Synthesis and characterization of Pd based on [2,2'- bipyridin]-4-amine functionalized nano cellulose as a novel and recyclable nano catalyst for Suzuki reaction

Article abstract of DOI:10.1016/j.inoche.2020.107993

In this work, it was designed and prepared an efficient nanocatalyst Pd based on [2,2'- bipyridin]-4-amine functionalized nano cellulose (Pd?BPA?CNC) and then characterized by FT-IR, XRD, ICP-AES, EDX, SEM, TEM and TGA techniques. The catalytic activity of the nanocatalyst was investigated through one-pot synthesis of biaryl derivatives from the reaction of aryl halides with arylboronic acids in DMSO solvent conditions. This Simple and mild procedure displayed excellent recyclability and provided cleaner conversion in a short reaction time. All of these advantages make the protocol feasible and economical attractive for researchers.

Full text of DOI:10.1016/j.inoche.2020.107993

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Short communication
Synthesis and characterization of Pd based on [2,2'- bipyridin]-4-amine func-
tionalized nano cellulose as a novel and recyclable nano catalyst for Suzuki
reaction
Yuqi Sun, Majid Mohammadnia
PII:
S1387-7003(20)30583-9
DOI:
https://doi.org/10.1016/j.inoche.2020.107993
INOCHE 107993
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Inorganic Chemistry Communications
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30 May 2020
31 May 2020
Please cite this article as: Y. Sun, M. Mohammadnia, Synthesis and characterization of Pd based on [2,2'-
bipyridin]-4-amine functionalized nano cellulose as a novel and recyclable nano catalyst for Suzuki reaction,
Inorganic Chemistry Communications (2020), doi: https://doi.org/10.1016/j.inoche.2020.107993
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Synthesis and characterization of Pd based on [2,2'- bipyridin]-4-amine
functionalized nano cellulose as a novel and recyclable nano catalyst for
Suzuki reaction
Yuqi Sun,a,*Majid Mohammadniab
aDepartment of Portuguese, Faculty of Arts and Humanities, University of Macau, Macau, China
bYoung researcher and elite club, Department of Chemistry, Bojnord Branch, Islamic Azad University, Bojnourd, Iran.
Email: viviann534@126.com
Abstract
In this work, it was designed and prepared an efficient nanocatalyst Pd based on [2,2'- bipyridin]-4-amine
functionalized nano cellulose (Pd@BPA@CNC) and then characterized by FT-IR, XRD, ICP-AES, EDX,
SEM, TEM and TGA techniques. The catalytic activity of the nanocatalyst was investigated through one-
pot synthesis of biaryl derivatives from the reaction of aryl halides with arylboronic acids in DMSO
solvent conditions. This Simple and mild procedure displayed excellent recyclability and provided cleaner
conversion in a short reaction time. All of these advantages make the protocol feasible and economical
attractive for researchers.
Keywords: Suzuki reaction, Nanocatalyst, biaryl derivatives, nanocellulose, palladium, [2,2'-bipyridin]-
4-amine
Introduction:
In recent years, the worthiness of nanoparticles (NPs) is one of the most important discoveries that has
been advanced to an scope that researchers could have never guess a century ago, and these particles are
present time ascending steadily in significance in the field of catalysis [1].
In fact, the nano catalysts is definited as the result of an fascinating and spreading out field of catalysts
that are intended at the nanoscalelevel, particularly for heterogeneous catalysis [2-3].

