Nanocellulose Supported PdNPs as in situ Formed Nano Catalyst for the Suzuki Coupling Reaction in Aqueous Media: A Green Approach and Waste to Wealth

Article abstract of DOI:10.1016/j.jorganchem.2021.121719

An effective and highly sustainable method has been developed for the Suzuki coupling reaction of aryl halides and phenylboronic acid using in situ generated nacocellulose (NC) supported palladium nanoparticles (Pd@NC NPs) as heterogeneous catalysts in water. The formation of PdNPs was observed in the absence of additional reagents, during the course of the Suzuki reaction from NC and Pd(OAc)₂. In situ formed Pd@NC NPs have been systematically characterized using TEM, EDX, XRD and FT-IR techniques. The in situ generated catalyst was separated and studied for its successful reusability up to 11 cycles. The application of aqueous media, use of in situ formed catalyst, mild reaction conditions, absence of volatile organic solvents, broad substrate scope, high product isolated yields are the significant developments of this protocol. The nanocellulose used for this protocol has been generated form the waste cotton cloth and hence it is an example for the waste to wealth and sustainable approach.

Full text of DOI:10.1016/j.jorganchem.2021.121719

Journal of Organometallic Chemistry 937 (2021) 121719
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Nanocellulose Supported PdNPs as in situ Formed Nano Catalyst for
the Suzuki Coupling Reaction in Aqueous Media: A Green Approach
and Waste to Wealth
Sreenath Reddy Aabakaa, Jincheng Maoa,∗, Mallu Lavanyaa,b,∗, Katta Venkateswarluc,∗
,
Zhiyu Huangb, Jinhua Maoa,∗, Xiaojiang Yang a, Chong Lina
a State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Xindu 610500, PR China
b School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, Xindu 610500, PR China
c Laboratory for Synthetic & Natural Products Chemistry, Department of Chemistry, Yogi Vemana University, Kadapa 516005, India
a r t i c l e i n f o
a b s t r a c t
Article history:
An effective and highly sustainable method has been developed for the Suzuki coupling reaction of aryl
halides and phenylboronic acid using in situ generated nacocellulose (NC) supported palladium nanopar-
ticles (Pd@NC NPs) as heterogeneous catalysts in water. The formation of PdNPs was observed in the
absence of additional reagents, during the course of the Suzuki reaction from NC and Pd(OAc)2. In situ
formed Pd@NC NPs have been systematically characterized using TEM, EDX, XRD and FT-IR techniques.
The in situ generated catalyst was separated and studied for its successful reusability up to 11 cycles. The
application of aqueous media, use of in situ formed catalyst, mild reaction conditions, absence of volatile
organic solvents, broad substrate scope, high product isolated yields are the significant developments of
this protocol. The nanocellulose used for this protocol has been generated form the waste cotton cloth
and hence it is an example for the waste to wealth and sustainable approach.
Received 18 November 2020
Revised 19 January 2021
Accepted 21 January 2021
Available online 28 January 2021
Keywords:
Pd@NC NPs
aryl halides
phenylboronic acid
green approach
biaryls synthesis
© 2021 Elsevier B.V. All rights reserved.
1. Introduction
to separate the catalyst and ligands from the final product in these
systems. On the other hand, to address this problem, researches
The today’s chemical science is making efforts to provide a
healthy environment to the mankind via green approaches. On
this concern, researchers are developing chemical products via eco-
friendly approaches [1–9]. Green chemistry has been promoting
significant awareness in the scientific community, particularly in
organic synthesis due to its financial and environmental advan-
tages. From the industrial point-of-view cost-effective and trouble-
free process always desirable. Nano-Pd-catalysis is a major multi-
disciplinary area in cross-coupling reactions. Among the coupling
reactions Suzuki coupling reaction is the widely employed strategy
for the preparation of biaryls and these are very essential in phar-
maceuticals and other industries [10,11].
are focused on heterogeneous system, which fecilitates the easy
separation and recovery of the Pd-catalysts [18,19]. Though, the
catalytic activity is slightly reduced when the recycled catalyst had
employed, but, giving priority to benignity, heterogeneous catalytic
systems significantly dominates homogenous catalytic systems.
