Synthesis, characterization and catalytic properties of a new binuclear copper(II) complex in the azide–alkyne cycloaddition

Article abstract of DOI:10.1016/j.poly.2020.114698

A new binuclear copper(II)–oxalate complex containing 2,9-dimethyl-1,10-phenanthroline (dmp), was synthesized via a simple and one-pot reaction. [Cu₂(dmp)₂(ox)Cl₂]·H₂O (1) was characterized by single-crystal X-ray crystallography and IR methods. The complex 1 was been used to efficiently catalyze the three-component 1,3-Dipolar cycloaddition CuAAC reaction to produce 1,4-disubstituted 1,2,3‐triazoles in good to excellent yields from aromatic or aliphatic halide, sodium azide, and acetylene in water as a green solvent with low catalyst amount.

Full text of DOI:10.1016/j.poly.2020.114698

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Synthesis, characterization and catalytic properties of a new binuclear cop‐
per(II) complex in the azide–alkyne cycloaddition
Ali Akbar Khandar, Ayda Sheykhi, Mojtaba Amini, Arkady Ellern, L. Keith
Woo
PII:
S0277-5387(20)30355-7
DOI:
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https://doi.org/10.1016/j.poly.2020.114698
POLY 114698
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Polyhedron
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2 July 2020
Please cite this article as: A. Akbar Khandar, A. Sheykhi, M. Amini, A. Ellern, L. Keith Woo, Synthesis,
characterization and catalytic properties of a new binuclear copper(II) complex in the azide–alkyne cycloaddition,
Polyhedron (2020), doi: https://doi.org/10.1016/j.poly.2020.114698
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Synthesis, characterization and catalytic properties of a new binuclear
copper(II) complex in the azide–alkyne cycloaddition
Ali Akbar Khandar,a Ayda Sheykhi,a Mojtaba Aminib, Arkady Ellernc and L. Keith Wooc
a Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, P.O. Box 5166616471,
Tabriz, Iran
b Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
c Chemistry Department, Iowa State University, Ames, Iowa 50011-3111, USA
Abstract
A new binuclear copper(II)–oxalate complex containing 2,9-dimethyl-1,10-phenanthroline
(dmp), was synthesized via a simple and one-pot reaction. [Cu2(dmp)2(ox)Cl2]·H2O (1) was
characterized by single-crystal X-ray crystallography and IR methods. The complex 1 was been
used to efficiently catalyze the three-component 1,3-Dipolar cycloaddition CuAAC reaction to
produce 1,4-disubstituted 1,2,3‐triazoles in good to excellent yields from aromatic or aliphatic
halide, sodium azide, and acetylene in water as a green solvent with low catalyst amount.
Keywords: CuAAC reaction; 1,2,3-Triazole; Crystal structures; Binuclear Cu(II) complex
Introduction
“Click chemistry” as a powerful route to the simple and high yielding synthesis of irreversible C-
C or C-X (X = heteroatom) bonds, is an interesting concept to the preparation of various
chemicals and pharmaceutical compounds [1–4]. In fact, this idea was presented by Sharpless
and coworkers for the first time and consists on modern organic synthesis among selective, atom
economically, various molecules generation, high yield with safe (or no) side-product and easy
experimentally routes [5–9]. A combination of click chemistry and green chemistry can provide
some rapid, effective and as well as environmentally friendly procedures [10]. 1,3-dipolar azide-
 Corresponding authors. Tel.: +98 41 37278900; Fax: +98 41 37276066; E-mail address: akhandar@yahoo.com
(A.K.) and mamini@maragheh.ac.ir (M.A.)
1