3
nanocatalysts show excellent catalytic activity due to their vast surface-to-volume ratio that they increas
contacting between the reactant molecules and catalyst considerably. Also, heterogeneous nanocatalysts
have good thermal stabilities with substantial recoverability and reusability [4-6].
recently, the trend of scientists is more using biopolymer supports from renewable, endurable and
abundant resources as efficient and interesting materials to reactions catalysis. Cellulose is the most
worth and ordinary biopolymer, which is obtained from plants, bacteria and algae known with qualities
such as hydrophobicity, chirality, biodegradability, economically, biocompability, and wide chemical-
functionalizing capacity. These abilities of the cellulose make it an attractive and efficient support [7, 8].
Supported nano-maerials are emerging as a charming protocol to confirmed some transition metal
complexes which are used for the synthesis of organic compounds [9-10]. The immobilization of metal
catalysts on solid supports has been considered an efficient approach. Nano cellulose supported with
palladium, platinum, zirconium, copper and nickel nano-particles have been advanced [8, 9, 11].
Recently, N-heterocyclic carbenes (NHCs) have attracted many researcher’s attention as transition metal
ligands. Nowadays, a extensive range of NHC ligands are commercially existent which show high
activities in different main organic transformations when connected to metallic pre-catalysts [12].
The employ of immobilized Pd complexes has not been entirely applied. Based on the literature, there
are the fewer cases for such support materials have been synthesized including nano cellulose-tagged
diphenylphosphinate [9, 13, 14], triphenylphosphine [12] and ethylenediamine [15]. NHCs bind through
stronger bonds with most of the metals, hindering the urgency of excess ligand in catalytic reaction [16].
These types of nanocatalysts (Pd based NHC functionalized nano cellulose) play a key role in formation
of carbon-carbon bonding reactions and have a long history in synthesis of organic compounds [17].
Suzuki cross-coupling reactions, founded by Nobel laureate Akira Suzuki, [18] are the most important
extensively employed methodology for the formation of carbon–carbon bonds [19, 20]. This reaction
has become one of the most affectional synthetic methods for the synthesis of biaryl compounds which

4
include a extensive range of natural products and pharmaceuticals [21-24]. Palladium-catalyzed Suzuki
cross-coupling reactions of arylhalides with arylboronic acids are the most impressive and attractive
protocoles to selectively form biaryl compounds in organic synthesis [25-27].
Also, suzuki cross-coupling reactions can synthesize a kinds of compounds, such as heterocycles,
naproxen anti-inflammatory drugs, montelukast asthma, chips and herbicides. In addition, they can be
employed in engineering materials such as conductive polymers, molecular wires and liquid crystal [28,
29].
we present the anchoring of [2,2'-bipyridin]-4-amine (BPA) onto a nano cellulose backbone as a precursor,
followed by coordination with Pd(OAc)2 to prepare a novel, efficient and fascinating nano catalyst
(Pd@BPA@CNC). Then it investigated Pd@BPA@CNC catalytic application for the Suzuki reaction of
aryl halides with arylboronic acids at 70 °C in DMSO (Scheme1).
X
B(OH)2
Pd@BPA@CNC (catalyst)
DMSO, 70 oC
+
R2
R1
R2
R1
Pd
N
N
HN
Pd@BPA@CNC =
O
O
n
HO
OH
Scheme. 1. Procedure for the Suzuki reaction of arylhalides and arylboronic acids in the presence of
Pd@BPA@CNC as nanocatalyst
Experimental
Chemicals and instruments
All reagents were purchased from Merck and Aldrich and used without further purification. The surface
morphology of samples was carried out by scanning electron microscopy (SEM, EM-3200).Transmission
electron microscopy (TEM) experiments were conducted on a Philips EM 208 electron microscope.
Melting points were measured with an Electrothermal 9100 apparatus. Thermo gravimetric analysis

