
Et3N was the best base for these protocols. The unique catalytic
behaviour of FMMWCNTs@CPA@SMTU@PdII NPs (IV)
in the Suzuki–Miyaura and Mizoroki–Heck cross-coupling
reactions was revealed by examining the standard reactions
individually in the presence of MWCNTs, FMMWCNTs (I),
FMMWCNTs@CPA (II), FMMWCNTs@CPA@SMTU (III),
and Pd(OAc)2 (entries 19–23 both Tables 1 and 2). After contin-
ued reaction times, a considerable yield of desired coupling
products was not obtained.
Catalytic Performance of the
FMMWCNTs@CPA@SMTU@PdII NPs (IV) in Suzuki–
Miyaura and Mizoroki–Heck Cross-Coupling Reactions
Recently, FMMWCNTs@CPA@SMTU@PdII NPs (IV) were
presented as an efficient ferromagnetic nanostructured catalyst
for the Sonogashira–Hagihara cross-coupling reaction under
solvent-free conditions.[43] In order to show another application
of the nanocatalyst, we applied it as a versatile nanocatalyst in
C–C cross-coupling reactions, namely Suzuki–Miyaura and
Mizoroki–Heck (see Scheme 2).
Subsequently, to elucidate whether these protocols could be
generalized, the Suzuki–Miyaura and Mizoroki–Heck products
were synthesized using various aryl halides including those
containing electron-donating or electron-withdrawing groups
with different arylboronic acids or alkenes in the presence
of FMMWCNTs@CPA@SMTU@PdII NPs (IV) at room
In order to investigate the catalytic activity of the pre-
pared nanocatalyst in Suzuki–Miyaura and Mizoroki–Heck

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
E
Table 1. Optimization of reaction conditions for the Suzuki–Miyaura cross-coupling reaction of iodobenzene with phenylboronic acid in the
presence of FMMWCNTs@CPA@SMTU@PdII NPs (IV)
FMMWCNTs@CPA@
SMTU@PdII NPs (IV)
+
I
B(OH)2
Entry
Catalyst [mol-%]
Molar ratios of iodobenzene/base
Base
Solvent
Temperature [8C]
Time [min]
Isolated yield [%]
1
—
—
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2.5
1 : 1.2
1 : 1
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
—
—
—
—
—
—
—
—
—
—
H2O
—
—
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
15 h
15 h
15 h
10
—
Trace
—
2
Et3N
3
0.6
—
4
0.6
Et3N
98
5
0.55
Et3N
10
98
6
0.53
Et3N
18
98
7
0.55
Et3N
10
98
8
0.55
Et3N
13
98
9
0.55
Et3N
15
98
10
11
12
13
14
15
16
17
18
19B
20C
21D
22E
23F
0.55
Et3N
10
98
0.55
DIPEAA
K2CO3
NaOAc
NaHCO3
KOH
20
98
0.55
50
98
0.55
56
90
0.55
—
—
—
—
—
—
—
—
—
—
68
98
0.55
48
95
0.55
n-Butylamine
Pyridine
K3PO4
Et3N
80
90
0.55
74
85
0.55
52
90
0.005 g
0.005 g
0.005 g
0.005 g
0.005 g
10 h
10 h
10 h
10 h
10 h
Trace
Trace
15
Et3N
Et3N
Et3N
25
Et3N
15
AN,N-Diisopropylethylamine.
BThe reaction was performed in the presence of MWCNTs.
CThe reaction was performed in the presence of FMWCNTs (I).
DThe reaction was performed in the presence of FMMWCNTs@CPA (II).
EThe reaction was performed in the presence of FMMWCNTs@CPA@SMTU (III).
FThe reaction was performed in the presence of Pd(OAc)2.
temperature. The results are summarized in Table 3. As
revealed in Table 3, the use of aryl iodides led to higher yields
compared with aryl chlorides and aryl bromides. The reaction
of aryl iodides containing electron-releasing (such as –Me,
–OMe) and electron-withdrawing substituents (such as –NO2,
–CN, and –CHO) proceeded easily, and the desired products
were obtained with excellent yields. The reactions of aryl
bromides and aryl chlorides were also carried out with high
yields. In our case, this could be evidenced by the parallel
reactions of arylboronic acids bearing electron-accepting sub-
stituents in the Suzuki–Miyaura cross-coupling reaction.
Electron-poor arylboronic acids furnished the corresponding
biaryl products more efficiently (Table 3, entries 1, 2, 3, 6, 8 and
9 (c, d versus a)). More importantly, as shown in Table 3, we
were pleased to observe that the Mizoroki–Heck cross-coupling
reaction of different aryl halides with methyl acrylate, ethyl
acrylate, and n-butyl acrylate produced the desired products
rapidly with yields considered high. The present method was
further used to study the coupling reactions of aryl halides with
acrylonitrile. The results obviously disclosed that the Mizor-
oki–Heck cross-coupling reaction of aryl halides with acrylo-
nitrile in the presence of FMMWCNTs@CPA@SMTU@PdII
NPs (IV) required longer reaction times to achieve reasonable
yields of the desired products under the optimized reaction
conditions (Table 3, entries 1, 2, 3, 6, and 8(g)). But as
expected, the cross-coupling reaction of styrene leads to low
product yield even after a long period of time (Table 3, entries
1, 2, 3, 6, and 8(h)).
The synthesized compounds were known and identified in
detail using physical and spectroscopic data (melting point, mass
spectrometry, 1H and 13C NMR spectroscopy), and were consis-
tent with those reported previously. The proposed structures of
the products were established by molecular ion peaks in the gas
chromatography mass spectrum. The coupled products were also
detected by 1H NMR spectroscopy, which showed that the
products of the Mizoroki–Heck cross-coupling reaction were
achieved purely in the E geometry of the double bonds. The
coupling constant (J) of the olefinic hydrogens of products 1f, 2d,
2f, 3d, 4b, 4d, 5b, 5d, and 6d were estimated to be 16–16.1 Hz,
which is a characteristic of E isomers (see Supplementary
Material, Figs S17–S40). In the 13C NMR spectra, resonating
signals at 152.1–142.2 and 167.8–166.01 ppm matched to C=C
and C=O of the products of the Suzuki–Miyaura and Mizoroki–
Heck cross-coupling reactions (see Supplementary Material).
