Palladium nanoparticles supported on cysteine-functionalized MNPs as robust recyclable catalysts for fast O- and N-arylation reactions in green media

Article abstract of DOI:10.1016/j.jorganchem.2019.05.011

A magnetically robust recyclable nanocatalyst was fabricated by immobilizing of Pd onto the surface of cysteine-functionalized magnetic nanoparticles (MNPs?Cys-Pd). This nanocatalyst was characterized using various techniques such as FT-IR, XRD, TEM, SEM, EDX, VSM, and ICP. The application of catalyst (MNPs?Cys-Pd) was investigated for O-arylation and N-arylation reactions. This phosphine-free complex was found as highly efficient heterogeneous catalyst in green media and mild reaction conditions. In addition, it gave excellent recyclability without significant deactivation after ten cycles.

Full text of DOI:10.1016/j.jorganchem.2019.05.011

Accepted Manuscript
Palladium nanoparticles supported on cysteine-functionalized MNPs as robust
recyclable catalysts for fast O- and N-arylation reactions in green media
Abdol R. Hajipour, Zahra Khorsandi, S. Fatemeh Mohammadi Metkazini
PII:
S0022-328X(19)30192-5
DOI:
https://doi.org/10.1016/j.jorganchem.2019.05.011
JOM 20793
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 10 January 2019
Revised Date: 7 May 2019
Accepted Date: 13 May 2019
Please cite this article as: A.R. Hajipour, Z. Khorsandi, S. Fatemeh Mohammadi Metkazini, Palladium
nanoparticles supported on cysteine-functionalized MNPs as robust recyclable catalysts for fast O-
and N-arylation reactions in green media, Journal of Organometallic Chemistry (2019), doi: https://
doi.org/10.1016/j.jorganchem.2019.05.011.
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ACCEPTED MANUSCRIPT
Palladium nanoparticles supported on cysteine-functionalized MNPs as robust recyclable
catalysts for fast O- and N-arylation reactions in green media
Abdol R. Hajipoura, b , Zahra Khorsandi and S. Fatemeh Mohammadi Metkazinia
aDepartment of Chemistry, Isfahan University of Technology, Isfahan 84156, IR Iran
bDepartment of Neuroscience, University of Wisconsin,Medical School, 1300 UniversityAvenue,
Madison, WI 53706-1532, USA
Corresponding author: Tel.: + 98 313 391 3262; fax: + 98 313 391 2350; e-mail: haji@cc.iut.ac.ir.

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Abstract
A magnetically robust recyclable nanocatalyst was fabricated by immobilizing of Pd onto the
surface of cysteine-functionalized magnetic nanoparticles (MNPs@Cys-Pd). This nanocatalyst
was characterized using various techniques such as FT-IR, XRD, TEM, SEM, EDX, VSM, and
ICP. The application of catalyst (MNPs@Cys-Pd) was investigated for O-arylation and N-
arylation reactions. This phosphine-free complex was found as highly efficient heterogeneous
catalyst in green media and mild reaction conditions. In addition, it gave excellent recyclability
without significant deactivation after ten cycles.
Keywords: Cysteine, palladium, magnetic nanoparticles, O-arylation, N-arylation reactions

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Introduction
Transition metal catalysis is a powerful methodology to construction of aryl-nitrogen and aryl-
oxygen bonds; therefore, development of catalytic systems and investigation of their applications
in organic transformations are so interesting [1]. Currently, palladium is the most popular
transition-metal which widely used as catalyst in carbon–carbon and carbon–heteroatom bond
formation reactions [2-10]. Homogeneous catalytic systems have attractive properties such as
high activity and selectivity but reusability of these systems limits their usage in industrial and
synthetic applications. So, studies have been focused on development of heterogeneous Pd
catalysts using different supports [11-14].
However, compared with their homogeneous counterparts, the immobilized catalyst often suffer
from lower activity and selectivity [15, 16]. In the last few decades nanomaterial-based catalysts
are attracted a great deal of attention due to their high densities of active sites and high specific
surface area which increase their catalytic activity [17]. In this context, wide variety of solid
supports such as metal oxides [18] and carbon based [19], mesoporous and amorphous silica [20-
26], polymers [27] and zeolites [28, 29] have been used for stabilizing of metal nanoparticles.
Among these, magnetic nanoparticles, besides easy separation by an external permanent magnet
[30], can stabilize metal nanoparticles using simple organic compounds such as silanes [31-38],
carboxylic acids [39-41] and phosphonic acids [42-44].
L-cysteine is an amino acid with a SH functional group which a range of metals can bind to it
[45, 50]. Some application of cysteine derivatives as catalyst in organic transformations are
available such as aldol condensation reaction reported by Li et al [51] and one-pot synthesis of 2-
amino-4H-chromene-3-carbonitriles introduced by Khalafi-Nezhad et al [52].

