Copper (I) complex of 2,9-dimethyl-1,10-phenanthroline: Synthesis, structure, and catalytic properties

Article abstract of DOI:10.1016/j.ica.2018.06.032

A copper (I) complex containing 2,9-dimethyl-1,10-phenanthroline (dmph), [Cu(dmph)₂]Cl·6H₂O, was prepared by reaction of CuCl₂·2H₂O and 2,9-dimethyl-1,10-phenanthroline in an aqueous solution at pH = 11 and characterized using elemental analysis, IR, EDX and X-ray crystallography. The complex consists of a mononuclear copper (I) surrounded by four coordinating nitrogen atoms of two dmph ligands, one Cl^? anion and six H₂O molecules. This novel cupper (I) complex was used as a catalyst for alkyne-azide cycloaddition (CuAAC) reaction to produce several 1,2,3-triazoles in high yields. The presented catalytic system fulfils the requirements of “click chemistry” with its soft and appropriate conditions, notably in water as solvent with low catalyst amount without any co-catalyst or activator.

Full text of DOI:10.1016/j.ica.2018.06.032

Accepted Manuscript
Research paper
Copper (I) complex of 2,9-dimethyl-1,10-phenanthroline: synthesis, structure,
and catalytic properties
Mojtaba Amini, Shabnam Najafi, Jan Janczak
PII:
S0020-1693(17)31701-2
https://doi.org/10.1016/j.ica.2018.06.032
ICA 18324
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
4 November 2017
23 May 2018
19 June 2018
Please cite this article as: M. Amini, S. Najafi, J. Janczak, Copper (I) complex of 2,9-dimethyl-1,10-phenanthroline:
synthesis, structure, and catalytic properties, Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.
2018.06.032
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Copper (I) complex of 2,9-dimethyl-1,10-phenanthroline: synthesis, structure,
and catalytic properties
∗a
Mojtaba Amini, Shabnam Najafi,a Jan Janczakb
aDepartment of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
bInstitute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O.Box
1410 Okolna 2 str., 50-950 Wroclaw, Poland
Dedicated to Professor Mojtaba Bagherzadeh, my dear supervisor at Sharif University of
Technology, for the helpful guidances, encouragement and valuable comments he has been
providing me to improve my scientific level and life issues.
Abstract
A
copper
(I)
complex
containing
2,9-dimethyl-1,10-phenanthroline
(dmph),
[Cu(dmph)2]Clꢀ6H2O, was prepared by reaction of CuCl2ꢀ2H2O and 2,9-dimethyl-1,10-
phenanthroline in an aqueous solution at pH=11 and characterized using elemental analysis, IR,
EDX and X-ray crystallography. The complex consists of a mononuclear copper (I) surrounded
by four coordinating nitrogen atoms of two dmph ligands, one Cl− anion and six H2O molecules.
This novel cupper (I) complex was used as a catalyst for alkyne–azide cycloaddition (CuAAC)
reaction to produce several 1,2,3-triazoles in high yields. The presented catalytic system fulfils
the requirements of ‘‘click chemistry” with its soft and appropriate conditions, notably in water
as solvent with low catalyst amount without any co-catalyst or activator.
Keywords: Complex; Copper; Phenanthroline; Azide- alkyne cycloaddition
Introduction
* Corresponding authors; Tel.: +98 41 37278900; Fax: +98 41 37276066. Email address: mamini@maragheh.ac.ir
1

