Magnetite@MCM-41 nanoparticles as support material for Pd-N-heterocyclic carbene complex: A magnetically separable catalyst for Suzuki–Miyaura reaction

Article abstract of DOI:10.1002/aoc.6233

The Magnetite@MCM-41@NHC@Pd catalyst was obtained with Pd metal bound to the NHC ligand anchored to the surface of Fe₃O₄@MCM-41. It was characterized by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse X-ray analysis (EDX), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The amount of Pd in the Magnetite@MCM-41@NHC@Pd was measure by inductively coupled plasma–optical emission spectroscopy (ICP-OES) analysis. The catalytic activity of Magnetite@MCM-41@NHC@Pd heterogeneous catalyst done on Suzuki–Miyaura reactions of aryl halides with different substituted arylboronic acid derivatives. All coupling reactions afforded excellent yields and up to 408404 Turnover Frequency (TOF) h^?1 in the presence of 2 mg of Magnetite@MCM-41@NHC@Pd catalyst (0.0564 mmol g^?1, 0.01127 mmol% Pd) at room temperature in 2-propanol/H₂O (1:2). Moreover, Magnetite@MCM-41@NHC@Pd catalyst was recover by applying the magnet and reused for another reaction. The catalyst showed excellent structural and chemical stability and reused ten times without a substantial loss in its catalytic performance.

Full text of DOI:10.1002/aoc.6233

Received: 4 February 2021
DOI: 10.1002/aoc.6233
Revised: 22 February 2021
Accepted: 27 February 2021
F U L L P A P E R
Magnetite@MCM-41 nanoparticles as support material for
Pd-N-heterocyclic carbene complex: A magnetically
separable catalyst for Suzuki–Miyaura reaction
2
Mitat Akkoç1
| Nesrin Bugday
| Serdar Altın3
| Sedat Yas¸ar2
ꢀ
1Hekimhan Vocational College,
Department of Property Protection and
Security, Malatya Turgut Özal University,
Malatya, Turkey
The Magnetite@MCM-41@NHC@Pd catalyst was obtained with Pd metal
bound to the NHC ligand anchored to the surface of Fe3O4@MCM-41. It was
characterized by Fourier transform infrared (FTIR) spectroscopy, transmission
electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spec-
troscopy (XPS), energy disperse X-ray analysis (EDX), thermogravimetric anal-
ysis (TGA), differential thermal analysis (DTA), and scanning electron
microscopy (SEM). The amount of Pd in the Magnetite@MCM-41@NHC@Pd
was measure by inductively coupled plasma–optical emission spectroscopy
(ICP-OES) analysis. The catalytic activity of Magnetite@MCM-41@NHC@Pd
heterogeneous catalyst done on Suzuki–Miyaura reactions of aryl halides with
different substituted arylboronic acid derivatives. All coupling reactions
afforded excellent yields and up to 408404 Turnover Frequency (TOF) h−1 in
the presence of 2 mg of Magnetite@MCM-41@NHC@Pd catalyst
(0.0564 mmol g−1, 0.01127 mmol% Pd) at room temperature in 2-propanol/
H2O (1:2). Moreover, Magnetite@MCM-41@NHC@Pd catalyst was recover by
applying the magnet and reused for another reaction. The catalyst showed
excellent structural and chemical stability and reused ten times without a sub-
stantial loss in its catalytic performance.
2Faculty of Science and Arts, Department
_
of Chemistry, Inönü University, Malatya,
Turkey
3Faculty of Science and Arts, Department
_
of Physics, Inönü University, Malatya,
Turkey
Correspondence
_
Sedat Yas¸ar, Inönü University, Faculty of
Science and Arts, Department of
Chemistry, 44280 Malatya, Turkey.
Email: sedat.yasar@inonu.edu.tr
Mitat Akkoç, Hekimhan Vocational
College, Department of Property
Protection and Security, Malatya Turgut
Özal University, Hekimhan, Malatya,
Turkey.
Email: mitat.akkoc@ozal.edu.tr
K E Y W O R D S
magnetic palladium catalyst, magnetite, MCM-41, Pd (II)-N-heterocyclic carbene, Suzuki–
Miyaura reaction
1 | INTRODUCTION
Magnetic nanoparticles (MNPs) and mesoporous
materials have attracted significant attention due to their
Supported materials have attracted considerable attention
in recent years. The materials have many uses in fields
such as chemistry, medicine, and biological sciences.[1–7]
In the last two decades, the use of these materials
increased rapidly. Therefore, the design and preparation
of the heterogeneous catalyst are crucial. Immobilization
of heterogeneous catalysts with homogeneous species is
an essential method for fabricating new types of
supported catalysts.[8–13]
outstanding features in the context of green chemistry.
The application of MNPs in catalysis increases has gained
great attention. Because MNPs are superparamagnetic,
have low toxicity, show biocompatibility, and have high
magnetic susceptibility,[14–20] MNPs are used either sup-
port materials or active components in catalysis due to
their chemical activity, robustness, and reusability.
Besides these superior properties of MNPs, they have
disadvantages such as low surface area and poor
Appl Organomet Chem. 2021;e6233.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6233

