Synthesis and characterization of Pd-γ-Fe2O3 nanocomposite and its application as a magnetically recyclable catalyst in ligand-free Suzuki-Miyaura reaction in water

Article abstract of DOI:10.1016/j.jorganchem.2018.06.016

A novel redox-driven method to synthesize Pd-γ-Fe₂O₃ nanocomposite from Fe₃O₄ and PdCl₂ under modified hydrothermal technique has been developed. The synthesized nanocomposite was characterized by XRD, FT-IR, XPS, FESEM, TEM and EDX to understand the composition as well as morphology. The Pd-γ-Fe₂O₃ nanocomposite was found to show excellent catalytic activity towards Suzuki-Miyaura cross-coupling reactions in water without the assistance of ligands, organic solvents or phase transfer catalysts. A wide range of functional substitutions in aryl halide as well as arylboronic acid moieties is tolerated in the developed protocol. The nanocatalyst can be recovered magnetically, and reused up to six cycles without significant loss in its catalytic activity.

Full text of DOI:10.1016/j.jorganchem.2018.06.016

Accepted Manuscript
Synthesis and characterization of Pd-γ-Fe O nanocomposite and its application as a
2 3
magnetically recyclable catalyst in ligand-free Suzuki-Miyaura reaction in water
Dipankar Paul, Siddheswar Rudra, Prabin Rahman, Snehadrinarayan Khatua, Mukul
Pradhan, Paresh Nath Chatterjee
PII:
S0022-328X(18)30350-4
10.1016/j.jorganchem.2018.06.016
JOM 20475
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 11 May 2018
Revised Date: 19 June 2018
Accepted Date: 21 June 2018
Please cite this article as: D. Paul, S. Rudra, P. Rahman, S. Khatua, M. Pradhan, P.N. Chatterjee,
Synthesis and characterization of Pd-γ-Fe O nanocomposite and its application as a magnetically
2 3
recyclable catalyst in ligand-free Suzuki-Miyaura reaction in water, Journal of Organometallic Chemistry
(2018), doi: 10.1016/j.jorganchem.2018.06.016.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Synthesis and characterization of Pd-γ-Fe2O3 nanocomposite and its
application as a magnetically recyclable catalyst in ligand-free Suzuki-
Miyaura reaction in water
Dipankar Paul,a,† Siddheswar Rudra,a,† Prabin Rahman,a,† Snehadrinarayan Khatua,b Mukul
Pradhan a,* and Paresh Nath Chatterjee a,*
a
Department of Chemistry, National Institute of Technology Meghalaya, Bijni Complex,
Laitumkhrah, Shillong 793003, Meghalaya, India.
b Centre for Advance Studies, Department of Chemistry, North Eastern Hill University, Shillong
793022, India.
† Equal contribution
*Corresponding author:
Email: paresh.chatterjee@nitm.ac.in
Abstract
A novel redox-driven method to synthesize Pd-γ-Fe2O3 nanocomposite from Fe3O4 and PdCl2
under modified hydrothermal technique has been developed. The synthesized nanocomposite
was characterized by XRD, FT-IR, XPS, FESEM, TEM and EDX to understand the composition
as well as morphology. The Pd-γ-Fe2O3 nanocomposite was found to show excellent catalytic
activity towards Suzuki-Miyaura cross-coupling reactions in water without the assistance of
ligands, organic solvents or phase transfer catalysts. A wide range of functional substitutions in
aryl halide as well as arylboronic acid moieties is tolerated in the developed protocol. The
nanocatalyst can be recovered magnetically, and reused up to six cycles without significant loss
in its catalytic activity.
Keywords
Pd-γ-Fe2O3, Nanocomposite, Ligand-free, Suzuki-Miyaura cross-coupling reaction, Magnetically
recyclable.
1. Introduction
Biaryls are important building blocks in the field of pharmaceuticals, natural products,
agrochemicals, fine chemicals, functional materials and valuable ligands for catalysis.1 Although
there are several methods by which biaryl compounds can be synthesized, Suzuki-Miyaura (SM)
cross-coupling reactions, between aryl halides and organoboron reagents, are generally preferred