Phenanthroline complexes of transition metal have been widely studied by researchers because
of their diverse applications in electrochemistry, photochemistry, materials science and
bioinorganic chemistry [1–8]. In particular, Cu-complexes containing phenanthroline ligands
have applications in the field of inorganic photochemistry, modeling enzyme activity, solar
energy conversion, and cleavage of DNA [9-15].
1,3-Dipolar cycloaddition reaction is powerful strategy for the synthesis of various functional
1,2,3-triazole molecules from organic azides and terminal alkynes as simple starting materials
[16-21]. Among various metal catalysts for cycloaddition process, copper (I)- catalyzed 1,3-
dipolar cycloaddition reaction proved to be the most versatile for the synthesis of 1,2,3-triazoles
in recent years [22-25].
We herein report synthesis and characterization of a copper (I) complex of 2,9-dimethyl-1,10-
phenanthroline (dmph) with using a copper (II) source by one-step method (Scheme 1). Further
we study the catalytic activity of this complex [Cu(dmph)2]Clꢀ6H2O, for the 1,3-dipolar
cycloaddition reaction of terminal alkynes and in situ generated azides to synthesize 1,2,3-
triazoles under ambient conditions.
H3C
CH3
N
N
N
N
N
N
H3C
CH3
Cu
CuCl2. 2H2O
H2O, sodium terephthalate, NH3
CH3
Cl
Scheme 1. Synthesis of complex [Cu(dmph)2]Cl
H3C
Experimental
Materials and Methods
All chemicals were received from commercial reagent suppliers and used without purification.
Copper chloride dehydrate and 2,9-dimethyl-1,10-phenanthroline were purchased from Sigma-
Aldrich. Complex [Cu(dmph)2]Cl2 was synthesized according to a published procedure [26]. The
2

composition of the obtained crystals was checked with energy dispersive spectrometry (EDS) as
well as with a Perkin-Elmer 240 elemental analyser. EDS spectra were acquired and analysed
using an EDAX Pegasus XM4 spectrometer with SDD Apollo 4D detector mounted on a FEI
Nova NanoSEM 230 microscope.
Synthesis of complex [Cu(dmph)2]Cl·6H2O
A solution of CuCl2·2H2O (0.17g, 1.00 mmol) and Na2CO3 (1 M, 1.0 mL) in 5.0 mL of H2O was
added to a mixture solution of methanol and water (1:1 V/V, 20 mL) of 2,9-dimethyl-1,10-
phenanthroline (0.21 g, 1.00 mmol) and sodium terephthalate (0.166 g, 1.00 mmol). The mixture
solution was adjusted with NH3·H2O to pH = 11 and allowed to stand at room temperature.
Orange-red needle crystals were grown by slow evaporation for over 2-3 days. Yield: 37%. IR
(KBr, 500−4000 cm-1): 3040, 2918. 1635, 1508, 1363, 855, 730, 547. Anal. Calcd for
C28H36ClCuN4O6: C, 53.93; H, 5.82; Cl, 5.68; Cu, 10.19; N, 8.98 and O, 15.39%. Found: C,
54.04; H, 5.92; Cl, 5.71 and N, 9.08 %.
General procedure for the azide–alkyne cycloaddition
Alkyne (0.5mmol), the organic halide (0.55mmol) and NaN3 (0.55mmol) were added to a
solution of [Cu(dmph)2]Clꢀ6H2O in 2 mL of H2O. The reaction mixture was warmed to 70 °C
and stirred and monitored by TLC. After a certain time, the resulting mixture was extracted with
EtOAc (2× 10 mL). The collected organic phase was dried with anhydrous CaCl2 and the solvent
was removed to give the corresponding triazoles, with no purification step.
Single crystal X-ray data collection.
X-ray intensity data for the [Cu(dmph)2]Clꢀ6H2O crystal were collected using graphite
monochromatic Mo Kα radiation on a four-circle κ geometry KUMA KM-4 diffractometer with
a two-dimensional area CCD detector. The ω-scan technique with ∆ω = 1.0o for each image was
used for data collection. One image was used as a standard after every 40 images for monitoring
of the crystal stability and data collection, and no correction on the relative intensity variations
was necessary. Data collections were made using the CrysAlis CCD program [27]. Integration,
scaling of the reflections, correction for Lorenz and polarisation effects and absorption
3

