Deposited zirconocene chloride on silica-layered CuFe2O4 as a highly efficient and reusable magnetically nanocatalyst for one-pot Suzuki-Miyaura coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2017.12.033

The novel core-shell magnetically nanoparticles of CuFe₂O₄@SiO₂@ZrCp₂Cl_x (x: 0–2) were synthesized and used as a highly efficient catalyst for Suzuki-Miyaura coupling reaction of various aryl halides with phenylboronic acid. The reactions were carried out in PEG-400 (70 °C) to afford biaryls in high to excellent yields. The core-shell nanocomposite was easily separated from the reaction by an external magnet and reused for 5 times without significant loss of its catalytic activity. Characterization of the zirconocene nanocomposite was carried out by FT-IR, SEM, EDX, XRD, ICP-OES, AGFM, TGA and BET analyses.

Full text of DOI:10.1016/j.jorganchem.2017.12.033

Accepted Manuscript
Deposited zirconocene chloride on silica-layered CuFe O as a highly efficient and
2
4
reusable magnetically nanocatalyst for one-pot Suzuki-Miyaura coupling reaction
Behzad Zeynizadeh, Farhad Sepehraddin
PII:
S0022-328X(17)30731-3
10.1016/j.jorganchem.2017.12.033
JOM 20228
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 2 October 2017
Revised Date: 8 December 2017
Accepted Date: 26 December 2017
Please cite this article as: B. Zeynizadeh, F. Sepehraddin, Deposited zirconocene chloride on
silica-layered CuFe O as a highly efficient and reusable magnetically nanocatalyst for one-pot
2
4
Suzuki-Miyaura coupling reaction, Journal of Organometallic Chemistry (2018), doi: 10.1016/
j.jorganchem.2017.12.033.
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ACCEPTED MANUSCRIPT
Deposited Zirconocene Chloride on Silica-Layered CuFe O as a Highly Efficient and Reusable
2
4
Magnetically Nanocatalyst for One-Pot Suzuki-Miyaura Coupling Reaction
Behzad Zeynizadeh and Farhad Sepehraddin*
Faculty of Chemistry, Urmia University, Urmia 5756151818, Iran
farhad.sepehraddin@gmail.com
Abstract:
The novel core-shell magnetically nanoparticles of CuFe O @SiO @ZrCp Cl (x: 0‒2) were synthesized and
2
4
2
2
x
used as a highly efficient catalyst for Suzuki-Miyaura coupling reaction of various aryl halides with
phenylboronic acid. The reactions were carried out in PEG-400 (70 °C) to afford biaryls in high to excellent
yields. The core-shell nanocomposite was easily separated from the reaction by an external magnet and
reused for 5 times without significant loss of its catalytic activity. Characterization of the zirconocene
nanocomposite was carried out by FT-IR, SEM, EDX, XRD, ICP-OES, AGFM, TGA and BET analyses.
Keywords: Aryl halides, Biaryls, C-C coupling, Cp ZrCl , PhB(OH) , Suzuki-Miyaura
2
2
2
1
. Introduction
In recent years, synthesis and application of reusable heterogeneous catalysts especially immobilization of
diverse homogeneous catalysts on the core of nanomagnetic materials has attracted a great deal of
attentions [1‒5]. The main advantage of this protocol is here that the prepared nanocomposites can be
easily removed from the reaction by a simple magnetic decantation. In addition, this type of nanocatalysts
possesses high surface area and accelerates the rate of reactions dramatically [6, 7].
In a past decade, various transition metals such as Pd [8], Ni [9], Zn [10], Cu [11], Ru [12], Co [13], Au [14],
Fe [15] and Pd/ZrO [16] have been widely used for many types of coupling reactions. The reaction of C-C
2
bond coupling has been frequently employed for synthesis of agrochemicals, pharmaceuticals, biologically
active compounds, polymers, liquid crystals and advanced materials [17‒20]. In this context, Suzuki-
Miyaura coupling reaction is one of the most important synthetic routes for the preparation of various
biaryls [21‒23].
In line with the outlined strategies, herein, we wish to report a synthesis of novel deposited zirconocene
chloride on silica-layered copper ferrite, CuFe O @SiO @ZrCp Cl (x: 0‒2), as a highly efficient magnetically
2
4
2
2
x
nanocatalyst for one-pot C-C bond coupling of various aryl halides with phenylboronic acid in PEG-400 (70
C).
°
2
2
. Experimental
.1. Materials and instruments
All reagents and solvents were purchased from commercially sources and used without further purification.
1
13
H, C NMR and FT-IR spectra were recorded on Bruker Avance 250/400 MHz and Bruker Vertex 70 FT-IR
spectrometers. Mass spectra were recorded on Agilent-5975C inert XL MSD operating at ionization
potential of 70 eV. Melting points were measured by Electrothermal 9100 apparatus. Thermogravimetric
analysis (TGA) was carried out on Shimadzu DTG-60 instrument. Size and morphology of particle was
determined using FESEM–TESCAN MIRA3 instrument. Powder XRD was obtained by an X'PertPro
Panalytical, Holland diffractometer in 40 kV and 30 mA with a CuKα radiation (λ=1.5418 Å), and the
diffraction patterns were recorded in 2θ range (10‒80°). Elemental analysis of Zr was carried out by
inductively coupled plasma-optical emission spectrometry (ICP-OES) model ARCOS, Germany. The N2
absorption-desorption isotherms were recorded on Belsorp-max instrument. The specific surface area of
samples was determined using Brunauer-Emmett-Teller (BET) method. The pore volume and pore size
distribution were obtained from desorption profile of isotherms using Barrett-Joyner-Halanda (BJH)
method. Magnetic properties of nanocomposites were measured on alternating gradient force
magnetometer (AGFM, Meghnatis Daghigh Caviar Co., Iran) at room temperature. Ultrasonic irradiation
1

