Immobilization of palladium nanoparticles on ionic liquid-triethylammonium chloride functionalized magnetic nanoparticles: As a magnetically separable, stable and recyclable catalyst for Suzuki-Miyaura cross-coupling reactions

Article abstract of DOI:10.1016/j.tetlet.2017.09.078

A facile procedure was applied to successfully synthesize novel Pd nanoparticles immobilized on triethanolamine-functionalized magnetic nanoparticles [Fe₃O₄/IL/Pd]. Diverse characterizations (HR-TEM, XRD, FT-IR, TGA, EDX, FE-SEM, ICP, XPS and VSM) were carried out to identify intrinsic traits of the nanoparticles. At room temperature, Fe₃O₄/IL/Pd demonstrated high catalytic activity toward Suzuki-Miyaura cross-coupling reactions in aqueous solution. Based on the results, Fe₃O₄/IL/Pd acted as zwitterionic IL-type heterogeneous catalyst, which could be separated from the reaction mixture, conveniently. Moreover, it exhibited excellent recyclability for at least eight cycles without considerable loss of its activity.

Full text of DOI:10.1016/j.tetlet.2017.09.078

Accepted Manuscript
Immobilization of palladium nanoparticles on ionic liquid-triethylammonium
chloride functionalized magnetic nanoparticles: as a magnetically separable,
stable and recyclable catalyst for Suzuki-Miyaura cross-coupling reactions
Hojat Veisi, Mozhgan pirhayati, Ali Kakanejadifard
PII:
S0040-4039(17)31229-7
https://doi.org/10.1016/j.tetlet.2017.09.078
TETL 49348
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
17 August 2017
23 September 2017
26 September 2017
Please cite this article as: Veisi, H., pirhayati, M., Kakanejadifard, A., Immobilization of palladium nanoparticles
on ionic liquid-triethylammonium chloride functionalized magnetic nanoparticles: as a magnetically separable,
stable and recyclable catalyst for Suzuki-Miyaura cross-coupling reactions, Tetrahedron Letters (2017), doi: https://
doi.org/10.1016/j.tetlet.2017.09.078
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Graphical Abstract
Immobilization of palladium nanoparticles
on ionic liquid-triethylammonium chloride
functionalized magnetic nanoparticles: as a
magnetically separable, stable and recyclable
catalyst for Suzuki-Miyaura cross-coupling
reactions
Leave this area blank for abstract info.
Hojat Veisi, Mozhgan pirhayati and Ali Kakanejadifard
R
R
X
B(OH)2
+
K2CO3, H2O-EtOH
H
X = I, Br, Cl
H
O
O
H
O
Cl
Cl
N
N
Pd
O
H
O
H
O
H
Si
Si
O
O
O
O
O
Fe3O4 NPs
O
Fe3O4 NPs/IL/Pd(0)

1
Tetrahedron Letters
Immobilization of palladium nanoparticles on ionic liquid-triethylammonium chloride
functionalized magnetic nanoparticles: as a magnetically separable, stable and recyclable
catalyst for Suzuki-Miyaura cross-coupling reactions
Hojat Veisi*,a Mozhgan pirhayati,b Ali Kakanejadifardb
aDepartment of Chemistry, Payame Noor University (PNU), Tehran, Iran
bDepartment of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:hojatveisi@yahoo.com
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A facile procedure was applied to successfully synthesize novel Pd nanoparticles immobilized on
triethanolamine-functionalized magnetic nanoparticles [Fe3O4/IL/Pd]. Diverse characterizations
(HR-TEM, XRD, FT-IR, TGA, EDX, FE-SEM, ICP, XPS and VSM) were carried out to identify
intrinsic traits of the nanoparticles. At room temperature, Fe3O4/IL/Pd demonstrated high
catalytic activity toward Suzuki-Miyaura cross-coupling reactions in aqueous solution. Based on
the results, Fe3O4/IL/Pd acted as zwitterionic IL-type heterogeneous catalyst, which could be
separated from the reaction mixture, conveniently. Moreover, it exhibited excellent recyclability
for at least eight cycles without considerable loss of its activity.
