L-Methionine-Pd complex supported on hercynite as a highly efficient and reusable nanocatalyst for C-C cross-coupling reactions

Article abstract of DOI:10.1039/c9nj05325e

A "green" method was suggested for the synthesis of hercynite magnetic nanoparticles (MNPs) as a novel heterogeneous catalytic support to immobilize homogeneous complexes. l-Methionine-Pd was immobilized on the surface of hercynite MNPs by a simple, rapid, and convenient route. The structure and composition of the prepared Hercynite@l-Methionine-Pd MNPs were characterized by X-ray diffraction spectroscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma-optical emission spectrometry, scanning electron microscopy, X-ray mapping, thermogravimetric analysis and vibrating-sample magnetometry (VSM). Besides, they were applied as green nanocatalysts for Suzuki and Heck cross-coupling reactions. Hercynite@l-Methionine-Pd MNPs offer several advantages (simple synthetic method under green conditions, thermal and chemical stability during organic reactions, short reaction times, high yields of products, excellent selectivity and easy work-up procedure). Moreover, the recycled nanocatalyst was reused for at least five cycles with no significant loss of activity. The hot filtration test indicated heterogeneous catalysis for Suzuki and Heck cross-coupling reactions. This work is useful for the development and application of a magnetically recoverable Pd nanocatalyst on the basis of green-chemistry principles.

Full text of DOI:10.1039/c9nj05325e

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The first report of hercynite as a solid support, L-methionine-Pd
complex supported on hercynite as highly efficient reusable
nanocatalyst for C-C cross coupling reactions
Received 00th January 20xx,
Accepted 00th January 20xx
Masoud Mohammadi, Arash Ghorbani-Choghamarani*
DOI: 10.1039/x0xx00000x
In this work, a green method was suggested for the synthesis of hercynite magnetic nanoparticles (MNPs) as a novel
heterogeneous catalytic support in order to immobilize the homogeneous complexes. In this sense, the study aims at
immobilizing L-Methionine-Pd complex on the surface of hercynite MNPs. L-Methionine-Pd which was immobilized on
hercynite MNPs surface by a simple, fast, and convenient route. The structure and composition of the prepared
Hercynite@L-Methionine-Pd MNPs were completely characterized by XRD, EDX, ICP, SEM, X-ray mapping and TGA and
VSM techniques. Besides, it was applied as a green nanocatalyst for Suzuki and Heck cross coupling reactions under green
conditions. The Hercynite@L-Methionine-Pd MNPs offer several advantages i.e. simple synthesis method under green
conditions, thermal and chemical stability during organic reactions, short reaction times, high yields of the products,
excellent selectivity and easy work-up procedure. Moreover, the recycled nanocatalyst was reused for at least five cycles
with no significant loss of its activity. Hot filtration test indicated heterogeneous catalysis for both of the mentioned
reactions. This work is useful for the development and application of the magnetically recoverable Pd nanocatalyst on the
basis
of
green
chemistry
principles.
importance of developing C-C cross coupling reactions in the
current modern organic chemistry.
Introduction
The use of nanotechnology and benign and clean synthetic
procedures is one of the most important ways to reduce
environmental concerns. The development of appropriate and
Belonging to the most important methodologies of the
modern catalytic organic synthesis, the C-C cross coupling
reactions between different aryl halide derivatives with aryl
boronic acids (Suzuki reaction) or olefins ( Heck reaction),
catalyzed by a transition-metal catalyst (specially Palladium)
under mild reaction conditions, have received profound
attention due to their one-step procedure1, no need to isolate
the intermediate 2, high yields of the products 2,3, good
efficient methods for the synthesis of nanometer-sized
10
materials has a special place in the scientific community
.
During recent years, heterogeneous nanomaterials have been
successfully applied as support for the heterogenization of
homogeneous catalysts by the immobilization of
homogeneous organometallic complexes, acid and base on the
2
4
reactivity of a less reactive aryl halide , good selectivity and
broad range of functional groups5.