In organic transformations, metal nanoparticles (NPs)-based
heterogeneous catalysts display outstanding performance, because,
metal NPs consists large surface area, which results in a very huge
number of catalytically active sites [20]. Recently, several solid-
supported Pd-catalysts have been accounted via mild and/or en-
vironmentally benign reaction conditions. These supported cat-
alysts were prepared by immobilizing Pd(II) on supported lig-
ands (like phosphine [21], amines [22], N-heterocyclic carbene
[23], cyclodextrin [24] and metformin [14]) or ligand-free Pd(0)
nanoparticles on various solid supports (such as Fe2O3 [25], silica
[26], polyionic polymers [27], cellulose [28], metal alloys [29] and
fullerene [30]) and bio-reductants [31–33]. These immobilizations
or captivity of Pd(0) NPs by various supports elates water-suspend
ability, biodegradability and the metal ion uptake capacity for Pd-
catalyzed cross-coupling reactions.
In general researchers follow two different routes in the prepa-
ration of biaryls; one through homogenous catalysis and the other
using heterogeneous catalytic systems. A considerable number of
homogenous palladium (Pd) catalytic systems were reported for
the easy synthesis of biaryls [11–17]. However, it is very difficult
∗
Corresponding authors.
E-mail addresses: jcmao@swpu.edu.cn (J. Mao), kvenkat@yogivemanauniversity.ac.in
(K. Venkateswarlu).
https://doi.org/10.1016/j.jorganchem.2021.121719
0022-328X/© 2021 Elsevier B.V. All rights reserved.

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
Table 1
Comparison of NC and cellulose in aqueous Pd(OAc)2-catalyzed Suzuki reaction.a
Entry
R
Support
Temp (˚C)
Time (h)
Isolated yield (%)
1
2
3
4
4-CH3
NC
rt
rt
rt
rt
5
6
5
6
99
70
98
74
4-CH3
Cellulose
NC
4-OCH3
4-OCH3
Cellulose
a
Reaction conditions: aryl bromide (0.4 mmol), phenylboronic acid (1.2 eq.), support (1 wt%), Pd(OAc)2 (0.1 mol%),
K2CO3 (2 eq.) and water (3 mL).
Fig. 1. TEM images and EDX of Pd@NC NPs.
The high health concern, safety and environmental regulations
mediated Pd(OAc)2 or Pd-KIT-6-catalyzed Suzuki cross-coupling re-
action [42]. The development of novel/new catalytic systems for
Suzuki coupling reaction in aqueous media is highly desirable due
to the environmental, economical and health concerns.
of today, promotes usage of safer solvents towards the reduc-
tion of environmental risks [34]. The application of aqueous me-
dia in organic transformations has been focused at extreme ex-
ploration. In addition, many organic chemists have prepared sig-
nificant attempts to replace the organic solvents in organic syn-
thesis with aqueous media owing to their safe, eco-friendly and
non-toxic properties [35–39]. Saikia et al. used ‘water extract of
rice straw ash’ and ‘water extract of banana’ in Pd(OAc)2-catalyzed
Suzuki coupling reaction under base/ligand/promoter/organic co-
solvents-free conditions at room temperature (rt) [40,41]. Recently,
Venkateswarlu et al. reported aqueous extract of pomegranate ash
Cellulose is the best option to be used as a support in chemi-
cal transformations, because it is a sustainable, cost-effective, and
most abundant natural biopolymer [43,44]. Xiang et al. introduced
a highly recyclable dip-catalyst produced from PdNPs-embedded
on bacterial cellulose and plant fibers for Suzuki reaction [45].
Baruah et al. synthesized cellulose supported PdNPs using hearth
wood extract of Artocarpus lakoocha and used as sustainable het-
erogeneous catalyst for microwave assisted Suzuki coupling in wa-
2

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
Fig. 2. Powder XRD spectra.
ter [46]. Applications of NC supported metal NPs have gained con-
siderable attention in the past decade [47] for the reason that NC
has a high surface area [48], water suspend ability, thermal sta-
bility, reductive surface functional groups and superior mechanical
strength [49]. Further, NC shows high stability in water is an im-
portant property that provides good stability to catalysts when it is
used as support. Opening a greener approach for metal NP synthe-
sis, NC with hydroxy and sulfate ester groups display the ability to
reducing metal species, without the use of any external reducing
agents. The high crystalline order of NC may contribute in catalytic
actions. Thus, we aimed in developing a new green protocol using
NC as biocompatible support for Pd-catalyzed Suzuki reaction and
found that the in situ formation of nanocatalyst which can be sep-
arated and reused for several times. The results are discussed in
the following section.