corrections were performed using the CrysAlis Red program [27]. The structure was solved by
the direct methods using SHELXS97 [28] and refined using SHELXL-2014 program [29]. The
hydrogen atoms were placed in their geometrical positions. The hydrogen atoms of one
disordered water molecule were not localised. The occupation factors of disordered water
molecule were refined and they are ~0.68 and ~0.32 for O6 and O7, respectively. The final
difference Fourier maps showed no peaks of chemical significance. Details of the data collection
parameters, crystallographic data and final agreement parameters are collected in Table 1.
Selected geometrical parameters are listed in Table 2 and the geometry of hydrogen bonding
interactions are collected in Table 3. Visualisation of the structure was made with the Diamond
3.0 program [30].
Results and Discussion
The composition of the prepared copper (I) complex, [Cu(dmph)2]Clꢀ6H2O, was characterized by
the elemental analyses, energy-dispersive X-ray spectroscopy (EDX) and IR, which confirmed
the successful assignment of composition for the complex. According to the EDX analysis, the
copper/chloride ratio of ~1 and it is in agreement to the atomic ratio in the formula
[Cu(dmph)2]Clꢀ6H2O.
The complex is stable enough to handle in air and can be stored for some days. The complex
[Cu(dmph)2]Clꢀ6H2O is not soluble in hexane and toluene, but is highly soluble in ethanol,
methanol and acetonitrile and slightly soluble in water. The view of the molecular structure of
[Cu(dmph)2]Clꢀ6H2O complex is shown in Figure 1. The environment of the metal center
exhibits a distorted tetrahedral geometry. The asymmetric unit of [Cu(dmph)2]Clꢀ6H2O consists
of one copper (I) cation which is surrounded by four coordinating nitrogen atoms of the two 2,9-
methyl-1,10-phenanthroline ligands, one Cl− anion and six H2O molecules. However, one of the
water molecules is disordered and occupied two positions (see Fig. 1) The Cu—N bonds linking
the phenanthroline ligands are in the range of 2.038(3)−2.062(3) Å, and are comparable with
those observed for [Cu(dpp)2](PF6), [Cu(tmp)2]BPh4 and [Cu(dpdmp)2]PF6 [31, 32]. Angular
distortions from the perfect tetrahedral geometry result from the chelating ligands. A search of
the CCDC Data Base (Version 5.39, November 2017) for structures containing the [Cu(dmph)2]+
4

cation yields over 40 structures, in which quite similar distorted tetrahedral environment of Cu(I)
cation as present in the investigated [Cu(dmph)2]Clꢀ6H2O compound is observed [33]. Most of
them contain various organic and inorganic anions to compensate the charge of the cation as well
as the different solvent molecules. One of them is the bromide analogue of the our
[Cu(dmph)2]Cl complex, however the bromide analogue crystallizes as monohydrate in the
centrosymmetric space group P21/c of monoclinic system [34], but our crystallizes in the triclinic
system as hexahydrate. Different composition of Br and Cl analogues (Br-monohydrate and Cl-
hexahydrate) results in different arrangement and the crystal packing.
Fig. 1 View of the complex [Cu(dmph)2]Clꢀ6H2O with labelling of the atoms. Thermal ellipsoids
are drawn at the 50% probability level, H atoms with arbitrary radii.
5

Table 1. Crystal data and structure refinement parameters for [Cu(dmph)2]Clꢀ6H2O
Empirical formula
Formula weight (g·mol–1)
Crystal system, space group
a, b, c (Å)
C28H36ClCuN4O6
623.59
Triclinic, P-1
7.0714(3), 15.1500(8), 15.2370(9)
α, β, γ (º)
110.60(1), 101.03(2), 93.37(1)
V (Å3)
1485.57(19)
2
Z
Dcalc (g·cm–3)
1.390
ꢁ (mm–1)
0.883
F(000)
648
Crystal size (mm)
Radiation type, wavelength, ꢂ (Å)
Temperature (K)
ꢄ range(o)
0.26 x 0.11 x 0.10
Mo Kꢃ , 0.71073
100(1)
2.414 ÷ 29.624
multi-scan
0.921 / 1.000
26534 / 7341 / 4378
0.0578
Absorption correction
Tmin/Tmax
Reflections collected / unique / observed
Rint
L.S. parameters
Refinement on
375
F2
R[F2>2ꢅ(F2)]
0.0725
wR(F2 all reflections)a
Goodness-of-fit, S
ꢆꢇmax, ꢆꢇmin (e Å–3)
0.1561
1.008
+1.041, -0.798
2
4
½
2
2
a)wR={ꢈ [w(Fo –Fc2)2]/ꢈwFo } ; w–1=[ꢅ2(Fo ) + (0.0622P)2], where P = (Fo + 2Fc2)/3.
6