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In continues of our previous experience on using heterogonous catalyst for cross coupling
reaction [53-61]. We decided to employing cysteine to preparing palladium catalyst
(MNPs@Cys-Pd) and study its efficiency in O-arylation and N-arylation reactions.
Results and Discussion
Preparation and characterization of the catalyst
The synthetic route for the preparation of MNPs@Cys-Pd is depicted in Scheme 1. The magnetic
nanoparticles (MNPs) were prepared by co-deposition method according to the reported
procedure [62] and subsequently coated by a silica layer upon reaction with tetraethyl
orthosilicate (TEOS). Then, 3-iodopropyl trimethoxysilane was added to the dispersed
Fe3O4@SiO2 in a nitrogen atmosphere to generate the iodo-functionalized MNPs. In this study,
the modified silica was applied in order to graft cysteine moiety on magnetic nanoparticles.
Afterwards, palladium acetate has immobilized onto the magnetic support in ethanol to obtain
the MNPs@Cys-Pd as final catalyst.
The catalytic system was well characterized using various techniques including FT-IR, TEM,
SEM, DLS, XRD, EDX, VSM and ICP. The progress of functionalization of magnetic
nanoparticles was confirmed by FT-IR spectroscopy (Figure 1).

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Scheme 1. The nanocatalyst preparation
The signal observed at 578 cm−1 is attributed to the Fe–O stretching vibration of Fe3O4 [63]. In
the spectra of Fe3O4/SiO2 nanoparticles (curve b), a strong broad peak at 1090 cm–1 is
corresponding to the Si–O–Si vibration, being revealing of the presence of a SiO2 layer around
the Fe3O4 nanoparticles [64]. A comparison between the FT-IR spectra of Fe3O4, Fe3O4@SiO2
and cysteine-modified nanoparticle (curve c) clearly revealed the successful immobilization of
cysteine moiety on the surface of magnetic nanoparticles [65]. For study in forming of
complexes of the Pd-species with cysteine moieties, the spectra of final catalyst was compared
with those of pure cysteine. As can be seen in supplemental data, in spectra of pure cysteine
stretching vibration of C-S and C-N are appeared at 1584 and 1342 cm-1, while in the spectra of
final catalyst these bonds shifted to 1670 and 1440 cm-1, respectively.
The quantitative determination of the palladium content was determined by ICP as 0.47 mol%.
The XRD spectrum was also performed. As shown in Figure 2, the characteristic diffraction
peaks clearly considered cubic spinel phase of Fe3O4 {JCPDS 01-075-0033}, 2θ = 30.1° (220),
35.5° (311), 43.1° (400), 47.2° (331), 53.5° (422), 57.0° (511), 62.6° (440), 75.1° (622), 82.0°
(551), 86.8° (642) and 89.8° (731). The wide diffraction peak at 2θ = 23° attributed to silica

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coated magnetite particles {Fe3O4@SiO2} and other peaks in the sample at 2θ of 39.9O, 46.4O,
67.7O, 81.6O can be well indexed to the diffraction of (111), (200), (220), (311) crystal planes of
Pd (0). The scanning electron microscopy (SEM) images was illustrated spherical external
morphologies of the catalyst. The EDX spectrum showed the elemental composition after
grafting reaction, confirming the presence of C, N, O, Si, S, Pd and Fe in the catalyst (Figure 3).
Figure 1. FT-IR spectra of (a) MNPs, (b) MNPs@SiO2, (c) MNPs@Cys-Pd
As displayed in Figure 4, TEM micrographs of the fresh catalyst reveals that nanoparticles are in
spherical shape with an average of 14 nm and good monodispersity. The magnetization curve of
the catalyst in comparison with pure MNPs and MNPs@SiO2 (the VSM spectra was given in
supplemental data, Figure 2S), represents the magnetic behavior of the catalyst and contact of
organic moieties on MNPs (Figure 5).
Figure 2. The XRD pattern of catalyst