are listed in Table 1. A test reaction between 4-bromotoluene (1a)
(0.4 mmol) and phenylboronic acid (2) (1.2 eq.) was conducted us-
ing NC (1 wt%), Pd(OAc)2 (0.1 mol%) and K2CO3 (2 eq.) in 3 mL
water. The formation of 99% of biaryl, 3a was observed at rt in 5
h (Table 1, entry 1). The same reaction was also conducted using
cellulose and found only the formation of 70% of 3a in 6h (Table 1,
entry 2). Similarly, the reaction of 4-bromoanisole (1b) with 2 us-
ing NC and cellulose under the above conditions shows the for-
mation of coupling product, 3b in 98% and 74% in 5 h and 6 h
(Table 1, entries 3,4). These results indicates that the NC as best
support than cellulose because of the small size and better adsorp-
tion and adhesive properties of NC.
The NC-based Suzuki reaction has further been screened to-
wards the optimization of the reaction conditions using 1a (0.4
mmol), 2 (0.48 mmol, 1.2 eq.) in 3 mL of water (Table 2). By us-
ing the bases such as Cs2CO3, Na2CO3, Et3N, KF, NaOH and KOH the
yields of 3a was observed in 50–90% at rt in 5–8 h (Table 2, entries
1–6), indicates that the K2CO3 is the best choice (Table 1, entry 1)
among the studied bases under present conditions. The model re-
action is then screened at 60 °C, 70 °C, 80 °C and 90 °C and found
the formation of 99% of yields in 3 h, 1.5 h, 1 h and 1h (Table 2, en-
2. Results and Discussion
NC was prepared from the waste cotton cloth according to
the procedure reported by Wang et al. [50]. NC has been inves-
tigated for the Pd(OAc)2-catalyzed Suzuki reaction and the results
3

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
Table 2
Screening for experimental conditions.a
Entry
Base (2 eq.)
Temp (˚C)
Time (h)
Pd(OAc)2 (mol%)
Isolated yield (%)
1
Cs2CO3
Na2CO3
Et3N
rt
7
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.15
79
90
65
50
75
77
99
99
99
99
55
99
2
rt
6
3
rt
8
4
KF
rt
7
5
NaOH
KOH
rt
6
6
rt
5
7
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
60
70
80
90
80
80
3
8
1.5
1
9
10
11
12
1
6
1
a
Reaction conditions: 1a (0.4 mmol), 2 (1.2 eq.), NC (1 wt%), base (2 eq.) and water (3 mL).
Fig. 4. Recyclability study (Series 1 = no of times; Series 2 = percentage of prod-
uct).
Fig. 3. FT-IR Spectra.
tries 7–10) and indicated that the reaction can be conducted con-
veniently at 80 °C. The catalyst loading was also screened using
0.05 mol% and 0.15 mol% of Pd(OAc)2 and identified the formation
of 3a in 55% and 99% of yields in 6 h and 1 h at 80 °C (Table 2,
entries 12,13) suggested the requirement of 0.1 mol% of catalyst
(Table 2, entry 9) for the current protocol.
With the above optimized conditions, we have utilized the cur-
rent NC-based Suzuki coupling reaction to a wide range of aryl
halides (Table 3). The aryl bromides with both the electron releas-
ing (methyl and methoxy) and electron withdrawing (formyl, acetyl
and nitrile) groups shows high yields of biaryls (3a–3g) (90–99%)
in 1–4 h (Table 3, entries 1–7). The Suzuki coupling reaction of aryl
iodides has observed to be quick on comparison with aryl iodides
and the reaction proceeds at 60 °C (Table 3, entries 8–17). The aryl
iodides with different substituents such as methyl, methoxy, acetyl
and nitro groups showed 90% - nearly quantitative yields in just
0.4–1 h (Table 3, entries 8–16). Unsubstituted aryl iodide such as
iodobenzene also showed high yield (95%) of biphenyl (3l) in 0.4
h (Table 3, entry 17). The position and nature of substituent on
aryl bromide or aryl iodide display negligible effect on the present
Suzuki coupling.
