Application of biosynthesized palladium nanoparticles (Pd NPs) on Rosa canina fruit extract-modified graphene oxide as heterogeneous nanocatalyst for cyanation of aryl halides

Article abstract of DOI:10.1002/aoc.5103

A green palladium (Pd)-based catalyst supported on Rosa canina fruit extract-modified graphene oxide [Pd nanoparticles (NPs)/reduced graphene oxide (RGO)-Rosa canina] hybrid materials has been used as a recoverable and heterogeneous nanocatalyst for cyanating aryl halides using K₄[Fe (CN)₆] as the resource of cyanide. The nitriles were achieved in good to high yield, and the catalyst can be recovered and reused for up to seven cycles with no remarkable decrease in its catalytic activity.

Full text of DOI:10.1002/aoc.5103

Received: 17 March 2019
DOI: 10.1002/aoc.5103
Revised: 12 June 2019
Accepted: 14 June 2019
F U L L P A P E R
Application of biosynthesized palladium nanoparticles
Pd NPs) on Rosa canina fruit extract‐modified graphene
(
oxide as heterogeneous nanocatalyst for cyanation of aryl
halides
1
2
3
4
Saba Hemmati
| Alireza Sedrpoushan | Negin Alizadeh | Kaveh Khosravi |
5
Malak Hekmati
1
Department of Chemistry, Payame Noor
University, Tehran, Iran
A green palladium (Pd)‐based catalyst supported on Rosa canina fruit extract‐
2
Department of Industrial Chemistry,
modified graphene oxide [Pd nanoparticles (NPs)/reduced graphene oxide
Iranian Research Organization for Science
and Technology, Tehran, Iran
(
RGO)‐Rosa canina] hybrid materials has been used as a recoverable and het-
erogeneous nanocatalyst for cyanating aryl halides using K [Fe (CN) ] as the
4
6
3
Department of Pharmaceutical
resource of cyanide. The nitriles were achieved in good to high yield, and the
catalyst can be recovered and reused for up to seven cycles with no remarkable
decrease in its catalytic activity.
Chemistry, Faculty of Pharmaceutical
Chemistry, Tehran Medical Sciences,
Islamic Azad University, Tehran, Iran
4
Department of Chemistry, Faculty of
Science, Arak University, Arak 38156‐8‐
KEYWORDS
8349, Iran
cyanation, graphene oxide, nanocatalyst, palladium, plant extract
5
Department of Organic Chemistry,
Faculty of Pharmaceutical Chemistry,
Tehran Medical Sciences,, Islamic Azad
University, Tehran, Iran
Correspondence
Malak Hekmati, Department of Organic
Chemistry, Faculty of Pharmaceutical
Chemistry, Tehran Medical Sciences,
Islamic Azad University, Tehran, Iran.
Email: mhekmatik@yahoo.com
Funding information
Payame Noor University; Pharmaceutical
Sciences Branch, Islamic Azad University,
(
IAUPS), Tehran, Iran
1
| INTRODUCTION
The production of these aryl nitriles needs a stoichio-
metric quantity of highly toxic cyanating reagents, such
[
6]
[7]
Aryl nitriles are one of the most adaptable organic
building blocks. They are available in many natural
products, and are utilized in agrochemicals, pharmaco-
logicals and fragrances.
group can be changed to several functional groups like
amides, carboxylic acids, aldehydes, ketones or amines.
as copper cyanide,
potassium cyanide,
sodium
[
8]
[1]
[9]
cyanide,
zinc cyanide
or trimethylsilylcyanide.
Moreover, applying relatively less toxic cyanating
[1–5]
[10]
Additionally, the nitrile
reagents, such as phenyl cyanates,
acetone cyanohy-
[
11]
[12]
drins
and benzyl thiocyanates,
is usually expensive
and risky. Applying potassium hexacyanoferrate (II)
Appl Organometal Chem. 2019;e5103.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5103

2
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HEMMATI ET AL.
trihydrate [K Fe(CN) ·3H O] as a cyanide resource in
synthesized well‐dispersed Pd NPs on the graphene
4
6
2
[13,14]
cyanation reactions by Schareina et al.
has
sheets used to degrade organic dyes in water in the exis-
[
38]
attracted attention because it is less toxic, inexpensive
tence of NaBH4.