heterogeneous nanomaterials such as (heteropoly acids11,
17–19
silica nanoparticles12, SBA-15 13, SBA-16 14–16, MCM-41
,
These synthetic techniques have been widely used in industrial
and laboratorial scale for the synthesis of important natural
products for example, in medicinal chemistry 3,6. In this sense,
C-C coupling reactions have been frequently used in the
synthesis of important bioactive compounds and drugs7. It is
worth mentioning that the Nobel Prize in chemistry 2010 was
awarded jointly to Akira Suzuki, Richard f. Heck, and Ei-ichi
Negishi for palladium-catalyzed C-C cross couplings in organic
synthesis8,9. This significant success fully demonstrates the
MCM-48 16, FSM-16 20–22, ZIF-8 23–25, alumina 26–28, Boehmite
2,29, graphene oxide 30,31, polymers 32, Biochar
peptide
33–37
nanofibers 38, Fe3O4 39–45, Fe3O4@SBA-15 46–48, Fe3O4@MCM-
52
4149, Fe3O4@FSM-16 50, Fe3O4@Boehmite 51, Fe3O4@ZIF-8
and spinel ferrites MNPs 53,54. Introducing the novel and stable
heterogeneous catalytic supports is a hot research topic in
industrial and catalysis science. The Spinel ferrites, (AB2O4,
which represents one or more bivalent transition metals such
60
as , Al 54, Ni 55, Co 56, Cu 57, Zr 53, Zn 58, Fe44, Mn 59, Bi etc.),
due to their magnetic properties and thermal and chemical
stability, have become significant and efficient tools in modern
catalytic organic synthesis53,54. In this category, Hercynite
(FeAl2O4) is a normal spinel ferrite with all or most of the
aluminium ions (Al+3) ions on both octahedral (B sites) and the
ferrous (Fe+2) ions occupying tetrahedral sites (A sites), while
oxygen occupies FCC sites 54,61. However, some ferric ions
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box, 69315516,
Ilam, Iran..
Address correspondence to A. Ghorbani-Choghamarani, Department of
Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran;
Tel/Fax: +98 841 2227022; E-mail address: arashghch58@yahoo.com or
a.ghorbani@ilam.ac.ir
*
Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
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(Fe3+) may be located in its structure 61, and in order to magnet, washed with water and ethanol and dried at 80 °C in
overcome this drawback, the synthesis of hercynite MNPs an oven for 12h.
requires oxygen-free conditions to prevent oxidation of Fe+2
ions to ions Fe3+ 62. Hercynite nanoparticles have received
profound attention due to their moderate saturation
View Article Online
DOI: 10.1039/C9NJ05325E
magnetization (because of the presence of iron oxide) 63, high
2.2 | General procedure for the Suzuki reaction
concentration of surface OH groups54, high specific surface
area 54, high ductility (fracture–mechanical strength) and
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A mixture of Phenylboronic acid (1 mmol), aryl halide (1
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flexibility against spalling and cracking
and excellent
mmol), K2CO3 (3 mmol) and Hercynite@L-Methionine-Pd (0.1
mol %) was dissolved in 3 mL ethanol and stirred at 80 ˚C
under reflux conditions. The progress of the reaction was
monitored by TLC. Upon the completion of the reaction, the
mixture was cooled down to room temperature and the
catalyst was separated by magnetic separation technique, and
washed with EtOAc. Finally, the reaction mixture was
extracted with H2O and EtOAc. The organic layer was dried
over Na2SO4. Finally, the solvent was evaporated, and the
corresponding pure products were obtained in excellent yields.
chemically, mechanically and thermally stabilities (compared
to Fe3O4) 54. Given the mentioned features, the use of
hercynite MNPs as a novel heterogeneous support for the
immobilization of homogeneous catalysts seems attractive.
According to the best of our knowledge, this is the first report
on the immobilization of homogeneous complex on the
surface of hercynite as support.
In the development of green chemistry principles; herein,
hercynite MNPs were introduced as a novel heterogeneous
catalytic support for the immobilization of L-Methionine-Pd
complex. Hercynite@L-Methionine-Pd nanoparticles were
efficiently applied as a reusable catalyst for the Suzuki and
Heck C-C cross coupling reactions under green conditions.
General procedure for the Heck reaction
A mixture of buthyl acrylate (1.2 mmol), aryl halide (1 mmol)
and K2CO3 (3 mmol) was dissolved in 2 mL PEG-400 and ,then,
Hercynite@L-Methionine-Pd (0.125 mol %) was added to the
Experimental
Preparation of L-Methionine-Pd heterogenized complex supported flask and, finally, the mixture was stirred at 80 ºC under reflux
on the surface of hercynite magnetic nanoparticles (Hercynite@L- conditions. The progress of the reaction was monitored by TLC.
Methionine-Pd)
After the completion of the reaction, the catalyst was
separated from the reaction mixtire via magnetic separation
The hercynite magnetic nanoparticles were prepared by the technique; the reaction mixture was extracted with ethyl
coprecipitation technique as it was previously reported 54. A acetate and water. The organic layer was dried over Na2SO4.
mixture of Al(NO3)3·9H2O (2 mmol) and FeCl2·4H2O (4 mmol) Finally, the solvent was evaporated and the corresponding
was dissolved in 100 mL of water and stirred at 80 °C under N2 pure products were consequently obtained.