Fig. 5. TEM image of recycled Pd@NC NPs.
4

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
Table 3
Substrate scope.a
e
Entry
X
R
Time (h)
Product
Isolated yield (%)
Mp (literature values) (°C)
TONd
TOF (h–1
)
1
Br
Br
Br
Br
Br
Br
Br
I
4-CH3
1
3a
3b
3c
3d
3e
3f
99
99
95
92
94
90
90
99
90
90
99
95
90
92
90
90
95
99
92
44–45 (42–44 [51])
80–81 (80–82 [51])
Oil (Oil [52])
990
990
950
920
940
900
900
990
900
900
990
950
900
920
900
900
950
990
920
990
2
4-OCH3
3-OCH3
2-OCH3
4-CHO
4-COCH3
4-CN
1
990
3
2
475
4
2
Oil (Oil [53])
460
5
3
58–59 (56–58 [51])
116–117 (117–118 [54])
84–85 (85–86 [51])
44–45 (42–44 [51])
Oil (Oil [55])
313.3
225
6
4
7
8b
9b
4
3g
3a
3h
3i
225
4-CH3
0.4
0.4
0.4
0.4
0.4
0.4
1
2475
2250
2250
2475
2375
2250
920
I
3-CH3
10b
11b
12b
13b
14b
15b
16b
17b
18c
19c
I
2-CH3
Oil (Oil [52])
I
4-OCH3
3-OCH3
2-OCH3
4-COCH3
4-NO2
2-NO2
H
3b
3c
3d
3f
80–81 (80–82 [51])
Oil (Oil [53])
I
I
Oil (Oil [54])
I
116–117 (117–118 [55])
110–111 (111–113 [51])
37–38 (37–38 [56])
65–66 (67–68 [51])
44–45 (42–44 [51])
80–81 (80–82 [51])
I
1
3j
900
I
1
3k
3l
900
I
0.4
8
2375
123.8
115
Cl
Cl
4-CH3
3a
3d
4-OCH3
8
a
Reaction conditions: aryl halide (0.4 mmol), phenylboronic acid (1.2 eq.), NC (1 wt%), Pd(OAc)2 (0.1 mol%), K2CO3 (2 eq.) and water (3 mL) at 80 °C.
Reaction has been conducted at 60 °C.
b
c
Reaction has been conducted at 100 °C
d
e
TON = Turnover number; number of moles of product formed/number of moles of catalyst used.
TOF = Turnover frequency; number of turnovers per hour.
Further, the least reactive of aryl halides such as aryl chlorides
at 39.9, 46.4, 67.5, which can be assigned to (1 1 1), (2 0 0), and (2
2 0) planes of the fcc Pd. The FT-IR spectra (Figure 3) also suggest
that the availability of Pd on NC.
showed excellent yields of coupling products under the present
experimental conditions. In this connection, 4-chlorotoluene and
4-chloroanisole on reaction with phenylboronic acid at 100 °C
formed 99% and 92% of biaryls, 3a and 3b (Table 3, entries 18,19).
The good reactivity of aryl chlorides is an additional advantage of
this method.
The separated Pd@NC NPs was also been studied for the study
of reusability using 1a and 2 as substrates (see at supplementary
material for the reusability experiment) and the results are showed
in Fig. 4. The in situ generated Pd@NC NPs showed a fair reusabil-
ity up to 11 cycles and showed 89% of the product, 3a in 11th cy-
cle (Fig. 4). Generally, the low amounts of Pd catalysts are diffi-
cult in the separation, however, these Pd@NC NPs are found easy
in separation and reuse. The fair reusability of Pd@NC NPs indi-
cates high stability of PdNPs on NC support. Further the high sta-
bility of PdNPs on NC support was also confirmed by hot-filtration
experiment (see supplementary material). The ICP-OES analysis of
the aqueous portion after the separation of the catalyst was also
showed no ‘Pd’ species and hence the PdNPs on the surface of NC
are observed to be highly stable. The TEM analysis of recycled cat-
alyst (Fig. 5) also indicated the negligible change in the size of Pd
species on NC surface.
