Fabrication and application of cellulose Schiff base supported Pd(II) catalyst for fast and simple synthesis of biaryls via Suzuki coupling reaction

Article abstract of DOI:10.1016/j.apcata.2016.12.005

Bio-supported catalysts, due to their green nature, are promising materials for coupling reactions. In this paper, the design and application of a new green cellulose Schiff base supported Pd(II) catalyst (CL-Sc-Pd) for the synthesis of different biaryls under microwave irradiation without the use of any organic solvent is reported. Firstly, a silane-modified cellulose Schiff base (CL-Sc) was synthesized as a support material, and then its heterogonous Pd(II) catalyst was easily prepared in water for the Suzuki coupling reaction. The synthesized materials were then characterized with various analytical tools. Finally, the catalytic performance of the green catalyst was investigated towards various C[sbnd]C reactions using a green, simple and fast microwave technique. The catalyst indicated excellent selectivity and activity in a very short time (6?min) under a solvent-free media. In addition, outstanding TON (19,800) and TOF (198,000) values were obtained with the green Pd(II) catalyst. The longevity of the green Pd(II) catalyst was studied and it was found to be reusable for at least eight runs. CL-Sc-Pd catalyst showed perfect catalytic efficiency for the Suzuki C[sbnd]C reaction when it was compared to commercial palladium catalysts.

Full text of DOI:10.1016/j.apcata.2016.12.005

Accepted Manuscript
Title: Fabrication and application of cellulose Schiff base
supported Pd(II) for fast and simple synthesis of biaryls via
Suzuki coupling reaction
Author: Nuray Yılmaz Baran Talat Baran Ayfer Mentes¸
PII:
S0926-860X(16)30590-7
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.apcata.2016.12.005
APCATA 16090
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Applied Catalysis A: General
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Accepted date:
6-10-2016
18-11-2016
3-12-2016
Please cite this article as: Nuray Yılmaz Baran, Talat Baran, Ayfer Mente s¸ , Fabrication
and application of cellulose Schiff base supported Pd(II) for fast and simple
synthesis of biaryls via Suzuki coupling reaction, Applied Catalysis A, General
http://dx.doi.org/10.1016/j.apcata.2016.12.005
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Fabrication and application of cellulose Schiff base supported Pd(II) for fast and simple
synthesis of biaryls via Suzuki coupling reaction
Nuray Yılmaz Baran*, Talat Baran, Ayfer Menteş
Department of Chemistry, Faculty of Science and Letters, Aksaray University, Aksaray,
6
8100 Aksaray, Turkey

Graphical Abstract

Highlights
Cellulose supported Pd(II) catalyst exhibited better performance in Suzuki coupling reactions
Catalyst was characterised by FTIR, TGA, SEM-EDAX, XRD, ICP-OES and magnetic
moment
This green catalyst showed a better recycles performance

Abstract
Bio-supported catalysts, due to their green nature, are promising materials for coupling
reactions. In this paper, the design and application of a new green cellulose Schiff base
supported Pd(II) catalyst (CL-Sc-Pd) for the synthesis of different biaryls under microwave
irradiation without the use of any organic solvent is reported. Firstly, a silane-modified
cellulose Schiff base (CL-Sc) was synthesized as a support material, and then its
heterogonous Pd(II) catalyst was easily prepared in water for the Suzuki coupling reaction.
The synthesized materials were then characterized with various analytical tools. Finally, the
catalytic performance of the green catalyst was investigated towards various C-C reactions
using a green, simple and fast microwave technique. The catalyst indicated excellent
selectivity and activity in a very short time (6 min) under a solvent-free media. In addition,
outstanding TON (19,800) and TOF (198,000) values were obtained with the green Pd(II)
catalyst. The longevity of the green Pd(II) catalyst was studied and it was found to be
reusable for at least eight runs. CL-Sc-Pd catalyst showed perfect catalytic efficiency for the
Suzuki C-C reaction when it was compared to commercial palladium catalysts.
Keywords: Schiff base; microwave irradiation; biaryls; bio-material; longevity