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for the low toxicity of substrates and mild reaction conditions.2 Conventionally, SM reactions are
performed using homogeneous palladium catalysts in the presence of phosphorous based
ligands,3 Schiff bases,4 N-heterocyclic carbenes,5 amines,6 and palladacycle complexes7 etc.
Recently researchers have developed ligand-free SM reactions using simple palladium precursors
9
such as Pd(OAc)2,8 PdCl2 etc. in homogeneous reaction medium. Despite the high reactivity and
selectivity of the homogeneous palladium catalysts, they have limited applications in industrial
processes due to the difficulties associated with the removal, recovery, and recycling of
expensive palladium precursors. To overcome these issues, the ligand-free, palladium-based
heterogeneous catalytic methods are developed for SM reactions,10 with the improvements in
handling and separation. In another blooming approach, the catalytic prowess of palladium
nanoparticles (PdNPs) is explored in the synthesis of biaryl compounds by SM reactions.11 An
increased surface area to volume ratio renders the nanoparticles very efficient towards
catalysis.12 However, to avoid agglomeration and to provide ease in purification, PdNPs are
required to be stabilized or immobilized on solid supports.12a-b,13 Over the years, various
supports, such as polymers,10e,14 resins,15 silica4f,11c,16 and metal oxides17 etc. are used to host and
stabilize the catalytically active PdNPs for SM reaction. Alternatively, in-situ generated PdNPs,
synthesized from palladium salts and appropriate reducing agents, are also known to catalyze the
SM reaction.18 However, the recyclability of these PdNPs is limited due to a problematic
separation of the expensive catalysts from the reaction mixture. Currently, the use of magnetic
nanoparticles (MNPs), as promising support, has made the physical separation of the catalysts
extremely convenient by an external magnet12c,19 after the completion of SM reaction. In this
context, various Pd(II) species, grafted on the surface-functionalized iron oxide (mostly Fe3O4
and γ-Fe2O3) MNPs, are utilized as efficient heterogeneous catalysts for promoting SM
reaction.20 There have been a variety of reports where Pd(0) NPs are strategically immobilized
on Fe3O4 and γ-Fe2O3 MNP support to achieve the combined advantages of catalytically active
Pd(0)NPs and easily separable iron oxide MNPs.21 Mostly, an external reducing agent21b-c,e-g,i-m,o
or a reducing solvent21a,h,n is used to convert the surface immobilized Pd(II) precursors to Pd(0)
on the iron oxide magnetic support. It is proposed in some recent literature that, the ultrasonic
waves21p and various hydroxyl and carboxyl functionalities present in carbon quantum dots
(CQD)21q can reduce Pd2+ ions to Pd(0) on Fe3O4 magnetic support. Veinot et. al reported that
Fe(0) core of Fe@FexOy nanoparticles not only reduces Pd2+ ions to catalytically active

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palladium metal but the core-shell NPs also act as a magnetically active support.21d Herein, we
report a novel method to synthesize magnetically retrievable Pd-γ-Fe2O3 nanocomposite from
PdCl2 and Fe3O4 MNPs under modified hydrothermal technique (MHT)22 (Scheme 1). In our
synthetic process, the Pd2+ ions are reduced to Pd(0) by the Fe(II) ions, already present in the
Fe3O4 mixed oxide, in water medium under MHT. The most intriguing feature of our recipe is
this in-situ reduction of Pd(II) by Fe(II) ions where no external reducing agents or reducing
solvents are utilized for the synthesis of the nanocomposite. This nanocomposite is applied to
catalyze the SM cross-coupling reaction in water without the assistance of any ligand, or phase
transfer catalyst (Scheme 2). Most importantly, the nanocatalyst is recovered magnetically and
reused for six cycles without significant loss in its catalytic efficiency.
Scheme 1: Synthesis of Pd-γ-Fe2O3 nanocomposite
Scheme 2: Suzuki-Miyaura coupling reaction catalyzed by Pd-γ-Fe2O3 nanocomposite in water
2. Experimental
2.1 Synthesis of magnetic Fe3O4 nanoparticles
For the synthesis of Fe3O4 nanoparticles, Fe(acac)3 (0.356 g, 1 mmol) and Mohr’s salt (0.196 g,
0.5 mmol) were dissolved in 10 mL distilled water in a screw cap tube. The solution was
deoxygenated with nitrogen gas for 15 min, followed by addition of 0.8 g (20 mmol) of NaOH in
it. After that, the solution was heated in a modified hydrothermal setup, at ~180 °C, for 48 h. The