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Figure 3. SEM photographs and the EDX spectrum of catalyst
Figure 4. The TEM images and histogram representing the size distribution of catalyst
Figure 5. The vibrating sample magnetometer (VSM) of the catalyst

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After synthesis and characterization of catalyst, its catalytic performance in the
O-arylation
coupling between a various types of alcohols and aryl halides was studied. In order to obtain
suitable conditions, the reaction of iodobenzen with phenol was selected as the model reaction.
The efficiency of various parameters such as base, solvents, different temperature and several
amount of catalyst were examined (Table 1). The initial experiments were performed by running
the model reaction in the presence of KOH, 10 mg of catalyst at 100 oC under aerobic conditions
in various reaction times. After founding the best reaction time, different solvent effect was
studied. Among different solvents, EtOH was chosen as the most effective solvent. In the next
step, to obtain the proper base, the effect of several types of bases was investigated. The KOH
gave rise to the most suitable effect. To optimum temperature of the reaction, the performance of
reaction was also checked by acting the model reaction at different temperatures while keeping
o
the other parameters fixed. The O-arylation reaction proceeds efficiently at 60 C, thus this
temperature was selected as optimum. The optimized amount of catalyst found as 5 mg.
With these favored reaction conditions in hand, the scope and generality of this procedure in the
O-arylation reaction for commercially available alcohols with some aryl halides was explored.
As clearly shown in Table 2, both aromatic and aliphatic alcohols can be coupled efficiently
under the defined reaction conditions. To our delight, the various substituted aryl iodides,
bromides and chlorides bearing both electron-rich and electron-poor groups were converted
effectively to desired products in good to excellent yields. It was also observed that increasing
steric hindrance of ortho-substituted phenols gave lesser yield than those obtained with para-
substituted ones.

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Table 1. Effect of different parameters in O-arylation reactiona
Entry
Reaction
time (h)
6
Solvent
DMSO
DMSO
DMSO
DMSO
EtOH
Base
T(o C)
Cat (mg)
10
Yieldb
96
1
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
K2CO3
K3PO4
KOH
KOH
KOH
KOH
60
2
3
60
10
97
3
0.5
0.25
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
60
10
96
4
60
10
84
5
60
10
98
6
Toluene
DMF
100
100
100
60
10
91
7
10
95
8
DMSO
EtOH
10
96
9
10
91
10
11
12
13
14
EtOH
60
10
89
EtOH
25
10
33
EtOH
40
10
91
EtOH
EtOH
60
5
97
60
15
95
aReaction conditions: iodoobenzene (1 mmol), phenol (1.2 mmol), base (2 mmol), solvent (5 ml).
bIsolated yield.
Encouraged by these results, we decided to apply our designed catalyst in the N-arylation
reaction of various types of aryl halides with different amines. The N-arylation reaction between
iodobenzene and morpholine was chosen as a model to evaluate optimum reaction conditions by
employing different solvents, bases, temperatures and catalyst loading (Table 3). In our first set
of experiments, the effect of the different solvent in this transformation was studied. The results
showed that the yield of product was enhanced to 96% when the reaction was carried out in
solvent-free conditions.