ACCEPTED MANUSCRIPT
was carried out in GT SONIC (VGT-1860QTS, China). Thin layer chromatography (TLC) was applied for the
purity determination of products and reaction monitoring over gel SILG/UV 254 aluminum plates.
2
.2 Preparation of CuFe O @SiO @ZrCp Cl (x: 0-2) MNPs
2 4 2 2 x
Synthesis of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs was carried out in a three-step procedure: At first,
2
4
2
2
x
magnetically nanoparticles of CuFe O were prepared through a chemical co-precipitation protocol [24] as
2
4
following:
FeCl ·6H O (2.216 g, 8.2 mmol) and CuCl ·2H O (0.699 g, 4.1 mmol) were dissolved in deionized water (75
3
2
2
2
mL) and stirred at room temperate under nitrogen atmosphere. After few minutes, a basic solution of
NaOH (3 g in 15 mL H O) was drop-wisely added to the prepared solution of iron and copper chlorides in 10
2
min and was continued to stirring vigorously. In a meanwhile of NaOH addition, fine brown-black particles
of CuFe O were precipitated. The resulting mixture was heated on an oil bath (90 °C) for 5 h. After cooling
2
4
to the room temperature, the precipitate was separated by an external magnet and washed with deionized
water (30 mL) and ethanol (20 mL), and was then dried at 80 °C for 12 h. The obtained CuFe O MNPs was
2
4
calcinated at 700 °C for 5 h.
At the second step, the obtained CuFe O MNPs (2 g) were dispersed in a mixture of EtOH‒H O‒25%
2
4
2
aqueous NH (50:20:10 mL, respectively) by sonication. Afterward, PEG-400 (3.36 g) and then tetraethyl
3
orthosilicate (2 mL) was added to the prepared suspension of CuFe O under vigorous stirring. The mixture
2
4
was then stirred for 38 h at room temperature. Magnetically nanoparticles of CuFe O @SiO were isolated
2
4
2
with an external magnet and washed with ethanol and deionized water and then dried at room
temperature [25].
Subsequently, a suspension of CuFe O @SiO (1 g) in n-hexane (50 mL) was prepared and irradiated in an
2
4
2
ultrasonic bath for 30 min under nitrogen atmosphere. To this mixture, a solution of Cp ZrCl (1 g) in n-
2
2
hexane (50 mL) was added and the resulting mixture was stirred for 10 h under reflux and nitrogen
atmosphere. The prepared magnetically nanoparticles of CuFe O @SiO @ZrCp Cl (x: 0‒2) were separated
2
4
2
2
x
by a simple magnetic decantation and washed with ethanol and deionized water to remove the residual
contaminants. The obtained nanoparticles were then dried under vacuum at room temperature to afford
the final nanocomposite material (1.76 g).
2
.3 A general procedure for C-C bond coupling of aryl halides with phenylbronic acid
In a round-bottom flask (10 mL), a mixture of aryl halide (1 mmol), phenylboronic acid (1 mmol), K CO (1.5
2
3
mmol) and CuFe O @SiO @ZrCp Cl (x: 0‒2) (5 mg) in PEG-400 (2 mL) was prepared and the mixture was
2
4
2
2
x
continued to stirring in oil bath (70 °C) for an appropriate time (Table 3). After completion of the reaction
monitored by TLC), the nanocatalyst was separated by an external magnet. Distilled water (5 mL) was then
(
added and the mixture was stirred for additional 5 min. The product was extracted with EtOAc (3 × 5 mL)
and the organic layer was then dried over anhydrous Na SO . Evaporation of the solvent under reduced
2
4
pressure affords the crude biaryl product following with a further purification by a short column
chromatography on silica gel (eluent, n-hexane:EtOAc / 7:3).
2
.4 Selected spectral data
Biphenyl (Table 3, entry 1)
1
White solid, m.p. 68‒69 °C, H NMR (250 MHz, CDCl ): δ (ppm) 7.36-7.39 (m, 2H), 7.46‒7.52 (m, 4H), 7.64
3
+
(
d, J = 7.5 Hz, 4H); EI-MS (70 eV): m/z (%) = 154 (M , 100).
2
-Methylbiphenyl (Table 3, entry 5)
1
Colorless oil, b.p. 255.5 °C/760 mmHg, H NMR (250 MHz, CDCl ): δ (ppm) 2.46 (s, 3H), 7.25‒7.57 (m, 9H);
3
+
EI-MS (70 eV): m/z: 168 (M , 100).
4
-Cyanobiphenyl (Table 3, entry 7)
1
White solid, m.p. 85‒87 °C, H NMR (400 MHz, CDCl ): δ (ppm) 7.77‒7.73 (m, 2H), 7.72‒7.70 (m, 2H),
3
7
.64‒7.61 (m, 2H), 7.54‒7.50 (m, 2H), 7.50‒7.44 (m, 1H)
4
-Nitrobiphenyl (Table 3, entry 8)
2