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black precipitate of Fe3O4 obtained from the reaction mixture was washed thoroughly with
distilled water until the pH of the solution was neutral.
2.2 Synthesis of Pd-γ-Fe2O3 nanocomposite
PdCl2 (0.044 g, 0.25 mmol) along with the already synthesized Fe3O4 nanoparticles were jointly
dispersed in 10 mL distilled water in a screw cap tube. The dispersed solution was heated in a
modified hydrothermal setup, at ~180 °C. After 48 h, the brownish-black solid obtained from the
reaction mixture was washed several times with distilled water. The brownish black Pd-γ-Fe2O3
nanocomposite was isolated from the aqueous solution by magnetic separation and dried at room
temperature in a vacuum desiccator for several hours. The nanoparticles were characterized by
powder XRD, FT-IR, XPS, FESEM, TEM and EDX.
2.3 Characterizations
Powder X-ray diffraction (XRD) data were recorded with a Philips PW1710 diffractometer.
Fourier transform infrared (FT-IR) spectroscopy was performed by using PerkinElmer Spectrum
Two spectrometer in the transmission mode using potassium bromide (KBr) pellet method. Field
emission scanning electron microscopy (FESEM) analysis was done with a Supra 40, Carl Zeiss
Pvt. Ltd. with an energy dispersive X-ray (EDX) machine (Oxford link and ISIS 300) attached to
it. Transmission electron microscopy (TEM) analysis was performed in a JEOL 2100, operating
at an acceleration voltage of 300 kV. X-ray photoelectron spectroscopy (XPS) analysis was
1
performed with PHI 5000 Versa Probe II, FEI Inc. scanning XPS microprobe. H and 13C NMR
spectra were measured on a Bruker Avance II (1H NMR: 400 MHz and 13C NMR: 100 MHz)
spectrometer.
2.4 General procedure for Suzuki-Miyaura reaction
5 mL distilled water was taken in a 25 mL round bottom flask, equipped with a water condenser
and a magnetic bar, and deoxygenated with nitrogen gas for 5 min. Aryl halide (1 mmol),
arylboronic acid (1.2 mmol), NaOH (1.2 mmol) and Pd-γ-Fe2O3 (20 mg) were added to it and
allowed to stir at 80 °C under nitrogen atmosphere. The progress of the reaction was monitored
by TLC. After completion of the reaction, the catalyst was recovered using an external magnet.
The reaction mixture was extracted with EtOAc (3 x 10 mL) and the combined organic layer was

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washed with water, brine solution and dried over anhydrous Na2SO4. The crude product was
concentrated in a rotary evaporator and purified by column chromatography. The purified
compounds were characterized by 1H and 13C NMR.
3. Results and Discussion
The Pd-γ-Fe2O3 nanocomposite was synthesized according to the aforementioned redox-driven
procedure (Scheme 1). At first, we synthesized Fe3O4 MNPs by the co-precipitation of Fe(acac)3
and Mohr’s salt in alkaline medium under MHT. Then, the Pd-γ-Fe2O3 nanocomposite was
obtained by reducing PdCl2 to Pd(0) by Fe(II) ions of the Fe3O4 MNPs in water under MHT
(E0
= 0.771 V and E0
= 0.951 V). The as-synthesized nanocomposite was
Pd(II)/Pd(0)
Fe(III)/Fe(II)
characterized by powder XRD, FT-IR, XPS, FESEM, TEM and EDX.
Powder XRD measurement of the synthesized Pd-γ-Fe2O3 nanocomposite was performed to
understand the crystallinity and phase purity of the nanocomposite. Figure 1 shows the XRD
pattern of the synthesized Pd-γ-Fe2O3 nanocomposite. The characteristic diffraction peaks at 2θ
= 40.21°, 46.69°, 68.01°, 82.01° and 86.51° corresponds to the (111), (200), (220), (311) and
(222) planes of Pd(0) (JCPDS card no. 87-0638) and 2θ = 30.27°, 35.76°, 43.41°, 54.20°, 57.34°
and 62.34° corresponds to the (220), (311), (400), (422), (511) and (440) planes of γ-Fe2O3
(JCPDS card no. 39-1356), respectively, in the Pd-γ-Fe2O3 nanocomposite. However, both γ-
Fe2O3 and Fe3O4 have similar powder XRD patterns (JCPDS card no. 39-1356 and 65-3107,
respectively). So, additional experiments were performed to understand the actual composition
of the nanocomposite.
Figure 1: XRD patterns of the synthesized Pd-γ-Fe2O3 nanocomposite.