Herein, in continuing on our previous
[
15,16]
[39]
and eco‐friendly.
In K Fe(CN) ·3H O, cyanide ions
work utilizing nanocatalysts,
we applied Pd
4
6
2
−
are bound powerfully, slowing down releasing CN ions
in the reaction environment, which in turn avoids fast
deactivation of palladium (Pd) catalysts as a result of
poisoning the palladium by CN ions.
studies on the application of palladium acetate,
NPs/RGO‐Rosa canina as an effective and heterogeneous
nanocatalyst for cyanating aryl halides (X = I, Br, Cl)
using low‐cost and non‐toxic K [Fe (CN) ] as a cyanation
4
6
−
[17]
There are
agent (Scheme 1).
[
18,19]
[
20]
[21]
palladium complex,
palladium on carbon
as catalysts for catalyzing cyanation reactions using
K Fe(CN) ·3H O. The key disadvantage of these cata-
2 | EXPERIMENTAL
4
6
2
lysts is the problem of recovering and recycling.
Therefore, improvement of palladium‐based catalysts,
2.1 | Rosa canina fruit extract preparation
[
22]
which have a highly active and heterogeneous nature, is
still a topic for studying as this can provide new benefits
while taking into account both environmental and eco-
nomical aspects.
The fresh Rosa canina fruits were rinsed thoroughly with
double‐distilled water before using. Fruits (10 g) were
added to deionized water (100 ml), and this mixture was
boiled in a water bath for 15 min. Next, the mixture
was passed through Whatman filter paper No. 1 to attain
aqueous extract and cooled down. The filtered extract was
kept in the refrigerator at a temperature of 4°C for the fol-
lowing experiments.
Amongst the available catalytic approaches for synthe-
sizing aryl nitriles, Pd‐catalyzed cyanation of aryl halides
has developed as one of the most commonly utilized pro-
[22–26]
cesses.
Though homogeneous Pd complexes,
frequently related with diverse phosphine ligands, are
[
20,27–32]
still the common studied catalysts in cyanation,
the application of heterogeneous systems is also
explained. Simple Pd/C was used primarily,
2.2 | The Pd NPs/RGO green synthesis
using Rosa canina fruit extract
[
1,33–37]
followed by developing polymer‐supported Pd (II)
complexes that were confirmed to be effective cyanation
Lastly, the Pd NPs/RGO‐Rosa canina was synthesized
with Rosa canina fruits aqueous extract. In order to syn-
thesize the Pd NPs/RGO‐Rosa canina, the extract was
mixed with the achieved GO from natural graphite pow-
[14,16,38–45]
catalysts in several cases.
In recent years,
with the advent of nanoparticle (NP) catalysis, diverse
[1,20,30–37]
Pd NP‐based catalysts have been developed.
[
40]
However, amongst supported/heterogeneous systems,
der by a modified Hummers method.
Next, 50 ml of
they have not been comparatively studied.
0.3 M Na PdCl was dropwise poured into the mixture
2
4
In recent years, we have developed the production
of Pd NPs supported on reduced graphene oxide (Pd
NPs/RGO‐Rosa canina) through reduction of the GO
at 100°C under agitation for 12 hr. The obtained Pd
NPs/RGO‐Rosa canina was isolated from the reaction
medium using centrifugation, rinsed using deionized
water several times, and characterized. The palladium
level in Pd NPs/RGO‐Rosa canina determined using
2+
and Pd ions with Rosa canina fruit extracts as a stabi-
[38]
lizer and reductant agent.
The utilized approach
SCHEME 1 Fabrication pathway of
palladium nanoparticles (Pd NPs)/reduced
graphene oxide (RGO)‐Rosa canina and its
application in the cyanation of aryl halides
4 6
using K [Fe (CN) ]

HEMMATI ET AL.
3 of 7
inductively coupled plasma‐atomic emission spectrome-
try was 5.42 wt%.
are known ingredients and were compared with real
samples.
3
| RESULTS AND DISCUSSION
2.3 | General procedure for cyanation
reactions catalyzed by Pd NPs/RGO‐Rosa
In the current study, Pd NPs/RGO‐Rosa canina was syn-
thesized over one step by reducing Pd (II) ions and GO
with the extract of Rosa canina fruit as a stabilizer and
reductant agent. In this study, it is assumed that the exis-
tence of phenols and acid compounds in the extract
results in bioreduction and stabilization of Pd NPs with-
out using toxic ingredients and toxic organic solvents.