ACCEPTED MANUSCRIPT
1
Yellow solid, m.p. 111‒114 °C, H NMR (400 MHz, CDCl ): δ (ppm) 8.35‒8.32 (m, 2H), 7.79‒7.75 (m, 2H),
3
7
.67‒7.64 (m, 2H), 7.56‒7.46 (m, 2H), 7.46‒7.29 (m, 1H)
3
. Results and discussion
The study was started by synthesis of novel magnetically nanoparticles of CuFe O @SiO @ZrCp Cl (x: 0‒2)
2
4
2
2
x
through a depicted three-step procedure in Scheme 1:
Cl Zr Cl
O
OH
OH
OH
O
O
O
HO
SiO2
O
SiO2
O
HO
HO
Cl
CuFe2O4
O
Zr Cl
CuFe2O4
OH
OH
Cl Zr
O
H
n-Hexane, reflux, 10 h
O
HO
HO
O
OH
O
OH
O
CuFe O @SiO MNPs
2
4
2
O
O
SiO2
O
O
O
O
O
O
SiO2
O
O
CuFe2O4
O
Zr
O
CuFe2O4
O
O
O
O
O
O
O
O
O
O
O
O
CuFe O @SiO @ZrCp Cl (x: 0-2)
2
4
2
2 x
Scheme 1. Synthesis of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
The scheme shows that magnetically nanoparticles of CuFe O were initially prepared by chemical co-
2
4
precipitation of FeCl ·6H O and CuCl ·2H O in aqueous NaOH [24]. So, the prepared nanocores of CuFe O
3
2
2
2
2
4
were coated with silica layer using tetraethyl orthosilicate. Through the functionalization of CuFe O @SiO
2
4
2
MNPs with zirconocene dichloride, magnetically nanoparticles of CuFe O @SiO @ZrCp Cl (x: 0‒2) was
2
4
2
2
x
finally synthesized. The prepared core-shell zirconocene nanocomposite was then characterized by
FT-IR, SEM, EDX, XRD, ICP-OES, AGFM, TGA and BET analyses.
3
.1. Characterization of CuFe O @SiO @ZrCp Cl (x: 0‒2)MNPs
2 4 2 2 x
Thermogravimetric analysis (TGA) of CuFe O @SiO @ZrCp Cl MNPs was shown in Figure 1. Through the
2
4
2
2
x
analysis, mass losing of the nanocomposite through dehydration, removing of organic moiety or fragmen-
tation was studied at a programmable heating. The recorded plot for zirconocene nanocomposite shows a
weight loss in the region of r.t.‒200 °C via dehydration of adsorbed water or surface hydroxyl groups. By
fragmentation and removing of organic moiety, a second weight loss at 200‒600 °C was also observed in
thermogravimetric curve of the nanocomposite.
3

