Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

Catalysis Letters

https://doi.org/10.1007/s10562-021-03755-w

Highly Active Fe₃O₄@SBA‑15@NHC‑Pd Catalyst for Suzuki–Miyaura

Cross‑Coupling Reaction

Mitat Akkoç^1,2· Nesrin Buğday²· Serdar Altın³· İsmail Özdemir^2,4· Sedat Yaşar^2,4

Received: 16 March 2021 / Accepted: 22 July 2021

Abstract

A novel Pd-NHC functionalized magnetic Fe₃O₄@SBA-15@NHC-Pd was synthesized and used as an efcient heterogene-

ous catalyst in the Suzuki–Miyaura C–C bond formation reactions. The Fe₃O₄@SBA-15@NHC-Pd characterized by X-Ray

Difraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) spectroscopy, Scanning

Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray analysis (EDX), Ther-

mogravimetric Analysis (TGA), Diferential Thermal Analysis (DTA). The Inductively Coupled Plasma-Optical emission

spectroscopy (ICP-OES) analysis was used to determine the exact amount of Pd (0.33 wt%) in Fe₃O₄@SBA-15@NHC-Pd.

The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the catalyst’s structure,

while no reducing agent was used. The NHC moieties in the catalyst structure could be stabilize Pd(0) nanoparticles prevents

agglomeration. The magnetic catalyst was efectively used in the Suzuki–Miyaura cross-coupling reaction of substituted

phenylboronic acid derivatives with (hetero)aryl bromides in the presence of a K₂CO₃at room temperature in aqueous media

and magnetic catalyst could be simply extracted from the reaction mixture by an external magnet. Diferent aryl bromides

were converted to coupled-products in excellent yields with spectacular TOFs values (up to 1,960,339 h⁻¹); in the presence

of 1 mg of Fe₃O₄@SBA-15@NHC-Pd catalyst (contains 3.1×10^–6mol% Pd) at room temperature in aqueous media. After

reusability experiments, it is found that this catalyst was efectively used up to ten times in the reaction with almost consist-

ent catalytic efciency. A decrease in the activity of the 10th reused catalyst was found as 9%.

Graphic Abstract

Catalyst

Keywords Magnetic palladium catalyst · Pd(II)-N-heterocyclic carbene complex · Suzuki–Miyaura cross-coupling

reaction · SBA-15 · Magnetite

Extended author information available on the last page of the article

Vol.:(0123456789)

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M. Akkoç et al.

chemistry and catalysis during the last 30 years. NHC

ligands have been used as an alternative to phosphine

ligands in homogeneous and heterogeneous catalysis in

recent years due to their superior properties such as easy

synthesis, stability against air and moisture, non-toxicity,

strong σ-donor, and weak π-acceptor features [31, 32].

These features make an essential contribution to the s ta-

bility of the catalyst in homogeneous and heterogeneous

catalysis systems. In catalysis, Pd-NHC complexes have

ofered similar or often better results than Pd-phosphine

complexes. For this reason, Pd-NHC complexes can be

considered as one of t he bes t options as a catalyst for

Suzuki–Miyaura [32–41], Heck [42–44], Sonogashira [44,

45], and Hiyama [46 ] cross-coupling r eactions [47 ]. Thus,

the immobilization of Pd-NHC species t o support materi-

als that generate heterogeneous catalysts is being studied

intensively [47]. The core-shell structure of magnetite

nanoparticles-mesoporous Silica provides high surface

area and magnetic properties essential for heterogeneous

catalyst features. The immobilization of Pd-NHC with

MNPs coated silicates such as SiO₂, MCM-41, SBA-15

have been reported and applied on C–C bond formation

reactions successfully [48–58]. Silica-coated magnetite

was frst used with diferent ligands for immobilizing Pd

metal. For example, Dong et al. synthesized a supported

Pd(II) complex on magnetite core–shell of Fe₃O₄@SiO₂

for the Suzuki–Miyaura cross-coupling reaction [49].

They claimed that their catalyst’s reusability is high and

can catalyze the Suzuki reaction six times without sig-

nifcantly decreasing the catalyst performance at 80 °C

in EtOH. Khazaei et al. prepared nano-Fe₃O₄@SiO₂sup-

ported Pd(0) nanocatalyst and used as a catalyst on Suzuki

coupling reaction of aryl iodide and aryl bromide with

aryl boronic acid derivatives in the presence of CaO as

a base at 85 °C in aqueous media [51]. This catalyst can

also show high catalytic activity and reusability without

loss on catalytic activity after fve runs. Fafee et al. also

prepared Fe₃O₄@SiO₂supported Vitamin B1-Pd complex

and investigated its catalytic activity on Suzuki coupling

of aryl halides at 60 °C in EtOH [59]. They reported good

to high yields of coupled products of aryl halides with

substituted phenylboronic acid derivatives. Also, the cata-

lyst reported showed fve reusabilities with a slight loss of

its activity. Tai et al. prepared mesoporous Silica, which

functionalized sulfonic acid, coated magnetite-Pd catalyst,

and used as a catalyst for propionic acid’s esterifcation

reaction. They have achieved satisfactory results with fac-

ile separation and reuse [60]. Pd(II)-Schif base complex

supported to Fe₃O₄nanoparticles synthesized by Keypour

et al., and they used this heterogeneous catalyst on the

Suzuki cross-coupling reactions of aryl halides (Cl, Br,

I) with phenylboronic acid and Heck coupling reactions

of aryl halides (Br, I) with styrene [61]. After that, recent

1 Introduction

Magnetic nanoparticles (MNPs) and mesoporous materials

take attention in recent years due to their outstanding prop-

erties in the context of green chemistry. The applications

of MNPs in the various felds are getting increase due to

the versatility of MNPs, such as low toxicity, biocompat-

ibility, and high magnetic susceptibility [1–4]. Last 3 dec-

ades, porous materials are prevalent beca use of the large

surface area combined with uniform pore size, well-defned

pores, enhanced accessibility, and their ability to anchor

diverse chemical functionalities on their surface. Santa Bar-

bara Amorphous (SBA), which is one of the most popular

a porous material, was considered a suitable candidate for

many applications such as catalysis, adsorption, immobi-

lization, drug delivery, and chromatographic techniques

thanks to their well-defned pore structure, large pore size,

inert matrix, thick pore layer, and high thermal and hydro-

thermal stability [5–8]. Diferent types of SBA materials

such as SBA-1 (Pm3n, cubic), SB A -15 (P6mm, hexago-

nal), and SBA-16 (Im3m, cubic) [9–11] were reported in

the literature. According to IUPAC nomenclature, SBA-15

is classifed as mesoporous materials [12–15] due to pore

size between 2 and 50 nm. For these reasons, it has been

considered for the simple functionalization inside for metal

removal [16], the release of large molecules [17], and as

support for catalysts [18].