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AKKOÇ ET AL.
durability. To overcome such disadvantages, the MNPs
doped with mesoporous materials such as SiO2, Santa
Barbara Amorphous (SBA-15), and Mobil Composition of
Matter (MCM-41). Mesoporous materials offer a high
surface area, large and uniform pore volume, high tem-
perature, and chemical stability.[21–24] The MCM-41 has
more superior properties such as considerable durability,
high specific surface area, air tolerance, large and
uniform pore size, and high thermal and mechanical sta-
bility when compared to other mesoporous materials
such as SiO2, Santa Barbara Amorphous (SBA-15).[21–24]
The Fe3O4 coated mesoporous materials offer superior
advantages. It includes functionalization and prepara-
tion, air stability, non-toxicity, and incredibly facile
separation from the reaction media by applied an exter-
nal magnet.[25–32] Due to the large surface area of Fe3O4/
MCM-41, the magnetite (Fe3O4) is introduced into the
mesopores channels of MCM-41 to generate an ideal and
excellent support for catalysts on catalytic applica-
tions.[33,34] Herein, to benefit from the superior features
of MCM-41 mentioned above, we preferred MCM-41
mesoporous material for coated MNPs instead of SBA-15
and SiO2.
N-heterocyclic carbenes (NHCs) are an excellent
alternative to phosphine ligands because of their superior
features. Thanks to its properties, such as ease to obtain,
stability against air and moisture, and non-toxicity. The
NHC ligands have better applications in homogeneous
and heterogeneous catalysis. In order to synthesize the
stable catalyst, the ligand has strong sigma donor prop-
erty that led to the formation strong Metal-NHC
bond.[35,36] This feature led to increasing the stability of
the catalyst in different catalytic systems. Combining
Pd-NHC with Fe3O4@MCM-41 is vital for synthesizing
new types of MNPs catalysts for the organic transforma-
tion reactions. To date, several Pd-doped MNPs were suc-
cessfully synthesized and used as the catalyst for C–C
bond formation reactions.[34,37–53] The C–C bond forma-
tion reaction is a critical synthesis procedure in synthe-
sizing natural products, agrochemicals, biologically active
compounds, and pharmaceuticals.[33,34,38,44,48,50,54–56]
Although structurally similar catalysts exist in the
literature, Pd complex of NHC ligand attached to the
supporting material via the OH-group is not available in
the literature. We synthesized this type of catalyst with
the intelligent guess that such type catalyst maybe
leads to high catalytic activity on the Suzuki–Miyaura
reactions. Herein, we reported the fabrication and
characterization of Fe3O4@MCM-41@NHC@Pd catalyst
and investigation of catalytic activity on Suzuki–Miyaura
reaction for a wide range of aryl bromides with
different PhB (OH)2 in aqueous media at room
temperature.
2 | EXPERIMENTAL SECTION
2.1 | Materials and methods
Otherwise stated, all manipulations carried out in aerobic
conditions. All chemicals purchased Sigma Aldrich or
Fluorochem or BLDpharm companies and used as
obtained. For NMR analysis, a Bruker Avance III
400-MHz Nuclear magnetic resonance (NMR) spectrome-
ter was used at room temperature with the decoupled
nucleus, using CDCl3 and DMSO-d6 as the solvent
referenced versus Tetramethylsilane (TMS) as standard.
All reactions were monitored on a Shimadzu GC2010
Plus system by gas chromatography–flame ionization
detector (GC–FID) with an HP-5 column. Some of the
catalytic products reported previously. The new catalytic
products are characterized by different spectroscopic
techniques. The GC–mass chromatography (MS) analysis
of compounds was measured by Shimadzu GC–MS 2010
plus using a TRX-5 column on positive Electron Sprey
Ionization (ESI) mode. The Fourier transform infrared
(FTIR) analysis was performed with a PerkinElmer Spec-
trum 100 GladiATR FTIR spectrometer. An X-ray diffrac-
tometer performed the crystal structure analysis of the
synthesized powder labeled Rigaku Rint 2000, powered
by Cu Kα radiation for characterization. The scan rate
chose as 2ꢀ min−1 between 2ꢀ and 80ꢀ min−1. The
microstructural properties and the synthesized powders'
surface morphology investigated by Leo EVO-40 VPX
scanning electron microscope (SEM). For X-ray photo-
electron spectroscopy (XPS) analyses: XPS instrument:
PHI 5000 VersaProbe II,
X rays: hn = 1486,6 eV
monochromatic, spot 200 μm and Energy resolution
(hi-resolution spectra): 0.8 eV were used. The transmis-
sion electron microscopy (TEM) analyses performed by
FEI TECNAI OSIRIS operating at 200 kV, morphological
analysis with HAADF-STEM imaging mode, chemical
analysis with the Super-X energy disperse X-ray
analysis (EDX) detector system (4 silicon drift detectors
[SDDs]).
2.1.1 | General procedure for Suzuki–
Miyaura reaction
Palladium nano-catalyst (2 mg, 0.01127 mmol%Pd),
arylboronic acid (1.2 mmol), aryl halide (1 mmol), and
K2CO3 (2 mmol) placed in a reaction tube under air
and 3 ml of aqueous solution (2-propanol/water mixture
[1:2, v:v]) were added to reaction tube and stirred at
room temperature. The Fe3O4@MCM-41@NHC@Pd
catalyst was removed by an external magnet from reac-
tion media, and then 3 ml of H2O and 3 ml of Et2O