The effective reactivity of aryl halides with phenylboronic acid
under the current reaction conditions is due to the in situ forma-
tion of PdNPs on NC (Pd@NC NPs) and these NPs are separated
from the reaction mixture (see at supplementary material for the
separation procedure) was characterized using TEM, EDX, powder
XRD and FT-IR analysis.
The TEM images of Pd@NC NPs (Fig. 1) showed the formation
PdNPs on the surface of NC and the average size of Pd was ob-
served as 2.46 nm. The EDX (Fig. 1) confirms the only Pd that is
available on the NC. The powder XRD studies (Figure 2) also re-
veals that the NC source adsorbed Pd, from the graph it is under-
stood that both are in same form. Main diffraction peaks indicates
5

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
Table 4
Comparison of some advanced heterogeneous Suzuki reactions with the present method.
Catalyst
Conditions
Reference
[51]
Remarks
Cu-Adenine@boehmite
Na2CO3, H2O,
80 °C
Na2CO3,
Requirement of nitrogen-based ligand is critical. The catalyst was
synthesized using multiple steps.
Pd-imi-CC@MCM-41/Fe3 O4
Pd-TBA@biochar
[52]
[53]
This method involves multi-step preparation of catalyst, use of PEG-400 as
medium and necessity of large reaction times in case of aryl chlorides.
Requires PEG-400, large reaction time for aryl chlorides and multi-step
preparation of ligand based catalyst.
PEG-400, 80 °C
Na2CO3,
PEG-400, 120
°C
Na2CO3,
Pd-imi@MCM-41/Fe3O4
[57]
Multi-step preparation of the catalyst, requirement of PEG-400 as medium
and necessity of large reaction times with aryl chlorides are reported in this
method.
PEG-400, 80 °C
Pd-isatin-boehmite
Pd-adenine@boehmite
Pd-ABA-MCM-41
Pd@rice husk ash
GO-NH2-Pd+2
K2CO3,
[58]
[59]
[60]
[61]
[62]
[63]
Complexicity in the preparation of the catalyst and necessity of PEG-400 as
media are reported in this protocol.
PEG-400, 80 °C
Na2CO3, water,
80 °C
The synthesis of Pd-complex-based catalyst needs multiple steps.
PEG, K2CO3, 60
°C
Requirement of PEG as reaction media and multi-step preparation of the
catalyst are the key features of this protocol.
EtOH, K2CO3,
100 °C
Requirement of ethanol as reaction media, large reaction times are the
decisive in this protocol.
EtOH, water
K2CO3, 60 °C
EtOH, water
K2CO3, vis.
light, 25 °C
EtOH, water
K2CO3, 80 °C
EtOH, water
K2CO3, rt
Requirement of 4 eq. of base is critical and very low yields are reported with
aryl chloride, even after large reaction time (24 h).
Very low yield of coupling product using aryl chlorides was observed in this
protocol.
GO-Pd@Ag-AgBr
GO-NHC-Pd+2
[64]
[65]
Low yields of the coupling products was reported using aryl chlorides (in 24
h) using this protocol.
Zn free MOF-5-NPC-900-Pd
Pd@NC NPs
Requirement of 3 eq. of base and multi-step preparation of catalyst are
crucial in this protocol.
Water, K2CO3,
60–100 °C
Present
method
In situ preparation of catalyst, use of water as reaction media and avoid of
ligand are the advantages of this protocol.
A systematic comparison of some advantageous heterogeneous
Suzuki coupling protocols with the present method has been pro-
vided in the Table 4. As can be seen the present protocol evidences
the advantage as in situ formation of PdNPs on NC (Pd@NC NPs)
as heterogeneous catalyst over the reported methods that are con-
sidered for the comparison. It also shows significance by avoiding
ligand and utilizing water as reaction media. Since, the NC used in
this protocol is produced from the waste cotton cloth, it is a very
good example for the waste to wealth approach in chemical syn-
thesis.