ACCEPTED MANUSCRIPT
Fig. 1. TGA analysis of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
Figure 2 shows the recorded FT-IR spectra for CuFe O and CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs. Both of
2
4
2
4
2
2
x
-
1
spectrum 2a and 2b show the stretching vibration bands at 410 and 580 cm attributed to the bonding of
-
1
Cu-O and Fe-O, respectively, and a broad absorbance around 3400 cm due to stretching vibration of
surface hydroxyl groups. Presence of silica layer on the surface of copper ferrite nanoparticles is confirmed
-
1
-1
by the absorbance at 1150 cm showing Si-O and 1620 cm showing C=C stretching vibration of Cp groups
Fig. 2b). These results demonstrated that zirconocene chloride was successfully immobilized on the surface
(
of CuFe O @SiO MNPs.
2
4
2
Fig. 2. FT-IR spectrum of a) CuFe O and b) CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
4
2
2
x
The morphology and size distribution of particles in CuFe O and CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
4
2
2
x
are illustrated in Figure 3. The SEM images show that in both of materials, the nanoparticles have uniform
shapes. SEM analysis exhibited that size of nanoparticles in CuFe O and CuFe O @SiO @ZrCp Cl (x: 0‒2)
2
4
2
4
2
2
x
MNPs is varied from 15‒20 and 30–35 nm, respectively. By EDX analysis, elemental composition of Cu, Fe,
O, Cl, Si, and Zr in CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs was also demonstrated (Figure 4).
2
4
2
2
x
4

ACCEPTED MANUSCRIPT
Fig. 3. SEM images of a) CuFe O and b) CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
4
2
2
x
Fig. 4. EDX analysis of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
The amount of Zr (4.72%) in CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs was determined successfully by ICP-
2
4
2
2
x
OES (inductively coupled plasma optical emission spectrometry) technique.
X-ray diffraction pattern of CuFe O @SiO @ZrCp Cl (x: 0‒2) nanoparticles was shown in Figure 5. In this
2
4
2
2
x
pattern, the phase of nanoparticle is identified by the peak position of 19° (101), 30° (112), 35° (211), 37°
202), 42° (220), 52° (312), 57° (321), 63° (224), 67° (400), 74° (420), 75 (413) and 77° (422) which is in
consistent with the standard XRD pattern of CuFe O (JCPDS 77-0010). This observation illustrated that
(
2
4
during the immobilization of ZrCp Cl , the crystalline structure of CuFe O was remained intact [24].
2
2
2
4
5

ACCEPTED MANUSCRIPT
Fig. 5. XRD pattern of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
Figure 6 shows N adsorption-desorption isotherms of CuFe O @SiO and CuFe O @SiO @ZrCp Cl (x: 0‒2)
2
2
4
2
2
4
2
2
x
MNPs. Based on these isotherms, the calculated BET specific surface area (S ) and total pore volumes
BET
(
Vtotal) are summarized in Table 1. Observation of the results shows that the presence of ZrCp Cl moieties
2 x
on the surface of CuFe O @SiO decreases S and increases Vtotal values.
2
4
2
BET
Fig. 6. N adsorption-desorption isotherm for CuFe O @SiO and CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
2
4
2
2
4
2
2
x
Table 1. The obtained parameters from N adsorption-desorption isotherms
2
2
3
Sample
SBET (m /g)
Vtotal (Cm /g)
CuFe O @SiO
2
2.762
1.787
0.031
0.036
2
4
CuFe O @SiO @ZrCp Cl (x: 0‒2)
2
4
2
2
x
Magnetic susceptibility of CuFe O and CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs was also studied by
2
4
2
4
2
2
x
obtaining the specific saturation magnetization (Ms), remanent magnetism (Mr) and coercivity field (Hc) of
6