Proposed Catalytic Mechanism for the Suzuki–Miyaura
and Mizoroki–Heck Cross-Coupling Reactions
Through a comprehensive analogy of previous reports in the
literature,[44–48] as well as our own research, the following
mechanism can be proposed for the Suzuki–Miyaura and
Mizoroki–Heck cross coupling reactions (see Scheme 3). In the
first step, the mechanism proceeded through oxidative addition of

F
M. S. Ghasemzadeh and B. Akhlaghinia
Table 2. Optimization of reaction conditions for the Mizoroki–Heck cross-coupling reaction of iodobenzene with methyl acrylate in the presence of
FMMWCNTs@CPA@SMTU@PdII NPs (IV)
O
O
FMMWCNTs@CPA@
SMTU@PdII NPs (IV)
O
+
I
O
Entry
Catalyst [mol-%]
Molar ratios of iodobenzene/base
Base
Solvent
Temperature [8C]
Time [min]
Isolated yield [%]
1
—
—
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2.5
1 : 1.2
1 : 1
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
—
—
—
—
—
—
—
—
—
—
H2O
—
—
—
—
—
—
—
—
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
12 h
12 h
12 h
15
—
Trace
—
2
Et3N
3
0.4
—
4
0.4
Et3N
98
5
0.35
Et3N
15
98
6
0.32
Et3N
24
98
7
0.35
Et3N
15
98
8
0.35
Et3N
17
98
9
0.35
Et3N
20
98
10
11
12
13
14
15
16
17
18
19B
20C
21D
22E
23F
0.35
Et3N
15
98
0.35
DIPEAA
K2CO3
NaOAc
NaHCO3
KOH
28
98
0.35
38
95
0.35
53
95
0.35
45
98
0.35
40
95
0.35
n-Butylamine
pyridine
K3PO4
Et3N
65
95
0.35
70
95
0.35
43
95
0.004 g
0.004 g
0.004 g
0.004 g
0.004 g
10 h
10 h
10 h
10 h
10 h
Trace
Trace
15
Et3N
Et3N
Et3N
20
Et3N
—
20
AN,N-Diisopropylethylamine.
BThe reaction was performed in the presence of MWCNTs.
CThe reaction was performed in the presence of FMWCNTs (I).
DThe reaction was performed in the presence of FMMWCNTs@CPA (II).
EThe reaction was performed in the presence of FMMWCNTs@CPA@SMTU (III).
FThe reaction was performed in the presence of Pd(OAc)2.
an alkyl halide to FMMWCNTs@CPA@SMTU@PdII NPs pro-
ducing intermediateIthrough the oxidation of PdII toPdIV. (Based
on the result of X-ray photoelectron spectroscopy (XPS) deduced
from previous research,[43] the oxidation state of the palladium
immobilized on the fresh FMMWCNTs@CPA@SMTU@PdII
NPs (IV) was PdII.)
Transmetalation of intermediate I with arylboronic acid in
basic media produced the intermediate II which upon reductive
elimination led to the formation ofdesired coupling product III of
the Suzuki–Miyaura cross-coupling reaction and the recovery of
FMMWCNTs@CPA@SMTU@PdII NPs for the next catalytic
trial. According to the suggested mechanism for the Mizoroki–
Heck cross-coupling reaction, it was expected to gain intermedi-
ate V by adding an alkene to intermediate I via the formation of
p-coordinated complex IV. Subsequently, b-hydride elimination
produced the desired product VII and VIII. Finally, a reductive
of Pd, the model Suzuki–Miyaura and Mizoroki–Heck cross-
coupling reactions were carried out in the presence of
FMMWCNTs@CPA@SMTU@PdII NPs (IV) in two separate
flasks. After the reactions were completed, the nanocatalyst was
separated from the reaction mixture via a magnet. Next, UV-vis
DRS of the nanocatalyst for the Suzuki–Miyaura and Mizoroki–
Heck cross-coupling reactions were performed. As can be seen
from Fig. 1, the presence of the peak at around 420 nm belongs to
a PdII species.[50–54]
The results of the XPS analysis demonstrated that the
palladium immobilized on the 7th recovered FMMWCNTs@-
CPA@SMTU@PdII NPs (IV) in the Suzuki–Miyaura and
Mizoroki–Heck cross-coupling reactions was PdII (see the
results of XPS analysis).
Hot Filtration Test
elimination in the presence of
a
base delivered the
To verify whether FMMWCNTs@CPA@SMTU@PdII NPs
(IV) was heterogeneous or not, the nanostructured catalyst was
removed from the Suzuki–Miyaura and Mizoroki–Heck cou-
pling reactions’ media by a magnet after 5 and 7 min, respec-
tively. The modal reactions were continued under the same
conditions and monitored using TLC (Fig. 2). Both the Suzuki–
Miyaura and Mizoroki–Heck cross-coupling reactions stopped
completely at 62 and 65 % isolated yield, respectively. The
FMMWCNTs@CPA@SMTU@PdII NPs to the next run.