The transmission electron microscopy and energy‐
dispersive X‐ray (EDX) analyses were used to prove the
nanostructure of Pd NPs/RGO‐Rosa canina that was
prepared again based on our earlier report with a little
canina
A solution of K [Fe (CN) ] (0.17 mmol), aryl halide
4
6
(
1.0 mmol), Na CO3 (1.5 mmol), Pd NPs/RGO‐Rosa
2
canina (10 mg, 0.5 mol%) and DMF (5 ml) was prepared
under stirring at a temperature of 120°C for the specified
time. The reaction was followed using thin‐layer chroma-
tography. After completing the reaction, the achieved
solution was cooled to room temperature and centri-
fuged, and the residue was washed with ethyl acetate
[38]
(3 × 10 ml). In order to extract the ethyl acetate from
modification in the resource of palladium ions.
The
the water phase (30 ml), it was combined with the
organic phase. The organic phase was dried using
Na SO . The products were obtained by evaporation of
the organic solvent. In the case of requiring more purifi-
cation, the products were passed through a short silica
gel column using the eluent of n‐hexane. All the products
image corresponding to nanocatalyst (Pd NPs/RGO‐Rosa
canina) at 100 nm indicated that the Pd NPs are well dis-
tributed on the surface of reduced GO. The results
showed that Rosa canina fruit extract plays a key role in
enhancing the dispersibility of Pd NPs (Figure 1). Most
of these particles are in the range of 10–15 nm.
2
4
FIGURE 1 Transmission electron microscopy image of palladium nanoparticles (Pd NPs)/reduced graphene oxide (RGO)‐Rosa canina

4
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HEMMATI ET AL.
FIGURE 2 Energy‐dispersive X‐ray (EDX) spectrum of palladium nanoparticles (Pd NPs)/reduced graphene oxide (RGO)‐Rosa canina
Furthermore, the presence of extract's biomolecules on
the surface of graphene and Pd NPs was proved using
EDX, which confirmed the existence of C, N, O and Pd,
as shown in Figure 2.
TABLE 1 The optimization of reaction parameters for cyanation
of 4‐iodotoluene using K
4
[Fe (CN)
6
] catalyzed by Pd NPs/RGO‐Rosa
a
canina
After characterizing prepared Pd NPs/RGO‐Rosa
canina, its catalytic performance was evaluated on
cyanation of aryl halides (Scheme 1). K [Fe (CN) ] was
Pd
T
Time
Yield
(%)
4
6
b
Entry (mol%) Solvent Base
(°C) (hr)
selected as the cyanide resource in aryl halide cyanation
because it is low toxic, readily available and cost‐effective.
The cyanation of 4‐iodotoluene was selected as the model
reaction to optimize the reaction conditions. The effect of
diverse reaction parameters, including solvent, base, tem-
perature and amount of catalyst, were studied in detail
1
2
3
4
5
6
7
8
9
1
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.4
0.7
0.0
DMF
K
K
K
K
K
K
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
120
120
120
120
120
120
120
120
120
120
8
12
12
24
12
12
12
12
5
82
40
25
25
75
50
45
25
96
30
0
Toluene
EtOH
2
H O
3
CH CN
(Table 1). The reaction did not proceed without using base
Xylene
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
and palladium resource (Table 1, entries 11 and 17).
However, introduction of the catalyst to the reaction solu-
tion rapidly resulted in the product in high yields. In the
case of solvent, DMF was found to be superior. Among
the studied bases, Na CO gave better outcomes over other
NaOAc
Et
Na
NaOH
3
N
2
CO
3
2
3
0
1
24
24
12
12
24
12
5
bases. Moreover, the effect of catalyst loading was
examined in the range of 0.4–0.7 mol% (Table 1, entries 9,
No base 120
1
5 and 16). According to the outcomes, the highest perfor-
mance can be obtained by 0.010 g (0.5 mol%) of the catalyst
Table 1, entry 9). Additionally, the optimum reaction tem-
12
Na
Na
Na
Na
Na
Na
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
100
80
75
60
20
75
96
0
13
14
15
16
(
25
perature was obtained as 120°C (entry 9 vs. entries 12–14).
Lower yield of the main product was studied at a reaction
temperature of 25°C (Table 1, entry 14).