alkyne cycloaddition reaction is one of the most well-known and powerful click chemistry
reactions because of their development in rate and regioselectivity [11,12]. The five-membered
heterocyclic 1,2,3-triazoles as synthetically and biologically valuable compounds are the
products of these reactions [13].
The application of transition metal complexes in wide range fields such as catalysis, material
sciences, nanotechnology and biological sciences makes them as important compounds [14]. In
recent decades, di- and poly-nuclear Cu(II) complexes due to their variety in structure, distortion
in coordination geometry and application in the catalytic systems, medical sciences,
biochemistry and sensing devices have attracted significant interest [15]. Copper-based
complexes and materials because of their widespread oxidation states (0, I, II and III) and
subsequently their ability to promote reactions via one and two-electron pathways, have many
attractions for use as organic transformations catalysts such as copper-catalyzed azide-alkyne
cycloaddition (CuAAC) reaction [16]. CuAAC catalytic system has some significant advantages
such as moderate heating condition, regioselectivity, broad area, green chemistry medium, and
tolerate the existence of high functional groups [17–20]. The Cu was applied as an efficient
catalyst for the synthesis of 1,2,3-triazoles in both ionic and complex forms (metal or salt)
[21,22] and using of this method (CuAAC) is one of the well-known procedures in modern
organic synthesis [23,24].
Herein, we report a newly binuclear copper complex synthesis route with 2,9-dimethyl-1,10-
phenanthroline bidentate ligand and oxalate anion as a bridge between Cu atoms and its
characterization with single-crystal X-ray crystallography. The application of this complex as an
effective catalyst in the selective formation of various 1,4-disubstituted 1,2,3-triazoles was also
investigated.
Experimental Section
Chemicals and materials
The chemicals and solvents were supplied from commercial sources and used without further
purification.
Synthesis of [Cu2(dmp)2(ox)Cl2].H2O (1)
2

[Cu2(dmp)2(ox)Cl2] was synthesized as follows: a certain amount of of CuCl2.2H2O (68 mg, 0.40
mmol) was dissolved in H2O (20 mL) and obtained solution was successively added to a mixed
solution of 2,9-dimethyl-1,10-phenanthroline (62 mg, 0.40 mmol) in ethanol (10 mL) and oxalic
acid (25 mg, 0.20 mmol) in water (10 mL) under stirring. The final solution was heated to 80 °C
for 1 h and then filtered. After some days standing and slowly evaporating, green crystals were
obtained at room temperature and a suitable single crystal of them chosen to X-ray diffraction
study.
Synthesis of alkyl azides
Alkyl azides was prepared according to reported procedure with some modification [25]. Sodium
azide (360 mg, 5.5 mmol) was added to 11 mL DMSO and stirred for 24 h at room temperature.
Then, the alkyl bromide (5.0 mmol) was transferred to the previous solution and the mixture was
stirred for 4 h. Diethyl ether (2 ×20 mL) was used to extraction of the obtained product. The
extracted solution was washed with water (2 ×20 mL) and then dried with MgSO4 and the
solvent was removed under reduced pressure to obtain pure alkyl azide.
Typical experimental procedure for the click reaction
A mixture of the alkyne (0.5 mmol), benzyl halide (0.52 mmol) and sodium azide (0.55 mmol)
was successively added to [Cu2(dmp)2(ox)Cl2] (0.004 mmol) in 2 mL water and heated at 70 °C
for 6 h (for aliphatic azides, alkyl azide (0.52 mmol) were used instead of benzyl halide and
sodium azide). Reaction completion was monitored by TLC. After the extraction of the organic
layer with ethyl acetate (2×10 mL), the residue water was removed by CaCl2. The ethyl acetate
was eliminated under vacuum to obtain the corresponding product. The recovered catalyst
washed with ether and ethyl acetate, dried and then utilized for the next run.
Results and Discussion
The complex 1 has been successfully synthesized by a one-pot reaction between copper chloride,
2,9-dimethyl-1,10-phenanthroline and oxalic acid. The oxalate bidentate ligand as a bridging
group has an imperative position in the binuclear Cu complexes. Heretofore several binuclear
copper complexes using oxalate ligand such as [Cu2(ox)(phen)2(H2O)2](NO3)2.2H2O (phen =
1,10-phenanthroline) [26], [Cu2(ox)(phen)2(C3H7NO)2](ClO4)2 (C3H7NO = 2,5-dihydroxy-1,4-
dithiane) [27], [Cu2(dpq)2(H2O)2(ox)](ClO4)2.2H2O (dpq = dipyridoquinoxaline) [28] and
3