DRS is a surface analytical technique. It uses UV, visible, or
IR light as a probing medium. The interaction of light with
strongly absorbing materials, such as metals, alloys, and semi-
conductors occurs in the first 10–20 nm. Thus the differential
reflectometer probes 50–100 atomic layers into non-transparent
solid surfaces.[49] In addition, to investigate the oxidation state

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
G
Table 3. Suzuki–Miyaura/Mizoroki–Heck cross-coupling reactions of aryl halides with different phenylboronic acids/alkyl acrylates in the presence
of FMMWCNTs@CPA@SMTU@PdII NPs (IV)
Entry
1
Aryl halide
Coupling substrate
Product
Time [min]
10
Isolated yield [%]
98
I
a
b
c
d
B(OH)2
8
22
15
98
90
98
Cl
B(OH)2
Cl
MeO
B(OH)2
MeO
O
O
O
O
O
O
O
O
O
O
O
e
f
25
35
95
95
Et
Et
O
Bun
Bun
CN
g
h
48
90
70
CN
2 h
I
2
a
b
c
d
5
12
20
10
95
98
90
95
B(OH)2
NO2
NO2
Cl
Cl
B(OH)2
B(OH)2
NO2
MeO
NO2
MeO
O
O
O
O
O2N
O
O
e
15
95
Et
Et
O
O
O2N
(continued)

H
M. S. Ghasemzadeh and B. Akhlaghinia
Table 3. (Continued)
Entry
Aryl halide
Coupling substrate
Product
Time [min]
18
Isolated yield [%]
95
O
O
f
Bun
O
Bun
O
O2N
O2N
CN
g
h
25
90
75
CN
NO2
1.80 h
I
3
a
8
95
B(OH)2
CN
b
c
d
13
15
14
95
90
95
Cl
Cl
CN
B(OH)2
B(OH)2
N
MeO
CN
MeO
O
O
O
O
O
O
NC
NC
O
e
f
22
25
90
90
Et
O
Et
O
O
Bun
O
Bun
O
NC
NC
CN
g
h
20
90
75
CN
CN
1.90 h
I
4
a
28
20
90
85
Me
O
B(OH)2
O
b
O
O
Me
(continued)

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
I
Table 3. (Continued)
Entry
Aryl halide
Coupling substrate
Product
Time [min]
33
Isolated yield [%]
85
O
O
c
Et
O
Et
O
Me
Me
O
O
d
48
85
Bun
O
Bun
O
I
5
a
1.50 h
1.40 h
85
80
OMe
B(OH)2
O
O
b
O
O
O
OMe
MeO
MeO
MeO
O
O
c
d
a
2 h
75
75
90
Et
O
Et
O
O
2.30 h
Bun
O
Bun
O
Br
6
22
B(OH)2
b
c
d
20
32
23
90
85
90
Cl
Cl
B(OH)2
B(OH)2
MeO
MeO
O
O
O
O
O
O
O
O
O
e
f
30
46
85
85
Et
Et
O
O
Bun
Bun
O
CN
g
h
65
90
65
CN
2.30 h
(continued)

J
M. S. Ghasemzadeh and B. Akhlaghinia
Table 3. (Continued)
Entry
7
Aryl halide
Coupling substrate
Product
Time [min]
15
Isolated yield [%]
90
Br
a
NO2
O
B(OH)2
O
b
17
24
38
30
90
90
85
80
O
NO2
O
N
O2
O
O
c
d
a
Et
O
Et
O
O2N
O
O
Bun
O
Bun
O
N
O2
Cl
8
B(OH)2
b
c
d
25
42
35
80
75
80
Cl
Cl
B(OH)2
B(OH)2
MeO
MeO
O
O
O
O
O
O
O
O
O
e
f
45
65
70
70
Et
Et
O
O
Bun
Bun
O
CN
g
h
1.45 h
2.40 h
65
55
CN
(continued)

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
K
Table 3. (Continued)
Entry
9
Aryl halide
Coupling substrate
Product
Time [min]
40
Isolated yield [%]
75
Cl
a
CHO
B(OH)2
b
c
d
25
35
40
70
70
75
CHO
Cl
Cl
B(OH)2
B(OH)2
CHO
MeO
CHO
MeO
O
O
O
O
O
O
O
O
O
OHC
OHC
OHC
e
f
45
75
65
Et
Et
O
O
1.20 h
Bun
Bun
O
results indicated that the catalytic cross-coupling reactions were
heterogeneous and occurred over the solid nanostructured cat-
alyst rather than in the solution.
negligible drop in the nanocatalytic activity after following four
runs was witnessed. In addition, in the fifth, sixth, and seventh
cycles, between 11 and 18 % of catalytic activity was lost. It is
worth adding that the nanocatalyst was not only very active, but
also very stable during the reaction runs.
Mercury Poisoning Test
This ferromagnetic nanostructured catalyst showed a good
stability and reusability which was confirmed by FT-IR spectros-
copy, XRD analysis, FE-SEM, TGA, VSM, XPS, and ICP-OES.
FT-IR spectroscopy of the 7th recovered FMMWCNTs@-
CPA@SMTU@PdII NPs (IV) from the Suzuki–Miyaura and
Mizoroki–Heck cross-coupling reactions clearly confirmed that
there are insignificant changes in the frequencies, intensities,
and shapes of absorption bands. The results also displayed
that palladium ions were coordinated to the organic moieties on
the surface of the FMMWCNTs@CPA@SMTU (III) NPs
(Fig. 5b, c).[43]
XRD patterns of the 7th recovered nanocatalyst exhibited
that the nanostructured catalyst underwent no changes during
the Suzuki–Miyaura and Mizoroki–Heck cross-coupling reac-
tion processes (Fig. 6b, c). Moreover, the average crystalline
size of the fresh and the 7th recovered FMMWCNTs@-
CPA@SMTU@PdII NPs (IV) from the Suzuki–Miyaura and
Mizoroki–Heck cross-coupling reactions were estimated to
be 22,[43] 26, and 24 nm, respectively, based on the Debye–
Scherrer equation.
The model Suzuki–Miyaura and Mizoroki–Heck cross-coupling
reactions were conducted in the absence and in the presence of
mercury (using an excess amount of Hg0 (Hg/Pd, 400 : 1)) under
the optimum conditions catalyzed by FMMWCNTs@-
CPA@SMTU@PdII NPs (IV). The reaction progress was
monitored by TLC. The yields of the corresponding products
(1,10-biphenyl and methyl cinnamate) were both 98 % after 1 h
from the Suzuki–Miyaura and Mizoroki–Heck cross-coupling
reactions. Time-dependent correlation of the product yields
indicated that the improvement of the cross-coupling reactions
has not been noticeably affected in the presence of mercury, and
the reaction progress was exactly the same either in the absence
or presence of the mercury (Fig. 3). This means that no leaching
of PdII (into the reaction media) took place during the course of
the reactions which confirmed the truly heterogeneous nature of
the nanostructured catalyst. As a result, the cross-coupling
reactions were carried out on the surface of the nanostructured
catalyst.