AKKOÇ ET AL.
3 of 21
was added to the solution. The organic phase was
separated and dried over MgSO4. Filtrate was
evaporated under reduced pressure to obtain the crude
product. Some of the compounds were purified by
column chromatography (Ethyl acetate/hexane as the
2.2 | Synthesis
2.2.1 | Synthesis of NHC salt
(1-(2,3,4,5,6-pentamethylbenzyl)-
3-(ethanol)-benzimidazolium iodine)
1
eluent [1:30, v/v]). H and 13C NMR spectra of the new
compounds
[1,10-biphenyl]-3-carbaldehyde
(4-Methoxy-40-nitro-30-(trifluoromethyl)-
The following procedure was used for the synthesis of
NHC salt.[57] 2-Iodoethanole (1,8 g; 110 mmol) was
added to 10 ml n-BuOH solution of 1-(2,3,4,5,6-pen-
tamethylbenzyl)benzimidazole (2.78 g; 100 mmol). Then,
the reaction solution refluxed for 4 h. After the reaction
and
40-(tert-Butyl)-
4-nitro-3-(trifluoromethyl)-1,10-biphenyl) are presented
in supporting information section (Figures S1 and S2,
respectively).
SCHEME 1 Synthesis pathway of the
Magnetite@MCM-41@NHC-Pd catalyst

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AKKOÇ ET AL.
cooled to room temperature, yellow crystals form by
themselves. Crystals were removed from the solution by
filtration, washed with diethyl ether (5 × 5 ml), and dried
by high vacuum. Yellow crystals were characterized by
reported with modifications using FeCl3.6H2O and
FeCl2.4H2O.[58] Synthesized Fe3O4 nanoparticles were
coated with silica by tetraethylorthosilicate (TEOS) then
doped in MCM-41 template to fabricate Fe3O4@MCM-
41.[59] At the next step, Fe3O4@MCM-41 nanoparticles
modified via the hydroxyl group on the NHC ligand. In
the final step, Pd2+ was introduced to Fe3O4@MCM-
41@NHC to afford Fe3O4@MCM-41@NHC@Pd catalyst
labeled as 3 (Scheme 1). These Pd-doped nanoparticles
characterize by TEM, SEM, FTIR, X-ray diffraction
(XRD), XPS, differential thermal analysis (DTA),
thermogravimetric analysis (TGA), and N2 adsorption–
desorption isotherms inductively coupled plasma–optical
emission spectroscopy (ICP-OES) techniques. As a result
of the ICP-OES analysis, it determined that the catalyst
contains 0.6 wt% Pd (0.0564 mmol g−1).
1
1H NMR, 13C NMR, and elemental analysis. The H and
13C NMR spectra are presented in supporting information
section (Figure S3).
1
Yield: 75%, H NMR (400 MHz, DMSO-d6) δ = 8.97
(s, 1H, NCHN), 8.19 and 8.12 (d, J = 28 Hz, 4H, C6H4),
5.72 (s, 2H, CH2C6[CH3]5–2,3,4,5,6), 5.02 (s, 1H,
CH2CH2OH), 4.54 (t, j = 4.6 Hz, 2H, CH2CH2OH), 3.74
(m, 2H, CH2CH2OH), 2.27 (s, 3H, CH2C6[CH3]5–
2,3,4,5,6), 2.24 (s, 6H, CH2C6[CH3]5–2,3,4,5,6), 2.21
(s, 6H, CH2C6[CH3]5–2,3,4,5,6).13C NMR (100 MHz,
DMSO-d6) δ = 141.8, 137.8, 134.4, 133.4, 132.1, 131.9,
127.1, 127.0, 125.9, 114.6, 114.3, 59.1, 49.8, 46.8, 17.5,
17.2, 16.9. Elemental analysis for C21H27N2OI: %Calc.
C:56.01, H:6.04, N:6.22; %found C:56.12, H:6.14, N:6.38.
3 | RESULT AND DISCUSSIONS
3.1 | Catalyst characterization
The XRD pattern of Magnetite@MCM-41@NHC-Pd is
given in Figure 1, and it is observed the reflection lines of
magnetite, Pd, and MCM-41. There are no reactions
between the components of the main structure. The mag-
netite is the center of the molecule, the MCM-41 was
coated on magnetite, and NHC-Pd was dispersed on the
MCM-41. The 2θ values at 30.18ꢀ, 35.6ꢀ, 42.92ꢀ, 54.94 ,
ꢀ
2.2.2 | Catalyst preparation
57.6ꢀ, and 63.13ꢀ belong to magnetite crystal planes, and
23.8ꢀ value is related to silica skeleton (JCPDF number:
19–0629). These 2θ values show the same pattern as the
standard XRD pattern of magnetite and MCM-41.[33]
Also, 2θ values at 39.67ꢀ (200), 46.19ꢀ (220), and 66.8ꢀ
(331) in the XRD pattern belong to Pd0 metal in the cata-
lyst (JCPDF number: 46–1043). According to the results,
it was observed that the target catalyst successfully
synthesizes, and the results were compatible with the
literature.[33]
The synthesis of the Fe3O4@MCM-41@NHC@Pd catalyst
summarize in Scheme 1. The MNPs magnetite was syn-
thesized via the coprecipitation method as previously
The FTIR spectra for NHC, Magnetite@MCM-41,
Magnetite@MCM-41@NHC, and magnetite@MCM-
41@NHC-Pd are given in Figure 2. The peak at 584 cm−1
belongs to Fe–O bonds vibration,[27,60] and the band at
3421 cm−1 was associated with the O–H groups in the
powders. The absorption bands at 1091, 799, and
464 cm−1 were attributed to Si–O–Si antisymmetric
stretching vibrations, Si–O–Si symmetric stretching, and
Si–O–Si or O–Si–O in MCM-41, respectively.[22,61]
According to the FTIR results of Magnetite@MCM-41,
Magnetite@MCM-41was successfully synthesized, and
the results were compatible with the literature.
The FTIR band at 3506 cm−1 belongs to the OH
group's symmetrical and asymmetrical stretching
FIGURE 1 X-ray diffraction (XRD) pattern of
magnetite@MCM-41@NHC-Pd