Recently, scientists have studied the catalytic potential of

mesoporous materials. Kqnoevenagel condensation, biomass

transformations, selective oxidation reactions in the conver-

sion of hydrocarbons and hydrodesulfurization, and C–C

bond formation reactions have been performed using diverse

mesoporous MCM-41, MCM-48, MCM-50, SAB-15, SiO₂,

SBA-16 as support materials [19–22]. Suzuki–Miyaura,

Negishi, Hiyama, Mizoroki–Heck, Sonogashira-Hagihara,

and Stille are the most efective palladium-catalyzed C–C

bonds formations reactions ever reported between two mol-

ecules to produce fne chemicals. The chemicals produced

by these catalytic systems are used in many industrial felds

suc h as polymers, agriculture, health, optics, and medicine

[23–27]. Therefore, it is crucial to develop catalytic systems

and catalysts to synthesize these valuable and essential prod-

ucts in green chemistry. However, the design and synthesis

of efective catalysts that can work in catalytic systems cre-

ated within green chemistry are still challenging. Immobi-

lization of homogeneous species to support materials with

a high surface area, easy functionalization capability, and

high thermal and chemical stability is a crucial method

frequently us ed to synthesize new types of heterogeneous

catalysts [28–30].

N-heteroc yclic carbenes (NHCs) have become an indis-

pensable ligand for transition metals in organometallic

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

studies have been reported to make optimum use of the

superior physical and chemical properties of mesoporous

support mater ials such as SBA-15 and MCM-41 deriva-

tives [58, 62–64].

2.2 Suzuki–Miyaura Cross‑Coupling Reaction

Aryl halide (0.5 mmol), aryl boronic acid (0.6 mmol), potas-

sium carbonate (1 mmol), and 1 mg of Fe₃O₄@SBA-15@

NHC@Pd catalyst (contains 3,1 × 10^–6mol% Pd) were

placed in the reaction tube under air, and 3 ml of 2-propanol/

water mixture (1:2, v:v) was added and stirred at room tem-

perature. Fe₃O₄@SBA-15@NHC@Pd was separated from

the reaction mixture by an external magnet after the reaction.

Then, 3 ml of water and 3 ml of DCM were added to the

reaction mixture, and the organic phase was separated by

extraction and dried over MgSO₄. All volatiles evaporated

to obtain the corresponding crude product.

To our kno wledge, a few SBA-15 supported Pd-NHC

complex catalyzed Suzuki reactions have been reported

so far [62]. Thus, we reported the synthesis and charac-

terization of the Fe₃O₄@SBA-15@NHC@Pd catalyst and

investigation of catalytic activity on Suzuki–Miyaura cross-

coupling reaction for (hetero)aryl bromides with substituted

phenylboronic acids at room temperature in aqueous media.

SBA-15 was chosen as a support material due to its high

surface area, high thermal and chemical stability, and abun-

dant Si–OH bonds that facilitate NHC ligand over -OH

group connection. As a result, the Fe₃O₄@SBA-15@NHC-

Pd catalyst showed spectacular efciency and TOFs up to

1,960,339 h⁻¹in Suzuki–Miyaura reactions with a simple

reaction condition at room temperature in aqueous media.

2.3 Synthesis

2.3.1 Synthesis of NHC Precursor

2.3.1.1 (1‑(2,3,4,5,6‑pentamethylbenzyl)‑3‑(etanole)‑ben‑

2 Experimental

2.1 General Considerations

Otherwise stated, all manipulations were carried out in aero-

bic conditions. All chemicals and solvents were purchased

from Sigma Aldrich, Fluorochem, and BLDpharm chemi-

cal companies and used as obtained. A Bruker Avance III,

400 MHz NMR spectrometer was used to perform NMR

analysis. All catalytic reactions were monitored on a Shi-

madzu GC2010 Plus system by GC-FID with an HP-5 col-

umn. New catalytic products were characterized with difer-

ent spectroscopic techniques and presented in the Supporting

Information section. The GC–MS analysis of compounds

was performed on a Shimadzu GC–MS 2010 plus using a

TRX-5 column on positive ESI mode. The FTIR analysis

was performed with a PerkinElmer Spectrum 100 Gladi-

ATR FT/IR spectrometer. The crystal structure analysis of

the synthesized powder was performed by an X-ray difrac-

tometer labeled Rigaku Rint 2000, which powered by Cu

K_αradiation was used for characterization. The scan rate

was chosen as 2⁰/min between 2° and 80°/min. The micro-

structural properties and the surface morphology of the syn-

thesized powders were investigated by Leo EVO-40 VPX

scanning electron microscope (SEM). For XPS analyse: XPS

instrument: PHI 5000 VersaProbe II, X rays: hn=1486,6 eV

monochromatic, spot 200 µm and Energy resolution (hi-res-

olution spectra): 0.8 eV were used. The TEM analyses were

performed by FEI TECNAI OSIRIS operating at 200 kV,

Morphological analysis with HAADF-STEM imaging mode,

Chemical analysis with the Super-X EDX detector system

(4 SDD detectors).

zimidazolium iodine)

The NHC precursor was synthesized according to the litera-

ture [65–67]. 2-iyodoethanole (1.8 g; 110 mmol) was added to

10 mL n-BuOH solution of 1-(2,3,4,5,6-pentamethylbenzyl)

benzimidazole (2.78 g; 100 mmol). Then, the reaction solution

was refuxed for 4 h. After the reaction cooled to room tem-

perature, yellow crystals were formed by themselves. Crystals

removed from the solution by fltration, washed diethyl ether

(5×5 mL), and dried under vacuum. Yellow crystals were

characterized by ¹H and ¹³C NMR spectroscopy.