Recovery and catalyst reuse are important aspects for cross-
coupling reactions. For this purpose, the reusability of the
heterogeneous nanostructured catalyst in the model Suzuki–
Miyaura and Heck–Mizoroki cross-coupling reactions was
investigated (Fig. 4). At the end of each cycle, the nanostruc-
tured catalyst was separated by a magnet, rinsed with ethyl
acetate (3 ꢁ 20 mL), and dried at ambient temperature for 24 h
before being re-employed directly in another fresh reaction
mixture of both catalytic systems. As can be seen in Fig. 4, a
FE-SEM images showed the preservation of the uniform
rod-like morphology in the recovered nanocatalyst after seven
cycles of the Suzuki–Miyaura and Mizoroki–Heck cross-
coupling reactions (Fig. 7a, b).[43]
The thermal stability of FMMWCNTs@CPA@SMTU@-
PdII NPs (IV) after seven runs from the Suzuki–Miyaura and
Mizoroki–Heck cross-coupling reactions was studied by TGA.

L
M. S. Ghasemzadeh and B. Akhlaghinia
R1
L
X
H
O
X
PdIV
O
H
L
β-hydride elimination
L
L
PdIV
O
Ar
Ar
R1
O
(VI)
(V)
Ar
O
R1
O
(VII)
O
R1
O
H
X
L
L
Ar
PdIV
PdIV
L
(VIII)
L
X
(IV)
NEt3
reductive elimination
O
–
+
NHEt3 X
R1
O
L
L
Ar
X
PdIV
(I)
Ar1
Ar1-B(OH)3 + NEt3
Ar
+
–
(III)
NEt3 B(OH)3 X
reductive elimination
L
L
Ar
Ar1
HN
S
PdIV
(II)
HN
H
O
P
NH
NH
N
S
O
P
S
P
NH
O
O
P
P
O
H
NH
N
NH
NH
S
S
Ar-X
oxidative addition
FMMWCNTs@CPA@SMTU@PdII NPs (IV)
Scheme 3. Plausible mechanism for the Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions in the
presence of FMMWCNTs@CPA@SMTU@PdII NPs (IV).
(a)
(b)
No filtration
100
90
80
70
60
50
40
30
20
No filtration
100
90
80
Hot filtration
70
60
50
40
Hot filtration
0
2
4
6
8
10 12 14 16 18 20 22 24 26 28 30
Time [min]
2
4
6
8
10 12 14 16 18 20 22 24 26 28 30
Time [min]
Fig. 2. Hot filtration experiment in the model reaction of the (a) Suzuki–Miyaura and (b) Mizoroki–Heck cross-coupling reactions using
FMMWCNTs@CPA@SMTU@PdII NPs (IV).

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
M
(a)
(b)
100
90
80
70
60
50
40
30
20
(c)
(d)
100
90
80
70
60
50
40
10
20
30
40
50
60
10
20
30
40
50
60
Time [min]
Time [min]
Fig. 3. Time-dependent correlation of the product yields of the model reactions of Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions catalyzed
by FMMWCNTs@CPA@SMTU@PdII NPs (IV) (a, c) in the presence and (b, d) in the absence of Hg0.
900
100
90
80
70
60
800
50
40
700
30
20
10
600
(c)
0
First Second Third Fourth
Fifth
87
85
Sixth Seventh
500
400
300
200
Suzuki–Miyaura
Mizoroki–Heck
98
95
93
90
85
83
98
94
92
90
83
80
(b)
(a)
Fig. 4. Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions of
iodobenzene with phenylboronic acid and methyl acrylate under the opti-
mized reaction conditions catalyzed by the recovered FMMWCNTs@-
CPA@SMTU@PdII NPs (IV).
20
30
40
50
60
70
80
260
2q [deg.]
(c)
240
Fig. 6. XRD patterns of (a) FMMWCNTs@CPA@SMTU@PdII NPs
(IV), the 7th recovered FMMWCNTs@CPA@SMTU@PdII NPs (IV) from
the (b) Suzuki–Miyaura and (c) Mizoroki–Heck cross-coupling reactions.
220
200
180
160
140
120
100
80
(b)
(a)
the former and 160 to 195 8C for the latter, which was attributed
to the release of water molecules. The second weight loss (14 %)
occurred in the temperature range of 195 to 3858C for the former
and 202 to 3938C for the latter and was due to the decomposition
of organic groups immobilized on the FMWCNTs (I) surface.
The amount of organic segment was found to be 0.552 or
0.565 mmol gꢀ1 (the organic segment of the fresh nanocatalyst
was estimated to be 0.581 mmol gꢀ1). Consequently, it means
that 2.9 or 1.6 % of the total amount of the organic linkers
anchored on the FMMWCNTs (I) surface were lost during the
seven cycles of the Suzuki–Miyaura and Mizoroki–Heck cross-
coupling reactions, respectively. The combustion of MWCNTs
happened during the third step of weight losses (13 or 14 %)
from 390 to 6408C for the former and 397 to 6658C for the latter.
Based on the results, the thermal stability of the 7th recovered
nanocatalyst is up to 7008C and the organic segments still
existed (Fig. 8b, c).[43]
1415
1078
60
590
500
1617
40
619
20
0
3500
3000
2500
2000
1500
1000
Wavenumber [cm–1
]
Fig. 5. FT-IR spectra of (a) FMMWCNTs@CPA@SMTU@PdII NPs
(IV), the 7th recovered FMMWCNTs@CPA@SMTU@PdII NPs (IV) from
the (b) Suzuki–Miyaura and (c) Mizoroki–Heck cross-coupling reactions.
The TGA curves of the 7th recovered nanostructured catalyst
from the Suzuki–Miyaura and Mizoroki–Heck cross-coupling
reactions indicated a weight loss (10 %) from 165 to 1908C for

N
M. S. Ghasemzadeh and B. Akhlaghinia
(b)
(a)
WD: 2.51 mm
Det: InBeam
SEM HV: 15.0 kV
View field: 1.98 μm
SEM MAG: 70.0 kx
SEM HV: 15.0 kV
View field: 1.38 μm
SEM MAG: 100 kx
WD: 2.52 mm
Det: InBeam
MIRA3 TESCAN
MIRA3 TESCAN
500 nm
200 nm
Mashhad (MUMS)
Date(m/d/y): 12/30/17
Mashhad (MUMS)
Date(m/d/y): 12/30/17
Fig. 7. The FE-SEM images of (a) the 7th recovered FMMWCNTs@CPA@SMTU@PdII NPs (IV) from the (a) Suzuki–Miyaura and (b) Mizoroki–Heck
cross-coupling reactions.