Table 2 demonstrates the results of investigating the
substrate scope in aryl halide cyanation reaction using
Pd NPs/RGO‐Rosa canina under optimal conditions
120
120
120
17
24
a
Reaction conditions: 4‐iodotoluene (1.0 mmol), K
catalyst, base (1.5 mmol) and solvent (5 ml).
4
[Fe (CN)
6
] (0.17 mmol),
b
(Table 1, entry 9) for different aryl halides with
Isolated yield.

HEMMATI ET AL.
5 of 7
TABLE 2 Pd NPs/RGO‐Rosa canina‐catalyzed cyanation of aryl
halides using K [Fe (CN) ]
4 6
products was less compared with their iodide and bro-
mide counterparts.
a
Recyclability is a key parameter to judge the adaptabil-
ity and importance of the catalyst. Thus, recyclability of
Pd NPs/RGO‐Rosa canina catalyst was studied over the
cyanation of 4‐iodotoluene with K [Fe (CN) ]. At the
b
c
Entry
Aryl halide
Time (hr)
Yield (%)
Ref
4
6
[
[
[
[
[
[
[
[
[
[
[
[
[
[
41]
41]
41]
16]
16]
16]
14]
14]
14]
14]
16]
16]
42]
42]
end of each cycle, the catalyst can be successfully retained
from the reaction solution through centrifugation, and is
rinsed with ethanol and water and dried. The retained
catalyst can be reused up to seven times with no decrease
in its performance (Figure 3).
Leaching of palladium ions is a major issue for
supported palladium catalysts, and avoids separating
and recovering catalyst. Consequently, leaching investi-
gation was accomplished from separating the Pd
NPs/RGO‐Rosa canina catalyst following 30 min of
reaction time for the model reaction, and the similar
reaction was also performed for more than 3 hr and
the separation yield obtained was about 55%. This
proves that leaching of palladium from the Pd
NPs/RGO‐Rosa canina catalyst was not taking place,
1
2
3
4
5
6
7
8
9
C
C
C
6
6
6
H
H
H
5
5
5
I
2
4
96
90
60
95
90
50
96
85
90
90
96
95
90
85
Br
Cl
7
p‐NCC
p‐NCC
p‐NCC
6
6
6
H
H
H
4
4
4
I
5
Br
Cl
8
10
5
p‐CH
p‐CH
p‐CH
p‐CH
3
3
3
3
C
C
6
6
H
H
4
I
4
Br
6
OC
6
6
H
H
4
4
I
4
1
1
1
1
1
0
1
2
3
4
OC
Br
6
p‐NO
2
C
6
H
4
I
5
p‐ NO
2
C
6
H
4
Br
6
o‐CH
o‐CH
3
3
OC
6
6
H
H
4
4
I
8
OC
Br
12
a
Reaction conditions: arylhalide (1.0 mmol), K
4 6
[Fe (CN) ] (0.2 mmol),
Na CO (1.5 mmol), Pd NPs/RGO (0.5 mol%) were stirred in DMF (5.0 ml)
2
3
at 120°C.
b
Isolated yield.
c
Earlier reference of the corresponding product.
electron‐withdrawing and electron‐donating groups. Aryl
halides with both electron‐withdrawing and electron‐
donating groups have good tolerance and result in good
to high yields by adjusting the reaction time. Both aryl
iodides and aryl bromides underwent the cyanation
reaction acceptably and their yields were comparatively
similar. However, converting aryl chlorides to cyanated
SCHEME 2 Proposed mechanism for palladium nanoparticles
(Pd NPs)/reduced graphene oxide (RGO)‐Rosa canina‐catalyzed
cyanation of aryl halides
FIGURE 3 The recycling of the palladium nanoparticles (Pd NPs)/reduced graphene oxide (RGO)‐Rosa canina

6
of 7
HEMMATI ET AL.
TABLE 3 Comparison efficiency of Pd NPs/RGO‐Rosa canina
with some reported catalysts for the cyanation of 4‐
and Payame Noor University for partial support of this
work.
bromonitrobenzene using K
4
[Fe (CN)]
6
as cyanide source
Time
(hr)
ORCID
Entry Reaction conditions
Yield% Ref.