protection. In the next step, 10 mL of aqueous NaOH solution
Selected spectral data
(0.2 M) was added to the reaction mixture (the pH of solution
was found to be 12). After 30 min of stirring the mixture, an
external magnet collected the prepared hercynite MNPs which
were washed with deionized water and ethanol few times and,
then, dried at 75 °C in an oven for 4 h. In order to immobilize
the L-Methionine amino acid on the surface of hercynite
heterogeneous support, 1 g of the prepared hercynite
nanoparticles was dispersed in 50 mL water by sonication for
30 min. and, then, L-Methionine (2.5 mmol) was added to the
reaction mixture which was stirred under the N2 atmosphere
at reflux conditions for 24 h. Afterwards, the obtained
Hercynite@L-Methionine MNPs were washed with hot
deionized water and hot ethanol few times and, then, dried at
75 °C in an oven for 4 h. Finally, in order to synthesize the
target Hercynite@L-Methionine-Pd heterogenized complex,
0.5 g of Hercynite@L-Methionine MNPs was dispersed in 30
mL ethanol by sonication for 30 min and, then, Pd(OAc)2 (0.25
g) was added to the reaction mixture. Subsequently, it was
stirred under the N2 atmosphere at 80 ºC for 24 h. In the next
step, 3 mmol of NaBH4 was added to the reaction and stirred
1
4-methylbiphenyl: H NMR (300 MHz, CDCl3) δ (ppm) = 7.66-
7.61 (m,2H), 7.55-7.52 (m, 2H), 7.49-7.44 (m, 2H), 7.38-7.333
(m,1H), 7.30- 7.227 (m,2H), 2.43(s, 3H, Me).
3-methoxybiphenyl: 1H NMR (300 MHz, CDCl3) δ (ppm) = 7.63-
7.55(m, 2H), 7.48-7.34(m, 2H), 7.21-7.18(m, 2H),7.22-7.14(t,
J=2, 1H), 6.94-6.90(m, 1H), 3.01(s,1H)
4-methoxybiphenyl: 1H NMR (300 MHz, CDCl3) δ (ppm) = 7.60-
7.53(m, 4H), 7.45(t, J=7.5, 2H), 7.35(t, J=7.2, 1H), 7.03-6.98(m,
2H), 3.88(s, 3H)
4-Nitro-1,1′-biphenyl: 1H NMR (300 MHz, CDCl3) δ (ppm) =
8.34-8.31 (d, J = 8 Hz, 2H), 7.78–7.75 (d, J = 12 Hz, 2H), 7.67–
7.65 (d, J = 12Hz, 2H), 7.55-7.51 (m, 2H) 7.50-7.45 (m, 1H).
Results and discussion
Catalyst preparation
for
2 more hours. Then, the obtained Hercynite@L-
Methionine-Pd MNPs were separated using an external
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In this research project, L-Methionine-Pd complex, which was overcome this drawback, hercynite nanoparticles were prepared
immobilized on the surface of hercynite magnetic nanoparticles under N2 atmosphere (oxygen-free conditions) to prevent oxidation
View Article Online
DOI: 10.1039/C9NJ05325E
(Hercynite@L-Methionine-Pd) has been introduced as a reusable of Fe+2 to Fe3+ ions. Then, L-Methionine ligand has been grafted on
magnetic nanocatalyst. Initially, the hercynite MNPs have been the surface of hercynite MNPs in green conditions. Finally, the L-
easily prepared in water by coprecipitation technique. It is worth to Methionine-Pd complex was synthesized by the reaction of
mention that in the synthesis of spinel ferrite materials some ferric Hercynite@L-Methionine-Pd with Palladium (II) acetate (Scheme 1).
ions (Fe3+) may be located in their structure, and, in order to
OH
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OH
OH
FeCl2•4H2O
+
HO
HO
deionized water, NaOH
N2, 80 °C, 30 min
L-Methini
ne
Hercynite
HO
HO
HO
Hercynite MNPs
OH
Al(NO3)3•9H2O
H
2O,N2
, reflux,
24
h
OH
OH
OH
S
Me
Pd
O
O
H2N
O
Hercynite
Hercynite
MNPs
1) Pd(OAc)2, EtOH, Reflux 24h
2) NaBH4, EtOH, Reflux 2h
S
Me
MNPs
O
NH2
Hercynite@L-Methionine
Scheme 1 The synthesis of Hercynite@L-Methionine-Pd nanoparticles.
Hercynite@L-Methionine-Pd
Catalyst characterizations
The as-prepared Hercynite@L-Methionine-Pd catalyst was
characterized by XRD, EDS, ICP, SEM, X-ray mapping, TGA, and VSM
techniques.
Fig. 1 The XRD patterns of hercynite and Hercynite@L-Methionine-
Pd nanocatalyst.