AKKOÇ ET AL.
5 of 21
The particle size, morphology, and the elemental dis-
tribution of Magnetite@MCM-41@NHC-Pd were studied
by SEM and EDX techniques and shown in Figure 3. It
was observed the spherical grain formations with uni-
form distribution as seen in the SEM mapping image.
Furthermore, SEM images approve the nano-sized
particle formation in the structure. The elemental
distribution of the Magnetite@MCM-41@NHC-Pd was
determined by EDX analysis and approved the existence
of C, Si, O, N, Fe, and Pd atoms in the Magnetite
@MCM-41@NHC@Pd catalyst with homogeneous distri-
bution (Figure 3).
The elemental distribution of catalyst was also deter-
mined by HAADF–STEM analysis as presented in
Figure 4. According to Figure 4, the elements are distrib-
uted homogeneously in the structure. Homogeneously
dispersed Pd nanoparticles in the designed catalyst are
desirable in the synthesis of heterogeneous catalysts.
Although TEM analysis confirms that the sizes of Pd par-
ticles are between 80 and 95 nm (Figure 4), the particle
size distribution should be calculated in detailed analysis.
For this purpose, the particle size distribution was calcu-
lated by ImageJ open source program using SEM images
and given in Figure 5. An area of 10 μm × 10 μm was
used to calculate the distribution of particle size.
According to the calculations, the catalyst particle size is
between 200 nm and 1.2 μm, and the average particle size
value was calculated as 650 ( 180) nm. So, it concludes
that nano-sized particles have characteristic structures
with a high surface area for Magnetite@MCM-41@NHC-
Pd catalyst which is important for catalytic reactions.
The XPS spectra of Magnetite@MCM-41@NHC-Pd
and the detailed XPS spectra for each ion are presented
FIGURE 2 Fourier transform infrared (FTIR) spectra of NHC,
Magnetite@MCM-41, Magnetite@MCM-41@NHC, and
Magnetite@MCM-41@NHC-Pd
vibrations on the MCM-41.[62,63] The 2970 cm−1
(CH (CbH2) stretching, 2937 [CH (CH2–CH2) stretching],
and 1600, 1400, 1300 cm−1 belong to NHC ligand. The
characteristic spectral for NHC is the intense peak at
3352 cm−1 due to the supposition of the OH bending
vibration. After immobilization of NHC to Mag-
netite@MCM-41 and Magnetite@MCM-41@NHC@Pd,
the band at 3352 cm−1 disappeared, which indicates func-
tionalization of Fe3O4@MCM-41 with NHC. The shift of
absorption band at 1563 cm−1 (CNC stretching of benz-
imidazole) to 1394 cm−1 may be related to the formation
of Pd–C bond (Pd-CNC stretching of benzimidazole) after
reaction with Pd (OAc)2.
FIGURE 3 Scanning electron microscopy (SEM) and energy disperse X-ray analysis (EDX) dot mapping of Magnetite@MCM-41@
NHC-Pd