1
. Introduction
Environmental friendly materials, such as chitosan, cotton, chitin and alginate and zeolite
have gained much recent attention as support materials for catalytic systems due to their
unique properties, such as renewable, nontoxic, low cost and abundance in nature [1-8]. The
most important natural polymer is cellulose (CL), which has high thermal stability and metal
binding capacity. More importantly, the hydroxyl groups on cellulose easily enable chemical
modifications, like carboxymethylation, silylation and periodate oxidation, to improve the
physical and chemical properties [9-11]. Especially, silylation can be easily obtained with the
reactive hydroxyl groups on the polymer chain of cellulose with silane containing agents. This
modification plays an important role in catalytic systems [12, 13]. With all these significant
features, cellulose and its derivatives are considered to be good support materials for catalyst
systems.
Biaryl compounds, which are produced via Suzuki coupling reactions in the presence of
palladium catalysts, have been widely used in various areas, such as cosmetics, medicine and
pharmacology [14, 15]. In recent years, different homogenous or heterogeneous palladium
catalytic systems have been designed and their activities have been tested towards the
synthesis of biaryl compounds in Suzuki C-C reactions [16-25]. Homogeneous catalytic
systems have serious disadvantages such as short life time, high operational costs, labour-
intensive and the difficulty of separation from the reaction mixture [26]. These problems
affect the reaction yields and recyclability of the catalyst. Especially in the last 10 years, to
improve the selectivity and longevity of the catalyst, solid supported heterogeneous palladium
2
2
catalysts have been extensively used in Suzuki C(sp )- C(sp ) reactions due to their ease of
removal from the reaction media [27-32]. In addition, these catalyst derivatives have
outstanding advantages, such as ease of use, low cost and thermal and chemical satiability.

These important properties determine whether a catalyst is feasible for various industrial
operations.
In this study, a new CL-Sc-Pd catalyst was designed for Suzuki coupling reactions. The
support material for palladium ions was prepared as follows: firstly, silylation of cellulose
(
CL-NH
2
) was carried out using 3-aminopropyltriethoxysilane (APTES). Then, the
with 2-amino pyridine was achieved. Finally, the Pd(II)
condensation reaction of CL-NH
2
catalyst was easily synthesized in water. The chemical structure of the support material and
Pd(II) catalyst was characterized with FTIR, SEM-EDAX, XRD, TG-DTG, ICP-OES and
magnetic moment techniques. The catalytic performance of CL-Sc-Pd catalyst was
investigated in the green synthesis of various biaryl compounds via Suzuki coupling reactions
under mild conditions by employing microwave irradiation in a solvent-free medium. The
biaryl products were identified on GC-MS. Longevity tests of the catalyst were done. The
catalytic activity of the catalyst was compared with different commercial palladium salts.
Catalytic tests showed that the CL-Sc-Pd catalyst has excellent selectivity as well as TON and
TOF values with low catalyst loading. In addition, the catalyst retained its activity even after
eight cycles.
2
. Materials and method
2
.1. Materials
CL, 2-aminopyridine, APTES, PdCl
2
, Na
2 4 2 3
PdCl , all aryl halides, phenyl boronic acid, K CO ,
NaOH, Na
Aldrich.
CO , KOH, MgSO , toluene, ninhydrin and ethanol were purchased from Sigma-
2 3 4
2
.2. Instrumentation
FT-IR spectra of the all compounds were analyzed on a Perkin Elmer Spectrum 100 FTIR
spectrophotometer. X-ray diffractograms were recorded on a Rigaku D max 2000 system (at