Available online
Keywords:
Magnetic
Nanoparticles
Palladium
Heterogeneous nanocatalyst
Suzuki
2009 Elsevier Ltd. All rights reserved.
prevents agglomeration and protects the particles from dissolving
in acidic solutions. SiO2 covers the surface of Fe3O4
Introduction
nanoparticles to form Fe3O4@SiO2 core-shell nanoparticles.17
Transition metals have had an important influence on
development of organic chemistry by evolving different novel
reactions, recently. Palladium, one of the precious noble metals,
catalyzes various important coupling chemical transformations,
such as Suzuki-Miyaura,1 Heck-Mizoroki2 and Sonogashira-
Hagihara3 reactions. Among these reactions, Suzuki-Miyaura
reaction, that involves cross coupling between aryl, vinyl or alkyl
(pseudo) halides and organoboron reagents, has turned out to be
an extremely powerful synthetic method for formation of
different types of compounds found in many building blocks of
pharmaceuticals and natural products. However, homogeneous
Pd catalysts suffer from some practical problems related to their
separation and recycling, which leads to product contamination
with metal, while Pd is high cost. Hence, heterogeneous Pd-based
catalysts can be considered as a great alternative due to their air-
stability, recoverability, reusability and non-residual assets.4
Numerous solid supports, such as microporous polymers,5
mesoporous silica,6 metal oxides,7 clays,8 carbon nanofibers,9 and
molecular sieves10, have been adopted for Pd-based
heterogeneous catalysts, in which Pd complexes or nanoparticles
are involved as the active species in coupling reactions.11
Thorough consideration of all these factors, and in
continuation of our previous works18,19
, herein a novel
nanocatalyst, i.e. Fe3O4/IL-supported Pd nanoparticle, will be
described as a heterogeneous catalyst (Scheme 1) and its
utilization in Suzuki-Miyaura cross coupling (Scheme 2) will be
investigated. The catalyst was fabricated by immobilizing Pd
NPs on triethanolamine-functionalized Fe3O4 magnetic NPs
(MNPs) modified with chloropropyl. The triethanolamine groups
on modified Fe3O4 act as strong and efficient stabilizers for the
Pd NPs, which provide high activity and durability of the catalyst
for the studied reaction. Using a magnet, the new catalyst can be
well dispersed in the reaction medium, conveniently separated
from the reaction mixture and utilized several times without
considerable loss of its activity.
Experimental
Synthesis of Fe3O4
Fe3O4 MNPs were prepared according to Ref. 18a via co-
precipitation of Fe (III) and Fe (II) ions with a molar ratio of 2:1
in presence of ammonium hydroxide. Generally, a mixture of
FeCl3.6H2O (5.838 g, 0.0216 mol) and FeCl2.4H2O (2.147 g,
Fe3O4 nanoparticles (NPs) tend to aggregate and are easily
oxidized or dissolved in an acidic medium.12 Coating Fe3O4 NPs
with organic or inorganic surfactants is one solution of avoiding
such limitations and improving physicochemical properties and
colloidal stability.13-15 Organic surfactants act as capping agents
but they give bigger particle sizes. Inorganic capping agents, e.g.
silica (SiO2), have exceptional chemical and physical traits. In
acidic solutions, SiO2 is chemically stable and apt to
modification.16 Additionally, coating Fe3O4 particles with SiO2
º
0.0108 mol) was dissolved in 100 mL deionized water at 85 C
under N2 atmosphere and intense mechanical stirring (500 rpm).
After that, 10 mL of 25% NH4OH was injected into the reaction
mixture, quickly. Addition of the base to the Fe2+/Fe3+ solution
resulted in formation of the black precipitate of MNPs, instantly.
The reaction was continued for another 25 min and the mixture

2
Tetrahedron
was cooled to room temperature. The magnetic
nanoparticles, as a dark solid, were isolated from the solution by
magnetic separation and washed several times by deionized
water.