[{Cu(NO3)(H2O)(bipy)}2(ox)] (bipy = 2,2′-bipyridine) [29] were reported. Also, oxalate ligand
was used for synthesis of some binuclear other metal complexes e.g.
[{(N)4}2M2(ox)](ClO4)2.xH2O (M = Mn, FeII, CoII; (N)4 = bispicen, bispictn, bispicMe2en;
bispicen = N,N′-bis(2-pyridylmethyl)-1,2-ethanediamine, bispictn = N,N′-bis(2-pyridylmethyl)-
1,3-propanediamine,
bispicMe2en
=
N,N′-bis(2-pyridylmethyl)-N,N′-dimethyl-1,2-
ethanediamine) [30] and [(acac)2Fe(ox)Fe(acac)2] (acac = acetylacetonate) [31]. The structure of
[Cu2(dmp)2(ox)Cl2] was determined by the single-crystal X-ray analysis. Crystallographic data
and details of the refinement parameters for complex 1 are summarized in Table 1. This
compound crystallized in P-1 space group and belongs to the triclinic crystal system. As shown
in Fig. 1 and 2, the copper complex 1 is built up of neutral dinuclear
[(dmp)ClCu(C2O4)CuCl(dmp)] building blocks with an inversion center in the midst of the
carbon-carbon bond of the oxalate bridging ligand. The Cu centers linked together by
carboxylate bridging ligands and also the complex entities held together by hydrogen bond and
π-π interactions. A five-coordinated distorted square pyramidal geometry is observed for each
copper center [15,26]. Also, each of copper atoms linked to one 2,9-dimethyl-1,10-
phenanthroline and one Cl- ligand.
Fig. 1. ORTEP drawing of [Cu2(dmp)2(ox)Cl2]
4

Fig. 2. Three-dimensional view of network in 1. Yellow: Cu, red: O, blue: N, green: Cl, white: C and
white sphere: H
Table 1. Summary of the crystal data and structure refinements for [Cu2(dmp)2(ox)Cl2]
[Cu2(dmp)2(ox)Cl2] •H2O
Formola
Formula weight
Temperature [K]
λ [Å]
C30H26Cl2Cu2N4O5
720.53
173(2)
0.71073
Crystal system
Space group
a [Å]
Triclinic
P -1
12.9002(9)
14.9391(10)
31.021(2)
103.9179(18)
95.984(2)
90.0493(19)
5769.1(7)
2, 2.462
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z, ρcalc [g cm-3]
5

μ [mm-1]
F(000)
2.445
2928
rflns: total
5779
Abs. corr.
Multi-Scan
Min., max.
0.7720,0.6110
Transmission factors
R1 [I > 2σ(I)]
wR2 (all data)
0.0461
0.1135
Fig. 3. shows the average of bond lengths and also the range of bond distances (except C-H
bonds) in the compound 1. The Cu-N bond distances are in the range of 2.001(4)-2.207(4) Å
(with a mean length of 2.107 Å). Cu-Cl bond lengths are 2.2390(13) and 2.2706(13) Å. The bond
lengths of Cu-O(ox) vary from 1.969(3) to 2.028(3) Å (with an average bond length of 2.004 Å).
The average of C(dmp)-N(dmp), C(ox)-O(ox), C(ox)-C(ox), C(dmp)-C(dmp) and C(dmp)-
C(Me) bond distances are 1.346, 1.256, 1.521, 1.395 and 1.487 Å, respectively, that are
comparable with same bond lengths in the previously reported compounds [32–34]. Also, the
N(dmp)-Cu-N(dmp) bond angles (79.49(15) and 79.61(15) °) are smaller than O(ox)-Cu-O(ox)
bond angles (82.58(12) and 83.36(12) °).
2.40
2.20
2.00
1.80
1.60
1.40
1.20
1.00
bond
6