4
0 kV, 30 mA and 2θ with a scan angle: 5−70°). Thermal and mechanical stability of the
samples were performed on an EXSTAR S11 7300 (nitrogen atmosphere; heating range: 30-
50°C). The surface images were obtained on a QUANTA-FEG 250 ESEM. The analyses of
6
palladium, chloride and silane ions on the catalyst were determined using an EDAX-Metek.
Palladium ion content of the catalyst was performed by using Perkin Elmer Optima 2100 DV
Inductively Coupled Plasma (ICP) Optical Emission Spectrometer (OES). Characterization of
biaryl compounds were done on GC-MS Agilent GC-7890 A- MS 5975. Magnetic moment
analysis of the catalyst was measured using Sherwood magnetic susceptibility balance. In the
catalytic performances tests a domestic microwave oven was used.
3
. Experimental studies
3
.1. Preparation of support material for palladium ion
3
.1.1. Synthesis of CL-NH
2
CL-NH
2
was prepared by refluxing cellulose (2 g) with APTES (10 mL) in anhydrous toluene
for 48 h. Following the reaction, the product was filtered and rinsed with ethanol and dried in
an oven (Scheme 1).
3
.1.2. Preparation of CL-Sc
2
CL-NH (1 g) and 2-aminopyridine (3 mL) were refluxed in 50 mL of ethanol for 72 h. The
condensation reaction was followed by the FTIR technique. Following the reaction, light
yellow Schiff base product was filtered and washed hot ethanol (Scheme 1).
3
.2. Synthesis CL-Sc-Pd catalyst
CL-Sc was suspended in water at room temperature for 2h. Then water solution of Na
2 4
PdCl
(0.4 g) was added into the reaction media and stirred for 6 h. At the end of the reaction, brown

product was filtered and rinsed with hot water to remove unreacted palladium salts. Finally,
the product was dried at room temperature (Scheme 1).
…
……………………………….……………Scheme 1………...…………..……………….
3
.3. General procedure for synthesis of biaryls via Suzuki C-C reactions
A mixture of 1.12 mmol aril halides, 1.18 mmol phenyl boronic acid, 3.75 mmol K
2
CO
CL-Sc-Pd catalyst (5x10 mol %) was irradiated in a microwave oven at 50 °C and 400 W for
min in solvent-free medium. After the reaction, the mixture was cooled and extracted with
toluene:water solution (2:1). The organic phase was separated with separatory funnel and
3
and
-3
6
MgSO
4
was added to completely remove the water. Finally, the organic phase, which
1
contained the biaryl compounds, was sent for GC/MS and H-NMR analysis.
3
.4. Recycle Tests
After the model coupling reaction was completed, the Pd(II) catalyst was filtered and washed
with hot water and methanol to reactive the catalyst. The same process was applied after the
ensuing runs and recyclability tests were performed on the model reaction.

4
4
4
. Results and discussion
.1. Characterization the catalyst
.1.1. FTIR analysis
The FTIR spectra of CL, CL-NH
the spectrum of CL-NH (Fig 1b), the decrease in the intensity of the peak that belongs to the
OH group (3337 cm ) of cellulose demonstrated that the APTES molecules bonded via the
2
, CL-Sc and CL-Sc-Pd catalyst are presented in Fig.1. In
2
-1
–
-1
hydroxyl groups of CL. In addition, the peaks at 3336 and 2886 cm were assigned to
stretching of the N–H and O-H as well as C–H groups, respectively [33]. On the other hand,
the Si-O-Si peak could not be precisely defined because this peak fell in the stretching region
of C-O-C belonging to CL. Thus, to confirm the silane modification of the CL, a ninhydrin
color test was done according to the literature (Fig. 2) [34]. As shown in Fig. 2, the color of
the CL-NH
ninhydrin in the ethanol. This sharp color conversion indicates that the silane molecules were
loaded on the CL chain. Following the condensation reaction of CL-NH and 2-
2 2
sample turned from light yellow to dark purple, by refluxing CL-NH with
2
-1
aminopyridine, a new sharp peak was observed at 1648 cm in the spectrum of the CL-Sc
which is attributed to imine bond (Fig. 1c) [27]. In addition, the stretching of the (-C=C)aromatic
-1
rings groups of 2-aminopyridine appeared at 1588 and 1567 cm in the spectrum. All these
significant peaks show that the Schiff base modification of CL was achieved. On the other
hand, after the coordination of the palladium ion to its ligand, the imine bond was shifted to
-1
lower wavenumber (1624 cm ) in the spectrum of the catalyst (Fig. 1d). This change
indicated that the metal ions were coordinated to the ligand via the imine groups of the CL-Sc
[35].