Fig. 2 exhibits the TGA diagram of Hercynite@L-Methionine-Pd. The
The X-ray diffraction analysis (XRD) patterns of hercynite and main weight loss, which was observed between 200 and 550 °C is
Hercynite@L-Methionine-Pd are shown in Figure 1. As it can be about 26.61 % and is related to the decomposition of organic
seen from Figure 1 (red pattern), the successful synthesis of moieties on the surface of the hercynite MNPs. The obtained results
hercynite MNPs was justified by the XRD peak positions at 2θ = from TGA analysis confirmed the successful supporting of L-
30.59, 32.15, 35.99, 43.65, 45.87, 54.11, 57.61, 63.27, 71.81, 74.65 Methionine-Pd on the surface of hercynite.
and 75.70, which are related to (2 0 0), (0 3 1), (3 1 1), (4 0 0), (1 1
0), (4 2 2), (1 1 1), (4 4 0), (6 2 0), (5 3 3) and (1 1 1) reflections,
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respectively.
Moreover, Hercynite@L-Methionine-Pd (Figure 1
green pattern) displays 11 characteristic peaks at 2θ = 30.38, 31.43,
35.73, 39.68 , 43.33, 45.65, 53.83, 57.33, 62.93, 71.04, and 74.39,
which were in agreement with the prepared hercynite XRD
standard data. On the other hand, it can be found that the surface
modification of the hercynite nanoparticles does not lead to change
its crystalline phase. Other peaks at 2θ values of 39.68°, 45.65° and
65.93° confirmed the presence of Pd(0) in Hercynite@L-
Methionine-Pd complex 2,64
.
Fig. 2 TGA curve of Hercynite@L-Methionine-Pd nanocatalyst.
The energy dispersive X-ray spectroscopy (EDS) analysis of
Hercynite@L-Methionine-Pd nano catalyst are shown in Fig 3. The
presence of Fe, Al, O, C, N, S and Pd in EDX pattern provides
evidences confirming the successful synthesis of Hercynite@L-
Methionine-Pd. In addition, the exact amount of Pd, which was
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Fig. 3 The EDX image of Hercynite@L-Methionine-Pd nanocatalyst.
immobilized on Hercynite@L-Methionine, was obtained by ICP-OSE:
1.21 × 10-3 mol g-1.
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DOI: 10.1039/C9NJ05325E
The morphology of the hercynite MNPs (a) and Hercynite@L-
Methionine-Pd (b) as probed by the scanning electron microscopy
(SEM) technique is shown in Fig 4. SEM images show that most of
the prepared nanoparticles were formed in approximately spherical
shape and uniform nanometer size for most particles.
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Fig. 3 SEM images of hercynite and Hercynite@L-Methionine-Pd nanocatalyst at different magnifications.
The X-ray mapping of Hercynite@L-Methionine-Pd magnetic catalyst, confirming the formation of the heterogeneous L-
nanocatalyst is shown in Fig 5. The elemental map images show the Methionine-Pd catalyst on the surface of hercynite.
good dispersion of Fe, Al, C, N, S and Pd on the surface of the
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Fig. 5 EDX-mapping analysis of Hercynite@L-Methionine-Pd nanocatalyst.
Fig 6 exhibits the magnetization curves of hercynite MNPs (a),
Hercynite@L-Methionine-Pd complex (b) and the recovered
Hercynite@L-Methionine-Pd catalyst (c). The value of the saturation
magnetic moment of hercynite MNPs (Fig. 6a) was found to be ~ 41
emu/g. demonstrated the superparamagnetic properties of
hercynite MNPS. The value of the saturation magnetic moment of
the Hercynite@L-Methionine-Pd complex (Fig. 6b) is 26 emu/g as
compared to the saturation magnetization of hercynite, which was
found to be ~ 41 emu/g. This decrease in the saturation
magnetization of Hercynite@L-Methionine-Pd complex is due to the
successful immobilization of L-Methionine-Pd complex on the
surface of hercynite MNPs. The value of the saturation magnetic
moment of the recovered Hercynite@L-Methionine-Pd (Fig. 6c) is
24 emu/g, in which no significant change was observed as
compaired to the fresh catalyst.
Fig. 6 VSM curve of hercynite (a) and Hercynite@L-Methionine-Pd
(b) and recovered Hercynite@L-Methionine-Pd nanocatalyst (c) at
room temperature.
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0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.100
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
KOH
NaOH
Na2CO3
Et3N
reflux
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Catalytic studies
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reflux
reflux
reflux
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DOI: 10.1039/C9NJ0583215E
After successful characterization of the synthezed Hercynite@L-
Methionine-Pd, its catalytic activity was evaluated in C-C cross
coupling reactions including Suzuki and Heck.
91
77
NR
NR
53
76
88
-
Intialy, the catalytic properties of Hercynite@L-Methionine-Pd were
examined in Suzuki reaction.
K2CO3
K2CO3
K2CO3
K2CO3
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In order to find the best conditions for Suzuki reaction, the coupling
of iodobenzene (1 mmol) with phenylboronic acid (1 mmol) under
different conditions was selected as the model reaction. Then, the
effect of the different experimental parameters; including, the
amount of the catalyst, solvent, base and also the effect of
temperature on the selected model substrate were investigated.