Table 2. Selected bond lengths [Å] and angles [°] for [Cu(dmph)2]Clꢀ6H2O
Bond lengths (Å) Bond angles (°)
Cu−N1
2.062(3)
2.049(3)
2.038(3)
2.056(3)
1.312(4)
1.357(5)
N1-Cu-N2
82.5(1)
132.5(1)
117.5(1)
118.5(1)
131.4(1)
81.7(1)
Cu−N2
Cu−N3
Cu−N4
N1−C1
N3−C15
N1-Cu-N3
N1-Cu-N4
N2-Cu-N2
N2-Cu-N2
N3-Cu-N4
The crystal packing structure of complex [Cu(dmph)2]Clꢀ6H2O is shown in Figure 2. The
cationic [Cu(dmph)2]+ units related by an inversion and translation along a-axis form stacks
along the [100] direction (Fig. 2b). The average planes of the 2,9-methyl-1,10-phenanthroline
ligand of neighboring cationic [Cu(dmph)2]+ units related by an inversion are separated by
~3.37(2) Å. This value is comparable with a distance of 3.4 Å for the interacting aromatic rings.
The O—H…O hydrogen bonded water molecules together with the O—H…Cl interactions (Table
3) are arranged into pseudo-one-dimensional anionic chains aligned along the a-axis (Fig. 2).
Both oppositely charged units, i.e. the stacks of ꢉ-ꢉ interacted [Cu(dmph)2]+ units and the
pseudo-one-dimensional anionic chains, interact each other and stabilize the architecture of the
crystal. The arrangement of water rich [Cu(dmph)2]Clꢀ6H2O molecules is different to that of the
bromide analogue monohydrate, especially in arrangement of the hydrogen bonded water
molecules that together with the chloride anions form tapes along a-axis, whereas in the bromide
analogue monohydrate the water molecule acts as donor in O-H…Br hydrogen bond forming …H-
O-H…Br…H-O-H…Br…H-O-H…Br…zigzag chains along c-axis [34].
Table 3. Hydrogen-bond geometry (Å, º)
D—H···A
D—H
0.82
0.83
0.83
0.80
0.82
0.82
0.83
H···A
2.43
2.11
2.00
2.32
2.14
2.04
2.60
D···A
D—H···A
135.6
O1—H1O1···O5
O1—H2O1···Cl1i
O2—H1O2···O1
O2—H2O2···Cl1ii
O3—H1O3···O4
O3—H2O3···O1
O4—H1O4···Cl1iii
3.064 (4)
2.916 (4)
2.755 (5)
3.102 (4)
2.818 (6)
2.814 (4)
3.392 (4)
165.4
150.6
163.5
140.0
157.4
159.4
7

O4—H2O4···Cl1ii
O5—H1O5···O1
O5—H2O5···O7iv
0.87
0.90
0.82
1.99
2.77
1.64
2.859 (5)
3.064 (4)
2.311 (10)
178.2
100.3
137.7
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x−1, y, z.
(a)
8

(b)
Fig 2. The crystal packing structure of the complex [Cu(dmph)2]Clꢀ6H2O viewed along a-axis (a)
and c-axis (b). The H atoms of 2,9-methyl-1,10-phenanthroline ligands are omitted for clarity.
Black dashed lines represent O—H…O hydrogen bonds between the water molecules and the red
dashed linens represent the O—H…Cl interactions.
9