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. Ele-

mental analysis for C₂₁H₂₇N₂OI: %Calc. C: 56.01, H: 6.04,

N: 6.22; %found C: 56.12, H: 6.14, N: 6.38.

2.3.2 Catalyst Preparation

The synthesis of the Fe₃O₄@SBA-15@NHC@Pd catalyst

was presented in Scheme 1. First, the nano magnetite (Fe₃O₄)

1 3

M. Akkoç et al.

was synthesized via the co-precipitation method reported

with modifcations using FeCl₃·6H₂O and FeCl₂·4H₂O [68].

Next, synthesized Fe₃O₄nanoparticles were coated with

Silica by tetraethylorthosilicate (TEOS) then doped in the

SBA-15 skeleton to produce Fe₃O₄@SBA-15 [62]. Then,

Fe₃O₄@SBA-15 was functionalized with the NHC ligand via

the hydroxyl group on the NHC. In the fnal step, Pd(OAc)₂

was introduced to Fe₃O₄@SBA-15@NHC to aford Fe₃O₄@

SBA-15@NHC@Pd catalyst labeled as 3 (Scheme 1). These

Pd-doped nanoparticles were characterized by TEM, SEM,

FT-IR, XRD, XPS, DTA, TGA, and ICP-OES techniques.

As a result of the ICP-OES analysis, it was determined that

catalyst 3 contains 0.33 wt% Pd (3,1×10^–6mol% Pd).

3 Result and Discussions

3.1 Catalyst Characterization

The structural properties of Fe₃O₄@SBA-15@NHC-Pd were

investigated by XRD pattern, as shown in Fig. 1. Due to the

layer-by-layer production process, the XRD pattern should

exhibit several phases, including the starting materials in

the powders. We should indicate that the XRD pattern con-

sists of an amorphous structure and crystalline phases. It

is well known that SBA-15 gives a broad peak in the XRD

pattern [69], and a similar formation was also observed in

Scheme 1 Synthesis pathway of the Fe₃O₄@SBA-15@NHC@Pd catalyst

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

bands at 3352 (OH stretching), 1445, 1563 (C–N stretching)

and C–H stretching 2920, 2964, 1078, 765, 614, 415 cm⁻¹

(Table 1) [70, 72]. After the connection of NHC to Fe₃O₄@

SBA-15 sur f ace, the bands at 3352 cm⁻¹disappeared, and

these results indicate that it was successfully performed the

functionalization of Fe₃O₄@SBA-15 with NHC. The loss

of signal at 1563 cm⁻¹(CNC stretching of benzimidazole)

was attributed to the formation of the Pd–C bond (Pd-CNC

stretching of benzimidazole) after reaction with Pd(OAc)₂.

The SEM image of Fe₃O₄@SBA-15@NHC-Pd is pre-

sented in Fig. 3a, and it is seen that the grain formation has

two diferent forms. We think that the large grain formation

may be due to the clustering of the small grains. The EDX

dot mapping analysis of Fe₃O₄@SBA-15@NHC-Pd was

presented in Fig. 3b–h, and it is seen that elements were

dispersed homogeneously on the surface.

Fig. 1 XRD pattern of Fe₃O₄@SBA-15@NHC-Pd

this study. The crystalline phase, which gives the Bragg

peaks in the pattern, was well matched by magnetite and Pd

phases. Furthermore, 2θ values at 30.47°, 35.82°, 43.63°,

53.61°, 57.31°, and 63.06° are assigned to the magnetite

phase (JCPDF number: 19-0629), the broad peaks below

2θ = 30° are matched by SBA-15 [69], and the peaks of

40.05°, 46.36° and 63.06° are assigned to Pd crystalline

phase (JCPDF number: 46-1043). According to the XRD

results, the Fe₃O₄@SBA-15@NHC-Pd catalyst was success-

fully synthesized, and the results are compatible with the

literature [62].

The HAADF-STEM analysis was used to determine the

elemental distribution in the particles (Fig. 4a). The ele-

mental distribution of the Fe₃O₄@SBA-15@NHC-Pd was

investigated by EDX analysis and revealed the presence of

the elemental distribution of C, Si, O, N, Fe, and Pd in the

Fe₃O₄@SBA-15@NHC@Pd catalyst. The particle size of Pd

was found below 100 nm (Fig. 4b). Figure 4c–g shows the

chemical analysis of the powders depending on the elements.

It is seen that Si, Fe, and O have a homogeneous distribution

in the structure which was also proven by EDX analysis.

At the same time, palladium particles have a homogeneous

distribution within the catalyst structure.

The bond structures of Fe₃O₄@SBA-15@NHC-Pd and

other chemical components were investigated by FTIR

spectroscopy (Fig. 2). The characteristic absorption peak

for Fe₃O₄was observed at 442 cm⁻¹which belongs to Fe–O

bands, and the peak at 3352 cm⁻¹associated with the O–H

stretching vibration groups on the surface and physisorbed

H₂O [70–73]. The absorption bands at 803 and 1056 cm⁻¹

were attr ibuted to Si–O–Si stretching vibrations [71, 72].