5
(TGA) was performed on a Stanton Red craft STA-780 (London, UK) using N2 as carrier gas with
temperature ramp of 10 °C/min and from room temperature to 800 °C. The content of palladium was
estimated by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) (Perkin Elmer Optima
2000 DV ICP-AES).
Nano catalyst preparation
Preparations of Cellulose Nanocrystals (CNC) (1)
Acidic hydrolysis of Whatman filter paper was used to obtain the cellulose nanocrystals as reported in the
literature with slight modification [30]. Hydrolysis of the cellulose was achieved after 3 h at 100 °C using
100 mL of 2.5 M HBr and alternative ultra-sonication. After dilution with twice-distilled water, the
mixture was subjected to five washing/centrifugation cycles to remove excess acid and water-soluble
residues. After neutralization up to around pH = 5, the fine cellulose nanoparticles started to disperse into
the aqueous supernatant which were collected and centrifuged at 12,000 rpm for 60 min to remove
ultrafine particles.
Tosylation of nanocellulose to synthesize Tos@CNC (2)
Tos@CNC was prepared according to the reported method [30, 31]. 0.5 g of Nanocallulose was suspended
in 10 mL of pyridine and the mixture was cooled to 10 °C. Afterwards, the Tosyl chloride (0.9 g, 5 mmol)
was added to the mixture and stirred for 2 days at room temperature.After completion of the reaction, 100
mL of ethanol was added to the reaction mixture and the precipitation was collected by filtration process.
The obtained product was washed with more ethanol (50 mL) for five times and kept in refrigerator with
no drying (Scheme 2).
Preparation of BPA@CNC (3)
A suspension containing 400 mg of Tos@CNC in methoanol was mixed with 20 mL of DMF (N, N-
dimethyl formamide) and centrifuged 3 times to exchange methanol with DMF. Then, 400 mg of [2,2'-
bipyridin]-4-amine (BPA) was added to the above mixture and stirred for 24h at 100 °C. Afterwards, 50

6
mL deionized water was added to reaction mixture and obtained precipitate was centrifuged and separated.
The product was washed more than 5 times with ethanol and water. The resulting product was dialyzed
against deionized water for 3 days using a cellulose membrane which led to the water replacing
(exchanging) with DMF and eventually the attained product was kept in refrigerator (Scheme 2).
Preparation of Pd@BPA@CNC catalyst
0.50 g of BPA@CNC in DMF was added to a solution of Pd(CL)2 (0.10 g, 0.45 mmol) in 10 mL DMF
under N2 atmosphere and the obtained mixture was stirred for 24 h at 60 °C. After the reaction was
completed, the mixture was cooled to room temperature and resulted product was collected by filtration
process. The resulting black solid product was washed carefully with deionized water (3×25 mL), absolute
ether (2×25 mL) and absolute ethyl alcohol (2×25 mL) and dried under vacuum oven at room temperature
(Scheme 2).
Pd
Pd
N
N
N
N
N
N
OTs
OH
PdCl2
O
HO
H2N
DMSO, 100 o
O
HO
O
HN
Tosyl chloride
pyridine, 10 o
HN
O
DMF, 60 o
C
C
OH
OH
O
HO
O
HO
C
O
O
n
n
n
n
OH
OH
CNC(1)
Tos@cnc(2)
BPA@CNC (3)
Pd@BPA@CNC (4)
Scheme. 2. General procedure for preparation of Pd@BPA@CNC catalyst
General procedure of Suzuki reaction of arylhalides with arylboronic acids by Pd@BPA@CNC
nanocatalysts
To synthesize biaryl derivatives using Suzuki reaction via C-C arylation reactions, aryl halide (1 mmol),
arylboronic acid (1.6 mmol) and K2CO3 (3 mmol) in DMSO (10 mL) were placed into a round bottom
flask containing 10 mg of the Pd@BPA@CNC as nanocatalyst. The above obtained mixture was stirred
at 70 ºC for a definite time which is required for each substrate. After completion of the reaction, the solid
catalyst was filtered and washed 5 times with deionized water and absolute ether and kept for reusability