…
……………………………….……………Figure 1………...…………..……………….
…
.1.2. TG/DTG analysis
Chemical and mechanical durability in catalyst are desirable properties because it can be used
in different industrial operations. Thus, the thermal stabilities of CL, CL-NH , CL-Sc and CL-
……………………………….……………Figure 2………...…………..……………….
4
2

Sc-Pd catalyst were investigated and the results are given in Fig.3. The maximum
decomposition temperature (Tmax) of CL was determined to be 360 °C (Fig. 3a). After the
silane and Schiff base formation of CL, the thermal stabilities were recorded as 383 and 389
°
2
C, respectively (Fig. 3b,c). These results show that CL-NH and CL-Sc have higher thermal
stability compared to CL. On the other hand, thermal durability of the catalyst was recorded to
be 366 °C (Fig. 3d). This result indicates that the catalyst is suitable for different coupling
reactions due to its higher thermal mechanical stability. The negligible decrease in the thermal
stability of the catalyst may be attributed to the catalytic effect of the palladium ions on the
degradation of the CL structure [36].
…
……………………………….……………Figure 3………...…………..……………….
.1.3. SEM-EDAX analysis
The surface morphologies of CL, CL-NH
with scanning electron microscope (SEM) and their images are given in Fig. 4. As seen in Fig.
a, while the CL has a practically flat structure, the surface images of the CL-NH and the
CL-Sc were completely changed following the chemical modifications (Fig. 4b,c). On the
4
2
, CL-Sc and CL-Sc-Pd catalyst were investigated
4
2

other hand, the surface image of the catalyst showed a regular surface image (Fig. 4d). It can
be concluded from the SEM image that the palladium ions were coordinated with CL-Sc. We
also conducted EDAX analysis to confirm the silylation of CL and the formation of the green
palladium catalyst (Fig 5). In the spectra, Si, Pd and Cl peaks were observed (Fig. 5a,b).
These observations confirm that chemical modification of the CS was achieved.
…
……………………………….……………Figure 4………...…………..……………….
…
……………………………….……………Figure 5………...…………..……………….

4
.1.4. XRD
The crystalline nature of CL, CL-NH
2
, CL-Sc and CL-Sc-Pd were investigated and
crystalline index values (CrI) were calculated using the equation presented below [37]. In the
XRD diagram of CL, two sharper peaks (~at 15 and 22°) and one small peak (~ at 34°) were
observed [38] (Fig. 6a). The CrI value of CL was determined to be 81 %. On the other hand,
2
decreases in the CrI values of CL-NH (74 %) and CL-Sc were observed (69 %) (Fig. 6b,c).
These decreases may be attributed to the deformation of the hydrogen bonds of CL following
the chemical modifications. In addition, we determined a decrease in the CrI of the catalyst
(64 %). The lower CrI value of the catalysts showed that palladium complex was formed and
the catalyst has an amorphous nature (Fig. 6d). In addition, in the spectrum of the catalyst,
palladium peaks seen at around 40.1 ° (Fig. 6d) indicate that designee of catalyst was
achieved [39].
CrI = [(I200–Iam)/I200] x100
I
I
200 is the height of the 200 peak (I200, 2θ = 22.7°).
am is the minimum between the 200 and 110 peaks (Iam, 2θ = 18°)
…
……………………………….……………Figure 6………...…………..……………….

4
.1.5. Magnetic moment and ICP-OES analysis
It was reported that Pd(II) complexes that have square planar geometry (low spine) showed
diamagnetic property [40, 41]. In this paper, to determine the geometry of the CL-Sc-Pd
catalyst, magnetic moment analysis was performed at room temperature and it was seen that
the catalyst had diamagnetic property. This result indicated that the catalyst has square planar
geometry [42]. In addition, the metal content of the catalyst was explored and the palladium
content was determined to be 18.2 (mass %).
4
.2. Catalytic activity of cellulose Schiff base supported Pd(II) catalyst
Before performing the catalytic activity test on the catalyst with various substrates containing
aril halides, the effects of catalyst loading, base and reaction time parameters on the C-C
reaction yield were investigated. To determine optimum reaction conditions, the synthesis
reaction of 4-methoxybiphenyl, which is obtained via the coupling reaction of phenyl boronic
acid with 4-bromoanisole, was selected as a model reaction under microwave irradiation and
solvent-free media. To detect the suitable catalyst loading, the coupling reactions were
carried out using a different amount of catalyst (Fig. 7). As seen from Fig. 7, the best
-3
conversion yield was obtained with 5x10 mol % catalyst. We also explored the effect of the
reaction time (Fig. 8) and base system on the model reaction (Table 1). We determined that
the highest conversion yield (99 %) was obtained at 6 min with the K
0°C under microwave heating without any organic solvent.
2 3
CO base system at
5