According to FT-IR analysis, Fe₃O₄was coated wit h a

silica layer successfully. The FT-IR spectra of NHC give

The structural characterization of the catalyst was con-

tinued using the X-ray photoelectron spectroscopy (XPS)

analysis and detailed XPS spectra for each ion present in

Fig. 5a–h. The XPS spectrum should be investigated by the

aspect of all layers in the Fe₃O₄@SBA-15@NHC-Pd. The

large window XPS spectrum in Fig. 5a shows the spectrum

of existing elements in the material. The XPS peaks of SBA-

15 were given in Figs. 5b and c. The Si2s, Si2p, C1s, and

O1s electrons were observed at 153, 102, 282, and 531 e V,

respectively (Fig. 5b–e). The energy level of C1s in Fig. 5c

should be related to C–C/C=C bonds [74 ]. The N1s electron

Fe₃O₄@SBA-15@NHC-Pd

Fe₃O₄@SBA-15@NHC

Table 1 FTIR characteristic absorption of NHC, Fe₃O₄@SBA-15,

Fe₃O₄@SBA-15

Fe₃O₄@SBA-15@NHC and Fe₃O₄@SBA-15@NHC@Pd

Entry

Functional group

Absorption (cm⁻¹

)

References

NHC

1

2

3

4

5

Fe–O streching

Si–O stretching

C–H bending

442

803, 1056

415, 614, 765, 1078

1186

1445, 1563

[70]

[71, 72]

[72]

C–O stretching

1000

2000

3000

4000

C–N stretching of

Wavenumber (cm^-1)

benzimidazole

6

7

C–H stretching

O–H stretching

2920, 2964

3352

[70, 72]

[73]

Fig. 2 FTIR spectra of Fe₃O₄@SBA-15@NHC-Pd and other chemi-

cal components

1 3

M. Akkoç et al.

Fig. 3 SEM image of a Fe₃O₄@

SBA-15@NHC-Pd, b elemental

dot mapping analysis of the

sample at 1kx, and individual

mapping of c Si, d Pd, e Fe, f O,

g C, h N

Fig. 4 a and b TEM images of

Fe₃O₄@SBA-15@NHC-Pd, c

EDX-dot mapping and d, e, f

and g elemental distribution of

Pd, Fe, O, and Si, respectively

peak at 397 eV in Fig. 5f is due to the imidazolate-N atom

[75], and the peak reveals at 531 eV for O1s belongs to

the O atom in the NHC ligand [76]. It is well known that

Fe3p shows the existence of Fe ions and Fe2p split into two

energy level at ∼708 eV for 2p1/2 and ∼721 eV for 2p3/2

(Fig. 5g), and it can be explained by the formation of Fe²⁺

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

1400

Si 2s

1200

1000

800

600

400

200

164 162 160 158 156 154 152 150 148 146

Binding Energy (eV)

(b)

(a)

C 1s

1600

Si 2p

1600

1200

800

400

0

1200

800

400

112

108

104

100

96

296

292

288

284

280

Binding Energy (eV)

(d)

(c)

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

O 1s

544

540

536

532

528

524

Binding Energy (eV)

(e)

(f)

(g)

(h)

Fig. 5 XPS spectra of a Fe₃O₄@SBA-15@NHC-Pd, b Si2s, c Si2p, d C1s, e O1s, f N1s, g Fe2p, and h Pd3d

1 3

M. Akkoç et al.

and Fe³⁺in the structure which is an expected result for

magnetite [77]. Figure 5h exhibits the XPS spectra of the

Pd element in the structure and gives peaks at 333.22 eV,

338.43 eV, 334,89 eV, and 340,09 eV which correspond

to 3d_5/2and 3d_3/2orbitals of metallic state Pd⁰and Pd^II,

respectively [6569]. As seen in the XPS analyzes, the syn-

thesized catal yst contains both Pd⁰and Pd²⁺. Unlike the

literature [75–79], these results show that Pd⁺²is reduced

to Pd⁰due to the heat applied in the synthesis process. The

reduction of Pd(II) without any particular reduction reagent

is the desired situation for synthesizing Pd⁰nanomaterials.

The net amount of palladium doped into the Fe₃O₄@

SBA-15@NHC was determined by ICP-OES analysis. 0.33

wt% Pd was measured in the structure of Fe₃O₄@SBA-15@

NHC-Pd.

3.2 Catalytic Studies

We performed a series of trial reactions to show the cata-

lyst’s activity on the Suzuki–Miyaura coupling reaction.

For this aim, a model reaction of bromoacetophenone and

PhB(OH)₂was chosen, and the results were presented in

Table 2. Initially, we se ttled on the reaction conditions in

our previous work [33–40], where 2-propanol/H₂O used an

ad solvent system and K₂CO₃as a base at room temperature.

After determining the solvent, these conditions were applied

to determine sufcient catalyst loading (Table 2, entries

1–4). When 1 mg of catalyst was used, the reaction was

completed simultaneously with the exact yield of 2 mg of the

catalyst used (Table 2, entries 1, 2). However, the catalyst

loading was reduced to 0.5 mg; a lower yield was obtained

(Table 2, entry 3). Thus, the sufcient amount of catalyst was

determined to be 1 mg (3.1×10^–6mol% Pd). Also, no prod-

uct formation was observed in our model reaction when no

catalyst was used (Table 2, entry 4). After defnition efcient

catalyst loading and reaction temperature, the suitability of

diferent types of bases was investigated on model reaction.

It is believed that carbonate-derived bases may be suitable

for this designed system due to their excellent solubility in

aqueous solutions (Table 2, entries 5, 6). The other standard

bases were also tried, and results showed that K₂CO₃is an

appropriate base for this designed catalytic system (Table 2,

entries 7–9). After that, we used diferent solvents and aque-

ous solutions to choose solvents for our catalytic system.