40
100
(a)
30
20
(b)
90
10
0
80
70
60
50
(c)
(d)
–10
–20
–30
(b)
(c)
(a)
200
400
600
800
–15000 –10000 –5000
0
5000
10000 15000
Temperature [°C]
H [Oe]
Fig. 8. TGA curves of (a) FMMWCNTs@CPA@SMTU@PdII NPs (IV),
the 7th recovered FMMWCNTs@CPA@SMTU@PdII NPs (IV) from the
(b) Suzuki–Miyaura and (c) Mizoroki–Heck cross-coupling reactions.
Fig. 9. Magnetization curves of (a) FMMWCNTs (I), (b)
FMMWCNTs@CPA@SMTU@PdII NPs (IV), the 7th recovered
FMMWCNTs@CPA@SMTU@PdII NPs (IV) from the (c) Suzuki–Miyaura
and (d) Mizoroki–Heck cross-coupling reactions.
Fig. 9c, d reveal that the saturation magnetization values (Ms)
of the 7th recovered FMMWCNTs@CPA@SMTU@PdII NPs
(IV) from the Suzuki–Miyaura and Mizoroki–Heck cross-
coupling reactions are 9.5 and 8 emu gꢀ1, which are lower than
the fresh nanostructured catalyst (26.95 emu gꢀ1).[43] As can be
clearly seen, the magnetization decreased while the ferromag-
netic properties of nanostructured catalysts were still present.
Other magnetic properties (coercivity (Hci) and remnant mag-
netization (Mr)) of the nanocatalysts are illustrated in Table 4.
The XPS study of the 7th reused nanostructured catalyst from
the Suzuki–Miyaura and Mizoroki–Heck cross-coupling reac-
tions exhibited that the binding energies of the doublet peak at
339 (assigned to Pd 3d5/2) and 345 eV (assigned to Pd 3d3/2)
could be attributed to the PdII species (Fig. 10a, b). Furthermore,
the peaks related to carbon (C 1s), nitrogen (N 1s), iron (Fe 2p),
palladium (Pd 3d), sulfur (S 2p), and oxygen (O 1s) were
observed in the XPS elemental survey scans of the 7th recovered
nanostructured catalyst from both the Suzuki–Miyaura and
Mizoroki–Heck cross-coupling reactions (Fig. 10c, d).
ICP-OES analysis revealed that the freshly prepared nanoca-
talystcontains 0.69mmolofpalladium per 1.000 g (7.31 wt-%)of
FMMWCNTs@CPA@SMTU@PdII NPs (IV),[43] while the 7th
recovered catalyst from the Suzuki–Miyaura and Mizoroki–Heck
cross-coupling reactions contains 0.618 and 0.64mmol of Pd per

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
O
Table 4. Magnetic properties of MMWCNTs (I), MMWCNTs@CPA@SMTU@PdII NPs (IV), and the 7th recovered MMWCNTs@CPA@-
SMTU@PdII NPs (IV) from the Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions
Sample
Saturation magnetization (Ms)
[emu gꢀ1
Coercivity (Hci)
Remnant magnetization
(Mr) [emu gꢀ1
]
]
[Oe]
FMMWCNTs (I)
31.98
26.95
9.5
560
440
298
14.04
11.60
6.48
FMMWCNTs@CPA@SMTU@PdII NPs (IV)
The 7th recovered catalyst from the Suzuki–Miyaura
cross-coupling reaction
The 7th recovered catalyst from the Mizoroki–Heck
cross-coupling reaction
8
276
6.08
(a)
(b)
Pd 3d
Pd 3d
350
346
342
338
334
352
348
344
340
336
332
Binding energy [eV]
Binding energy [eV]
(c)
(d)
C 1s
O 1s
C 1s
∗
∗
∗
O 1s
∗
Fe 2p
∗
Fe 2p
∗
Pd 3d
∗
N 1s
∗
Pd 3d
∗
N 1s
∗
S 2p
S 2p
∗
∗
400
1200
1000
800
600
200
1200
1000
800
600
400
200
Binding energy [eV]
Binding energy [eV]
Fig. 10. XPS spectra and XPS elemental survey scans of the 7th reused FMMWCNTs@CPA@SMTU@PdII NPs (IV) in (a, c) Suzuki–Miyaura and
(b, d) Mizoroki–Heck cross-coupling reactions.
1.000 g (6.55 and 6.78wt-%) of the nanostructured catalyst. The
results indicate that 89.5 and 92 % of PdII could be found in the
structure of the catalyst after seven runs. According to the results,
an insignificant leaching of palladium from the surface of the
FMMWCNTs@CPA@SMTU@PdII NPs (IV) was detected. The
above analysis revealed that the structure of FMMWCNTs@-
CPA@SMTU@PdII NPs (IV) had no changes even after seven
following cycles.
Withthepurposeofexaminingtheefficiencyoftheprocedures
presented, we compared the results of the Suzuki–Miyaura and

P
M. S. Ghasemzadeh and B. Akhlaghinia
Table 5. The comparison of the catalytic activity of FMMWCNTs@CPA@SMTU@PdII NPs (IV) with some literature precedents for Suzuki–
Miyaura and Mizoroki–Heck cross-coupling reactions
Entry
Catalyst [mol-%]
Reaction conditions
Time [h]
Yield [%]
Reference
1A
2A
3A
4A
5B
6B
7B
8B
9B
Fe3O4@SiO2@C22-PdII (0.5)
Et3N, DMF/H2O (1 : 1), 758C
K2CO3, TBAB, H2O, 808C
K2CO3, TBAB, H2O, 408C
Et3N, s.f., r.t.