Saba Hemmati https://orcid.org/0000-0003-2672-7948
Malak Hekmati https://orcid.org/0000-0003-0790-569X
r
r
[44]
1
Pd@CC
40°C
1
/Pd@CC
2
, DMF,
15
99
1
[
[
45]
46]
2
3
Pd‐Zeolite, DMF, 130°C
PdNCs/C@Fe , DMF,
20°C
Pd/C, PEG4000‐H
10
18
90
96
REFERENCES
3 4
O
1
[
1] H. Yu, R. N. Richey, W. D. Miller, J. Xu, S. A. May, J. Org. Chem.
011, 76(2), 665.
[2] T. Chatterjee, R. Dey, B. C. Ranu, J. Org. Chem. 2014, 79
12), 5875.
a
a
[21]
[47]
2
4
5
6
7
2
O, 140°C
2
7
8
6
75
92
87
95
Palladacycle‐1, DMF, 130°C
(
[
48]
Pd/PPy, NMP, 120°C
[
[
[
[
3] H. Veisi, S. Hemmati, P. Safarimehr, J. Catal. 2018, 365, 204.
4] R. Ghorbani‐Vaghei, H. Veisi, Synthesis 2009, 345.
5] H. Veisi, Synthesis 2010, 2010, 2631.
Pd NPs/RGO‐Rosa canina,
DMF, 120°C
This
work
a
Under microwave irradiation.
6] T. Sakamoto, K. Ohsawa, J. Chem. Soc. Perkin Trans. 1999,
1
(16), 2323.
7] M. Sundermeier, A. Zapf, M. Beller, J. Sans, Tetrahedron Lett.
001, 42(38), 6707.
8] A. V. Ushkov, V. V. Grushin, J. Am. Chem. Soc. 2011, 133(28),
0 999.
[
[
[
perhaps owing to the particular nature of the prepared
Pd NPs/RGO‐Rosa canina catalyst.
2
A likely mechanism for the Pd NPs/RGO‐Rosa
canina‐catalyzed cyanation reaction is a well‐known
mechanism relating to cyanation of aryl halides, which
1
9] M. Sundermeier, S. Mutyala, A. Zapf, A. Spannenberg, M.
Beller, J. Organomet. Chem. 2003, 684(1–2), 50.
[14,43]
occurs on the catalyst surface (Scheme 2).
The
[
10] N. Sato, Tetrahedron Lett. 2002, 43(36), 6403.
reaction progressed by the oxidative addition of aryl
halide over catalyst and continued via moving cyanide
anion from K [Fe (CN)] , and finally the reductive
[
11] T. Schareina, A. Zapf, A. Cotté, M. Gotta, M. Beller, Adv. Synth.
Catal. 2011, 353(5), 777.
4
6
[
12] J. Kim, H. J. Kim, S. Chang, Angew. Chem. Int. Ed. 2012, 51(48),
removal phase resulted in the aryl cyanide product.
In order to prove the application of Pd NPs/RGO‐Rosa
canina catalyst in cyanation of 4‐bromonitrobenzene
using K [Fe (CN)] as cyanide source, this catalyst was
1
1 948.
[
13] T. Schareina, A. Zapf, M. Beller, Chem. Commun. 2004, 12, 1388.
14] T. Schareina, A. Zapf, M. Beller, J. Organomet. Chem. 2004,
[
4
6
689(24), 4576.
compared with several other proposed palladium cata-
lysts (Table 3). As presented in Table 3, our catalyst sys-
tem is comparable with the proposed homogeneous and
heterogeneous catalysts in terms of efficiency.
[
15] H. Veisi, Polyhedron 2018, 159, 212.
[
16] M. Nasrollahzadeh, S. M. Sajadi, J. Colloid Interface Sci. 2016,
469, 191.
[
[
[
[
[
[
17] S. Erhardt, V. V. Grushin, A. H. Kilpatrick, S. A. Macgregor, W.
J. Marshall, D. C. Roe, J. Am. Chem. Soc. 2008, 130(14), 4828.
18] P. Y. Yeung, C. M. So, C. P. Lau, F. Y. Kwong, Org. Lett. 2011,
1
3(4), 648.
19] S. Velmathi, N. E. Leadbeater, Tetrahedron Lett. 2008, 49
32), 4693.
20] T. D. Senecal, W. Shu, S. L. Buchwald, Angew. Chem. Int. Ed.
013, 52(38), 10 035.