Fig 3. The average of bond lengths in the compound 1
Catalytic Studies
The catalytic properties of the [Cu2(dmp)2(ox)Cl2] complex were investigated in the synthesis of
1,2,3-triazoles from alkynes, halides and sodium azide as precursors. The reactions were
conducted on a model multicomponent procedure of benzyl chloride, phenylacetylene and NaN3
to studying of azide-alkyne cycloaddition reaction in the present of water as the green solvent
under air at 70 °C for 6 h. The reaction conditions were optimized with respect to the solvent,
quantity of catalyst, reaction time and the reaction mixture temperature and the results are
collected in Table 2. It was found that [Cu2(dmp)2(ox)Cl2] complex showed higher efficiency
than catalyst-free condition and CuCl2 powder (entries 1, 2) in the synthesis of 1-Benzyl-4-
phenyl-1H-1,2,3-triazole. Solvents have an overriding influence on the azide-alkyne
cycloaddition reaction. As can be seen from Table 2, in the comparison of aprotic solvents
(acetonitrile, n-hexane, tetrahydrofuran, ethyl acetate and toluene) with protic solvents (water,
ethanol and methanol), protic solvents displayed higher performance (entries 3-10). Among all
solvents, synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole in the presence of water as a green
solvent obtained the best isolated yield (99%). For the investigation of the amount of catalyst
effect, a series of experiments were carried out by using of 0.001, 0.002, 0.004 and 0.006 mmol
Cu2(dmp)2(ox)Cl2 in H2O at 70 °C for 6 h (entries 10-13), results were illustrated that with
increasing of catalyst from 0.001 to 0.004 mmol, an increase in the reaction yield from 73% to
99% was observed. However, further increase in the catalyst amount to 0.006 mmol, didn’t have
an influence in the isolated yield of triazole product. Based on some results related to the
investigation of the influence of temperature in the azide-alkyne cycloaddition reaction, it was
observed that increasing reaction mixture temperature has a positive effect on the product yield.
Increasing reaction temperature from room temperature to 70 °C leads to increasing reaction
yield from 14% to 99% (entries 10 and 14-16). Furthermore, with a view to finding optimal
reaction time, we examined the model reaction in different reaction times from 2-8 hours. The
maximum yield was achieved when the reaction carried out for 6 h. Above 6 h of the reaction
time, no noteworthy change in the reaction yield took place (entries 17-19).
7

Table 2. The influence of various conditions on the azide–alkyne cycloadditiona
Cl
N
N
N
N
O
O
O
Cu
Cu
N
N
O
Cl
Cl
N
+
NaN3
Catalyst dosage Temperature
Yieldb
(%)
-
62
56
2
10
4
4
82
92
99
73
81
99
14
53
81
75
83
98
Entry
Catalyst
Solvent
Time (h)
(mmol)
(°C)
70
70
70
70
70
70
70
70
70
70
70
70
70
25
40
55
70
70
70
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
-
H2O
H2O
MeCN
n-hexane
THF
MeCOOEt
Toluene
EtOH
MeOH
H2O
-
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
2
4
8
CuCl2
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.001
0.002
0.006
0.004
0.004
0.004
0.004
0.004
0.004
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
Cu2(dmp)2(ox)Cl2
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
a
Reaction conditions: phenylacetylene (0.50 mmol), benzyl chloride (0.52 mmol), sodium azide (0.55
mmol), solvent (2.0 mL).
b Isolated yield.
With this optimal system in hand, various alkynes including phenyl acetylene, propargyl alcohol
and dimethyl propargyl alcohol, benzyl halides such as benzyl chloride, 2-methylbenzyl chloride,
4-nitrobenzyl chloride and benzyl bromide, and alkyl halides including azidocyclohexane and 1-
azidooctane were examined to the synthesis of triazoles at 70 °C and the results are shown in
Table 3. We explored the effect of different substitution on the benzyl chloride (both electron-
donating and electron-withdrawing substituted groups) witch reacted with phenylacetylene,
results indicated a reduction in the isolated yields for 2-methyl and 4-nitro substituted benzyl
chloride versus unsubstituted benzyl chloride (entries 1-3). It seems 2-methyl substituted benzyl
chloride due to the steric hindrance effect, showed more decrease in the yield of reaction with
phenylacetylene. Substituting the phenylacetylene with propargyl alcohol and dimethyl
8

propargyl alcohol leads to a decreasing in the reaction yield (entries 4 and 5). Moreover, the
reaction of propargyl alcohol and dimethyl propargyl alcohol with benzyl bromide were obtained
noticeably higher yields than benzyl chloride (entries 7 and 8).
Table 3. Click reaction of various benzyl halides with terminal alkynes in the presence of 1a
Entry
Benzyl halide
Alkyne
Product
Yieldb (%)
N
N
N
Cl
1
99
N
N
N
Cl
2
3
77
87
N
N
N
Cl
O2N
O2N
N
N
N
N
Cl
Cl
OH
4
5
64
34
OH
OH
N
N
OH
N
N
N
Br
6
99
N
N
N
N
Br
Br
OH
OH
7
8
74
73
OH
OH
N
N
a
Reaction conditions: alkyne (0.50 mmol), benzyl halide (0.52 mmol), sodium azide (0.55 mmol),
catalyst (0.004 mmol), in H2O (2.0 mL), 70 °C. b Isolated yield.
9