ACCEPTED MANUSCRIPT
the nanoparticles. The plot of saturation magnetization (Ms) versus coercivity field (Hc) for examined
nanomagnetic materials clearly shows ferromagnetic behavior of CuFe O . Ms, Mr and Hc values for
2
4
CuFe O are about 0.03, 0.002 a.u. and 100 Oe, respectively (Figure 7). At the same field, the values for
2
4
CuFe O @SiO @ZrCp Cl (x: 0‒2) are about 0.007, 0.001 a.u. and 0 Oe, respectively. These nanoparticles
2
4
2
2
x
easily separated by using an external magnet.
Fig. 7. Magnetization curve of a) CuFe O and b) CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs at r.t.
2
4
2
4
2
2
x
3
.2. Catalytic activity of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs for C-C bond coupling
2 4 2 2 x
After synthesis and characterization of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs, the catalytic activity of this
2
4
2
2
x
nanocomposite was examined in Suzuki-Miyaura C-C bond coupling of aryl halides with phenylboronic acid.
Reaction conditions were optimized by performing the coupling reaction of iodobenzene with
phenylboronic acid in the presence of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs using various solvents, bases,
2
4
2
2
x
varying the amounts of nanocatalyst as well as temperature of the reaction. The results of these
investigations are summarized in Table 2.
Table 2. Optimization experiments for C-C bond coupling of PhI with PhB(OH)2
CuFe O @SiO @ZrCp Cl MNPs
2
4
2
2
x
I
+
PhB(OH)2
o
b
Entry
Zr-cat. (mg)
Solvent
Base
Temp. ( C)
Time (min)
180
75
Yield (%)
–
1
2
3
4
5
6
7
8
9
‒
3
5
7
5
5
5
5
5
5
5
5
5
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
EtOH
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
120
70
70
70
rt
86
30
98
25
98
300
150
160
120
200
35
84
70
60
60
70
70
70
70
69
EtOAc
73
CH Cl2
69
2
H O
2
70
1
1
1
1
0
1
2
3
DMF
95
PEG-400
PEG-400
PEG-400
Et N
3
140
190
45
60
n
-Pr N
62
3
KOH
70
70
a
b
All reactions were carried out with the molar ratio of PhI:PhB(OH) :Base (1:1:1.5). Isolated yield.
2
7

ACCEPTED MANUSCRIPT
Observation of the results reveals that the influence of nanocatalyst on the rate of coupling reaction is
noteworthy. Entry 1 shows that performing of the model reaction in the absence of nanocatalyst did not
produce any product. However, using the little amounts of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
dramatically accelerated the rate of reaction. Carrying out of the coupling reaction inside various solvents
and using different amounts of nanocatalyst resulted that completion of the reaction of PhI (1 mmol) with
PhB(OH) (1 mmol) requires 5 mg CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs and 1.5 mmol K CO in PEG-400
2
2
4
2
2
x
2
3
(
70 °C) as the optimum reaction conditions (Entry 3). In order to determine the influence of Zr moiety on
Suzuki-Miyaura bond coupling reaction, we also performed the model reaction in the presence of CuFe O
2
4
and CuFe O @SiO MNPs at the optimized reaction conditions. Investigation of the results showed that the
2
4
2
progress of the reactions was poor (25‒30%) and did not exhibit any impressive results.
At the next, the capability of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs was further studied by performing C-C
2
4
2
2
x
bond coupling of diverse aryl halides with phenylboronic acid at the optimized reaction conditions. The
results of this investigation are illustrated in Table 3. As seen, all reactions were carried out successfully to
afford biaryl products in high to excellent yields within 10‒100 min. The table also exhibited that aryl
halides containing electron-withdrawing groups has higher rate enhancement in comparison to those
containing electron-releasing groups (Table 3, entries 6 and 8). Moreover, the obtained results for coupling
reaction of aryl bromides and chlorides with PhB(OH) reveals that the present protocol was also efficient
2
and produced the corresponding biaryls in high yields (entries 4‒12). As it is anticipated, the reactivity of
aryl iodides was higher than their bromide and chloride derivatives.
Table 3. C-C bond coupling of aryl halides with phenylboronic acid in the presence of CuFe O @SiO @ZrCp Cl (x:
2
4
2
2
x
a
0
‒2) MNPs
CuFe O @SiO @ZrCp Cl ( 5 mg)
2
4
2
2
x
Ar-X
+
PhB(OH)2
Ar-Ph
o
K CO , PEG-400, 70 C
2
3
X: I, Br, Cl
b
Entry
ArX
Product
Time (min)
Yield (%)
98
Mp (°C) [Ref.]
68‒69 [26]
45‒47 [27]
1
2
30
50
96
3
4
80
40
89
97
86‒89 [28]
68‒69 [26]
2
55.5/760
5
90
87
mmHg [27]
6
7
55
15
87
97
45‒47 [29]
85‒87 [26]
8
9
10
100
30
98
70
92
111‒114 [29]
68‒69 [26]
1
0
111‒114 [29]
8