Results and discussion
Characterization
Synthesis of the Fe3O4/IL
In this paper, we aimed to design a new hybrid magnetic
nanocomposite with ionic nature and lipophilic feature. Fe3O4
particles were fabricated according to the aforementioned
procedure, and were subsequently functionalized with 3-
chloroproplytriethoxysilane (CPTES) to obtain chloropropyl-
1.0 g of Fe3O4 NPs was dispersed in 80 ml of toluene by an
ultrasonic bath for 25 min. Then, 1 ml (5 mmol) of 3-
Chloropropyl-trimethoxysilane (CPTS) was added and the
solution was stirred at 40 °C for 18 h. The chloropropyl-
functionalized solid (Fe3O4/Si-Pr-Cl) was washed with toluene,
separated by a magnet and dried in vacuum at 50 °C. The
acquired Fe3O4/Si-Pr-Cl was suspended in ethanol (50 mL) with
sonication about 20 min. Triethanolamine (1 mL) was added to
the mixture under mechanical stirring and the reaction mixture
was refluxed for 24 h. After cooling down to room temperature,
the obtained solid was separated magnetically, washed with
absolute ethanol several times and dried under vacuum at 50 °C.
functionalized
magnetic
nanoparticles
(Fe3O4/Si-Pr-Cl).
Ultimately, upon the reaction of the MNPs with triethanolamine,
their surfaces conducted an ionic nature through
triethylammonium chloride formation. The ionic liquid (IL)-
bonded on Fe3O4 NPs was then navigated using PdCl2 and its
subsequent reduction by NaBH4 led to the corresponding Pd
nanoparticles being supported on the magnetic nanoparticles
(Fe3O4/IL/Pd). Finally, the mixture was collected by an external
magnet and dried by vacuum. The reactions undergone for the
synthesis of the catalyst are shown in Scheme 1. Additionally, the
Pd content of the catalyst as estimated by ICP-AAS to equal
0.21±0.001 mmol g-1. Characterization of the catalyst was
achieved through FTIR, XRD, FE-SEM, EDS, HR-TEM, XPS,
TGA, ICP and VSM.
Fig. 1 depicts the fourier transform infrared (FTIR) spectra of
Fe3O4, Fe3O4/IL and Fe3O4/IL/Pd). In curve a, absorption peaks
located at about 582 cm-1 and 637 cm-1 are characteristics of Fe-O
bonds that are present in Fe3O4 NPs. The peaks appeared at 1625
and ∼3400 cm-1 correspond to surface-adsorbed water and
hydroxyl groups.20
Preparation of Fe3O4/IL/Pd(0)
Fe3O4/IL was dispersed in CH3CN (30 mL) in an ultrasonic
bath for 30 min. Then, a yellow solution of PdCl2 (30 mg in 40
mL acetonitrile) was added to the dispersed Fe3O4/IL solution
and the mixture was stirred for 12 h at room temperature. After
that, Fe3O4/IL/Pd(II) was separated by magnetic decantation and
washed by ethanol to remove the unattached substrates.
Fe3O4/IL/Pd(II) was reduced to Fe3O4/IL/Pd(0) by sodium
borohydride. The final product (Scheme 1) was washed by
ethanol and dried at room temperature. The Pd content of the
catalyst was estimated by ICP-AAS to be 0.21±0.001 mmol g-1.
Suzuki-Miyaura coupling reactions
Catalytic activity of the synthesized Fe3O4/IL/Pd(0)
nanocomposite was investigated for Suzuki-Miyaura reaction.
The novel nanocatalyst (0.2 mol%), the aryl halides (1.0 mmol),
phenylboronic acid (1.1 mmol), K2CO3 (2.0 mmol) and
EtOH/H2O (1:1) (3 mL) were added to a round bottomed flask
and stirred for the desired time at room temperature (Scheme 1).
The reaction was monitored by thin layer chromatography (TLC,
n-hexane/acetone; 4:1). When the reaction was completed, 5 mL
of ethanol was added and an external magnet removed the
catalyst. Further purification was achieved by column
chromatography.
Cl
Cl
MeO
S
Si
Si
i
Cl
O
MeO
O
O
O
O
Fe3O4 NPs
MeO
Fe3O4 NPs
Fe3O4 NPs
O
Fe3O4 NPs/Si-Pr-Cl
A
E
T
H
OH
O
OH
OH
HO
Cl
H
O
Cl
N
Cl
N
N
O
H
Pd
Cl
N
HO
HO
O
O
OH
H
H
Si
Si
Si
Si
O
O
O
O
O
O
O
O
Fe3O4 NPs
O
O
Fe3O4 NPs
1. PdCl2
2. NaBH4
O
O
Fe3O4 NPs/IL/Pd(0)
Fe3O4 NPs/IL
Scheme 1. Preparation of the Fe3O4/IL/Pd catalyst.