Catalytic effects
The considerable stability of the complex [Cu(dmph)2]Cl toward heat, oxygen and moisture
prompted us to use it as a catalyst in the 1,3-dipolar cycloaddition reaction of in situ generated
azides and terminal alkynes in water. To find the optimum condition for the cycloaddition
reactions, the catalytic potential of the complex [Cu(dmph)2]Cl was explored in a cycloaddition
reaction of benzyl chloride (0.5 mmol), phenylacetylene (0.55 mmol) and NaN3 (0.5 mmol) as
model reactants to form 1,2,3-triazole (Table 4). In the absence of catalyst, reaction is not
occurred between reactants, but with 0.32 mol% catalyst loading, the reaction was carried out at
70 °C and product was isolated in 97% yield after 12 h in water under atmospheric conditions
(Table 1, entries 1,2). In order to compare the efficacy of complex [Cu(dmph)2]Cl with others
simple sources of copper such as CuCl2ꢀ2H2O and [Cu(dmph)2]Cl2, the following reactions were
performed. Using the copper catalysts, CuCl2ꢀ2H2O and [Cu(dmph)2]Cl2, under the same
conditions, the triazole was obtained with a 63% and 50% yield respectively (entries 3, 4).
Satisfyingly, it was found that water is a suitable solvent for cycloaddition reaction and product
is isolated in 97% yield, but the reaction gave poor results if other solvents, such as ethanol,
toluene, acetonitrile and acetone, were screened as solvents, maybe because of the poor solubility
of NaN3 and catalyst in them (entries 4-8). The azide–alkyne cycloaddition reaction was further
conducted under a series of temperatures and we found that the reaction does not occur at room
temperature (entry 9), while at high temperatures (e.g. 40-70 °C) a significant increase in the
product yield was achieved (entries 10, 11). After 12 hours, 1-benzyl-4-phenyl-1,2,3-traizole was
isolated in 97% yield at 70 °C (entry 2) and thus, temperature 70 °C was chosen as the optimum
reaction temperature in all of the experiments hereafter. Also, in reaction times of less than 12
hours, low amount of the cycloaddition product was isolated, (entries 12–15).
Table 4. The results for different conditions on the azide–alkyne cycloaddition
Entry
Catalyst
Solvent
Temperature (°C) Time (h) Yield (%)a
1
2
3
4
5
6
-
H2O
H2O
H2O
H2O
C2H5OH
CH3CN
70
70
70
70
70
70
12
12
12
12
12
12
0
[Cu(dmph)2]Cl
CuCl2
[Cu(dmph)2]Cl2
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
97
63
50
70
30
10

7
8
9
10
11
12
13
14
15
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
[Cu(dmph)2]Cl
toluene
acetone
H2O
H2O
H2O
H2O
H2O
H2O
H2O
70
70
r.t.
40
60
70
70
70
70
12
12
12
12
12
2
4
8
10
5
90
20
40
90
10
25
75
95
aIsolated yield.
To further evaluate the scope of the complex [Cu(dmph)2]Clꢀ6H2O, the same process was
successfully applied to a wide range of diversely substituted phenylacetylenes and a mixture of
benzyl halides and NaN3 under the optimal conditions. As demonstrated in Table 5, a single
regioisomer, namely 1,4-disubstituted 1,2,3-triazoles, was obtained in 19-95% yields (entries 1-
11). Substrates with electron-donating and electron-withdrawing groups in the aryl ring were all
directly converted into desired 1,2,3-triazoles in good yields (entries 2-4), but the reactivity of
benzyl chlorides with electron-withdrawing substituent was higher than those with electron-
donating substituent (entries 2-4). Due to the steric hindrance of the ortho substituents on the
benzyl halides, benzyl chloride substituted with nitro group at ortho position was less reactive to
the cycloaddition reaction than the para derivative (entries 3, 4). Replacement of benzyl bromide
with benzyl chloride showed a conclusive effect on the isolated yield of 1,2,3-triazoles products
(entries 8-11). However, the cycloadditions of aliphatic alkyne containing -OH group, propargyl
alcohol, 3-butyn-2-ol and 2-methyl-3-butyn-2-olproceed with lower yield (entries 5-7, 9-11).
Table 5. Cycloaddition of various substrates in the presence of the complex [Cu(dmph)2]Clꢀ6H2O
Benzyl halide
Alkyne
Yield (%)
97
Entry
1
2
60
11