6 of 21
AKKOÇ ET AL.
FIGURE 4 Transmission electron microscopy (TEM) images of Magnetite@MCM-41@NHC-Pd (a and b), energy disperse X-ray
analysis (EDX)-dot mapping (c), and elemental distribution of Pd, Fe, Si, and O (d–g)
Si, C, O, N, Fe, and Pd2+ and Pd0 atoms. To learn more
detail about each component in Figure 6a, we focused on
each element in the powders shown in Figure 6b–g.
The energy level of C1s electrons observed at 285 eV,
in Figure 6b and should be related to C–C/C=C bonds in
the structure.[64] The N1s electron peak at 398 eV in
Figure 6c is due to the imidazolate-N atom in the struc-
ture.[65] The peak at 531 eV for O1s belongs to the O
atom in the NHC ligand, which has a −1 oxidation state
(Figure 6d). The energy values of Si2s and Si2p electrons
were observed at 152 and 102 eV, respectively, shown in
Figure 6e,f. It is known that Fe3p represents the existence
of Fe ions and Fe2p split into two energy levels at
ꢁ708 eV for 2p1/2 and ꢁ721 eV for 2p3/2 (Figure 6g),
and it explains by the formation of Fe2+ and Fe3+ in the
structure of magnetite.[66] Figure 6h exhibits the XPS Pd
FIGURE 5 The particle size distribution of Magnetite@MCM-
3d spectrum of catalyst reveals that Pd0 and Pd2+
41@NHC-Pd
oxidation states were observed. We attribute the binding
energies of 332.84 and 338.17 eV for Pd0 3d5/2 and 3d3/2
in Figure 6a–g. The XPS spectrum gives information
about the aspect of all layers in the Magnetite@MCM-
41@NHC-Pd. The XPS peaks of Magnetite@MCM-
41@NHC-Pd given in Figure 6a confirm the presence of
levels and the binding energies of 334.77 and 339.96 eV
to PdII 3d5/2 and 3d3/2.
The PdII 3d5/2 peak of Pd
[67]
(OAc)2 shifted from 338.7 to 334.77 eV, which verifies the
synthesis of Pd (II)-NHC complex (Figure 6h). We can

AKKOÇ ET AL.
7 of 21
FIGURE 6 X-ray photoelectron spectroscopy (XPS) spectra of Magnetite@MCM-41@NHC@Pd (a), C1s (b), N1s (c), O1s (d), Si2p (e),
Si2s (f), Fe2p (g), and Pd3d (h)
explain the presence of both Pd0 and Pd2+ in the catalyst
structure by the heating process during the synthesis of
the catalyst, which reduces metals.[68] Although not all of
Pd2+ reduced into Pd0, the formation of any Pd0 spices is
the desired situation without using an extra agent. As a
result, the XPS data show the presence of the atoms men-
tioned in the structure of the synthesized catalyst.[69]
The net amount of palladium doped into the structure
of the catalyst was determined by ICP-OES analysis.
According to the result, 0.6 wt% Pd (0.0564 mmol g−1
)
was measured in the structure of Magnetite@MCM-
41@NHC@Pd.
TGA was used for the determination of organic
groups, which were immobilized on the surface of

8 of 21
AKKOÇ ET AL.
Magnetite@MCM-41. The thermal stability of the
Magnetite@MCM-41@NHC@Pd catalyst was evaluated
by TGA and DTA as presented in Figure 7. DTA and
TGA show that there are three regions for both data
related to endothermic activity in the samples. The mass
loss in low temperatures corresponds to the removed
water and solvents.[70] The second weight loss at 234ꢀC is
related to the calcination of organic groups on
the catalyst. The other two reactions at high tempera-
Magnetite@MCM-41@NHC@Pd catalyst has high
magnetization in the solvent. Figure 8 shows the tube
containing the catalyst with an Nd magnet, which the
catalyst in the solution accumulates near the magnet in a
short time.
3.1.1 | Catalytic studies
tures are related to
a
thermal transformation of
We examine the catalytic activity of 3 for the Suzuki–
Miyaura coupling reaction. The optimum reaction condi-
tions for the Suzuki–Miyaura coupling reaction examine
in a model reaction with bromoacetophenone and PhB
(OH)2, and the results are given in Table 1. Our previous
studies[71–73] showed that the 2-propanol/H2O solvent
system and K2CO3 base are well compatible at room tem-
perature in the homogeneous catalyze systems. There-
fore, to determine the sufficient amount of catalyst
directly, different reaction conditions are tested. To find
an adequate amount of catalyst and reaction time, differ-
ent catalyst loading at room temperature tested as shown
in Table 1, Entries 1–5. When 2 mg of catalyst was used,
the reaction was completed simultaneously with the
same yield of 4 mg of the catalyst used (Table 1, Entries
1 and 3). However, the catalyst loading was reduced to
1 and 0.5 mg, reaction time increasing, and the product
obtained in lower yield (Table 1, Entries 2 and 4). Thus,
the sufficient amount of catalyst was determined to be
2 mg (0.01127 mmol% Pd). Also, the model reaction did
not give any product when no catalyst was used (Table 1,
Entry 5). After optimized catalyst loading and reaction
temperature, different bases used model reaction. The
K2CO3 base seems an appropriate base due to the high
solubility feature in water (Table 1, Entries 6–10). When
it comes to choosing the proper solvent for the catalytic
system, the solvents such as 2-propanol, EtOH, water,
dimethylformamide (DMF), and dioxane did not give
good results due to insolubility or low solubility of
4-bromoacetophenone and PhB (OH)2 in the same sol-
vent (Table 1, Entries 11–18). The polar solvents mixture
such as 2-propanol/H2O mixture (1:2, v/v) creates the
best solvent environment for the catalyst to give high
efficiency. This solvent mixture causes good solubility
in both substrates in the same environment. This
aqueous mixture stands out as the best solvent for
the reaction since they mix well with each other.
4-chloroacetophenone also tried to show the efficiency of
catalyst on aryl chloride substrate. Unfortunately, no
product formed in the reaction of 4-chloroacetophenone
under the same reaction condition settled for aryl
bromides (Table 1, Entry 19). However, an average yield
was obtained in the reaction performed at 80ꢀC for
12 h (Table 1, Entry 20). From these results, the
the crystal phase to the new stage, losing some
oxygen and nitrogen ions from the structure, and
condensation of the silanol groups of MCM-41.[22,33] So
the Magnetite@MCM-41@NHC@Pd phase has stability
without any decomposition up to 234ꢀC which can be
used for catalytic reactions in this temperature range.
FIGURE 7 Differential thermal analysis (DTA) and
thermogravimetric analysis (TGA) curve of Magnetite@MCM-
41@NHC-Pd catalyst
FIGURE 8 Magnetization of the Magnetite@MCM-
41@NHC@Pd catalyst in the i-PrOH