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Table 2. O-arylation of aryl halides and different alcohols
X
MNPs@Cys-Pd
Optimized conditions
Yieldb
Ether
Alcohol
R
Entry
R
X
Alcohol
phenol
TONc
TOF(h-1)d
1
H
I
98
72
7.2×103
5.3×103
7.0×103
6.5×103
7.2×103
6.5×103
7.4×103
5.4×103
5.2×103
6.8×103
5.6×103
6.6×103
6.8×103
3.6
2.7
3.5
×
×
×
103
103
103
2
H
I
2,3,6-trimethylphenol
3
H
I
(4-chlorophenyl)methanol
2-chloro-6-nitrophenol
phenol
95
88
97
4
H
I
3.2×103
3.6×103
3.2×103
3.7×103
2.7×103
2.6×103
3.4×103
2.8×103
3.3×103
3.4×103
5
H
I
6
H
I
5bromo-2-hydroxybenzaldehyde 86
7
H
I
3,5-dinitrophenol
100
8
H
I
resorcinol
73
71
92
76
90
93
9
4-Me
H
I
2,6-dimethylphenol
4-hydroxybenzaldehyde
naphthalen-1-ol
10
11
12
13
Br
Br
Br
Cl
H
4-NO2
H
(4-chlorophenyl)methanol
(4-chlorophenyl)methanol
aReaction conditions: aryl halide (1 mmol), alcohols (1.2 mmol), KOH (2 mmol), EtOH (4 ml), catalyst (5
mg), 60 in 0.5 h;
℃
bIsolated yield;
c(Mol product/mol palladium);
d(Mol product/mol palladium) (h−1)
Then, the type of base was changed and the best result is obtained when KOH is used as base.
The 60
℃ was found as the best considering to good yield and energy safe aims. Moreover,
efficient amount of catalyst was selected as 5 mg. To specify the scope and generality of this
procedure for obtained aryl amine derivatives, a various types of aryl halides have reacted with
some commercially available amines under optimized reaction conditions. As depicted in Table
4, N-arylation reaction of various substrates (iodo-, bromo- and chloro- derivatives) and

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substituents (electron-rich and electron-poor), provided very good to excellent yields of coupling
products.
Table 3. Effect of different parameters in N-arylation reactiona
Entry Reaction time (h) Solvent
Base
T(o C)
100
100
100
100
80
Yieldb
22
1
6
H2O
KOH
KOH
KOH
KOH
KOH
KOH
KOH
K3PO4
K2CO3
KOH
KOH
2
3
H2O
20
3
0.5
0.25
0.5
0.5
0.5
0.5
0.5
0.5
0.5
H2O
20
4
H2O
11
5
CH3CN
DMF
43
6
110
110
110
110
60
86
7
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
95
8
81
9
84
10
11
93
25
36
aReaction conditions: iodobenzene (1 mmol), morpholine (1.2 mmol), base (2 mmol), in 0.5 h.
bIsolated yield.
The hot filtration test was accomplished for
N-arylation as same as the O-arylation reaction.
After removal of catalyst, using an external magnetic bar, no further progress in product yield
was determined. The ICP analysis of resultant supernatant only showed 0.03 ppm palladium in
solution, it indicated heterogeneously nature of our catalytic system. The recyclability of catalyst
was investigated in model reaction of O-arylation (the reaction of iodobenzen with phenol) and
no significant decrease in catalytic activity was observed until the ten runs (Table 5).

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Table 4. N-arylation of aryl halides and different amines
X
MNPs@Cys-Pd
Products
Amine
R
Optimized conditions
Entry
1
R
X
Amine
Yieldb
93
TONc TOF(h-1)d
3.4×103 6.9×103
3.5×103 6.9×103
3.0×103 6.0×103
2.9×103 5.8×103
2.7×103 5.3×103
3.2×103 6.4×103
H
I
morpholine
2
H
Br
Br
Cl
Cl
Br
Br
Br
Br
Br
Br
Cl
Cl
morpholine
94
3
4-NO2
4-NO2
diphenylamine
diphenylamine
morpholine
81
4
79
5
2,4-di-NH2
4-OMe
H
72
6
morpholine
87
7
propan-1-amine
morpholine
trace
81
-
-
8
2-NO2
H
3.0×103 6.0×103
3.4×103 6.0×103
3.6×103 7.2×103
3.4×103 3.4×103
3.2×103 6.4×103
2.9×103 5.9×103
3.2×103 6.4×103
9
N-methylbenzenamine
N-methylbenzenamine
morpholine
93
10
11
12
13
14
15
4-NO2
4-Br
98
92
4-NO2
H
morpholine
87
morpholine
80
9-bromophenanthrene Br
morpholine
86
3- COCH3 Br
morpholine
trace
-
-
aReaction conditions: aryl halide (1 mmol), amine (1.2 mmol), KOH (2 mmol), catalyst (5 mg), 60 oC; in
0.5 h.
bIsolated yield.
c(Mol product/mol palladium);
d(Mol product/mol palladium) (h−1)
TEM images of recycled catalyst (after ten runs) was shown in Figure 6, in comparison with
fresh catalyst no significant change was done. The comparison between the XRD spectra of fresh
and reused catalyst also indicated that the state of Pd was kept during the reaction progress
(Figure 6).