1
92
94
98
98
90
96
94
88
98
52
Fe3O4@EDTA-PdCl2 (20 mg)
g-Fe2O3/AEPH2-TC-PdC (0.1)
FMMWCNTs@CPA@SMTU@PdII NPs (IV) (0.55)
Pd-ZnFe2O4 MNPs (4.62)
3
10 min
10 min
3
53
54
Present study
Et3N, DMF, 1208C
55
g-Fe2O3/AEPH2-TC-Pd (0.1)
Fe3O4@SiO2-T/PdD (20 mg)
MNPs@Cs-Ms-CoE (1.1)
K2CO3, TBAB, H2O, 658C
Et3N, DMF, 1208C
K3PO4, PEG, 808C
20 min
2
54
56
57
1
FMMWCNTs@CPA@SMTU@PdII NPs (IV) (0.35)
Et3N, s.f., r.t.
15 min
Present study
ASuzuki–Miyaura cross-coupling reaction of iodobenzene with phenylboronic acid.
BMizoroki–Heck cross-coupling reaction of iodobenzene with methyl acrylate.
CTC: thiophene-2-carbaldehyde.
DFe3O4@SiO2-T/Pd: Magnetic nanoparticle-supported tetrazole functionalized palladium catalyst.
ECs: chitosan, Ms: methyl salicylate.
Mizoroki–Heck cross-coupling reactions here with previously
reported results (Table 5). As can be seen, the present nanostruc-
tured catalyst is superior in terms of price, non-toxicity, and
stability and also displays good to excellent yields of the coupled
productswithshorterreactiontimesthantheothercatalysts, while
each of these catalytic systems has their own advantages.
,200 and 500 nm (manufactured in the Czech Republic). TGA
analysis was carried out on a Shimadzu Thermogravimetric
Analyzer (TG-50) in the temperature range of 25–9208C at a
heating rate of 108C minꢀ1 under air atmosphere. The magnetic
properties of the catalyst were measured using a vibrating sample
magnetometer (Magnetic Danesh Pajoh Inst.). XPS was per-
formed using a Thermo Scientific, ESCALAB 250 Xi Mg X-ray
resource and Bestec Al X-ray Ka: 1486.6 (manufactured in
Germany). UV-Vis DRS was measured using an Ava Spec 2048
TECH spectrometer. ICP-OES was carried out with a Varian
VISTA-PRO, CCD (Australia). All yields refer to isolated pro-
ducts after purification by TLC and/or column chromatography.
Conclusion
FMMWCNTs@CPA@SMTU@PdII NPs (IV) has been found
to show remarkable catalytic activity in the Suzuki–Miyaura and
Heck–Mizoroki cross-coupling reactions under solvent-free
conditions at room temperature. Factors such as simple sepa-
ration of the nanocatalyst, easy recovery of final products, and
milder reaction conditions than current catalytic systems illus-
trate that this procedure is proficient, economic, and environ-
ment friendly. In addition, it is found that the ferromagnetic
nanostructured catalyst with uniform rod-like morphology and a
particle size of ,20–30 nm does not change significantly even
after seven recovery cycles.
Preparation of FMMWCNTs (I)
The raw MWCNTs (diameter 10–20 nm) (0.3g) were dispersed
in distilled water (50 mL) for 30min under ultrasonication.
Afterwards, a solution of FeSO4ꢂ7H2O (50 mL, 0.0179mol Lꢀ1
)
and H2SO4 (2mL, 18M) was added to the MWCNT suspension
with ultrasonication for 30min. NaBH4 (100mL, 0.135 mol Lꢀ1
)
was gradually added over 30min to the transferred suspension
in an open beaker under vigorous stirring. After cooling the
reaction mixture to ambient temperature, the solid product was
collected using filtration followed by washing with anhydrous
ethanol and water to remove residual acid and dissociative FeII.
The prepared Fe/MWCNTs NPs were soaked in anhydrous
ethanol for 60min. Finally, the FMMWCNTs (I) were obtained
after the separationofthe solid residue using anexternalmagnetic
field and drying at 808C overnight.[43]
Experimental
Materials and Instruments
All chemical reagents and solvents were purchased from Merck
and Sigma–Aldrich chemical companies and were used as
receivedwithoutfurtherpurification.Thepuritydeterminationsof
the products were accomplished by TLC on silica gel polygram
STL G/UV 254 plates. The melting points of the products
were determined with an Electrothermal Type 9100 melting
point apparatus. The FT-IR spectra were recorded on an Avatar
370 FT-IR Therma Nicolet spectrometer. Elemental analyses
were performed using a Thermo Finnegan Flash EA 1112 Series
instrument.TheNMRspectrawereobtainedusingBrukerAvance
300 and 400 MHz instruments in CDCl3. Mass spectra were
recorded with a CH7A Varianmat Bremem instrument at 70eV
electron impact ionization. The crystal structure of the catalyst
was analyzed by XRD using a Model Explorer Co.: GNR (Italy)
diffractometer Dectvis operated at 40 kV and 30 mA utilising Cu
Ka radiation (l 0.154 A8). TEM was performed with a Leo 912
AB microscope (Zeiss, Germany) with an accelerating voltage of
120 kV. FE-SEM images, EDS, and EDS maps were recorded
using a TESCAN, Model: MIRA3 scanning electron microscope
operating at an acceleration voltage of 30.0kV and a resolution of
Preparation of FMMWCNTs@CPA (II)
FMMWCNTs (I) (1.5 g) in dry toluene (40 mL) was sonicated
for 1 h. Next, CPA (5 mmol, 0.72 g) was added to the obtained
suspension. The reaction mixture was refluxed and stirred for
20 h. The resulting FMMWCNTs@CPA (II) was separated by a
magnet and rinsed in turn by diethyl ether (3 ꢁ 15 mL), CH2Cl2
(3 ꢁ 15 mL), and dried under vacuum at ambient temperature.
Elemental analysis and TGA revealed that the loading amount of
Cl was 0.35 mmol per gram of catalyst.[43]
Preparation of FMMWCNTs@CPA@SMTU (III)
The obtained FMMWCNTs@CPA (II) (1 g) was sonicated
in ethanol (50 mL) for 30 min. Next, S-methylisothiourea

FMMWCNTs@CPA@SMTU@PdII Catalyzed Coupling Reaction
Q
hemisulfate salt (2.5 mmol, 0.347 g) and potassium carbonate
(2.5 mmol, 0.345 g) were added to the reaction mixture and
refluxed for 24 h. Afterwards, the resulting FMMWCNTs@-
CPA@SMTU NPs (III) were collected by an external magnet
and washed with ethanol (4 ꢁ 20 mL) and dried at room tem-
perature for 24 h. Elemental analysis and TGA revealed that the
loading amount of S was 0.46 mmol per gram of catalyst.[43]
128.7, 128.1, 126.7, 114.2, 55.3. m/z 184 (Mþ, 80 %), 183
([M – H]þ, 102), 168 ([M – CH3]þ, 84), 152 ([M – CH4O]þ,
42), 140 ([M – C3H8]þ, 82), 115 ([M – C4H5O]þ, 80), 92
([M – C6H5O]þ, 44).