The results are summarized in Table 1.
65
70
a Isolated yield.
b
Reaction conditions: aryl halide (1mmol), phenylboronic acid
(1mmol), Hercynite@L-Methionine-Pd, base (1.5 mmol) and solvent
(3mL).
In the first step, the influence of different amounts of the catalyst After optimizing the reaction conditions, the catalytic effectiveness
on the outcome of the reaction was studied, and it was revealed of Hercynite@L-Methionine-Pd MNPs was investigated in the
that the best yield was obtained in the presence of 0.1 mol% of Suzuki C-C cross-coupling reactions of a wide range of commercially
Hercynite@L-Methionine-Pd. Meanwhile, in the absence of the available aryl halides with phenylboronic acid as phenylating
catalyst, the reaction didn’t proceed at all even after 48 hours source. The results are listed in (Table 2) in which the target
(Table 1, entry 1). In the next step, the effects of the solvent, base products were afforded in moderate to excellent yields. The
and the reaction temperature were screened, and the best C-C experimental results show that various ortho-, meta-, and para-
coupling product was obtained in EtOH in the presence of K2CO3 as substituted aryl halides; including, aryl iodide, aryl bromides and
the most effective base under reflux conditions with the highest aryl chlorides having both electron-withdrawing and electron-
yield of the biphenyl product. According to the observed results, donating groups such as NO2, NH2, CN, CF3, CH3 and OCH3 produced
the optimal conditions for this reaction are: Hercynite@L- their corresponding derivatives in good to excellent yields.
Methionine-Pd catalyst (0.1 mol%), K2CO3 (1.5 mmol) as base in the However, it is worth mentioning that the reaction time of the aryl
EtOH at reflux conditions (Table 1, entry 6).
halides with electron-donating groups on the aromatic ring was
longer than aryl halides with electron-withdrawing groups. Due to
the fact that the aryl halides are electrophilic partners in Suzuki
reaction, they have been activated by electron-withdrawing (EWD)
groups in the ortho or para positions, in oxidative addition step as
compared to those with electron-donating groups 65. Moreover, the
Suzuki C-C cross-coupling of phenylboronic acid with aryl iodide and
aryl bromides, is easier than those with aryl chlorides. Because the
order of reactivity of the electrophilic partners in Suzuki coupling,
based on the power of leaving groups, is: I >> Br > OTf >> Cl > F , the
chloride electrophiles are the most nonreactive ones as they are
reluctant to participate in oxidative addition 66. In order to show the
chemoselectivity of this new catalytic system, the reaction of 1-
bromo-4-chloro benzene was also investigated in which the
bromide group showed more reactivity (Tables 2 entry 9). This
selectivity allows to remain an active halide site for further
functionalization.
Table 1 Optimization of the reaction conditions for the C-C cross
coupling of iodobenzene with phenylboronic acid.
I
B(OH)2
catalyst
R
+
Base, solvent,

Catalyst
(mol%)
Temperature Time Yield
Entry
Solvent
Base
(ºC)
(min) (%)a
2 days NR
1
-
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
DMSO
DMF
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
reflux
2
0.020
0.035
0.050
0.075
0.100
0.100
0.100
0.100
0.100
0.100
reflux
reflux
reflux
reflux
reflux
110
15
15
15
15
15
15
15
15
15
15
48
76
85
92
99
96
91
95
37
74
3
4
5
6
7
8
110
9
PEG-400 K2CO3
H2O K2CO3
110
10
reflux
reflux
EtOH:H2O K2CO3
(1:1)
11
12
0.100
Dioxane K2CO3
reflux
15
83
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Table 2 Catalytic Suzuki C-C coupling reaction in the presence of catalytic amounts of Hercynite@L-Methionine-Pd in EtOH at V8i0ew°CAr.ticle Online
DOI: 10.1039/C9NJ05325E
X
B(OH)2
Hercynite@L-Mwthionine-Pd (cat)
K2CO3, EtOH, Reflux
R
+
R
X= Cl, Br, I
Melting point
measured literature
TON TOF (min-1)
Time (min) Yield (%)a
Entry
Aryl halide
Product
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
I
15
30
99
97
990
970
66
61-63
62-64 67
1
I
43-45 67
Me
32.33
43-44
2
3
4
5
6
Me
I
82-85 67
MeO
20
98
980
49
81-83
MeO
Br
30
25
93
93
930
930
31
62-64
43-45
62-64 67
43-45 67
Br
Br
Me
NC
37.2
Me
NC
25
80
97
90
970
900
38.8
84-86
80-82
82-84 67
81-82 69
Br
Br
11.25
7
8
MeO
OMe
CF3
90
84
840
9.33
26-27
72-73
27 38
F3C
Cl
Br
30
20
92
97
920
970
30.66
48.5
70-72 68
9
Cl
Br
111-113 111-114 67
O2N
10
11
12
O2N
Cl
75
60
87
92
870
920
11.6
67-68
62-64 67
Cl
111-112 111-113 68
O2N
15.33
O2N
a Isolated yield.
b Reaction conditions: aryl halide (1mmol), Hercynite@L-Methionine-Pd (0.1 mol %), phenylboronic acid
(1mmol) and K2CO3 (1.5 mmol) in EtOH at 80 ˚C (reflux conditions).