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FT-IR analysis of the nanocomposite supports the existence of γ-Fe2O3 in the composite (Figure
2). The FT-IR spectrum of the composite shows absorption band at 635, 588, 562 and 453 cm-1
which matches well with the literature of γ-Fe2O3.23 In contrast, Fe3O4 shows the absorption band
at 580 and 451 cm-1.
Figure 2: FT-IR Spectra of the synthesized (a) Fe3O4 and (b) Pd-γ-Fe2O3 nanocomposite.
Furthermore, to ascertain the oxidation state of Pd and Fe present in the Pd-γ-Fe2O3
nanocomposite, the material was analysed by XPS (Figure 3). The nanocomposite containing γ-
Fe2O3 matrix shows the Fe 2p3/2 peak at 724.0 eV and Fe 2p1/2 peak at 710.5 eV which are in
excellent agreement with the literature value of the γ-phase of the iron (III) oxide.23 The satellite
peak, characteristic of the γ-Fe2O3, is also noticeable in the XPS spectrum of the Pd-γ-Fe2O3
nanocomposite at 718.0 eV. The observed XPS spectrum of Pd-γ-Fe2O3 nanocomposite shows
two peaks at 340.5 eV and 335.2 eV which are assigned to the Pd 3d3/2 and Pd 3d5/2 signals,
respectively.21p
Figure 3: XPS spectra of (a) O 1s, (b) Fe 2p and (c) Pd 3d peaks in the Pd-γ-Fe2O3
nanocomposite.

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From the FESEM analysis, we have observed the nanorod morphology of the synthesized
nanocomposite (Figure 4a). TEM image revealed that the nanorods have a diameter of around
10-15 nm (Figure 4b). The composition of synthesized nanocomposite has also been observed
from EDX analysis. The EDX pattern of the Pd-γ-Fe2O3 nanocomposite confirms the presence of
O, Fe, and Pd as evident from the weight percentage of 40.94, 51.17, 7.89 % respectively (Figure
S2, Supplementary information).
Figure 4: (a) FESEM and (b) TEM image of Pd-γ-Fe2O3 nanocomposite.
After characterizing the Pd-γ-Fe2O3 nanocomposite, we were interested to study its catalytic
prowess in SM cross-coupling reactions. In this pursuit, we began our investigation by taking 4-
bromoanisole 1a and phenylboronic acid 2a as the model substrates and the in-house synthesized
Pd-γ-Fe2O3 nanocomposite as the potential catalyst in absence of any ligand. To find the
optimum reaction conditions, we screened several protic and aprotic solvents (Table 1, entries 1-
6) and we found that water provides the best medium for the desired C-C coupling reaction. This
is particularly helpful in making our method economical, non-toxic and environment-friendly.24
Since bases are known to play a crucial role in activating the organoboron compounds by
enhancing their nucleophilicity, thus, we next studied the effect of the base on the C-C coupling
reaction between 4-bromoanisole 1a and phenylboronic acid 2a. Sodium hydroxide was found to
be the best candidate as compared to other bases (Table 1, entries 1, 7-11). The reaction failed to
proceed in absence of base making it a necessary component for the reaction (Table 1, entry 12).
It was also found that equimolar amount of NaOH is required to activate the organoboron
compound in the SM coupling reaction (Table 1, entries 1, 13-14). Furthermore, to study the
effect of temperature on SM coupling reaction, we carried out the reaction at two lower
temperatures, viz. 50 °C and 25 °C. Lowering the reaction temperature from 80 °C to 50 °C
showed a significant decline in the yield of the desired product 3a while lowering the
temperature further to 25 °C virtually stopped the desired reaction (Table 1, entry 15-16). The