AKKOÇ ET AL.
9 of 21
TABLE 1 Optimization of the
conditions of phenylboronic acid and
4-bromoacetophenone catalyzed by 3
Entry
1
Catalyst loading
2 mg
1 mg
4 mg
0.5 mg
-
Base
Solvent
Temp./time
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 0.5 min
rt, 12 h
aYield %
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
NaOH
Na2CO3
Cs2CO3
KtOBu
KOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O/i-PrOH
H2O
100
56
100
15
0
2
3
4
5
6
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
2 mg
75
66
58
40
33
3
7
8
9
10
11
12
13
14
15
16
17
18
19
20
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
i-PrOH
8
EtOH
5
DMF
12
6
Dioxane
DMF/H2O
H2O/EtOH
H2O/Dioxane
H2O/i-PrOH
H2O/i-PrOH
68
92
56
2
80ꢀC, 12 h
80
aReaction conditions: Magnetite@MCM-41@NHC@Pd (2 mg, 0.01127 mmol%Pd), phenylboronic acid
(0.6 mmol), 4-bromoacetophenone (0.5 mmol), base (1.0 mmol), and solvent (3 ml). Gas chromatography
(GC) yields determine according to 4-bromoacetophenone using (trifluoromethyl)benzene as an internal
standard.
developed catalytic system here is more suitable for
cross-coupling reactions of aryl bromides than aryl
chlorides. As a result of the reactions tested with different
parameters, the optimum reaction condition determined
as follows: 2 mg (0.01127 mmol% Pd) of catalyst,
0.5-mmol ArBr, 0.6-mmol PhB (OH)2, 1-mmol K2CO3,
and 2-propanol/H2O mixture (1:2, v/v) at room
temperature.
The optimization reaction condition on hand, the
Suzuki–Miyaura cross-coupling reaction of different
aryl bromides with various phenylboronic acid deriva-
tives, was examined (Table 2). First, the cross-coupling
reaction of various electron-withdraw p-substituted aryl
bromides contains CN, NO2, COCH3, CH3, OCH3, and
CF3 groups with substituted phenylboronic acid such
as 4-tert-buthylboronic acid, 2-methoxyboronic acid,
and 3-formyl-4-methoxybornic acid investigated. The
results clearly showed that the reaction could be
completed in 0.3–5 min with excellent yields for
electron-withdrawing substituted aryl bromides and
substituted phenylboronic acids. The Suzuki cross-
coupling reaction of electron-donating aryl bromides
with substituted phenylboronic acids takes a longer
time for high yields. Besides, the cross-coupling reac-
tion of o-substituted aryl bromides with boronic acid
derivatives needs more reaction time due to the
substituted group's steric hindrance. The cross-coupling
reaction of 5-bromofuraldehyde was also tested, and
the result was satisfactory (Table 2, Entry 10). In the
coupling reaction of 2,6-dibromopyridine, mono or
diarylated products were obtained with high or moder-
ate selectivity, depending on the type of phenylboronic
acid used (Table 2, Entries 12, 34, 41, and 47). The
cross-coupling reactions of heteroaryl compounds can
be important for different applications such as biologi-
cal and doing more chemistry.

10 of 21
AKKOÇ ET AL.
TABLE 2 Suzuki–Miyaura cross-coupling reactions catalyzed by Magnetite@MCM-41@NHC@Pd catalyst
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
1
15
15
15
0.3
100
2217/8867
2230/8740
2229/8379
2228/405056
2
3
4
98
94
100
5
6
7
0.3
0.3
5
100
100
95
2195/399040
2246/408404
2192/24992
8
9
1
100
100
2192/131538
2333/406016
0.3

AKKOÇ ET AL.
11 of 21
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
10
1
100
2229/133760
11
1
32
65
2254/131197
12
13
14
15
16
15
60
60
60
1
100
2245/6734
2217/1751
2230/1627
2229/1315
2228/133668
79
73
59
100
(Continues)