2-propanol, EtOH, water, DMF, and dioxane did not give

good results due to insolubility or low solubility of 4-bro-

moacetophenone and PhB(OH)₂at the same time (Table 2,

entries 10–17). The aqueous solution of 2-propanol (1:2,

v/v) creates the best solvent environment to reveal the cata-

lyst’s activity. The aqueous solution of 2-propanol provides

optimum solubility of the substrate and boronic acid deriva-

tives together. 4-chloroacetophenone also tried to show the

efciency of catalyst on aryl chloride substrate. Unfortu-

nately, no product formed in the reaction of 4-chloroaceto-

phenone under the same reaction condition settled for aryl

bromides (Table 2, entry 19). However, an average yield

was obtained in the reaction performed at 80 °C for 12 h

Thermogravimetric analysis was used to determine the

presence of organic groups immobilized on the surface of

Fe₃O₄@SBA-15. Thermal gravimetric analysis (TGA) and

diferential thermal analysis (DTA) of the Fe₃O₄@SBA-15@

NHC-Pd are presented in Fig. 6. DTA and TG analysis show

three regions for both data related to endothermic activity in

the samples. The mass loss at a temperature below 166.4 °C

corresponds to the removed water and solvents from the

structure [43]. The second weight loss at 166.4 °C is related

to the calcination of the NHC ligand on the catalyst. The

other two reactions at 398.2 °C and 802.9 °C are related to a

thermal transformation of the crystal phase to the new stage,

losing some oxygen and nitrogen ions from the structure and

condensation of the silanol groups of SBA-15 [22, 75]. It

can be seen from these results that the catalyst has str uctural

stability at high temperatures and can be used for catalytic

reactions in this temperature range safely.

Fe₃O₄@SBA-15@NHC@Pd catalyst has a high mag-

netic response in the solvent. Figure 7 shows that when an

external magnetic feld is applied, the catalyst shows high

magnetization quickly.

Fig. 7 Magnetic response of the Fe₃O₄@SBA-15@NHC@Pd catalyst

in the i-PrOH

Fig. 6 DTA and TGA curve of the Fe₃O₄@SBA-15@NHC-Pd

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

Table 2 Optimization of the Suzuki-cross coupling reaction of phenylboronic acid and 4-bromoacetophenone catalyzed by Fe₃O₄@SBA-15@

NHC@Pd

Entry^a

Catalyst loading

Base

Solvent

Temp/Time

Yield (%)

1

2

3

4

5

6

7

8

2 mg

1 mg

0.5 mg

–

1 mg

K₂CO₃

Na₂CO₃

Cs₂CO₃

K^tOBu

NaOH

KOH

K₂CO₃

H₂O/i-PrOH

H₂O

i-PrOH

EtOH

DMF

Dioxane

DMF/H₂O

H₂O/EtOH

H₂O/Dioxane

H₂O/i-PrOH

rt, 1 min

rt, 5 h

100

40

0

66

38

23

63

53

8

9

8

0

2

81

94

76

–

30

70

33

25

100

9

10

11

12

13

14

15

16

17

18^b

19^b

20^b

21

22

23^c

1 mg

3 mg

80 °C, 5 h

80 °C, 5 min

rt, 1 min

Pd(OAc)₂, 0,0069 mg

PdCl₂, 0.0055 mg

1 mg

^aReaction conditions: 1 mg of Fe₃O₄@SBA-15@NHC@Pd (contains 3.1×10^–6mol% Pd), phenylboronic acid (0.6 mmol), 4-bromoacetophe-

none (0.5 mmol), Base (1.0 mmol), solvent 3 ml. GC yields determine according to 4-bromoacetophenone using (trifuoromethyl)benzene as an

internal standard

^b4-Chloroacetophenone used as aryl halide

^c4-Iodoanisole is used as aryl halide

(Table 2, entry 20). The developed catalytic system here is

more suitable for cross-coupling reactions of aryl bromides

than aryl chlorides from these results. Trials were carried out

with 4-chloroacetophenone to examine the efectiveness of

the catalyst in reactions with chlorinated aryl halides. Unfor-

tunately, no product formed in the reaction of 4-chloroace-

tophenone under the same reaction condition settled for aryl

bromides in 5 h (Table 2, entry 18). It was understood from

this experiment that the Suzuki cross-coupling reaction of

chlorinated aryl halides requires heat for product formation.

Thus, we applied heat to the reaction of 4-chloroacetophe-

none with PhB(OH)₂, and an average yield was obtained in

the reaction performed at 80 °C for 12 h (Table 2, entry 19).

In order to see the efect of the catalyst loading on prod-

uct formation in the same reaction, a relatively better result

was obtained in our experiment by increasing the amount of

catalyst by three times (Table 2, entry 20). The developed

catalytic system here is more suitable for cross-coupling

reactions of aryl bromides than aryl chlorides from these

results. For comparison, diferent commercially available

palladium sources such as PdCl₂and Pd(OAc)₂were tested

at the same concentration in the catalytic system we created.

From the results we obtained, it was seen that the catalyst

we synthesized had much better activity than commercially

available palladium sources (Table 2, entries 20–22). The

reaction with 4-iodoanisole showed that the catalyst could

also have high activity in iodo aryl halides (Table 2, entries

23). After these optimization experiments, the optimum con-

ditions for the Suzuki–Miyaura coupling reactions of the

aryl bromides and substituted boronic acid derivatives are

as follows: 1 mg of catalyst (contains 3.1×10^–6mol% Pd),

1 3

M. Akkoç et al.

0.5 mmol ArBr, 0.6 mmol PhB(OH)₂, 1 mmol K₂CO₃, and

2-propanol/H₂O (1:2, v/v) at room temperature.

necessary for various applications such as biological and

doing more chemistry. 1,4-Dibromobenze was also used

on Suzuki cross-coupling reaction with diverse phenylbo-

ronic acid derivatives. Results show that both mono and di-

coupled products were formed simultaneously except in the

case of 3-formyl-4-methoxyboronic acid, where the mono-

coupled product formed selectively (Table 3, entry 22). In

other cases, the di-coupled products are formed proportion-

ally more selective than mono coupled products (Table 3,

entries 11, 33, 46). All these results show that the developed

catalytic system in this work works perfectly except for the

2-methylboronic acid case.