4
| CONCLUSION
(
In conclusion, Pd NPs/RGO‐Rosa canina can be applied
as an effective and recyclable heterogeneous nanocatalyst
for cyanating aryl halides with K [Fe (CN) ] as the
2
4
6
21] G. Chen, J. Weng, Z. Zheng, X. Zhu, Y. Cai, J. Cai, Y. Wan, Eur.
J. Org. Chem. 2008, 20, 3524.
cyanation agent. The nitriles were produced in good to
high yield, and the catalyst can be recovered and reused
for up to seven cycles without considerably changing its
catalytic behavior.
22] (a) E. Farzad, H. Veisi, J. Indus. Eng. Chem. 2018, 60, 114. (b) H.
Veisi, S. Razeghi, P. Mohammadi, S. Hemmati, Mater. Sci. Eng.
C 2019, 97, 624. (c) H. Veisi, S. B. Moradi, A. Saljooqi, P.
Safarimehr, Mater. Sci. Eng. C 2019, 100, 445. (d) H. Veisi, M.
Ghorbani, S. Hemmati, Mater. Sci. Eng. C 2019, 98, 584. (e)
H. Veisi, P. Safarimehr, S. Hemmati, Mater. Sci. Eng. C 2019,
ACKNOWLEDGEMENTS
96, 310. (f) H. Veisi, M. Pirhayati, A. Kakanejadifard, P.
The authors are thankful to Pharmaceutical Sciences
Branch, Islamic Azad University, (IAUPS), Tehran, Iran
Mohammadi, M. R. Abdi, J. Gholami, S. Hemmati, ChemSelect
2018, 3, 1820. (g) H. Veisi, M. Pirhayati, A. Kakanejadifard,

HEMMATI ET AL.
7 of 7
Tetrahedron Lett. 2017, 58, 4269. (h) H. Veisi, S. A. Mirshokraie,
H. Ahmadian, Int. J. Biol. Macromol. 2018, 108, 419. (i) H. Veisi,
S. Najafi, S. Hemmati, Int. J. Biol. Macromol. 2018, 113, 186.
54, 1640. (i) G. Shaham, H. Veisi, M. Hekmati, Appl.
Organomet. Chem. 2017, 31, e3737. (j) S. Mirfakhrae, M.
Hekmati, F. Hosseini Eshbala, H. Veisi, New J. Chem. 2018,
42, 1757. (k) H. Veisi, Y. Metghalchi, M. Hekmati, S.
[
23] (a) P. Anbarasan, T. Schareina, M. Beller, Chem. Soc. Rev. 2011,
Samadzadeh, Appl. Organomet. Chem. 2017, 31, e3676. (l) E.
Akhavan, S. Hemmati, M. Hekmati, H. Veisi, New Chem
4
0, 5049. (b) M. Sundermeier, A. Zapf, M. Beller, Eur. J. Org.
Chem. 2013, 19, 3513.
2
018, 42, 2782. (mH. Veisi, M. Kavian, M. Hekmati, S.
[
[
[
[
[
[
[
[
24] K. Takagi, T. Okamoto, Y. Sakakibara, A. Ohno, S. Oka, N.
Hemmati, Polyhedron 2019, 161, 338. (n) S. Hemmati, L.
Mehrazin, M. Hekmati, M. Izadi, H. Veisi, Mater. Chem. Phys.
2
Chem. 2017, 31, e3600. (p) M. Hajighorbani, M. Hekmati,
RSC Adv. 2016, 6, 88 916.
Hayama, Bull. Chem. Soc. Jpn. 1975, 48, 3298.
25] T. Schareina, R. Jackstell, T. Schulz, A. Zapf, A. Cotte´, M.
018, 214, 527. (o) S. Abbasi, M. Hekmati, Appl. Organomet.
Gotta, M. Beller, Adv. Synth. Catal. 2009, 351, 643.
26] M. Vafaeezadeh, M. M. Hashemi, M. Karbalaie‐Reza, Inorg.
Chem. Commun. 2016, 72, 86.
[
40] N. I. Kovtyukhova, P. J. Ollivier, B. R. Martin, T. E. Mallouk, S.
27] M. Sundermeier, A. Zapf, M. Beller, Angew. Chem. Int. Ed.
A. Chizhik, E. V. Buzaneva, A. D. Gorchinskiy, Chem. Mater.
2
003, 42, 1661.