Acknowledgement
The research is partly supported by Sichuan Youth Science &
Technology Foundation (2017JQ0010), National High Technology
Research & Development Program (2016ZX05053, 2016ZX05014-
005-007), Key Fund Project of Educational Commission of Sichuan
Province (16CZ0008), Explorative Project Fund (G201601) of State
Key Laboratory of Oil and Gas Reservoir Geology and Exploita-
tion (Southwest Petroleum University), China Postdoctoral Sci-
ence Foundation (2019M650250), and the National Natural Science
Foundation of China (41902303).
Supplementary materials
3. Conclusion
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jorganchem.2021.
121719.
In conclusion, we have developed a sustainable and convenient
Suzuki coupling reaction using in situ formed Pd@NC NPs [from NC
and Pd(OAc)2] as heterogeneous catalyst without the aid of exter-
nal reducing agents and ligand in water. The in situ generated cat-
alyst, Pd@NC NPs has been systematically characterized using TEM,
EDX, powder XRD and IR techniques. The successful reusability (up
to eleven tested cycles) is an added advantage of this finding. The
application of in situ generated catalyst, use of water as reaction
media, heterogeneous catalytic conditions, preparation of catalyst
from the waste cotton cloth, high scope of reusability of the cata-
lyst, easy separation of the catalyst by simple filtration and avoid of
toxic ligands or volatile organic solvents are the striking and sus-
tainable assets of this protocol.
References
[1] H.C. Erythropel, J.B. Zimmerman, T.M. de Winter, L. Petitjean, F. Melnikov,
C.H. Lam, A.W. Lounsbury, K.E. Mellor, N.Z. Jankovic´, Q. Tu, L.N. Pincus,
M.M. Falinski, W. Shi, P. Coish, D.L. Plata, P.T. Anastas, Green Chem. 20 (2018)
1929–1961.
[2] N.A. Elessawy, J.El Nady, W. Wazeer, A.B. Kashyout, Sci. Rep. 9 (2019) 1129.
[3] M. Hong, E.Y.X. Chen, Green Chem 19 (2017) 3692–3706.
[4] M. Rezayat, R.K. Blundell, J.E. Camp, D.A. Walsh, W. Thielemans, ACS Sustain.
Chem. Eng. 2 (2014) 1241–1250.
[5] L.S. Zhang, S.P. Gao, Y.P. Huang, Z.S. Liu, Talanta 154 (2016) 335–340.
[6] D.M. Alonso, J.Q. Bond, J.A. Dumesic, Green Chem 12 (2010) 1493–1513.
[7] B. Fresco-Cala, E.J. Carrasco-Correa, S. Cárdenas, J.M. Herrero-Martínez, Mi-
crochem. J. 139 (2018) 222–229.
[8] A. Kumar, K.P. Thompson-Adewumi, J.M. Nandhini, F. Collins, B.G.de la
Torre Albericio, Org. Process Res. Dev. 23 (2019) 1096–1100.
Declaration of Competing Interest
[9] M. Cortes-Clerget, J.Y. Berthon, I. Krolikiewicz-Renimel, L. Chaisemartin,
B.H. Lipshutz, Green Chem 19 (2017) 4263–4267.
Authors declare no known competing personal relation or fi-
nancial interest that could appear to influence the work presented
in this paper.
[10] K. Luo, L. Zhang, R. Yang, Y. Jin, J. Lin, Carbohydr. Polym. 200 (2018) 200–210.
[11] K.U. Rao, R.M. Appa, J. Lakshmidevi, R. Vijitha, K.S.V.K. Rao, M. Narasimhulu,
K. Venkateswarlu, Asian J. Org. Chem. 6 (2017) 751–757.
6

S.R. Aabaka, J. Mao, M. Lavanya et al.
Journal of Organometallic Chemistry 937 (2021) 121719
[12] T. Li, X. Qu, G. Xie, J. Mao, Chem. Asian J. 6 (2011) 1325–1330.
[13] J. Mao, Q. Hua, J. Guo, D. Shi, S. Ji, Synlett (2008) 2011–2016.
[14] S. Fortun, P. Beauclair, A.R. Schmitzer, RSC Adv. 7 (2017) 21036–21044.
[15] J. Mao, Q. Hua, G. Xie, Z. Yao, D. Shi, Eur. J. Org. Chem. (2009) 2262–2266.