7
study of the catalyst under resembling reaction conditions. The filtrate was extracted with ethyl acetate (
), washed with deionized water and dried by anhydrous MgSO4. After that, MgSO4 was filtered,
the solvent was evaporated and the resulting product was purified by preparative TLC (eluent: petroleum
ether/ethyl acetate, 20/1) (scheme 1).
Selected spectra for two known products are given below:
4-Cyano-2'-methoxybiphenyl
1H NMR (400 MHz, DMSO-d6): δ = 3.86(s, 3H, OCH3), 7.11 (d, J= 7.0 Hz, 1H Ar), 7.17-7.21 (m, 3H
Ar), 7.32 (d, J= 7.8 Hz, 2H Ar), 7.50 (d, J= 7.8 Hz, 2H Ar) ppm.; 13C NMR (100 MHz, DMSO-d6): δ =
56.8, 111.0, 116.5, 117.2, 120.6, 125.1, 127.6, 129.2, 131.6, 132.4, 146.6, 159.7 ppm.
4-Cyano-3'-methoxybiphenyl
1H NMR (400 MHz, DMSO-d6): δ = 3.79(s, 3H, OCH3), 7.07-7.20 (m, 4H Ar), 7.56 (d, J= 7.3 Hz, 2H
13
Ar), 7.70 (d, J= 7.3 Hz, 2H Ar) ppm.; C NMR (100 MHz, DMSO-d6): δ = 57.6, 110.9, 112.2, 113.8,
119.5, 120.6, 129.9, 131.7, 134.6, 140.1, 140.0, 159.9 ppm.
Results and discussion
Characterization of prepared nanocell-AMPD-Pd
Energy dispersive x-ray (EDX)
The EDX analysis of Pd@BPA@CNC is shown in Fig 1. As can be seen, Pd@BPA@CNC is composed
of C, O and Pd, indicating Pd has been inserted in desired catalyst. In other words, there is a Pd peak,
which is consistent with the ICP-AES results.

8
Fig. 1. EDX spectra of Pd@BPA@CNC
ICP-AES analysis
The ICP-AES analysis was performed to determine the amount of Pd (82517 mg /L) in Pd@BPA@CNC
as catalyst.
CHNS/O total elemental analysis
The CHNS/O analysis was employed to identify the elemental contents of the BPA@CNC. The results of
the elemental analysis are reported in Table 1.
Table 1 Elemental analysis of BPA@CNC with the CHNS/O analysis
Elemental name
Weight (%)
N/A
Weight (mg)
N/A
Response
75.623
Reten time (min)
1.283
N
C
39.07
6.12
1.544
10298.835
5436.099
101.895
2.187
H
0.242
8.497
S
0.28
0.011
18.477
Total
45.47
3.951
Catalytic application of Pd@BPA@CNC for the Suzuki reaction
In order to investigate the optimum conditions, the reaction of 4-Bromoanisole and phenylboronic
acid for the synthesis of 4-Methoxy biphenyl in the presence of the catalyst was selected as a model

9
reaction. The reaction was carried out with various amounts of the Pd@BPA@CNC as catalyst (5, 10 and
15 mg) at different temperatures (25 and 70 °C) in various solvents. As can be seen in table 2, the yield of
the product was increased upon enhancing the temperature. In addition, as expected, different results were
obtained by employing various solvents and amounts of the catalyst. According to the Table 2, 10 mg of
the catalyst was determined as the optimum amount of the catalyst. The obtained results in Table 2 showed
that optimal condition was 10 mg of Pd@BPA@CNC and 3 mmol K2CO3 as base at 70 ºC in DMSO
(Table 2, entry 7).
Table 2 Optimization conditions for preparation 4-Methoxy biphenyl in the presence of Pd@BPA@CNC
as nanocatalyst
Entry
Solvent
Temperature (oC) Catalyst (mg)
Base
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Et3N
Time (min)
Yield(%)a
1
2
3
DMF
DMSO
H2O
25
25
25
25
25
70
70
70
70
70
70
10
10
10
10
10
5
10
15
10
10
10
100
45
75
70
73
35
30
30
42
38
40
28
70
34
35
33
87
98
99
87
82
86
4
5
6
Ethanol
Ethanol/H2O(1:1)
DMSO
7
8
9
10
11
DMSO
DMSO
DMSO
DMSO
Cs2CO3
KH2PO4
DMSO
Next, the obtained optimal conditions were exploited to assess the efficiency and generality of our catalytic
procedure in Suzuki coupling reactions. For this purpose, the reaction of several substituted aryl halides
(1 mmol) with arylboronic acids (1.6 mmol) in the presence of K2CO3 (3 mmol) by using Pd@BPA@CNC
(10 mg) as nano catalyst at 70 °C in DMSO were estimated (Table 3). Based on the obtained results from
the Table 3 , using 4-bromoanisole, the reaction was carried out in short time and higher yield in respect
of 4-bromobenzonitrile. Also, arylboronic acids including electron-donating groups (CF3, F) showed
shorter time and better yield than those electron-withdrawing groups (OCH3). By comparing the results
of arylboronic acids, it can be concluded that arylboronic acids with ethyl groups have longer reaction
times and lower yields than other groups. As shown in Table 3, Most of the substituted bromobenzenes,
chlorobenzenes and iodobenzenes afforded the corresponding biphenyl with similar yields and reaction