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yield of desired product 3a was significantly decreased when the amount of catalyst was reduced
even after allowing longer reaction time (Table 1, entry 18-19). The reaction did not proceed at
all in absence of the Pd-γ-Fe2O3 nanocomposite (Table 1, entry 17).
Table 1: Optimization of reaction conditions for SM cross-coupling reaction.a
Yield of 3a (%)b
Entry
Solvent
Base
Temperature
Time (min)
1
2
3
4
5
6
7
8
9
10
11
12
13c
14d
15
16
17e
18f
19g
H2O
DMF
NMP
EtOH
Toluene
Dioxane
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
KOH
Na2CO3
K2CO3
Cs2CO3
Et3N
80 °C
80 °C
80 °C
reflux
80 °C
80 °C
80 °C
80 °C
80 °C
80 °C
80 °C
80 °C
80 °C
80 °C
50 °C
25 °C
80 °C
80 °C
80 °C
30
30
30
30
30
30
30
30
30
30
30
360
30
30
360
360
360
360
240
97
60
45
61
26
33
91
65
85
88
43
-
46
97
63
<5
-
-
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
36
70
a
Reaction conditions: 4-bromoanisole 1a (1 mmol), phenylboronic acid 2a (1.2 mmol), Pd-γ-
b
Fe2O3 (20 mg), base (1.2 mmol), solvent (5 mL); isolated yields; c NaOH (0.5 mmol); d NaOH
(2 mmol); e No Pd-γ-Fe2O3 catalyst; f Pd-γ-Fe2O3 catalyst (5 mg); g Pd-γ-Fe2O3 catalyst (10 mg).
After optimizing the reaction conditions, we explored the scope of the protocol by employing
functionally diverse aryl halides 1 and arylboronic acids 2 (Table 2) in the SM coupling reaction.
We observed aryl bromides 1a-g to be vastly efficient coupling agent with arylboronic acids 2
producing excellent yields of biaryls 3 within 30 min. A wide range of functional groups such as
–OMe, –Me, –tBu, –CHO, –C(O)Me, –C(O)Ph and –NO2 groups are well tolerated in the

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optimized reaction conditions (Table 2, entries 1-16). The SM cross-coupling reactions of aryl
iodides are known to be very facile and this is precisely observed in our reaction medium. The
coupling of aryl iodides (1h and 1i) with arylboronic acids (2b and 2a, respectively) completes in
10 min producing the desired biaryl derivative 3a in nearly quantitative yield (Table 2, entries
17-18). In spite of the high catalytic prowess of the Pd-γ-Fe2O3 nanocomposite, it fails to
catalyze the coupling of arylboronic acids 2a and 2b with aryl chlorides 1j and 1k, respectively,
in our reaction conditions (Table 2, entries 19-20).
Table 2: Suzuki-Miyaura cross-coupling of various aryl halides 1 with arylboronic acids 2.a
Entry
1; R, X
2; R′
Time (min)
Yield of 3 (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
1a; 4-CH3O, Br
1b; 4-CH3, Br
1c; H, Br
1d; 4-CHO, Br
1e; 4-COCH3, Br 2a; H
1f; 4-COPh, Br
1g; 4-NO2, Br
1a; 4-CH3O, Br
1d; 4-CHO, Br
1a; 4-CH3O, Br
1d; 4-CHO, Br
1a; 4-CH3O, Br
1d; 4-CHO, Br
1a; 4-CH3O, Br
1c; H, Br
2a; H
2a; H
2a; H
2a; H
30
30
30
20
20
20
20
30
30
30
30
30
30
30
30
30
10
10
360
360
3a (97)
3b (89)
3c (95)
3d (98)
3e (98)
3f (98)
3g (96)
3h (90)
3i (92)
3j (97)
3k (90)
3l (96)
3m (89)
3n (90)
3e (94)
3o (88)
3a (98)
3a (98)
-
2a; H
2a; H
2b; 4-CH3O
2b; 4-CH3O
2c; 4-C(CH3)3
2d; 4-Cl
2d; 4-Cl
2e; 4-F
2e; 4-F
2f; 4-COCH3
1e; 4-COCH3, Br 2g; 3-NO2
1h; H, I
1i; 4-CH3O, I
1j; 3-NO2, Cl
1k; H, Cl
2b; 4-CH3O
2a; H
2a; H
2b; 4-CH3O
-
a
Reaction conditions: 1 (1 mmol), 2 (1.2 mmol), Pd-γ-Fe2O3 (20 mg), NaOH (1.2 mmol), H2O
(5 mL), 80 °C; b isolated yields.