[16] A.C. Tenchiu, I.K. Ventouri, G. Ntasi, D. Palles, G. Kokotos, D. Kovala-Demertzi,
I.D. Kostas, Inorganica Chim. Acta 435 (2015) 142–146.
[17] J. Mao, Q. Hua, G. Xie, J. Guo, Z. Yao, D. Shi, S. Ji, Adv. Synth. Catal. 351 (2009)
635–641.
[40] P.R. Boruah, A.A. Ali, B. Saikia, D. Sarma, Green Chem 17 (2015) 1442–1445.
[41] M. Chetia, P.R. Boruah, B. Saikia, A.A. Ali, D. Sarma, Chem. Commun. 51 (2015)
11489–11492.
[42] (a) R.M. Appa, S.S. Prasad, J. Lakshmidevi, B.R. Naidu, M. Narasimhulu,
K. Venkateswarlu, Appl. Organometal. Chem. 33 (2019) e5126; (b) J. Laksh-
midevi, V. Vakati, B.R. Naidu, M. Raghavender, K.S.V.K. Rao, K. Venkateswarlu,
Sustain. Chem. Pharm. 19 (2021) 100371.
[43] T. Baran, E. Açiksöz, A. Mentes¸ , J. Mol. Catal. A Chem. 407 (2015) 47–52.
[44] X. Wang, P. Hu, F. Xue, Y. Wei, Carbohydr. Polym. 114 (2014) 476–483.
[45] Z. Xiang, Y. Chen, Q. Liu, F. Lu, Green Chem 20 (2018) 1085–1094.
[46] D. Baruah, R.N. Das, S. Hazarika, D. Konwar, Catal. Commun. 72 (2015) 73–80.
[47] M. Hirota, N. Tamura, T. Saito, A. Isogai, Carbohydr. Polym. 78 (2009) 330–335.
[48] G. Morandi, L. Heath, W. Thielemans, Langmuir 25 (2009) 8280–8286.
[49] Y. Habibi, L.A. Lucia, O.J. Rojas, Chem. Rev. 110 (2010) 3479–3500.
[50] Z. Wang, Z. Yao, J. Zhou, Y. Zhang, Carbohydr. Polym. 157 (2017) 945–952.
[51] A. Ghorbani-Choghamarani, P. Moradi, B. Tahmasbi, Polyhedron 163 (2019)
98–107.
[18] S.E. Hooshmand, B. Heidari, R. Sedghi, R.S. Varma, Green Chem 21 (2019)
381–405.
[19] S. Banerjee, C. Basheer, R.N. Zare, Angew. Chem. Int. Ed. 55 (2016)
12807–12811.
[20] B. Yuan, Y. Pan, Y. Li, B. Yin, H. Jiang, Angew. Chem. Int. Ed. 49 (2010)
4054–4058.
[21] Y. Liu, H. Peng, J. Yuan, M.-Q. Yan, X. Luo, Q.-G. Wu, S.-H. Liu, J. Chen, G.-A. Yu,
Org. Biomol. Chem. 14 (2016) 4664–4668.
[22] W. Zawartka, P. Pos´piech, M. Cypryk, A.M. Trzeciak, J. Mol. Catal. A Chem. 417
(2016) 76–80.
[52] B. Tahmasbi, A. Ghorbani-Choghamarani, New J. Chem. 43 (2019)
14485–14501.
[53] P. Moradi, M. Hajjami, F. Valizadeh-Kakhki, Appl. Organometal. Chem. 33
(2019) e5205.
[54] N. Jamwal, R.K. Sodhi, P. Gupta, S. Paul, Int. J. Biol. Macromol. 49 (2011)
930–935.
[23] D. Kale, G. Rashinkar, A. Kumbhar, R. Salunkhe, React. Funct. Polym. 116 (2017)
9–16.
[24] S. Sadjadi, M. Akbari, E. Monflier, M.M. Heravi, B. Leger, 42 (2018) 15733–
15742.
[25] M. Esmaeilpour, A.R. Sardarian, H. Firouzabadi, J. Organomet. Chem. 873 (2018)
22–34.
[26] F. Heidari, M. Hekmati, H. Veisi, J. Colloid Interface Sci. 501 (2017) 175–184.
[27] K. Mennecke, A. Kirschning, Beilstein J. Org. Chem. 5 (2009) 21.