1999, 11, 771.
28] A. Littke, M. Soumeillant, R. F. Kaltenbach, R. J. Cherney, C.
[
41] K. Niknam, A. Deris, F. Panahi, Chinese J. Catal. 2013, 34, 718.
42] D. Ganapathy, S. Srinivas Kotha, G. Sekar, Tetrahedron Lett.
M. Tarby, S. Kiau, Org. Lett. 2007, 9, 1711.
[
29] J. Zhang, X. Chen, T. Hu, Y. Zhang, K. Xu, Y. Yu, J. Huang,
2
015, 56, 175.
43] M. Gholinejad, A. Aminianfar, J. Mol, Catal. A Chem. 2015,
97, 106.
Catal. Lett. 2010, 139, 56.
[
[
[
[
30] M. Utsugi, H. Ozawa, E. Toyofuku, M. Hatsuda, Org. Process
Res. Dev. 2014, 18, 693.
3
44] B. Mondal, K. Acharyya, P. Howlader, P. S. Mukherjee, J. Am.
Chem. Soc. 2016, 138(5), 1709.
31] J. R. Coombs, K. J. Fraunhoffer, E. M. Simmons, J. M. Stevens,
S. R. Wisniewski, M. Yu, J. Org. Chem. 2017, 82, 7040.
45] S. M. Sajadi, M. Maham, S. A. Mahmoud, J. Chem. Res. 2013,
[
[
[
[
[
[
32] S. Shi, M. Szostak, Org. Lett. 2017, 19, 3095.
37(10), 620.
33] M. Hatsuda, M. Seki, Tetrahedron 2005, 61, 9908.
34] M. Hatsuda, M. Seki, Tetrahedron Lett. 2005, 46, 1849.
35] Y.‐Z. Zhu, C. Cai, Eur. J. Org. Chem. 2007, 2007, 2401.
36] Y.‐Z. Zhu, C. Cai, Synth. Commun. 2007, 37, 3359.
46] B. Suresh Kumar, A. J. Amali, K. Pitchumani, ACS Appl. Mater.
Interfaces 2015, 7(41), 22 907.
[47] A. R. Hajipour, K. Karami, G. Tavakoli, A. Pirisedigh,
J. Organomet. Chem. 2011, 696(4), 819.
37] G. Chen, J. Weng, Z. Zheng, X. Zhu, Y. Cai, J. Cai, Y. Wan, Eur.
J. Org. Chem. 2008, 2008, 3415.
[48] T. V. Magdesieva, O. M. Nikitin, E. V. Zolotukhina, M. A.
Vorotyntsev, Electrochim. Acta 2014, 122, 289.
[
38] S. Hemmati, L. Mehrazin, H. Ghorban, S. Hossein Garakani, T.
Hashemi Mobaraki, P. Mohammadi, H. Veisi, RSC Adv. 2018,
8
, 21 020.
39] (a) F. Bonyasi, M. Hekmati, H. Veisi, J. Colloid Interface Sci.
017, 496, 177. (b) H. Veisi, M. Hekmati, S. Hemmati,
How to cite this article: Hemmati S,
Sedrpoushan A, Alizadeh N, Khosravi K, Hekmati
M. Application of biosynthesized palladium
nanoparticles (Pd NPs) on Rosa canina fruit extract‐
modified graphene oxide as heterogeneous
nanocatalyst for cyanation of aryl halides. Appl
Organometal Chem. 2019;e5103. https://doi.org/
10.1002/aoc.5103
[
2
J. Heterocyclic Chem. 2017, 54, 1630. (c) M. Shahriary, H. Veisi,
M. Hekmati, S. Hemmati, Mater. Sci. Eng. C 2018, 90, 57. (d) S.
Lebaschi, M. Hekmati, H. Veisi, J. Colloid Interface Sci. 2017,
4
85, 223. (e) F. Heidari, M. Hekmati, H. Veisi, J. Colloid
Interface Sci. 2017, 501, 175. (f) S. Taheri, H. Veisi, M. Hekmati,
New J. Chem. 2017, 41, 5075. (g) H. Veisi, S. Taheri, S.
Hemmati, Green Chem. 2016, 18, 6337. (h) S. Hemmati, P.
Safarimehr, M. Hekmati, H. Veisi, J. Heterocyclic Chem. 2017,