(E)-Butyl cinnamate (1f) (0.229 g, 95 %): white solid; mp
141–1428C (Lit.[59,62,63] 140–1428C). dH (400 MHz, CDCl3)
7.60 (d, J 16.4, 1H), 7.45–7.43 (m, 1H), 7.31–7.28 (m, 1H),
6.38 (d, J 16, 1H), 6.34 (d, J 16, 1H), 4.13 (t, J 6.8, 2H), 1.62–
1.59 (m, 2H), 1.36–1.34 (m, 2H), 0.88 (t, J 7.6, 3H). dC
(100 MHz, CDCl3) 166.8, 144.4, 134.4, 130.1, 128.8, 128.0,
118.2, 64.3, 30.8, 19.2, 13.7.
(E)-Methyl 3-(4-nitrophenyl) acrylate (2d) (0.277 g, 95 %):
white solid; mp 161–1628C (Lit.[59,64,65] 160–1628C). dH
(300 MHz, CDCl3) 8.25 (d, J 8.8, 2H), 7.72 (d, J 16.1, 1H),
7.67 (d, J 8.7, 2H), 6.56 (d, J 16.1, 1H), 3.84 (s, 3H). dC (75 MHz,
CDCl3) 166.6, 148.7, 142.1, 140.7, 128.8, 124.4, 122.3, 52.3.
m/z 207 (Mþ, 62 %), 206 ([M – H]þ, 92), 189 ([M – C2H6O]þ,
38), 175 ([M – CH4O]þ, 102), 148 ([M – C2H3O2]þ, 52), 129
([M – C3H10O4]þ, 80), 118 ([M – C4H9O2]þ, 78), 102
([M – C6H1O2]þ, 88).
Preparation of FMMWCNTs@CPA@SMTU@PdII NPs (IV)
FMMWCNTs@CPA@SMTU (III) (1 g) was added to a solu-
tion of palladium acetate (0.26 mmol, 0.06 g) in dry acetone
(40 mL). The reaction mixture was stirred at ambient tempera-
ture overnight. The resulting product was separated via a mag-
net, washed three times with acetone (15 mL), and dried under
vacuum to obtain FMMWCNTs@CPA@SMTU@PdII NPs
(IV). ICP-OES analysis showed that the loading amount of Pd
was 0.69 mmol per gram of catalyst.[43]
Typical Procedure for the Suzuki–Miyaura Cross-Coupling
Reaction
(E)-Butyl 3-(4-nitrophenyl)acrylate (2f) (0.216 g, 95 %):
white solid; mp 68–698C (Lit.[59,63,66,67] 67–698C). dH
(400 MHz, CDCl3) 8.20 (d, J 8, 2H), 7.66 (d, J 16.1, 1H), 7.44
(d, J 8.7, 2H), 6.53 (d, J 16, 1H), 4.20 (t, J 6.7, 2H), 1.69–1.62
(m, 2H), 1.44–1.35 (m, 2H), 0.92 (t, J 7.2, 3H). dC (100 MHz,
CDCl3) 166.0, 148.3, 141.5, 140.5, 130.1, 128.6, 124.0, 122.5,
64.7, 30.6, 19.1, 13.6.
(E)-Methyl 3-(4-cyanophenyl)acrylate (3d) (0.243 g, 95 %):
white solid; mp 124–1268C (Lit.[62] 122–1268C). dH (300 MHz,
CDCl3) 7.69–7.61 (m, 4H), 7.58 (d, J 16.1, 1H), 6.51 (d, J 16,
1H), 3.82 (s, 3H). dC (75 MHz, CDCl3) 166.6, 142.5, 138.8,
132.7, 128.5, 121.5, 118.4, 113.6, 52.0. m/z 187 (Mþ, 55 %), 186
([M – H]þ, 87), 155 ([M – CH6N]þ, 103), 127 ([M – C2H4O2]þ,
90), 101 ([M – C4H6O2]þ, 78).
Triethylamine (NEt3) (2 mmol, 0.202 g) was added to a mixture
of iodobenzene (1.0 mmol, 0.203 g) and phenylboronic acid
(1.2 mmol, 0.146 g) in solvent-free conditions at ambient
temperature. FMMWCNTs@CPA@SMTU@PdII NPs (IV)
(0.55 mol-%, 0.025 g) were then added to the resulting mixture
under stirring. After the completion of the reaction (10 min)
which was monitored by TLC, the nanocatalyst was separated
by a magnetic field, washed with ethyl acetate, and dried at room
temperature for 24 h to be used in the next run. The reaction
mixture was then extracted with ethyl acetate (5 ꢁ 5 mL) and the
combined organic layer was dried over anhydrous Na2SO4.
After evaporation of the solvent, the crude product was purified
by TLC (or column chromatography using n-hexane/ethyl
acetate (50 : 1)) using n-hexane/ethyl acetate (8 : 2) to produce
the pure 1,10-biphenyl (0.144 g, 98 % yield).