The catalytic cyclic mechanism for Suzuki reaction in the presence
of Hercynite@L-Methionine-Pd is shown in the Scheme 2 based on
previously reported mechanism53.
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Pd(0)
2
3
4
5
6
7
8
9
0.025
0.050
0.075
0.100
0.125
0.150
0.125
0.125
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
120
Vie4w5Article O3n1line
45 63
45 84
X
1D2O0I: 10.1039/C9NJ05325E
Oxidative
Addition
120
120
120
120
120
120
120
Reductive
Elimination
45
45
45
45
45
45
91
98
98
79
64
83
Pd(II)
Intermediate 2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Pd(II)
X
EtOH
H2O
K2CO3
K2CO3
Intermediate 1
0.125 EtOH: H2O K2CO3
(1:1)
10
11
12
CO3-K+
Pd(II)
K2CO3
0.125
0.125
DMSO K2CO3
Solvent- K2CO3
free
120
120
45
96
Transmetalation
45 Trace
K+
HO
B-(CO3-K+) + KX
ArB-(OH)2
HO
CO3-K+
13
12
13
14
15
16
17
18
19
20
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
PEG-400 Na2CO3
PEG-400 KOH
PEG-400 NaOH
PEG-400 Et3N
120
120
120
120
120
r.t
45
45
45
45
94
43
46
88
K2CO3
Ar-B(OH)2
Scheme 2. Mechanism of the palladium-catalyzed Suzuki reaction.
PEG-400
-
2 day NR
In the next part of this research project, the catalytic activity of
Hercynite@L-Methionine-Pd for the Heck reaction was investigated.
For this purpose, the coupling of iodobenzene with butyl acrylate as
olefin source was selected as the model reaction to optimize the
reaction conditions. Then, the effect of various parameters was
studied including amount of the catalyst, solvent, base and
temperature on the reaction efficiency (Table 3). Initially, the effect
of different amounts of the catalyst on the outcome of reaction was
investigated. Among the various catalyst loadings (e.g., 0.025,
0.050, 0.075.0.100, 0.125 and 0.15 mol% ), 0.125 mol% of the
catalyst on the basis of Pd was selected as the most effective
amount (Table 3, entry 5). Meanwhile, in the absence of the
catalyst, the reaction didn’t proceed at all even after 48 hours
(Table 3, entry 1). Then, the influence of the solvent on the
outcome of the reaction was studied. The obtained results revealed
that PEG-400 is the most effective solvent for this type of coupling
reaction. Subsequently, the effect of base and temperature was
examined, the results revealed that the highest yield of the coupling
product was obtained in the presence of K2CO3 as base at 120 ˚C.
Eventually, PEG-400 at 120 ˚C in the presence of Hercynite@L-
Methionine-Pd (0.125 mol%) was found to be the best choice for
mentioned model reaction.
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
PEG-400 K2CO3
45
45
45
45
45
NR
48
69
83
91
50
60
65
70
a Isolated yield
b Reaction conditions: aryl halide (1mmol), Hercynite@L-Methionine-
Pd, butyl acrylate (1.2 mmol), base (3 mmol), and solvent (2ml).
In order to investigate the scope and generality of this procedure,
different electron-withdrawing or electron-donating groups, such as
OCH3, NO2, NH2, and CH3 were selected to react with butyl acrylate
under optimized reaction conditions. The results are summarized in
Table 4. The experimental results show that various aryl halides;
including, aryl iodide, aryl bromides and aryl chlorides having both
electron-withdrawing and electron-donating groups (such as NO2,
NH2, CN, CF3, CH3 and OCH3) produced their corresponding
derivatives in good to excellent yields. However, it is worth
mentioning that the reaction time of the aryl halides with electron-
donating groups on the aromatic ring was longer than aryl halides
with electron-withdrawing groups due to the fact that oxidative
addition is the most difficult step of the entire catalytic cycle 65. The
rate of oxidative addition also depends on the chemical property of
halides. As mentioned above, electron-withdrawing (EWD) groups
on aryl halides increase their reactivity in oxidative addition step as
Table 3 Optimization of reaction conditions for C-C coupling
reaction of iodobenzene with butyl acrylate.
O
I
Catalyst
O
Bu
+
O
Bu
R
O
compared to those with electron-donating groups 66
.