Table 1. The effect of the base system on the Suzuki reaction
Base
NaOH
KOH
Yield (%)
TON
8000
TOF
80000
110000
78000
198000
40
55
39
99
11000
7800
Na
2
CO
3
K
2
CO
3
19800
-3
Reaction conditions: 1.12 mmol 4-bromoanisole, 1.87 mmol phenyl boronic acid, 3.75 mmol base, 5x10 % mol catalyst, 50
C, 0.1 h under MW and solvent-free media
°
…
……………………………….……………Figure 7………...…………..……………….
…
……………………………….……………Figure 8………...…………..……………….

Following the optimum reaction conditions, the catalytic performance of the CL-Sc-Pd
catalyst was tested in the the coupling reactions of various aril substrates (20 different
substrates) with phenyl boronic acid under microwave heating, and the results are given in
Table 2. When the results were examined, the highest conversion yields were obtained with
the C-C coupling reaction substrates bearing aril bromides. We recorded substrates containing
aril iodides giving higher yields than aril chlorides. In addition, we observed that all coupling
reactions in the presence of the withdrawing groups yielded higher reaction conversions than
those with the substrates containing the electron-donor groups (Table 2). Moreover, the
effects of the substitute groups of the substrates on the yields of the Suzuki coupling reactions
were examined, and it was determined to be para>meta >ortho. In addition, the order of the
catalytic performance of the substrates (containing aril bromide, aril chloride and aril iodide)
was detected as follows: Br > I > Cl. These results may be explained by the size of the halide
atoms and the bond dissociation energies. These findings are in accord with the previous
literature [1]. TON and TOF values were calculated for all C-C reactions, and the results are
listed in Table 2. It can be clearly seen from Table 2, CL-Sc-Pd catalyst gave remarkable
TON and TOF values with very small loading of the catalyst and very short time. These high
values indicated that the green catalyst can be used efficiently for different coupling reactions.
In addition, the catalytic efficiency of CL-Sc-Pd catalyst was tested against different
commercial palladium salts with the model reaction under optimum conditions (Table 2).
These tests showed that the CL-Sc-Pd catalyst had much higher catalytic activity as well as
TON and TOF values than the commercial palladium catalysts. We compared the
conventional heating system with microwave heating system on the model reaction (Table 2)
and we have found that microwave heating system was more effective than the reflux system.
1
All of the synthesized biaryl compounds were illuminated using the GC/MS and H-NMR
techniques (please refer to Supplementary data).

Table 2. Effect of the Pd(II) catalyst on C-C coupling reactions
Entry Boronic acid
Substrate
Product
Reaction Yield (%) TON TOF
1
97
19400 194000
2
98
19600 196000
3
4
5
99
84
80
19800 198000
16800 168000
16000 160000
6
7
90
82
18000 180000
16400 164000

8
9
59
53
11800 118000
10600 106000
1
0
78
15600 156000
1
1
1
2
53
68
10600 106000
13600 136000
1
1
3
4
64
54
12800 128000
10800 108000

1
1
5
6
32
68
7000
70000
13600 136000
1
1
7
8
72
60
14400 144000
12000 120000
1
2
9
0
39
5
7800
1000
78000
10000
a
2
1
39
7800
78000

b
c
2
2
2
3
49
15
9800
3000
98000
125
-3
Reaction conditions: 1.12 mmol 4-bromoanisole, 1.87 mmol phenyl boronic acid, 3.75 mmol K
2
CO
3
, 5x10 mol % catalyst, 50 °C, 0.1 h under MW and solvent-free media
, 50 °C, 0.1 h under MW and solvent-free media
PdCl , 50 °C, 0.1 h under MW and solvent-free media
CO
-
3
a: 1.12 mmol 4-bromoanisole, 1.87 mmol phenyl boronic acid, 3.75 mmol K
2
CO
3
, 5x10 mol % PdCl
2
-
3
b: 1.12 mmol 4-bromoanisole, 1.87 mmol phenyl boronic acid, 3.75 mmol K
2
CO
3
, 5x10 mol % Na
2
4
-3
c: Conventional heating method: 1.12 mmol aryl halide, 1.87 mmol phenyl boronic acid, 3.75 mmol K
TON: (turnover number, yield of product/ per mol of Pd).
2
3
, 5x10 mol % catalyst, 100 °C, 24 h, 5 mL toluene
TOF: (turn over frequency, TON/time of reaction)