Aliphatic azides were also effectively clicked with the terminal alkynes in the presence of
Cu2(dmp)2(ox)Cl2 in H2O at 70 °C for 6 h and yielded relating 1,2,3-triazole products between
62-95% (Table 4). It looks when azidocyclohexane was used, the corresponding product due to
the steric hindrance, was obtained in lower yield than in the case of 1-azidooctane (entries 1-4).
Table 4. Cycloaddition of aliphatic azides and terminal alkynes in the presence of catalyst 1a
Entry
alkyl azide
Alkyne
Product
Yieldb (%)
N
N
N
N3
1
72
N
N
N
OH
N3
2
3
62
95
OH
N
N
N
N3
N
N
N
OH
4
79
OH
N3
a Reaction conditions: alkyne (0.50 mmol) and alkyl azide (0.52 mmol), catalyst (0.004 mmol), in H2O
(2.0 mL), 70 °C. b Isolated yield.
Reusability
Reusability of the catalyst is one of the most important features in catalytic reactions. Thus, after
the first 1,3-dipolar azide-alkyne cycloaddition reaction, the catalyst was taken out from the
reaction mixture by centrifuging and after several times washing with ethyl acetate and diethyl
ether, dried at 50 °C overnight and subjected to the second cycle without any additional
treatment. Although slow weakening of activity was detected, after three cycles the reaction
yield is decreased to 60% (Fig. 4)
10

Fig. 4. Recycling studies of the [Cu2(dmp)2(ox)Cl2] in the azide–alkyne cycloaddition reaction
The infrared spectrum of complex 1 before and after of reuse as a catalyst in the wavenumber
region 400 to 4000 cm-1 is shown in Fig. 5. The broad and strong peak of hydroxyl group
stretching vibration appeared at 3280 cm-1. The band at 1368 cm-1 attributed to C-O symmetry
vibration [29]. Peaks with wavenumber from 1426 to 1602 cm-1 are assigned to the C-C and C-N
stretching vibration of the phenanthroline rings [35]. The IR spectra of the fresh and reused
catalyst are slightly different and a comparison between these two spectra illustrated the decrease
in catalytic performance after three cycles are due to destruction and structural changing of the
complex 1 under reaction condition.
11

Fig. 5. Infrared spectra of a) fresh and b) reused complex 1
In order to investigate the catalytic advantages for complex 1, we compared our reported catalyst
with some copper-containing complexes in the synthesis of 1,4-disubstituted 1,2,3-triazole from
phenylacetylene, benzyl chloride and sodium azide. Under the conditions described in Table 4,
the complex 1 in some items is superior to other catalysts. For example, among all of these
catalysts, only the compound 1 can complete the azide-alkyne cycloaddition reaction and this is
while the lowest amount of catalyst mol% was used in our catalytic system. Furthermore, it was
obtained that the complex 1 demonstrated some other preponderances in comparison to other
systems, such as using green solvent (entry 5) and low reaction time (entries 2, 3 and 5).
Table 5. Azide-alkyne cycloaddition reaction with various Cu-containing complexes
Entry Catalyst
Conditions
Yield (%)
99
Ref.
present
work
[36]
1
[Cu2(dmp)2(ox)Cl2] ·H2O
Catalyst: 0.8 mol%/2 mL H2O/6 h/70
°C
2
[CuL2], HL = 1-
Catalyst: 1.4 mol%/2 mL H2O/12
h/70 °C
95
((4˗bromophenylimino)methyl)na
12