Fig 1. FT-IR spectra of (a) Fe3O4, (b) Fe3O4/IL and (c) Fe3O4/IL/Pd.

3
In curve b, 1049 and 1088 cm-1 peaks are associated with Si-
O-Si stretching mode while 956 cm-1 peak refers to Si-O bending
mode of the silanol group.21 These peaks state that silica has been
properly functionalized on the Fe3O4 NPs.22a The FTIR spectra of
Fe3O4/IL and Fe3O4/IL/Pd show Fe-O vibrations at similar
wavenumbers. Three new absorption peaks around 2366, 2881
and 2969 cm-1 have emerged in the FT-IR spectra of Fe3O4/IL
and Fe3O4/IL/Pd, which are characteristic of C-H stretching mode
of the alkyl chain, demonstrating that ILs have been successfully
immobilized on the surface of Fe3O4 NPs. Also, the peak located
at 1439 cm-1, in curve b, can be attributed to presence of
quaternary amine, probabely.22b In curve c, which relates to the
Pd nanocatalyst, no dramatic changes in the FTIR spectrum is
observed.
solvents. Decomposition of covalently bonded organics led to a
weight loss of around 3% at 200-450 °C. The results from TGA
imply that the core/shell structure has been successfully modified
with triethanolamine.
EDX analysis for the catalyst (Fig. 5) approved elemental
composition of the modified nanoparticles and existence of Si,
Fe, N, O, C and Pd in the NPs.
The room temperature magnetization curves, Fig. 2, proved
that Fe3O4/IL/Pd nanoparticle is super paramagnetic. It is worth
pointing out that reduction in the magnetization value of
Fe3O4/IL/Pd, in comparison with Fe3O4 NPs, signifies successful
immobilization of the organic groups on Fe3O4 surface. Even
with this decrease in the saturation magnetization, the solid could
still be effectively separated from the solution with a permanent
magnet.
The nanostructure was further affirmed by HR-TEM analysis in
Fig. 3, demonstrating that the particles are relatively uniform in
diameter and spherical in shape. Though Fe3O4 NPs prefer to
gather together due to their small size and magnetism, they have
not aggregated. This observation indicates successful coating of
the MNPs.
Fig. 4: TGA/DTG curves of Fe3O4/IL/Pd.
Fig. 5: EDX spectra of Fe3O4/IL/Pd.
Fig. 2. VSM spectra of Fe3O4, Fe3O4/IL/Pd.
The XRD patterns of Fe3O4/IL/Pd(0) are illusterated in Fig. 6.
Strong characteristic diffractions at 2θ values of 30.09º, 35.44º,
43.07º, 53.43º, 57.06º and 63.2º corresponding to the (220),
(311), (400), (422), (511) and (440) diffractions of Fe3O4 (JCPDS
89-3854) were detected in the sample, implying that the modified
nanoparticles have been synthesized successfully without
damaging the crystal structure of Fe3O4 core. Furthermore, apart
from the original peaks, new peaks appearing at 2θ of 40.01º,
46.54º and 67.93º (weak peak), associated with (111), (200) and
(220) crystalline planes of Pd in the spectrum, demonstrate that
Pd element exists in the form of Pd0 not Pd+2. These three
diffraction peaks are broad, which clarifies that the Pd
composition is made of small nanocrystals and agrees well with
the HRTEM analysis results.
The morphology and structure of Fe3O4/IL/Pd were
investigated by field emission scanning electron microscopy (FE-
SEM). It was approved that the catalyst was made of uniform
nanometer-sized particles (Fig. 7).
Fig. 3. HR-TEM image of Fe3O4/IL/Pd.
The triethanolammonium coating on the surface of Fe3O4 NPs
was also confirmed by thermogravimetric analysis. As shown in
Fig. 4, the weight loss of Fe3O4/IL is mainly divided into three
temperature ranges: below 200 °C, 200-450 °C and above 450
°C. The weight loss during heating from 25 to 200 °C is
attributed to the loss of moisture23,24 and physically adsorbed
X-ray photoelectron spectroscopy (XPS) is an influential
instrument for investigating electronic characteristics of the
species created on surfaces, including environment of electrons,
states of oxidation and binding energy of metal core electrons.