3
4
80
90
5
6
10
15
HO
HO
7
8
40
97
9
43
HO
To check the reusability of the catalyst, after extraction of cycloaddition product, aqueous media
containing dissolved [Cu(dmph)2]Clꢀ6H2O was reused for the next batch of reaction by addition
of fresh substrates. The yield of cycloaddition product was found to be decreased by 41 % by the
second recycle. This decrease in the yield may be due to degradation of complex during reaction
condition, which reduces the catalytic activity of [Cu(dmph)2]Clꢀ6H2O upon repeated use.
A reaction mechanism proposed for the [Cu(dmph)2]Clꢀ6H2O catalysed 1,3-dipolar cycloaddition
which lead to 1,4-disubstitued 1,2,3-triazoles is outlined in Scheme 2 on the basis of the previous
reports [35, 36]. Reaction is started with the generation of the copper (I) acetylide intermediate
via attraction of cation [Cu(dmph)2]+ towards the phenylacetylene. Next, with the addition of
azide and formation a six-membered copper metallacycle and next step a copper triazole
complex, final 1,2,3-triazole product can form and the [Cu(dmph)2]Cl catalyst is regenerated.
12

H3C
CH3
N
N
Cu
N
N
R'
N
N
H
N
R
H
CH3
R
H3C
R
[Cu(dmph)2]
R'
N
N
N
R'
X
+
R' N3
NaN3
R
[Cu(dmph)2]
R
[Cu(dmph)2]
R
N
N
N
[Cu(dmph)2]
R'
N
N
N
R'
Scheme 2. Proposed mechanism of [Cu(dmph)2]Clꢀ6H2O catalytic cycle for the formation of
1,2,3-triazole.
Conclusion
In conclusion, we have synthesized a copper (I) complex containing 2,9-dimethyl-1,10-
phenanthroline and demonstrated that this complex is excellent catalyst for the azide–alkyne
cycloaddition reactions of terminal alkynes and in situ generated azides to synthesize 1,2,3-
triazoles under mild and convenient conditions.
Supplementary Data
The CIF file of crystal structure complex, [Cu(dmph)2]Clꢀ6H2O has been deposited with the
CCDC, No. 1581109. 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