phthalen˗2˗ol
3
4
[Cu(tzol)2], tzol = 2-
Catalyst: 2 mol%/ 2 mL H2O/12 h/70
°C
96
32
[37]
[38]
(2′˗hydroxyphenyl)˗2˗thiazoline
[(NHC)CuI], NHC = 5,6-
Dimethyl˗1,3˗bis(2,3,4,5,6˗pentam
ethylbenzyl)˗2,3˗dihydro˗1H˗benz
o[d]imidazol˗2˗yl
Catalyst: 3 mol%/1 mL H2O/2 h/r.t.
5
TBA4H2[γ-
Catalyst: 2 mol%/2 mL
81
[39]
CH3CN/CH3OH/31 h/60 °C
SiW10O36Cu2(μ˗1,1˗N3)2], TBA =
tetrabutylammonium
Conclusion
In summary, a binuclear Cu(II) complex was synthesized by reaction of copper(II) chloride with
2,9-dimethyl-1,10-phenanthroline ligand and oxalic acid. This complex has been used as a
catalyst in the 1,3-dipolar cycloaddition reaction of benzyl chloride, phenylacetylene and NaN3
for the generation of 1,2,3-triazoles. The catalyst 1 exhibited high catalytic activity for
cycloaddition reaction of different organic halides and terminal acetylenes in water.
Additionally, this compound is a reusable catalyst at least for three runs.
Acknowledgments
Support for this research by the University of Tabriz and the University of Maragheh is
gratefully acknowledged.
Supplementary Data
The CIF file of crystal structure complex, [Cu2(dmp)2(ox)Cl2]·H2O has been deposited with the
CCDC, No. 1991276. This data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk
13

References
[1]
X.L. Shi, Y. Chen, Q. Hu, W. Zhang, C. Luo, P. Duan, J. Ind. Eng. Chem. 53 (2017) 134–
142.
[2]
M. Amini, H. Naslhajian, S.M.F. Farnia, H. Kyoung Kang, S. Gautam, K.H. Chae, New J.
Chem. 40 (2016) 5313–5317.
[3]
[4]
[5]
S.G. Agalave, S.R. Maujan, V.S. Pore, Chem. Asian J. 6 (2011) 2696–2718.
H. He, C. Gao, Curr. Org. Chem. 15 (2012) 3667–3691.
C.R. Becer, R. Hoogenboom, U.S. Schubert, Angew. Chem. Int. Ed. 48 (2009) 4900–
4908.
[6]
[7]
S. Chassaing, V. Bénéteau, P. Pale, Catal. Sci. Technol. 6 (2016) 923–957.
Z. hao Huang, Y. yan Zhou, Z. mu Wang, Y. Li, W. Zhang, N. chen Zhou, Z. biao Zhang,
X. lin Zhu, Chinese J. Polym. Sci. (Engl. Ed.) 35 (2017) 317–341.
[8]
[9]
B. Schulze, U.S. Schubert, Chem. Soc. Rev. 43 (2014) 2522–2571.
F. Jalilian, B. Yadollahi, S. Tangestaninejad, H.A. Rudbari, RSC Adv. 6 (2016) 13609–
13613.
[10] S. Shaabani, A. Tavousi Tabatabaei, A. Shaabani, Appl. Organomet. Chem. 31 (2017) 1–
6.
[11] M.S. Singh, S. Chowdhury, S. Koley, Tetrahedron. 72 (2016) 5257–5283.
[12] V. Castro, H. Rodríguez, F. Albericio, ACS Comb. Sci. 18 (2016) 1–14.
[13] M. Rajabzadeh, R. Khalifeh, H. Eshghi, M. Sorouri, Catal. Letters. 149 (2019) 1125–
1134.
[14] H. Struthers, T.L. Mindt, R. Schibli, Dalt. Trans. 39 (2010) 675–696.
[15] S. Goswami, S. Singha, R. Saha, A. Singha Roy, M. Islam, S. Kumar, Inorganica Chim.
14