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In view of commercial applications and green chemistry, we also investigated the potential for
reuse of our in-house synthesized Pd-γ-Fe2O3 nanocatalyst in SM cross-coupling reaction of 4-
bromoanisole 1a and phenylboronic acid 2a under optimized reaction conditions. After
completion of the reaction in each cycle, the catalyst was recovered by an external magnet
(Figure 5), washed several times with water and acetone. The recovered catalyst was dried at
room temperature in a vacuum desiccator for several hours and reused under similar reaction
conditions for six consecutive cycles without significant loss in its catalytic efficiency (Figure 6).
Figure 5: Photographs of the Pd-γ-Fe2O3 magnetic nanocatalyst (a) dispersed in the reaction
medium and (b) Separation of the nanocatalyst by external magnet from the reaction medium.
Figure 6: Recycling of Pd-γ-Fe2O3 nanocatalyst in SM coupling reaction.

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4. Conclusion
In summary, we have developed a convenient protocol to synthesize Pd-γ-Fe2O3 nanocomposite
from PdCl2 and Fe3O4 MNPs under modified hydrothermal conditions. The Fe(II) species of
Fe3O4 MNPs reduces the Pd2+ ions to Pd(0) in water medium. The as-synthesized Pd-γ-Fe2O3
nanocomposite acts as a magnetically recyclable and efficient catalyst for SM cross-coupling
reaction in water, which gives excellent yields of corresponding biaryls without the use of any
ligands, phase transfer catalysts or organic solvents. A wide range of functional substitutions in
aryl halide as well as arylboronic acid moieties is well tolerated in our optimized reaction
conditions. The Pd-γ-Fe2O3 nanocatalyst is successfully reused for six cycles without significant
loss in the catalytic activity. The ligand-free, environmentally benign and cost-effective SM
cross coupling protocol, presented in this paper, could be a valuable addition to the existing
methods in the literature.
5. Acknowledgement
Scientific and Engineering Research Board (SERB) is gratefully acknowledged for financial
support to P.N.C (sanction order no. SB/FT/CS-115/2014; dated 24/08/2015). M.P. is thankful to
DST-INSPIRE, GoI, for financial assistance (Project no. DST/INSPIRE/04/2015/003227). We
thank NIT Meghalaya (for financial support to D.P.). IIT Kanpur, IIT Kharagpur and SAIF,
NEHU are also acknowledged for analytical facilities.
6. Supplementary Information
Supplementary information is available.
7. References and Notes
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HIGHLIGHTS
• A simple modified hydrothermal technique to synthesize Pd-γ-Fe2O3 nanocomposite via
redox-driven path.
• Pd-γ-Fe2O3 catalyzed Suzuki-Miyaura reactions were performed in water with excellent
yields.
• The reactions were carried out without any ligand, phase transfer catalyst and organic
solvent.
• Wide substrate scope and magnetically recyclable nanocatalyst.
• The catalyst can be reused for six consecutive cycles.