12 of 21
AKKOÇ ET AL.
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
17
1
100
2195/131683
18
19
20
21
22
1
3
1
1
3
100
2246/134773
2192/41215
2192/131538
2233/133985
2254/29756
94
100
100
66
23
24
10
10
94
2217/12502
2230/13378
100

AKKOÇ ET AL.
13 of 21
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
2229/12970
Entry Ar–B (OH)2
Ar–Br
Product
)
25
10
97
26
0.3
100
2228/405056
27
28
29
0.3
0.3
2
100
100
100
2195/399040
2246/408404
2192/65769
30
31
0.3
0.3
100
100
2192/398601
2233/406016
32
33
1
1
100
38
2229/133760
2254/135254
(Continues)

14 of 21
AKKOÇ ET AL.
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
62
34
15
65
2245/8979
35
35
36
37
38
20
20
20
2
94
100
100
100
2217/6251
2230/6689
2229/6686
2228/66834
39
2
100
2192/65769

AKKOÇ ET AL.
15 of 21
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
40
1
9
2254/135254
91
41
15
75
25
2245/8979
42
43
1
1
100
2228/133668
2192/131538
100
(Continues)

16 of 21
AKKOÇ ET AL.
TABLE 2 (Continued)
Time
(min)
Yield
(%)[a]
TON/TOF/
(h−1
Entry Ar–B (OH)2
Ar–Br
Product
)
44
1
100
2195/131683
45
46
1
3
100
2246/134773
2254/45084
62
38
47
15
54
35
2245/7991
aReaction conditions: Magnetite@MCM-41@NHC@Pd (0.01127 mmol% Pd), phenylboronic acid (0.6 mmol), aryl bromide (0.5 mmol), base (1.0 mmol),
i-PrOH/water (1:2, 3 ml), room temperature. Gas chromatography (GC) yields determine according to aryl bromide using (trifluoromethyl)benzene as an
internal standard.
The reusability of the catalyst was examined in the
coupling of 4-bromoacetophenone with PhB (OH)2. The
results from reusing this catalyst are shown in Figure 9.
For this purpose, after each reaction, the catalyst was
removed from reaction media by a magnet and prepared
for the next run by washing with 2-propanol and water
and dried at 80ꢀC for 3 h. The results show that the Mag-
netite@MCM-41@NHC@Pd catalyst can be used up to
10 times without a significant decrease in its catalytic
performance.

AKKOÇ ET AL.
17 of 21
FIGURE 9 Recyclability of
the Magnetite@MCM-
41@NHC@Pd catalyst for the
Suzuki–Miyaura cross-coupling
reaction
FIGURE 10 (a) The scanning electron microscopy (SEM) image and (b) energy disperse X-ray analysis (EDX) spectra of 10 times used
catalyst
A filtration test was performed at room temperature
to understand whether the palladium is leaching from
the catalyst structure while performing the reaction. For
this aim, we used 4-methoxybenzene with phenylboronic
acid. Five minutes after starting the reaction, the catalyst
was removed from the reaction medium by a magnet.
Meanwhile, the sample taken from the reaction medium
analyzes by GC. The rest solution, with no catalyst, was
stirred for a further 5 min at room temperature. After
5 min, the sample for GC analysis was taken. According
to the GC results, the yield was observed the same after
the 5th and 10th minutes. It concludes that the Pd metal
did not leach out, and the catalyst seems to be very stable
under these reaction conditions. To validate the room
temperature filtration test, the Pd amount in the 10 times
used catalyst was determined by ICP-OES analysis and
found a value very close to the initial amount (0.589 wt%
Pd), which indicated that the leaching of Pd from the
support material is very limited and thus not affect to
catalyst performance significantly. For this reason, the
reused catalyst can catalyze 10 times Suzuki reactions
without substantially losing performance. The strong
sigma NHC ligand bond with the Pd metal plays a vital
role in preventing Pd leaching from the support material.
As it is known, NHCs show powerful sigma donor
properties than many known famous ligands such as
phosphines and pyridine. These are some of the prime
properties in both heterogeneous catalysis and homoge-
neous catalysis.
3.2 | Characterization of the recovered
catalyst
The SEM and EDX analysis were used to investigate the
changes in the catalyst structure and stability. The SEM
and EDX results show minimal structural changes and
agglomeration on the catalyst structure (Figure 10). The