The optimization reaction condition on hand,

Suzuki–Miyaura cross-coupling reaction of wide-range

aryl bromides with diferent phenylboronic acid derivatives

were examined (Table 3). First, the cross-coupling reaction

of electron-withdraw p -substituted aryl bromides contains

CN, NO₂, COCH₃, CH₃, and CF₃groups with phenylbo-

ronic acid, 4-tert-buthylboronic acid, 2-methoxyboronic

acid, and 3-formyl-4-methoxyboronic acid were studied.

With this catalytic system, approximately 2 million TOFs

values were obtained for the Suzuki coupling reaction of

electron-withdrawing substrates with 4-methoxy-3-formyl-

boronic acid and napthylboronic acis (Table 3, entries 34,

35, 36, 38, 39, 41). The results clearly showed that the reac-

tion could be completed in 0.5–5 min with excellent yields

for electron-withdrawing substituted aryl bromides and sub-

stituted phenylboronic acids. The reaction of 2-bromoben-

zonitrile with phenylboronic acid derivatives was also suc-

cessfully achieved in a short time with high yields (Table 3,

entries 7, 19, 29). While the reaction of 4-bromobenzonitrile

with the same phenylboronic acid derivatives is completed

in 1 min (Table 3, entries 8, 20, 30) 2-bromobenzonitrile is

completed in 5 min. It was seen from these results that steri-

cally compelling aryl bromides prolong the reaction time

at least fve times. The cross-coupling reaction of 2-meth-

ylboronic acid with aryl bromides needs at least 12 h to get

over 90% yields. However, reactions of 2-methoxyboronic

acid with aryl bromides resulted in high yields in a short

time. From these results, it is seen that the electronic efect

of substituents on the ortho position of phenylboronic acid

more critical rather than its steric efect. Here, it is thought

that the methoxy group’s mesomeric efect is more efec-

tive than its steric efect for high yields. The Suzuki cross-

coupling reaction of electron-donating aryl bromides with

substituted phenylboronic acids takes a longer time for

high yields (Table 3, entries 1–3, 13–15, 31–33, 43–45).

Although this is the case, the Suzuki reactions of electron-

donating substrates resulted in high yields in a maximum

of 30 min. The cross-coupling reaction of heteroaryl bro-

mides was also tested, and results were delighted with the

selectivity of mono or di-coupled products (Table 3, entries

10, 12, 22, 24, 49). The 2,6-dibomopyridine with phenylbo-

ronic acid and 4-tert-butylboronic acid resulted in the high

mono-coupled product, while napthylboronic acid gave a

di-coupled product. The reaction of 5-bromofuraldehyde

with phenylboronic acid and 4-tert-boronic acid formed

coupled products with high yields in minutes. The cross-

coupling reaction of heteroaryl compounds can be signif-

cant in the content of the obtained products, which may be

The catalyst’s reusability was investigated in the Suzuki

cross-coupling reaction of 4-bromoacetophenone with

PhB(OH)₂(Fig. 8). In repeated experiments, after the reac-

tion, the catalyst was separated from the reaction medium

with a magnet’s help. It was washed with a sufcient amount

of double distilled water and ethyl alcohol and dried in the

oven at 80 °C for hours to be used in the following reac-

tion. For each recent run, new substrates were used. Losses

amount of catalyst occurring in each separation was not con-

sidered. The results showed that the catalyst exhibit excellent

performance without signifcant loss in its catalytic activity

even on the 10th run.

In order to understand the leaching of Pd from the catalyst

structure, a fltration test was performed during the reaction.

For this purpose, we chose the Suzuki–Miyaura coupling

reaction of 4-methoxybenzene with PhB(OH)₂. Five min-

utes after the reaction started, the reaction was stopped, and

the catalyst was removed from the reaction medium by an

external magnet, and the 0.1 mL of the reaction solution

was taken and analyzed by GC. Then, the solution without

catalyst was stirred at room temperature for an additional

5 min. After 5 min, another sample was taken for GC analy-

sis. After GC results, the 5th and 10th minutes yields were

found the same. In the light of these results, it can be consid-

ered that Pd metal is not leaching from the catalyst structure

under these reaction conditions. The amount of Pd in the ten

times used catalyst was determined by ICP-OES analysis

to validate the room temperature fltration test and found a

value very close to the initial amount (0.29 wt% Pd). This

result may shed light on the high catalytic activity of the

catalyst on reuse. However, the NHC ligand in the catalyst

structure may prevent the leaching of Pd metal. As is known,

NHCs are capable of forming strong covalent bonds with

transition metals. This strong covalent bond between Pd and

NHC contributes to the catalyst’s stability and saves the Pd

metal within the catalyst. The chemical stability of catalysts

is essential for both homogeneous and heterogeneous cata-

lytic systems under harsh conditions. Figure 9 shows the

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

Table 3 Suzuki–Miyaura cross-coupling of aryl bromides with substituted phenylboronic acids derivatives catalyzed by Fe₃O₄@SBA-15@

NHC@Pd

Entry

1

Ar-B(OH)₂

Ar-Br

Pruduct

Time (min)

5

Yield^a(%)

72

TON/TOF/(h⁻¹

16,121/139287

)

2

3

4

5

1

69

64

16,215/134264

16,207/124472

16,202/972133

100

5

6

7

1

5

100

94

15,961/957696

16,336/980170

15,944/179849

8

9

1

100

15,944/956643

16,240/974438

10

11

3

1

95

16,213/308053

16,121/967273

62

38

35

12

13

20

10

16,053/16856

16,121/89956

93

14

15

16

10

1

90

86

16,215/87563

16,207/83630

16,202/972133

100

17

18

19

1

5

100

15,962/957695

16,336/980169

15,944/191328

20

21

1

100

15,944/956643

16,240/974437

22

23

2

1

96

16,213/466944

16,121/967273

58

42

1 3

M. Akkoç et al.

Table 3 (continued)

Entry

24

Ar-B(OH)₂

Ar-Br

Pruduct

Time (min)

20

Yield^a(%)

43

TON/TOF/(h⁻¹

16,053/20709

)