Acta. 486 (2019) 352–360.
[16] M.B. Gawande, A. Goswami, F.X. Felpin, T. Asefa, X. Huang, R. Silva, X. Zou, R.
Zboril, R.S. Varma, Chem. Rev. 116 (2016) 3722–811.
[17] N. V. Sokolova, V.G. Nenajdenko, RSC Adv. 3 (2013) 16212–16242.
[18] C. Wang, D. Ikhlef, S. Kahlal, J.Y. Saillard, D. Astruc, Coord. Chem. Rev. 316 (2016) 1–
20.
[19] M. Amini, S. Najafi, J. Janczak, Inorganica Chim. Acta. 482 (2018) 333–339.
[20] H. Woo, H. Kang, A. Kim, S. Jang, J.C. Park, S. Park, B.S. Kim, H. Song, K.H. Park,
Molecules. 17 (2012) 13235–13252.
[21] M. Amini, R. Hassandoost, M. Bagherzadeh, S. Gautam, K.H. Chae, Catal. Commun. 85
(2016) 13–16.
[22] A. Banan, F. Nikbakht, S. Ataie, J. Porous Mater. 26 (2019) 1427–1433.
[23] M. Amini, M. Nikkhoo, S.M.F. Farnia, Appl. Organomet. Chem. 31 (2017) 1–5.
[24] A. Mandoli, Molecules. 21 (2016) 1174.
[25] S.G. Alvarez, M.T. Alvarez, Synthesis. 1997 (1997) 413-414.
[26] X.D. Zhang, Z. Zhao, J.Y. Sun, Y.C. Ma, M.L. Zhu, Acta Crystallogr. Sect. E Struct. 61
(2005) 2643–2645.
[27] H.D. Wang, Y.L. Zhou, H.Y. He, X.H. Tu, L.G. Zhu, Acta Crystallogr. Sect. E Struct. 62
(2006) 1081–1082.
[28] A.M. Thomas, G. Neelakanta, S. Mahadevan, M. Nethaji, A.R. Chakravarty, Eur. J. Inorg.
Chem. 2002 (2002) 2720–2726.
[29] O. Castillo, I. Muga, A. Luque, J.M. Gutiérrez-Zorrilla, J. Sertucha, P. Vitoria, P. Román,
Polyhedron. 18 (1999) 1235–1245.
[30] J. Glerup, P.A. Goodson, D.J. Hodgson, K. Michelsen, Inorg. Chem. 34 (1995) 6255–
15

6264.
[31] T. Fujino, Y. Hoshino, S. Igarashi, Y. Masuda, Y. Yukawa, Inorganica Chim. Acta. 357
(2004) 11–18.
[32] S. Reinoso, P. Vitoria, J.M. Gutiérrez-Zorrilla, L. Lezama, J.M. Madariaga, L. San
Felices, A. Iturrospe, Inorg. Chem. 46 (2007) 4010–4021.
[33] A.C. Fabretti, G. Franchini, P. Zannini, M. Divaira, Inorganica Chim. Acta. 105 (1985)
187–191.
[34] J. Novosad, A.C. Messimeri, C.D. Papadimitriou, P.G. Veltsistas, J.D. Woollins, Transit.
Met. Chem. 25 (2000) 664–669.
[35] O. Castillo, A. Luque, P. Román, J. Mol. Struct. 570 (2001) 181–188.
[36] M. Bagherzadeh, A. Bayrami, R. Kia, M. Amini, L.J.K. Cook, P.R. Raithby, Inorganica
Chim. Acta. 466 (2017) 398–404.
[37] M. Amini, A. Bayrami, M.N. Marashi, A. Arab, A. Ellern, L.K. Woo, Inorganica Chim.
Acta. 443 (2016) 22–27.
[38] N. Touj, I. Özdemir, S. Yaşar, N. Hamdi, Inorganica Chim. Acta. 467 (2017) 21–32.
[39] K. Yamaguchi, M. Kotani, K. Karnata, N. Mizuno, Chem. Lett. 37 (2008) 1258–1259.
CRediT author statement
Ali Akbar Khandar: Supervision, Ayda Sheykhi: Conceptualization & Methodology, Mojtaba
Amini: Supervision 2, Arkady Ellern; Software 1; L. Keith Woo; Software 2
Graphical abstract-S
16

The azide–alkyne cycloaddition reactions were conducted by a new binuclear copper(II)–oxalate
complex containing 2,9-dimethyl-1,10-phenanthroline without any additional agents.
Highlights
1. A new binuclear copper(II)–oxalate complex containing 2,9-dimethyl-1,10-phenanthroline is
synthesized.
2. The complex is applied for the three-component 1,3-Dipolar cycloaddition CuAAC reaction .
3. Excellent yield has been achieved.
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