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Table 6. Reusability of the catalyst
Run
Yielda(%)
Run
69
7
8
9
Yielda(%)
1
2
3
4
98
98
97
97
96
96
95
95
94
90
5
10
aIsolated yield
Figure 6. TEM image and XRD pattern of the recovered catalyst
A comparison study between efficiency of MNPs@Cys-Pd with some reported heterogeneous
Pd-catalysts in O-arylation and N-arylation reactions was given in Table 6. It can be obviously
seen that the current MNPs@Cys-Pd is superior to others in terms of catalytic efficiency. Our
efficient heterogeneous palladium catalytic system gave high catalytic activity in short time
while green media and mild reaction conditions was applied.

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Table 6
.
Comparison of catalytic activity of nanocatalyst with literature examples for
O
-arylation
TOF(h-1)
and N-arylation reactions
Entry[ref.]
Catalyst
Conditions
Yield (%)
TON
1 [66]
2 [67]
3 [68]
Pd/ZnO
K2CO3, DMF, 120 oC, 5 h
NaOH, Bu4NOH, 70 °C
Cs2CO3, isopropanol
98
98
83
98
3.6×106
5.4×103
2.7×102
3.6×103
7.2×105
1.8×103
1.35×103
7.2×103
PdCl2, SDPP
[Pd(P3S4)(dba)]
5(This work) MNPs@Cys-Pd KOH, EtOH, 0.5 h, 60 °C
7 [69]
8 [70]
9 [71]
Pd/Nf-G
DMSO, tBuONa, 12 h, 110 oC
Cs2CO3, Isopropanol, 24 h
NaOtBu, toluene,12 h, 110 oC
93
80
90
4.6×102
5.2×103
4.8×102
3.4×103
3.9
[Pd(pp3S4)(dba)]
PFG-Pd
2.2×102
4.0×10
6.9×103
10 [This work] MNPs@Cys-Pd KOH, solvent-free, 0.5 h, 60 °C 93
Experimental
Chemical, instrumentation and analysis
All chemical reagents were purchased from Merck and Aldrich chemical companies and were
used without further purification. 1H-NMR was recorded on a Brucker (250 MHZ) Avance DRX
in pure CDCl3 solvent with tetramethylsilane (TMS) as internal standards. FT-IR spectra were
obtained as KBr pellets on a JASCO 680- Plus spectrophotometer. Magnetic measurement was
done by vibrating sample magnetometer (VSM) in 0.0001-50 emu. The transmission electron
microscopy (TEM) using TEM device (Zeiss–EM10C–80 KV) and scanning electron
microscopy [MIRA3 TESCAN] were acquired for characterization of the catalyst. The X-ray
diffraction (XRD, D8, Advance, Bruker, axs) was engaged. The reaction monitoring was