10
times. Besides, evaluating the effect of substituent position (ortho, meta and para)-either on the aromatic
ring of aryl halides or arylboronic acids- over the yields and reaction times exhibited no evident preference
for any of these positions.

Table 3 one-pot reactions of biphenyl derivative using aryl halides and arylboronic acid derivative with Pd@BPA@CNC (10 mg) as
nano catalyst in DMSO (10ml) conditions
Melting Point (°C)
Time
(min)
TOF
(h-1)
Entry
Ar-X
Product
Yield (%)
TON
Found Reported
[Rf]
arylboronic acid
85-86
86 [32]
OCH3
OCH3
OCH3
B(OH)2
Br
Br
Br
OCH3
1
2
3
30
70
25
98
78
85
980
780
850
1960
672
115-116 115-117
[33]
176
B(OH)2
F3C
F3C
OCH3
OCH3
175-178
[34]
B(OH)2
H3CO
H3CO
2073
59-60
59 [34]
B(OH)2
OCH3
OCH3
Br
4
25
81
810
1975
H3CO
H3CO
67-69 67-68 [34]
B(OH)2
OCH3
OCH3
OCH3
OCH3
OCH3
Br
Br
Br
5
6
7
25
75
75
77
92
82
770
920
820
1833
526
OCH3
91-92
46
90 [34]
B(OH)2
F
F
OCH3
45-47 [35]
B(OH)2
OCH3
539
F
F
65-66 65-67 [36]
B(OH)2
OCH3
OCH3
Br
8
75
51
510
408
F
F
220
221 –
224 [37]
OCH3
CN
B(OH)2
C2H5
Br
Br
C2H5
OCH3
9
75
30
94
99
940
990
752
86-87 85-86 [38]
B(OH)2
CN
10
1980
100
101-102
[38]
CN
B(OH)2
Br
H3CO
H3CO
CN
11
60
99
990
990

3
Colorles Colorless
B(OH)2
CN
s oil
oil[38]
CN
Br
Br
12
13
60
60
96
95
960
950
960
950
H3CO
H3CO
73
72-74 [38]
B(OH)2
CN
CN
CN
OCH3
OCH3
191
188-190
[39]
B(OH)2
Br
I
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
CN
14
15
16
17
18
19
35
60
60
60
50
50
98
65
57
42
92
55
980
650
570
420
920
550
1690
650
211-212 211-213
[40]
211-212 211-213
[40]
211-212 211-213
[40]
B(OH)2
B(OH)2
B(OH)2
Br
Cl
Br
Cl
570
420
70
70
[32]
70
B(OH)2
B(OH)2
1108
662
70
[32]
Comparing superiority of Pd@BPA@CNC over some previously reported protocols
To estimate the performance and efficiency of our method, it was compared with several reported results in the literature, which were
summarized in Table 4. The results displayed short times and remarkable yields in the presence of Pd@BPA@CNC nanocatalyst relative to
other catalysts. Simple reaction conditions as well as, convenient work-up procedure makes it an advantageous protocol for the synthesis of
the corresponding biaryl compounds in comparison with the other reported works in the literature (Table 4).