(E)-Methyl 3-(p-tolyl)acrylate (4b) (0.238 g, 85 %): yellow
solid; mp 56–578C (Lit.[59,68,69] 55–578C). dH (400 MHz,
CDCl3) 7.69 (d, J 16, 1H), 7.43 (d, J 8, 2H), 7.20 (d, J 8 2H),
6.41 (d, J 16, 1H), 3.81(s, 3H), 2.38 (s, 3H). dC (100 MHz,
CDCl3) 167.6, 144.8, 140.7, 131.6, 129.6, 128.0, 116.7, 51.6,
21.4. m/z 177 (Mþ, 10 %), 175 ([M – 2H]þ, 94), 160
Typical Procedure for the Mizoroki–Heck Cross-Coupling
Reaction
FMMWCNTs@CPA@SMTU@PdII NPs (IV) (0.35 mol-%,
0.015 g) were added to a mixture of triethylamine (NEt3)
(2 mmol, 0.202 g), methyl acrylate (1.2 mmol, 0.108 mL), and
iodobenzene (1.0 mmol, 0.203 g) in solvent-free conditions at
room temperature. After the completion of the reaction (15 min)
which was monitored by TLC, the nanocatalyst was separated
by a magnetic field, washed with ethyl acetate, and dried at room
temperature for 24 h to be used in the next run. The reaction
mixture was then extracted with ethyl acetate (5 ꢁ 5 mL) and the
combined organic layer was dried over anhydrous Na2SO4.
After evaporation of the solvent, the crude product was purified
by TLC (or column chromatography using n-hexane/ethyl
acetate (50 : 1)) using n-hexane/ethyl acetate (8 : 2) to produce
the pure methyl cinnamate (0.153 g, 98 % yield).
1,10-Biphenyl (1a) (0.279 g, 98 %): white solid; mp 70–718C
(Lit.[58,59] 70–728C). dH (400 MHz, CDCl3) 7.54 (d, J 8, 4H),
7.39 (t, J 8, 4H), 7.31–7.27 (m, 2H). dC (125 MHz, CDCl3)
141.2, 128.7, 127.2, 126.1. m/z 154 (Mþ, 80 %), 153 ([M – H]þ,
102), 115 ([M – C3H3]þ, 32), 102 ([M – C4H4]þ, 28), 76
([M – C6H6]þ, 78).
([M
– –
CH4]þ, 40), 144 ([M CH4O]þ, 100), 130
([M – C3H10]þ, 38), 115 ([M – C2H5O]þ, 90), 102
([M – C3H6O2]þ, 52), 91 ([M – C4H5O2]þ, 82).
(E)-Butyl 3-(p-tolyl)acrylate (4d) (0.244 g, 85 %): oil;
(Lit.[59,63,67,69,70]). dH (400 MHz, CDCl3) 7.52 (d, J 16.1, 1H),
7.32–7.28 (m, 2H), 7.07–7.04 (m, 2H), 6.30 (d, J 16, 1H), 4.09
(t, J 5, 2H), 2.24 (s, 3H), 1.32–1.40 (m, 2H), 1.23–1.31 (m, 2H),
0.85 (t, J 7.4, 3H). dC (100 MHz, CDCl3) 167.2, 144.5, 140.5,
131.7, 129.5, 128.0, 117.1, 64.2, 30.8, 21.4, 19.2, 13.7.
(E)-Methyl 3-(4-methoxyphenyl)acrylate (5b) (0.261 g,
80 %): yellow solid; mp 89–918C (Lit.[62,69] 88–918C). dH
(400 MHz, CDCl3) 7.67 (d, J 16, 1H), 7.50–7.47 (m, 2H),
6.94–6.90 (m, 2H), 6.33 (d, J 16, 1H), 3.85 (s, 3H), 3.81
(s, 3H). dC (100 MHz, CDCl3) 167.8, 161.4, 144.6, 129.8, 127.2,
115.3, 114.4, 55.4, 51.6. m/z 192 (Mþ, 95), 191 ([M – H]þ, 100),
160 ([M – CH4O]þ, 100), 133 ([M – C2H3O2]þ, 98), 118
([M – C3H6O2]þ, 37), 89 ([M – C7H3O]þ, 49).
(E)-Butyl 3-(4-methoxyphenyl)acrylate (5d) (0.176 g,
75 %): white solid; mp 90–928C (Lit.[59,63,67,69,70] 90–928C).
dH (400 MHz, CDCl3) 7.67 (d, J 16, 1H), 7.39 (d, J 4.2, 2H), 6.81
(d, J 4.8, 2H), 6.24 (d, J 16, 1H), 4.13 (t, J 7, 2H), 3.72 (s, 3H),
1.60–1.62 (m, 2H), 1.35–1.40 (m, 2H), 0.91 (t, J 7, 3H). dC
(100 MHz, CDCl3) 167.8, 161.4, 144.6, 129.8, 127.2, 115.3,
4-Methoxy-1,10-biphenyl (1c) (0.265 g, 90 %): white solid;
mp 88–908C (Lit.[59,60,61] 87–908C). dH (400 MHz, CDCl3) 7.45
(t, J 8.4, 4H), 7.34 (t, J 7.6, 2H), 7.21 (t, J 6.8, 1H), 6.89 (d, J 8.8,
2H), 3.75 (s, 3H). dC (125 MHz, CDCl3) 159.1, 140.8, 133.8,

R
M. S. Ghasemzadeh and B. Akhlaghinia
114.4, 55.4, 51.6. m/z 234 (Mþ, 5 %), 232 ([M – 2H]þ, 97), 190
([M – C2H5O]þ, 15), 177 ([M – C4H9]þ, 100), 160
([M – C4H10O]þ, 100), 133 ([M – C5H9O2]þ, 92), 120
([M – C6H10O2]þ, 80).
(E)-Methyl cinnamate (6d) (0.254 g, 90 %): white solid; mp
36–378C (Lit.[59,64,69] 35–378C). dH (400 MHz, CDCl3) 7.60
(d, J 16, 1H), 7.43–7.41 (m, 2H), 7.29–7.27 (m, 3H), 6.34
(d, J 16, 1H), 3.70 (s, 3H). dC (100 MHz, CDCl3) 166.9, 144.3,
133.9, 129.8, 128.4, 127.6, 117.3, 51.2. m/z 162 (Mþ, 62), 161
([M – H]þ, 89), 131 ([M – CH3O]þ, 101), 117 ([M – C3H9]þ, 34),
103 ([M – C2H3O2]þ, 92), 91 ([M – C3H3O2]þ, 58).
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Supplementary Material
Physicochemical characterization data of products (including
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the characterization data of the nanocatalyst are available on the
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Conflicts of Interest
The authors declare no conflicts of interest.
Acknowledgements
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The authors gratefully acknowledge the partial support of this study by
Ferdowsi University of Mashhad Research Council (Grant no. p/3/43366).
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