Base, Solvent,

Catalyst
(mol%)
-
Temperature Time Yield
Entry
Solvent
Base
(˚C)
120
(min) (%)a
2 days NR
In order to show the chemoselectivity of this new catalytic system,
the reaction of 1-bromo-4-chloro benzene was also investigated in
which the bromide showed more reactivity (Tables 4 entry 8). This
1
PEG-400 K2CO3
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selectivity allows an active halide site to remain for further
functionalization.
View Article Online
DOI: 10.1039/C9NJ05325E
5
6
7
8
Table 4 Coupling of aryl halides and butyl acrylate in the presence of catalytic amounts of Hercynite@L-Methionine-Pd.
O
X
Hercynite@L-Mwthionine-Pd (cat)
K2CO3, PEG-400, 120 °C
O
Bu
+
R
O
Bu
R
9
O
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
X= Cl, Br, I
Melting point
measured measured
Entry
Aryl halide
product
Time (min) Yield (%)a TON TOF (min-1)
O
I
Bu
O
O
Oil 70
Oil
1
45
70
98
96
784
768
52.266
10.971
I
Bu
O
Oil 70
Oil
2
3
4
Me
Me
O
I
Bu
O
Oil 70
Oil
50
93
91
744
728
14.88
4.044
MeO
MeO
O
I
Bu
O
Oil 70
Oil
180
OMe
O
OMe
Br
Bu
O
Oil 70
Oil
5
6
50
80
96
89
768
712
15.36
8.9
O
O
O
Br
Br
Br
Br
Bu
O
O
O
Oil 70
Oil
Me
NC
Cl
Me
NC
Bu
39-42 70
40-42
7
8
9
35
65
50
96
91
97
768
728
776
21.94
11.2
726
Bu
Oil 70
Oil
Cl
O
Bu
O
58-63 70
59-62
O2N
O2N
O
Cl
Bu
O
O
Oil 70
Oil
10
11
240
320
93
95
744
760
3.1
Cl
Cl
Bu
O
60-63 71
60-62
2.375
O2N
NC
O2N
NC
O
Bu
O
39-42 71
39-41
12
380
93
744
1.957
a Isolated yield.
b Reaction conditions: aryl halide (1mmol), Hercynite@L-Methionine-Pd (0.125 mol %) butyl acrylate (1.2 mmol) and K2CO3 (3
mmol) in PEG-400 at 120 ˚C.
The purposed mechanism for Heck cross coupling reaction in the
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presence of Hercynite@L-Methionine-Pd has been outlined in was obtained by ICP-OSE: 1.18
×
10-3 mol g-1. These
View Article Online
Scheme 3, based on the previously reported mechanism 72,73
.
characterizations confirmed that the structuDreOoI:f1r0e.1c0o3v9e/Cre9dNJc0a5ta3l2y5sEt
dose not change in morphology and content during coupling
reactions.
HX / Base
Ar
X
Pd(0)
Base
Oxidative
Addition
Reductive
Elimination
H
Pd(II)
X
Ar
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
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38
39
40
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42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ar Pd(II)
X
Z
-H Elimination
Z
H
Pd
Z
X
Ar
Alkene
Coordination
H
Ar Pd(II)
X
Insertion
Fig 8. SEM images of recovered Hercynite@L-Methionine-Pd
nanocatalyst.
Z
complex

Scheme 3. Mechanism of the palladium-catalyzed Heck reaction.
Hot filtration test
Recyclability of the catalyst
Recyclability of heterogeneous catalysts is an important advantage
in industrial applications. Therefore, the recoverability and
reproducibility of Hercynite@L-Methionine-Pd were explored in the
synthesis of 1,1'-biphenyl (Fig. 7 series 1) and butyl cinnamate (Fig.
7 series 2). After the completion of the reaction, the Hercynite@L-
Methionine-Pd catalyst was separated using an external magnet,
washed with EtOAc and water and dried at 80 °C. Then, it was
reused for the next run. As shown in Fig. 8, the recycling process
was repeated for five times with a slight decrease in the activity of
the catalyst.
The heterogeneity of Hercynite@L-Methionine-Pd MNPs in the
reaction mixture was studied using the hot filtration test. The hot
filtration test was performed in Suzuki cross-coupling reaction in
the synthesis of 1,1'-biphenyl under the optimal reaction
conditions. After the half reaction time, the reaction was
terminated and the corresponding product was obtained in 61 % of
yield. Then, the reaction was repeated, and at the half time of the
reaction, the catalyst was separated by magnetic separation from
the reaction mixture, which was allowed to react further.
Accordingly, we found that only a trace conversion (<3%) of the
coupling reaction was observed upon heating of the catalyst-free
solution for another half time of the reaction, which means that the
described nanocatalyst is completely heterogeneous in the reaction
media.