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accomplished by TLC or gas chromatography (GC) (BEIFIN 3420 gas chromatograph equipped
with a Varian CP SIL 5CB column: 30 m, 0.32 mm, 0.25 mm). Column chromatography was
carried out on columns of silica gel 60 (70–230 mesh).
Catalyst preparation
Synthesis of 3-iodopropyltrimethoxysilane
To a solution of anhydrous sodium iodide (5 mmol) in dry acetone (50 mL), 3-
chloropropyltrimethoxysilane (5 mmol) was added and the mixture was refluxed for 24 h under a
nitrogen atmosphere. After that, the solvent was removed under vacuum. The residue was then
diluted in CH2Cl2, filtered and washed twice with CH2Cl2.
Preparation of MNPs@Cys-Pd catalyst
Magnetic nanoparticles were prepared via co-precipitation of Fe (III) and Fe (II) ions according
to a reported procedure.27 After sonication, to a mixture containing 1 g of Fe3O4, 20 mL water, 80
mL ethanol, 3 mL ammonia and 3 mL tetraethyl orthosilicate (TEOS) were added. The solution
was refluxed to obtain MAGNPS-Silica core–shell materials.30 Afterward, 1 g of prepared SiO2-
coated Fe3O4 nanoparticles were suspended in dry toluene by sonication for 30 min, and 3-
iodopropyltriethoxysilane was then added. The solution was refluxed for 24 h under nitrogen
atmosphere. After being cooled to room temperature, the product was collected and washed with
toluene and acetone several times. For the synthesis of MNPs@Cys-Pd, 2 mmol of l-cysteine and
3 mmol K2CO3 were added in to a prepared solution containing 1g of iodo-functionalized γ-
Fe2O3 in 30 mL acetonitrile. The mixture was then refluxed for 24 h under nitrogen atmosphere.
The resulting precipitate was collected by external magnetic field, washed with water and
ethanol. To a mixture of magnetic cysteine -functionalized chitosan (MNPs@Cys) (0.5 g) in

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ethanol (20 mL), Pd(OAc)2 (0.05 g) was added and stirred for 24 h in room temperature. Then,
the catalyst was separated from the mixture and washed with acetone several times. The final
catalyst was obtained as a black powder.
General procedure for coupling of N-arylation
In a round
mmol), catalyst (5 mg) and KOH (2 mmol) were stirred in ethanol (5 ml) under air atmosphere at
60 for 0.5 h. The progress of the reaction was monitored by TLC and GC. After completion of
‐bottomed flask equipped with mechanical stirrer, aryl halide (1 mmol), amine (1.2
℃
the reaction, CH2Cl2 (15 ml) was added and the catalyst was separated using an external magnet.
The organic layer was washed with water (3 × 10 ml) and dried over anhydrous MgSO4. The
product was isolated by column chromatography (n‐hexane–ethyl acetate, 5:1) to afford the
corresponding products. The products were characterized by their physical properties, melting
IR, 1H NMR and 13C NMR [69-71].
points, and FT
‐
General procedure for O-arylation
In a round bottomed flask equipped with mechanical stirrer, aryl halide (1 mmol), phenol (1.2
mmol), catalyst (3 mg) and KOH (2 mmol) were stirred in solvent-free conditions under air
atmosphere at 60 for 0.5 h. The progress of the reaction was monitored by TLC (eluent: n
‐
℃
‐
hexane–ethyl acetate, 5:1) and GC. After completion of the reaction, CH2Cl2 (15 ml) was added
and the catalyst was separated using an external magnet. The organic layer was washed with
water (3 × 10 ml) and dried over anhydrous MgSO4. The product was isolated by column
chromatography (n‐hexane–ethyl acetate, 5:1) to afford the corresponding products. The

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1
products were characterized by their physical properties, melting points, and FT
‐IR, H NMR
and 13C NMR [66-68].
Conclusions
In conclusion; herein, efficient heterogeneous palladium catalytic system was synthesized
via immobilizing of Pd-NPs on the surface of magnetic cysteine material and its
application in O-arylation and N-arylation reactions was investigated. Addition to a high
catalytic activity in green media and mild reaction conditions, it exhibited excellent
reusability.
Acknowledgement
We gratefully acknowledge the funding support received for this project from the Isfahan
University of Technology (IUT), IR of Iran.
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Table of content
This work provides an active magnetically separable catalyst based palladium nanoparticle
supported on cysteine functionalized magnetic nanoparticle for the
reactions in mild condition.
O-arylation and N-arylation

ACCEPTED MANUSCRIPT
Highlights
‹
A heterogeneous catalyst, MNPs@Cys-Pd, was synthesized by anchoring a
palladium (0) on cysteine-functionalized magnetic nanoparticle.
‹
The catalytic activity of these catalytic systems was evaluated for the O-
arylation in ethanol and N-arylation in solvent-free media under phosphine-
free conditions.
‹
This nanocatalyst could be easily recovered from the reaction mixture and
also exhibited good reusability.