25

26

27

28

20

1

82

80

16,121/39658

16,215/38917

16,207/35980

16,202/972133

74

100

29

30

1

94

20

65

15,944/899244

16,121/41109

31

32

33

30

91

95

89

16,121/29341

16,215/30809

16,207/28849

34

35

36

0.5

100

16,202/1944267

15,962/1915392

16,336/1960339

37

38

39

40

1

99

100

99

15,944/947076

15,944/1913287

16,240/1948875

16,394/973831

0.5

1

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

Table 3 (continued)

Entry

41

Ar-B(OH)₂

Ar-Br

Pruduct

Time (min)

0.5

Yield^a(%)

100

TON/TOF/(h⁻¹

)

16,202/1944266

42

43

44

45

46

47

48

1

100

85

15,944/956643

16,121/54812

16,215/51890

16,207/49270

15,961/957696

16,336/980170

16,394/983667

15

1

80

76

100

62

1

38

49

50

20

55

5

16,325/29386

16,202/1256

12 h

93

51

52

53

54

12 h

87

85

82

89

16,121/1169

16,215/1149

16,207/1108

15,944/1183

1 3

M. Akkoç et al.

Table 3 (continued)

^aReaction conditions: 1 mg of 3 (contains 3.1×10^–6mol% Pd), phenylboronic acid (0.6 mmol), aryl bromide (0.5 mmol), Base (1.0 mmol),

i-PrOH/water (1:2, 3 mL), room temperature (rt). GC yields determine according to aryl bromide using (trifuoromethyl)benzene as an internal

standard

Fig. 8 Recyclability of the

catalyst for the Suzuki–Miyaura

cross-coupling reaction

Recyclability

100

95

90

85

80

1

2

3

4

5

6

7

8

9

10

Run

3.2.2 Poisoning Test

O

Si

O

Si

As it is known from the literature, the commercially avail-

able PVP and mercury are used for poisoning tests of cata-

lysts to determine the nature of catalysis [80–82]. According

to the XPS analysis, it is understood that t he Pd metal is

bound to the NHC ligand by a covalent bond. If it is consid-

ered that some Pd leach from the structure of the catalyst and

passes into the solution, both heterogeneous (supported) and

homogeneous (leached) catalytic systems take palace. How-

ever, the activity of the homogeneous catalyst can be stopped

by adding PVP ligands to bind palladium. Herein, the PVP

ligand has been used to inhibit Pd metals in the solution. On

the other hand, the addition of water-insoluble PVP to the

reaction of 4-bromoastophenone with phenylboronic acid

does not afect the reaction yield. This result suggests that

the catalyst described here has only heterogeneous.

O

Si

O

Si

O

S i

O

S

i

O

Si

O

Ar-X

O

Ar-Ph

Fe₃O₄@SBA-15@NHC@Pd

Ar

X

Ph

Ar

Reductive

elimination

Oxidative

addition

O

Si

O

Si

O

Si

O

Si

O

S i

S

O

i

O

Si

O

Si

O

Si

O

Si

O

S i

O

Transmetallation

Si

O

Si

O

S i

O

Si

O

K₂CO₃

PhB(OH)₃

+ B(OH)₃

X

PhB(OH)₂

After many catalytic reactions, our Fe₃O₄@SBA-15@

NHC-Pd catalyst has shown high catalytic activity on

the Suzuki–Miyaura cross-coupling reaction for various

boronic acids and aryl bromides. Comparing the activities

of Fe₃O₄@SBA-15@NHC-Pd catalyst with similar types of

palladium catalysts on Suzuki–Miyaura coupling reactions

[83–85], it is seen that our catalyst has excellent catalytic

activity, spectacular TOFs values, and good recy clability

than many reported catalysts (Table 4) [48, 51, 79, 84–92].

Generally, most reported catalysts req uire high tem per ature

and high catalyst loading on Suzuki–Miyaura cross-coupling

reactions of aryl bromides with phenylboronic acid [48, 51,

79, 84–92]. In contrast, similar products were easily synt he-

sized at r oom temperature with high yields and spectacular

TOFs values via our catalyst. Another advantage of our cata-

lyst is the number of catalyst loadings. As seen in Table 4,

the reported works’ catalyst loadings are much higher than

Fig. 9 Proposed reaction mechanism of the Suzuki–Miyaura cross-

coupling reaction catalyzed by Fe₃O₄@SBA-15@NHC-Pd catalyst

possible mechanism of the Suzuki coupling reaction cata-

lyzed by Fe₃O₄@SBA-15@NHC-Pd catalyst schematically.

3.2.1 Characterization of the Recovered Catalyst

To see the changes in the used catalyst structure, the SEM

and EDX analyses were carried out. According to the SEM

and EDX analyses, there were small agglomerations without

severe catalyst structure changes (Fig. 10).

1 3

Highly Active Fe₃O₄@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

Fig. 10 SEM image and EDX spectrum of recycled catalyst

Table 4 Comparison of Fe₃O₄@SBA-15@NHC@Pd in the Suzuki–Miyaura reaction of 4-bromobenzonitrile with phenylboronic acid with

reported catalysts

Refs

Cat. (mol%), solvent, temperature

Time (min)

Yield (%)

[48]

[51]

[79]

[84]

[85]

[86]

[87]

SBA-15/CCPy/Pd(II) (0.3 mol%), EtOH/H₂O (2:1), 50 °C, X=I, X^b=Cl

Fe₃O₄@SiO₂-Pd(II)(0.03 mol%), EtOH, 85 °C, X=Br

60

98

65, 30^a

20, 20^a

120, 30^a

180, 300^b

120

85, 90^a

98, 95^a

92, 96^a

94, 52^b

99

Fe₃O₄@SiO₂@VB1-Pd NPs (0.022 mol%), EtOH, 60 °C, X=Br

γ-Fe₂O₃-acetamidine-Pd, DMF, 100 °C, X=Br

CMC-NHC-Pd (0.8 mol%), EtOH/H₂O (1:1), 60 °C, X=Br, X^b=Cl

Cell-NHC-Pd (0.75 mol%), DMF/H₂O (1:1), 80 °C, X=Br

Pd/C-NHC-P(OR)₃(0.03 mol%), EtOH, 80 °C, X=Br

60

98

[88]