ACCEPTED MANUSCRIPT
3
24‒325/760
1
1
1
2
75
90
88
mmHg [30]
3
24‒325/760
85
mmHg [30]
a
All reactions were carried out with the molar ratio of ArX:PhB(OH) :K CO (1:1:1.5) in the presence of CuFe O @SiO @
2
2
3
2
4
2
o
b
ZrCp Cl (5 mg) in PEG-400 (2 mL) at 70 C. Isolated yield.
2
x
3
.3. Recycling of CuFe O @SiO @ZrCp Cl (x: 0-2) MNPs
2 4 2 2 x
Reusability of the nanocatalyst was studied by performing C-C bond coupling of PhI with PhB(OH) in the
2
presence of recycled CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs. After completion of the reaction at the first
2
4
2
2
x
run, the catalyst was recovered by an external magnet, washed with ethyl acetate, dried in an oven and
then reused for the next run of the coupling reaction. Figure 8 shows the yield of five consecutive cycles of
biphenyl synthesis through the coupling reaction of phenyl iodide with phenylboronic acid in the presence
of recycled Zr-nanocomposite. After five recycling and reusing the nanocatalyst, ICP-OES analysis showed
that the amount of Zr was 4.71%. This result obviously indicates that the activity of nanocatalyst was
remained intact during the recycling process.
Fig. 8. Reusability of CuFe O @SiO @ZrCp Cl (x: 0‒2) MNPs
2
4
2
2
x
4
. Conclusions
In this study, the immobilization of zirconocene chloride on silica-layered copper ferrite as a novel core-
shell Zr-based nanocomposite, CuFe O @SiO @ZrCp Cl (x: 0‒2), was carried out successfully. The nano-
2
4
2
2
x
catalyst was characterized by FT-IR, SEM, EDX, XRD, ICP-OES, AGFM, TGA and BET analyses. The prepared
core-shell zirconocene MNPs exhibited an excellent catalytic activity and reusability towards C-C bond
coupling of diverse aryl halides with phenylboronic acid. All reactions were carried out in the presence of 5
mg of the nanocatalyst using K CO in PEG-400 at 70 °C. The nanocatalyst was used at least for 5 catalytic
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3
cycles without significant loss of its catalytic activity. Remarkable reusability and easy separation of the
catalyst, first application of zirconium in Suzuki-Miyaura C-C bond coupling reaction, high yields and mild
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basic reaction conditions as well as the benefits of using PEG-400 as a green solvent are the advantages
which make this protocol a perfect choice for the titled transformation.
5
. Acknowledgements
The authors gratefully appreciated the financial support of this work by the research council of Urmia
University.
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Highlights
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•
Synthesis of magnetically nanoparticles of CuFe O @SiO @ZrCp Cl
2 4 2 2 x
Bond coupling of aryl halides with PhB(OH) catalyzed by CuFe O @SiO @ZrCp Cl MNPs
2
2
4
2
2
x
Using PEG-400 as a green solvent and K CO as a mild base
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3
Aryl bromides (chlorides) as well as aryl iodides perform the coupling reaction.
CuFe O @SiO @ZrCp Cl MNPs can be reused for 5 catalytic cycles.
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2
2
x