4
Table 4 Comparison the results of Pd@BPA@CNC with other catalysts in the Suzuki reaction
Entry
1
Catalyst
Conditions
Time
7 h
Yield (%)a
[Ref]
aminomethyldiphosphine–Pd(II)
(1.2mmol)
DMF/H2O(3/3 ml), 80 °C
95[12]
2
3
ferrocene-tagged N-heterocyclic
carbene (NHC)-Pd(II) (2 mol%)
Na2CO3 (3 mmol),
DMF:H2O(3:1), 80 °C
2 h
6 h
88[16]
98[41]
Palladium N-Heterocyclic Carbene
(0.02 mmol), K2CO3 (1.2 eq)
i-PrOH (4 mL), r.t
4
5
Pd(OAc)2 /LHX (15mol%)
Pd (1.0 mol)
DMF/H2O(2 mmol), 50oC
3 h
3 h
93[42]
98[43]
K3pO4 .3H2O (1.5 mmol),
H2O/Ethanol (2 ml), 80 °C
6
CNC@BIA@Pd(10 mg), K2CO3 (3
mmol)
70 °C, DMSO (10ml)
30 min
98
(Present
work)
aYields refer to isolated pure products

5
The recyclability of the Pd@BPA@CNC was investigated using the one pot reactions of 4-bromoanisole with phenylboronic acid at 70 ºC
in DMSO solvent for the synthesis of 4-methoxy biphenyl as model reaction (Experimental section). After completion of the reaction, the
solid nanocatalyst was filtered and washed carefully with deionized water and absolute ether to checking the reusability of the catalyst under
the resembling reaction conditions. The results demonstrated that Pd@BPA@CNC is stable catalyst under reaction conditions and it can be
recovered and reused four times without substantial loss of its catalytic activity (Fig. 2).
98
96
93
90
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
Reaction cycles
Fig. 2. The recycling of Pd@BPA@CNC as nanocatalyst
Conclusion

6
In conclusion, Pd based on [2,2'-Bipyridin]-4-amine functionalized nano cellulose (Pd@BPA@CNC) has been successfully synthesized and
characterized by FT-IR, XRD, ICP-AES, EDX, SEM, TEM and TGA techniques. The catalytic activity of the nanocatalyst was investigated
by one-pot synthesis of biphenyl products using aryl halides and arylboronic acid derivatives. This promising and effective methodology
resulted in excellent yields of the products along with short reaction times, which makes this protocol a novel, biocompatible and
economically noteworthy process for the Suzuki coupling reactions.
Acknowledgments
The author acknowledges the University of Macau for support of this work.
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Graphical Abstract
Pd based on [2,2'-Bipyridin]-4-amine functionalized nano cellulose as a
novel and recyclable nano catalyst for Suzuki reaction
X
B(OH)2
Pd@BPA@CNC (catalyst)
DMSO, 70 oC
+
R2
R1
R2
Yuqi Sun*
R1
Pd
Majid Mohammadnia
N
N
HN
Pd@BPA@CNC =
O
O
n
HO
OH

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Highlights
 Pd based on [2,2'-Bipyridin]-4-amine functionalized nano cellulose (Pd@BPA@CNC) as
a novel nanocatalyst
 The catalytic activity of the nanocatalyst was probed through one-pot synthesis of biaryl
derivatives
 This nanocatalyst can easily be separated and recycled from the products.
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Yuqi Sun: chemistry, Arts and Humanities
Majid Mohammadnia: organic chemistry, nano catalyst, magnetic catalyst, Suzuki reaction,
coupling reaction
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Declaration 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.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
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