4
Tetrahedron
XPS elemental survey scans of the surface of the
0.2% mol of the palladium catalyst suffices to complete the
reaction (Table1, entry 7).
Fe3O4/IL/Pd catalyst is shown in Fig. 8. The peaks related to
oxygen, carbon, nitrogen, silicon, iron and palladium are obvious
in this spectrum. XPS analysis was also performed to determine
Pd oxidation state. Results displayed presence of an intense
doublet at binding energies (BEs) of 335.7 and 340.9 eV related
to Pd(0), which correspond to Pd 3d5/2 and Pd 3d3/2 peaks,
respectively. This result indicates that Pd is just present in its
reduced form, which confirms successful reduction of Pd(II) to
Pd(0) in the process.25 The characteristic peaks corresponding to
carbon (C 1s), nitrogen (N 1s) and iron (Fe 2p) are also clearly
present in XPS elemental survey of Fe3O4/IL/Pd.
The Suzuki coupling reactions of various substituted aryl
halides with phenylboronic acids were studied using 0.2 mol% of
the magnetic catalyst at room temperature in air (Table 2).
Aqueous ethanol was utilized as the reaction medium for
environmental protection and economic advantage. Under the
optimized circumstances, phenyl iodides, bromides and chlorides
reacted actively with phenylboronic acid (Table 2, entries 1-17).
.
Fig. 6. XRD patterns of Fe3O4/IL/Pd.
Fig. 8. XPS spectrum related to the elemental survey scan of
Fe3O4/IL/Pd and the Fe2p, C1s, Pd3d, and N1s regions.
O
OH
H
Fig. 7. FE-SEM image of Fe3O4/IL/Pd.
Cl
O
N
N
Cl
OH
H
O
HO
Pd
Si
Evaluation of the catalytic activity of Pd NPs through Suzuki-
Miyaura coupling reaction
Si
O
O
O
O
O
O
Fe3O4 NPs
Catalytic property of the Fe3O4/IL/Pd catalyst was tested via
Suzuki cross-coupling reaction (Scheme 2). In order to develop a
better catalytic system, influences of solvent, base and the
amount of catalyst on Suzuki cross coupling were accurately
probed at room temperature using the reaction of bromobenzene
and phenylboronic acid, as the model reaction (Table 1). Solvent
is known to play a vital role in the rate and the product
distribution of Suzuki coupling reactions. Various solvents were
screened and the reactions were conducted using H2O/EtOH (1:1)
as the best solvent. Among the evaluated bases, K2CO3 was
found to be the most efficient base. As expected, no target
product was detected in the absence of catalyst (Table 1, entry
10) and adding the catalyst to the mixture is necessary. Table 1
implies that decreasing the amount of the catalyst (Table 1,
entries 8 and 9), decreases the yields, apparently. Therefore,
Fe3O4 NPs/IL/Pd(0)
R
X
K2CO3, H2O-EtOH
X = I, Br, Cl
+
R
B(OH)2
Scheme 2: Fe3O4/IL/Pd nanocatalyst for Suzuki-Miyaura cross-
coupling reaction.
In the para-positions, aryl halides with electron-donating
groups were less active than those with electron-withdrawing

5
groups. A range of activated and deactivated aryl chlorides have
also been investigated to study catalytic activity of the magnetic
catalyst. According to the results, moderate yields were achieved
at the given reaction condition (Table 2, entries 3, 6 and 9), as the
bond energy of C–Cl in aryl chlorides is higher than that of C–Br
in aryl bromides.
considerable loss of activity, successively. Catalyst reusability
was investigated using iodoobenzene with phenylboronic acid as
model substrates (Fig. 8).