4
.3. Recyclability of CL-Sc-Pd catalyst
The recyclability of the catalyst was explored on a model C-C reaction, and the recyclability
of the catalyst as well as the TON and TOF values for each run are presented in Table 3. At
th
the end of the longevity tests, the catalyst showed activity up to 8 cycle without loss of its
activity. In addition, as seen from Table 3, excellent TON and TOF values were recorded with
short reaction time and small catalyst loading. To determine the changes in the chemical
structure of the catalyst following the eighth cycle, SEM and FTIR analyses were performed
and the results are presented in the Supplementary data. These analyses showed that CL-Sc-
Pd catalyst maintained its chemical structure after the longevity tests.
Table 3. Reusability of CL-Sc-Pd
Suzuki C-C reaction
The number of cycle
Reaction yield (%)
TON
19800
19000
16600
16000
14600
14400
14400
14200
TOF
st
1
99
95
83
83
73
72
72
71
198000
190000
166000
160000
146000
144000
144000
142000
nd
2
rd
3
th
4
th
5
th
6
th
7
th
8
-3
Reaction conditions: 1.12 mmol 4-bromoanisole, 1.87 mmol phenyl boronic acid, 3.75 mmol base, 5x10 % mol catalyst,
0 °C, 0.1 h under MW and solvent-free media
5

5
. Conclusion
In conclusion, a new green Pd(II) catalyst was designed and characterized by FTIR, TG/DTG,
SEM-EDAX, XRD, ICP-OES and magnetic moment analyses. Then, the catalytic
performance of the catalyst was tested against 20 coupling reactions using a fast and simple
microwave heating technique. The longevity of the activity of the CL-St-Pd catalyst was
done. In addition, the activity of the catalyst was tested against commercial palladium salts.
To prove the efficiency of the microwave irradiation, the model coupling reaction was also
performed using conventional heating systems. As shown by all of the tests performed, the
green CL-St-Pd catalyst had excellent TON (19,800) and TOF (198,000) values, catalytic
activity and selectivity in the presence of a low amount of the catalyst under mild conditions
for a very fast reaction time. As a result, this paper demonstrated that the new green catalyst
and green microwave technique could be used with different catalytic systems. Finally, this
catalyst is superior to the other catalysts because of its unique properties, such as high thermal
stability, ease of removal by filtration from the reaction media, usability under an oxygen
atmosphere, long life time and provision of high product yields with a very small catalyst
loading.
Justification for publication
How the content of the manuscript relates to the Aims and Scope of the Journal:
In this study we synthesized an green cellulose Schiff base supported Pd(II) catalyst. The
catalytic activity tests of this green catalyst were conducted in green synthesis of biaryl
compounds under mild conditions. The method involved a very short-time microwave
irradiation at low temperature in absence of any chemical solvents (e.g., 6 min treatment in
microwave oven at 400W at 50°C). Considering these aspects of the catalyst and the test
technique employed in the study, we believe that this study is suitable for the journal Applied
Catalysis A: General.

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Figure and Scheme Captions
2
Fig.1. FT-IR spectra of a) CL b) CL-NH c) CL-Sc d) CL-Sc-Pd catalyst
Fig.2. Color test of CL-NH
2
2
Fig.3. TG/DTG spectra of a) CL b) CL-NH c) CL-Sc d) CL-Sc-Pd catalyst
2
Fig.4. SEM images of a) CL b) CL-NH c) CL-Sc d) CL-Sc-Pd catalyst
2
Fig. 5. EDAX spectra of a) CL-NH b) CL-Sc-Pd catalyst
2
Fig. 6. XRD diagram of a) CL b) CL-NH c) CL-Sc d) CL-Sc-Pd catalyst
Fig. 7. The effect of catalyst loading on Suzuki coupling reaction
Fig. 8. The effect of reaction time on Suzuki coupling reaction
Scheme 1. Design of green CL-Sc-Pd catalyst