[89]

[49]

[90]

[91, 92]

This work

Pd-TEG, (0.005 mol%) H₂O, 25 °C, X=Br

840

91

(Pd^II-NHC)_n@SiO₂(0.27 mol%), DMF/H₂O (2:1), 60 °C, X=Br

Fe₃O₄@SiO₂@mSiO₂-Pd(II)(0.5 mol%), EtOH, 80 °C, X=Br

Fe₃O₄@SiO₂-NHC-Pd^(II)(0.37 mol%), H₂O, 60 °C, X=I

Fe₃O₄@MCM-41@NHC@Pd (0.01127 mmol%, i-PrOH/H₂O (1:2), rt, X=Br

Fe₃O₄@SBA-15@NHC@Pd (3.1×10^–8mol Pd, i-PrOH/H₂O (1:2), rt, X=Br

8^a

95^a

480^a

95^a

60, 90^a

1, 15^a

1, 5^a

92, 93^a

100, 100^a

100,72^a

^aYield obtained for 4-bromobenzene substrate

^bYield obtained for 4-chlorobenzene substrate

our catalytic system. However, our catalytic system does

not have the same efectiveness for aryl chlorides at room

temperature despite these superior features. For example,

although product formation is observed when the heat is

applied to the Suzuki reaction of 4-chloroacetophenone with

PhB(OH)₂, the result is still unsatisfactory.

the amount of active catalyst, high reusability, high yields,

and a reasonably wide substrate tolerance, this catalytic

system seems to be more efective than the Pd catalyzed

Suzuki–Miyaura catalytic systems reported so far. Therefore,

we hope that this catalyst may have the potential for other

C–C bond formation reactions that require high temperatures

from these results.

Consequently, this catalyst showed extraordinary cata-

lytic activity on Suzuki–Miyaura reactions of very wide

aryl bromides and substituted PhB(OH)₂. When considering

1 3

M. Akkoç et al.

12. Chen Y, Wang M, Zhang L, Liu Y, Han J (2017) RSC Adv

7:47104–47110. https://doi.org/10.1039/C7RA09947A

13. Nasrollahzadeh M, Issaabadi Z, Tohidi MM, Mohammad Sa jadi S

(2018) Chem Rec 18:165–229. https://doi.org/10.1002/tcr.20170

0022

4 Conclusions

We could synthesize essential chemicals for many felds with

the catalytic system composed of a highly active and reus-

able magnetic Fe₃O₄@SBA-15 supported NHC-Pd catalyst

within the boundaries of green chemistry. In this catalytic

system we created, the catalyst reached very high TOF val-

ues. This novel catalyst showed spectacular catalytic activity

for an extensive range of aryl bromides in Suzuki–Miyaura

cross-coupling reactions with high reusability without

activity loss. The catalyst’s facilitating features, such as

the catalyst’s chemical stability, together with its moisture

and oxygen tolerance, high reusability, and strong magnetic

properties, make the catalyst very attractive. The appli-

cability of this catalyst in other palladium-catalyzed C–C

bond formation systems is under research. We expect that it

will provide high catalytic activity with reusability in other

reactions.

14. Komiyama T, Minami Y, Furuya Y, Hiyama T (2018) Angew

Chem 130:2005–2008. https://doi.org/10.1002/anie.201712081

15. Komiyama T, Minami Y, Furuya Y, Hiyama T (2018) Angew

Chem Int Ed 57:1987–1990. https://doi.org/10.1002/anie.20171

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Chem 31:1537–1544. https://doi.org/10.13005/ojc/310331

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1:1–14. https://doi.org/10.1155/2015/972025

18. Vavsari VF, Ziarani GM, Badiei A (2015) RSC Adv 5:91686–

91707. https://doi.org/10.1039/C5RA17780D

19. Ghorbani-Choghamarani A, Tahmasbi B, N oori N, Ghafouri-

Nejad R (2017) J Iran Chem Soc 14:681–693. https://doi.org/10.

1007/s13738-016-1020-x

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J Magn Magn Mater 448:199–207. https://doi.org/10.1016/j.

jmmm.2017.09.018

21. Saeedi MS, Tangestaninejad S, Moghadam M, Mirkhani V,

Mohammadpoor-Baltork I, Khosropour AR (2013) Polyhedron

49:158–166. https://doi.org/10.1016/j.poly.2012.09.026

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3708646

Supplementary Information The online version contains supplemen-

tary material available at https://doi.org/10.1007/s10562-021-03755-w.

Acknowledgements XPS and TEM studies performed in France

(CEA LETI/DTSI/SCMC Grenoble Cedex 9 FRANCE and thanks

to N. GAMBACORTI for the organization of XPS and TEM analy-

sis) within the framework of the NFFA-Europe Transnational Access

Activity (NFFA Project ID: 723).

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(2016) Appl Organometal Chem 30:843–851. https://doi.org/10.

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M. Akkoç et al.

Authors and Afliations

Mitat Akkoç^1,2· Nesrin Buğday²· Serdar Altın³· İsmail Özdemir^2,4· Sedat Yaşar^2,4

2

* Mitat Akkoç

mitat.akkoc@ozal.edu.tr

Catalysis Research and Application Center, İnönü University,

44280 Malatya, Turkey

3

4

* Sedat Yaşar

sedat.yasar@inonu.edu.tr

Faculty of Science and Arts, Department of Physics, İnönü

University, 44280 Malatya, Turkey

Faculty of Science and Arts, Department of Chemistry, İnönü

University, 44280 Malatya, Turkey

1

Hekimhan Vocational College, Department of Property

Protection and Security, Malatya Turgut Özal University,

Hekimhan, Malatya, Turkey

1 3

Article Doi

Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction

DOI: 10.1007/s10562-021-03755-w

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Full text of DOI:10.1007/s10562-021-03755-w

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