Further, metal leaching, as another important factor for
commercial application of noble metal catalysts, was studied by
ICP analysis. The new Pd NPs showed exceptional stability
throughout the catalytic runs against leaching and sintering so
that they retained >90% of their activity even at the 8th cycle of
catalytic reuse. To determine heterogeneity of the catalyst, a hot
filtration test was conducted for the Suzuki reaction between
iodoobenzene and phenylboronic acid using Fe3O4/IL/Pd under
the same optimum conditions. After proceeding for 8 minutes,
65% yield was obtained from the reaction. Then, the catalyst was
separated to be reused. There was no increase in yield of the
desired product when the reaction was sustained for another 8
minutes after magnetic removal of the catalyst, verifying
heterogeneous property of the catalyst.
Table 1
Optimization of the reaction conditions in Suzuki-Miyaura
coupling reaction of bromobenzene with phenylboronic acid.a
Entry
Pd (mol%) Solvent
Base
Time
(min.)
60
Yield
(%)b
65
1
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.10
0.15
0.0
Toluene
K2CO3
K2CO3
K2CO3
K2CO3
Et3N
NaOAc
K2CO3
K2CO3
K2CO3
K2CO3
No base
2
3
4
5
6
7
8
9
DMF
EtOH
H2O
80
60
90
90
60
60
60
60
80
77
55
80
65
96
65
82
EtOH/H2Oc
EtOH/H2Oc
EtOH/H2Oc
EtOH/H2Oc
EtOH/H2Oc
EtOH/H2Oc
EtOH/H2Oc
100
80
60
40
20
0
10
11
40
90
0.0
Trace
0.2
a Reaction conditions: bromobenzene (1.0 mmol), phenylboronic acid (1.1
mmol), catalyst, base (2 mmol) and solvent (3 mL).
b Isolated yield.
c 1: 1
1
2
3
4
5
6
7
8
9 10
As expected, electron rich aryl boronic acids provided coupling
products in good yields (Table 2, entries 15-17). Steric hindrance
of the substituent did not affect the product yield in Suzuki-
Miyaura reaction of deactivated aryl halides using Pd NPs (Table
2, entry 15).
Run
Fig. 8. Recycling of Fe3O4/IL/Pd in Suzuki reaction.
Table 2
Conclusion
Suzuki–Miyaura coupling reaction of different aryl halides
with phenylboronic acid.a
In the present study, a nanosized Fe3O4/IL/Pd catalyst with high
magnetic and excellent dispersion characteristics was
synthesized, successfully. The magnetic catalyst provided well
decent reactivity and reusability in Suzuki reaction of aryl halides
with phenylboronic acids. The magnetic catalyst could be easily
recovered by an external magnet and reused eight times without
significant loss of its activity. Additionally, the new magnetic
catalyst is more economic and environment friendly because of
its low Pd leaching after eight cycles. It is assumed that this
novel heterogeneous magnetic nanocatalyst can be more widely
applied to Pd-catalyzed reactions.
Entry
RC6H4X
R2C6H4B(OH)2
X
I
Br
Cl
I
Br
Cl
I
Br
Cl
I
Time(h)
0.25
1.00
18.0
0.25
0.75
18.0
0.45
0.80
18.0
0.25
0.75
0.25
2.00
0.50
1.50
1.50
1.50
Yield(%)b
96
95
75
95
92
65
96
96
80
96
92
1
2
3
4
5
6
7
8
H
H
H
H
H
H
H
H
H
H
H
4-CH3
4-CH3
4-CH3
4-COCH3
4-COCH3
4-NO2
4-CH3O
4-CH3O
4-NO2
4-NO2
2-Me
4-NO2
H
9
H
H
H
10
11
12
13
14
15
16
17
Acknowledgement
We are thankful to Payame Noor University (PNU) and
Lorestan University for partial support of this work
Br
I
Br
I
H
H
96
90
H
80
References
4-MeO
3-MeO
2-OMe
I
95
Br
Br
90
H
85
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excess base) and ethanol and dried in an oven at 50 °C. The dried
recovered catalyst was applied for eight cycles with no

6
Tetrahedron
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7
Highlights
 A novel Fe3O4/IL/Pd nano structure was
synthesized.
 Fe3O4/IL/Pd show good activity in the
Suzuki reactions.
 The products were produced in excellent
yields under mild conditions.
 Low palladium loading (∼0.2 mol%) was
used in the reaction.
 The catalyst can be reused several
consecutive cycles.