[28] Z. Jebali, A. Granados, A. Nabili, S. Boufi, A.M.B. do Rego, H. Majdoub, A. Vall-
ribera, Cellulose 25 (2018) 6963–6975.
[55] L.-J. Zhang, X. Yao, Y.-x. Sun, J.-w. Zhang, C. Cai, J. Chem. Res. 42 (2018)
419–423.
[56] J.I.G. Cadogan, M. Cameron-Wood, R.K. Mackie, R.J.G. Searle, J. Chem. Soc.
(1965) 4831–4837.
[57] A. Ghorbani-Choghamarani, B. Tahmasbi, R.H.E. Hudson, A. Heidari, Microp-
orous Mesoporous Mater 284 (2019) 366–377.
[29] M. Enneiymy, L. Drian, C.M. Ghimbeu, J.-M. Becht, RSC Adv.
17176–17182.
8 (2018)
[58] A. Jabbari, B. Tahmasbi, M. Nikoorazm, A. Ghorbani-Choghamarani,
Organometal. Chem. 32 (2018) e4295.
[30] J. Li, P. Huo, J. Zheng, X. Zhou, W. Liu, RSC Adv. 8 (2018) 24231–24235.
[31] M. Nasrollahzadeh, S.M. Sajadi, A. Rostami-Vartooni, M. Khalaj, J. Mol. Catal. A
Chem. 396 (2015) 31–39.
[59] B. Tahmasbi, A. Ghorbani-Choghamarani, P. Moradi, New J. Chem. 44 (2020)
3717–3727.
[32] M. Nasrollahzadeh, S.M. Sajadi, M. Maham, J. Mol. Catal. A Chem. 396 (2015)
297–303.
[60] M. Nikoorazm, N. Noori, B. Tahmasbi, S. Faryadi, Transit. Met. Chem. 42 (2017)
469–481.
[33] M. Khan, G.H. Albalawi, M.R. Shaik, M. Khan, S.F. Adil, M. Kuniyil, H.Z. Alkhath-
lan, A. Al-Warthan, M.R.H. Siddiqui, J. Saudi Chem. Soc. 21 (2017) 450–457.
[34] K. Alfonsi, J. Colberg, P.J. Dunn, T. Fevig, S. Jennings, T.A. Johnson, H.P. Kleine,
C. Knight, M.A. Nagy, D.A. Perry, M. Stefaniak, Green Chem 10 (2008) 31–36.
[35] K. Tahir, S. Nazir, B. Li, A. Ahmad, T. Nasir, A.U. Khan, S.A.A. Shah, Z.U.H. Khan,
G. Yasin, M.U. Hameed, J. Photochem. Photobiol. B Biol. 164 (2016) 164–173.
[36] A.J. Kora, L. Rastogi, Arab. J. Chem. 11 (2018) 1097–1106.
[37] D. Liu, F. Wu, Int. J. Electrochem. Sci. 12 (2017) 2125–2134.
[38] T.S.A. Heugebaert, S. de Corte, T. Sabbe, T. Hennebel, W. Verstraete, N. Boon,
C.V. Stevens, Tetrahedron Lett 53 (2012) 1410–1412.
[61] D.S. Rosa, B.P. Vargas, M.V. Silveira, C.H. Rosa, M.L. Martins, G.R. Rosa, Waste
Biomass Valor 10 (2019) 2285–2296.
[62] N. Shang, C. Feng, H. Zhang, S. Gao, R. Tang, C. Wang, Z. Wang, Catal. Commun.
40 (2013) 111–115.
[63] S. Gao, N. Shang, C. Feng, C. Wang, Z. Wang, RSC Adv. 4 (2014) 39242–39247.
[64] N. Shang, S. Gao, C. Feng, H. Zhang, C. Wang, Z. Wang, RSC Adv. 3 (2013)
21863–21868.
[65] W. Dong, L. Zhang, C. Wang, C. Feng, N. Shang, S. Gao, C. Wang, RSC Adv. 6
(2016) 37118–37123.
[39] M. Sathishkumar, K. Sneha, I.S. Kwak, J. Mao, S.J. Tripathy, Y.S. Yun, J. Hazard.
Mater. 171 (2009) 400–404.
7