18 of 21
AKKOÇ ET AL.
slight decrease in the catalytic performance of the cata-
lyst supports these data.
should be due to the heterogeneous nature of the Mag-
netite@MCM-41@NHC@Pd.
After these catalytic reactions, our Magnetite@MCM-
41@NHC@Pd catalyst has shown fanciful catalytic activ-
ity on the Suzuki–Miyaura reaction of various boronic
acids and different aryl bromides. Comparing the
activities of our catalyst with similar types of magnetic or
nonmagnetic heterogeneous palladium catalysts in
Suzuki reactions,[37,39,77–85] it shows that the catalyst in
this study has better catalytic activity and applications
than many reported similar catalysts (Table 3). In the
literature,[37,39,77–85] the most of the Suzuki–Miyaura
cross-coupling reactions catalyzed by similar types of
catalysts require high temperatures for coupled product
formation. However, in our catalytic system, similar
products were easily synthesized at room temperature
with high yields and very high turnover frequency (TOF)
values. Furthermore, it is seen that the amount of catalyst
loadings in the literature is considerably higher than our
catalytic system. As far as we know, the amount of
catalyst loading at our system has the lowest value
for the Suzuki cross-coupling system. Although our cata-
lytic system positively differentiated from reported
3.2.1 | Poisoning test
The poisoning tests were performed using poly-
vinylpyrrolidone (PVP) and mercury to determine
the homogeneity/heterogeneity nature of catalysis
described here.[74–76] As shown in Scheme 1, palladium
immobilized on the surface of Magnetite@MCM-
41@NHC@Pd by a covalent bond. If the Pd metal leaches
from the catalyst structure and takes place in the reaction
solution, both heterogeneous (supported) and homoge-
neous (leached) palladium catalyze the reaction as a
catalyst. However, the homogeneous catalyst activity can
be stopped by adding ligands, which insoluble in the
reaction medium, that can bind palladium. Commercially
available PVP often uses for this purpose. Herein, the
PVP ligand was used in the poisoning test. Addition of
the PVP ligand to the Suzuki–Miyaura reaction of
4-bromoacetophenon with PhB (OH)2 did not prevent
product formation. The obtained yield was 100%, and it
TABLE 3 Comparison of Magnetite@MCM-41@NHC@Pd in the Suzuki–Miyaura reaction of 4-bromobenzonitrile with phenylboronic
acid with reported catalysts
Reference
Cat. (mol%), solvent, temperature
Time (min)
Yield (%)
Ghorbani-Choghamarani et al.[76]
CMC-NHC-Pd (0.8 mol%), EtOH/H2O (1:1), 60ꢀC,
X = Br, Xa = Cl
180, 300a
94, 52a
Karimi and Akhavan[77]
Ke te al.[78]
γ-Fe2O3-acetamidine-Pd, DMF, 100ꢀC, X = Br
Cell-NHC-Pd (0.75 mol%), DMF/H2O (1:1), 80ꢀC,
120, 30b
120
92, 96b
99
X = Br
Khajehzadeh and Moghadam[79]
Esmaeilpour et al.[39]
Pd/C-NHC-P (OR)3 (0.03 mol%), EtOH, 80ꢀC,
X = Br
60
20, 20b
60, 90b
98
98, 95b
92, 93b
Fe3O4@SiO2@VB1-Pd NPs (0.022 mol%), EtOH,
60ꢀC, X = Br
Fe3O4@SiO2-NHC-Pd(II) (0.37 mol%), H2O, 60ꢀC,
X = I
Dhameliya et al.[37]
Khazaei et al.[80]
Le et al.[81]
Pd-TEG, (0.005 mol%) H2O, 25ꢀC, X = Br
(PdII-NHC)n@SiO2 (0.27 mol%), DMF/H2O (2:1),
60ꢀC, X = Br
840
8b
91
95b
Singha Roy et al.[82]
Sobhani et al.[83]
Veisi et al.[84]
SBA-15/CCPy/Pd (II) (0.3 mol%), EtOH/H2O
(2:1), 50ꢀC, X = I
60
480b
98
95b
Fe3O4@SiO2@mSiO2-Pd (II)(0.5 mol%), EtOH,
80ꢀC, X = Br
Fe3O4@SiO2-Pd (II)(0.03 mol%), EtOH, 85ꢀC,
X = Br
65,30b
1, 15b
85, 90b
100, 100b
This work
Fe3O4@MCM-41@NHC@Pd (0.01127 mmol%,
i-PrOH/H2O (1:2), rt, X = Br
aYield obtained for 4-chlorobenzene substrate.
bYield obtained for 4-bromobenzene substrate.

AKKOÇ ET AL.
19 of 21
catalytic systems,[35,37,77–85] the disadvantage of the cata-
lytic system in this study is ineffective with aryl chloride
substrates at room temperature. Consequently, our cata-
lyst showed extraordinary catalytic activity when consid-
ering the reaction parameters such as catalyst loading,
high efficiency with aryl bromides, and reaction tempera-
ture. It may be a potential catalyst for other organic
transformations due to encouraging catalytic results.
CONFLICT OF INTERESTS
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
ORCID
Mitat Akkoç https://orcid.org/0000-0001-8641-8958
ꢀ
Nesrin Bugday https://orcid.org/0000-0002-3882-035X
Serdar Altın https://orcid.org/0000-0002-4590-907X
Sedat Yas¸ar https://orcid.org/0000-0001-7285-2761
4 | CONCLUSIONS
REFERENCES
An efficient and green Magnetite@MCM-41@NHC@Pd
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408404 h−1) with high reusability in Suzuki–Miyaura
reactions. This catalyst has high strong magnetic and dis-
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lytic activity and recovery of catalyst from reaction
media. Stability toward the air, moisture, low loading,
easy handling, and recyclability is the unique features of
our catalyst. The applicability of this catalyst in other
palladium-catalyzed catalytic systems is under research
in our lab. We expect that it will provide high catalytic
activity with reusability in different reactions.
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