Comparison
In order to demonstrate the superiority of our catalyst to the other
reported catalysts for the synthesis of 1,1′-biphenyl (Table 5 entry
Fig 7. Recyclability of Hercynite@L-Methionine-Pd in the synthesis
of 1,1'-biphenyl (series 1) and butyl cinnamate (series 2).
1-9) and Butyl cinnamate (Table
5 entry 10-17) as the
representative examples, they were compared to the best of the
well-known data from the literature as outlined in the Table 5. As it
can be seen in this Table, this new method was better than the
other catalysts in terms of reaction conditions, time and yield
factors.
In addition, to examine stability of this catalyst during organic
reactins, the recycled catalyst has been characterized by ICP-OSE
and SEM techniques. The SEM image of the recycled catalyst is
shown in fig. 8. As found in the SEM images of Fig. 8, the
morphology of the recovered Hercynite@L-Methionine-Pd is
compairable with fresh catalyst, which indicates the structural
stability of the catalyst after 5 consecutive cycles. In addition, the
exact amount of Pd in the recovered Hercynite@L-Methionine-Pd,
Table 5. Comparing catalytic activity of Hercynite@L-Methionine-Pd with previously reported methods in the Suzuki and Heck reactions.
10 | J. Name., 2012, 00, 1-3
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Entry
Substrate
Catalyst
VO(IV)–MCM-41
Time (mine) Yield (%)a ViewRAertifc.le Online
DOI: 10.1039/C9NJ05325E
74
1
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Phenylboronic acid
Butyl acrylate
720
900
120
15
100
83
95
91
95
94
74
98
99
92
92
96
89
85
76
95
98
53
75
76
77
78
79
2
2
Zirconium ferrite MNPs
Pd@DCA-SBA
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3
4
Fe3O4@SiO2@L-arginine@Pd(0)
Fe3O4@Boehmite-NH2-CoII NPs
Pd@DCA-MCM
5
30
6
120
1440
30
7
MCM-Pd
8
Boehmite@Tryptophan-Pd
Hercynite@L-Methionine-Pd
Pd-DABCO-γ-Fe2O3
9
15
This work
80
10
11
12
13
14
15
16
17
30
81
82
83
84
85
2
Butyl acrylate
Fe3O4/SiO2-DTZ-Pd
30
Butyl acrylate
PdCl2
360
1440
720
1440
85
Butyl acrylate
Dibromobis(1-(4-Methoxyphenyl)-1H-imidazole)palladium(II)
[Pd(PPh3)2Cl2]
Butyl acrylate
Butyl acrylate
Pd(OAc)
Butyl acrylate
Boehmite@Tryptophan-Pd
Hercynite@L-Methionine-Pd
Butyl acrylate
45
This work
a Isolated yield.
Conclusions
In this study, we described a simple strategy to immobilize L-
methionine-Pd complex on the surface of hercynite MNPs by
covalent cross-linking. The structure and composition of the
prepared Hercynite@L-Methionine-Pd MNPs were completely
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characterized by FT-IR, XRD, EDX, ICP, SEM, X-ray mapping, and
TGA and VSM techniques. Moreover, the catalytic activity of
this nanocomposite was investigated in Suzuki and Heck C-C
cross-coupling reactions of aryl halides with phenylboronic
acid as phenylating source and butyl acrylate as olefin source
in EtOH and PEG-400 under green conditions. Therefore, high
surface area, convenient recoverability and reusability for
several times without any significant loss of catalyst activity,
the use of a commercially available materials, eco-friendly
procedure, operational simplicity, ease of separation by simple
filtration, cheap and chemically stabile reagents, good reaction
times, simple practical methodology and ease of use make the
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prepared catalyst
a promising candidate for potential
applications in some organic reactions.
Conflicts of interest
There are no conflicts to declare
Acknowledgements
This work was supported by the research facilities of Ilam
University, Ilam, Iran.
25
26
27
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Notes and references
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Page 14 of 14
View Article Online
DOI: 10.1039/C9NJ05325E
GRAPHICAL ABSTRACT:
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The first report of hercynite as a solid support, L-methionine-Pd complex
supported on hercynite as highly efficient reusable nanocatalyst for C-C cross
coupling reactions
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Masoud Mohammadi, Arash Ghorbani-Choghamarani*
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box, 69315516, Ilam, Iran.
B(OH)2
K2CO3, EtOH, Reflux
R
Pd
S Me
X
O
O
H2N
Hercynite
MNPs
R
X= Cl, Br, I
O
Hercynite@L-Methionine-Pd
Bu
O
O
R
Bu
O
K2CO3, PEG-400, 120 °C
L-Methionine-Pd complex was covalently immobilized on the surface of hercynite (FeAl2O4) MNPs,
and its catalytic properties has been studied in C-C coupling reactions.
* Address correspondence to A. Ghorbani-Choghamarani, Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran; Tel/Fax:
+98 841 2227022; E-mail address: arashghch58@yahoo.com or a.ghorbani@ilam.ac.ir