Acknowledgments
Partial funding support was provided by the Research Council of University of Maragheh
(M.A.).
References
[1] B. Paul, K. Chakrabarti, S. Kundu, Dalton Trans., 45 (2016) 11162-11171.
[2] T. Tao, H. Fang, Y-X. Peng, M-D. Zhang, W. Huang, Inorg. Chem. Commun., 84 (2017) 15-
19.
[3] B. Z. Momeni, F. Haghshenas, S. Hadi, J. Mol. Str. 1142 (2017) 156-167.
[4] M. Shiotsuka, T. Asano, Y. Kurono, R. Ono, R. Kawabe, J. Organomet. Chem., 851 (2017)
1-8.
[5] B.S. Rajebhosale, S. N. Dongre, S. S. Deshpande, A. N. Kate, A. A. Kumbhar, J. Inorg.
Biochem., 175 (2017) 129-137.
[6] H. Li, Y. Wang, Z. Lai, K-W. Huang, ACS Catal., 7 (2017) 4446–4450.
[7] K. Singha, P. Laha, F. Chandra, N. Dehury, A. L. Koner, S. Patra, Inorg. Chem., 56 (2017)
6489–6498.
[8] L. Xie, Z. Luo, Z. Zhao, T. Chen, J. Med. Chem., 60 (2017) 202–214.
[9] A. J. Pallenberg, K. S. Koenig, D. M. Barnhart, Inorg. Chem. 34 (1995) 2833-2840.
[10] M. Schmittel, V. Kalsani, J. W. Bats, Inorg. Chem. 44 (2005) 4115-4117.
[11] A. Y. Mitrofanov, Y. Rousselin, R. Guilard, S. Brandès, A. G. Bessmertnykh-
Lemeune, M. A. Uvarova, S. E. Nefedov, New J. Chem., 40 (2016) 5896-5905.
[12] J. A. Aligo, L. Smith, J. L. Eglin, L. E. Pence, Inorg. Chem., 44 (2005) 4001–4007.
[13] J. Cody, J. Dennisson, J. Gilmore, D. G. VanDerveer,M. M. Henary, A. Gabrielli, C.
D.Sherrill, Y. Zhang, C-P. Pan, C. Burda, C. J. Fahrni, Inorg. Chem.,42 (2003) 4918–4929.
[14] S. M. G. Leite, L.M. P. Lima, S. Gama, F. Mendes, M. Orio,I. Bento, A. Paulo, R.
Delgado, O. Iranzo, Inorg. Chem., 55 (2016) 11801–11814.
[15] A. O. Razgoniaev, C. E. McCusker, F. N. Castellano, A. D. Ostrowski, ACS Macro Lett., 6
(2017) 920–924.
[16] H. Zhang, T. Piacham, M. Drew, M. Patek, K. Mosbach, L. Ye, J. Am. Chem. Soc., 128
(2006) 4178–4179.
14

[17] M. Amini, M. Nikkhoo, S. M. F. Farnia, Appl. Organometal. Chem. 31 (2017) e3710-
e3715.
[18] S. Díez González, S. P. Nolan, Angew. Chem. Int. Ed. 47 (2008) 8881-8884.
[19] M. Bagherzadeh, A. Bayrami, R. Kia, M. Amini, L. J. K. Cook, P. R. Raithby, Inorg. Chim.
Acta 466 (2017) 398–404.
[20] M. Amini, S. B. Tekantappeh, B. Eftekhari-Sis, P. G. Derakhshandeh, K.Van Hecke, J.
Coord. Chem., 70 (2017) 1564–1572
[21] K. Kamata, Y. Nakagawa, K. Yamaguchi, N. Mizuno, J. Am. Chem. Soc., 130 (2008)
15304–15310
[22] E. Haldon, M.C. Nicasio, P.J. Perez, Copper-catalysed azide-alkyne cycloadditions
(CuAAC): an update, Organic & Biomolecular Chemistry, 13 (2015) 9528-9550.
[23] T.S. Rodrigues, A.G. da Silva, L.C. de Oliveira, A.M. da Silva, R.R. Teixeira, P.H.
Camargo, Tetrahedron Lett., 58 (2017) 590-595.
[24] P.W. Szafraꢊski, P. Kasza, M.T. Cegła, Tetrahedron Lett., 56 (2015) 6244-6247.
[25] M. Bagherzadeh, N-S. Mousavi, M. Amini, S. Gautam, J. Pal Singh, K. H. Chae, Chinese
Chem. Lett., 28 (2017) 1125–1130.
[26] J. R. Hall, N. K. Narchant, R. A. Plowman, Aust. J. Chem 15(1962) 480-485.
[27] CrysAlis CCD and CrysAlis Red 1.171.38.41, Rigaku Oxford Diffraction, 2015.
[28] G.M. Sheldrick, SHELXS97, Programs for Crystal Structures Solution and Refinement,
University of Göttingen, Göttingen, Germany, 1997.
[29] G.M. Sheldrick, Acta Cryst. C71 (2015) 3-8.
[30] K. Brandenburg, H. Putz, DIAMOND Version 3.0, Crystal Impact GbR, Bonn, Germany,
(2006).
[31] M. T. Miller, P. K. Gantzel, T. B. Karpishin, Inorg. Chem. 37 (1998) 2285-2290.
[32] C. T. Cunningham, J. J. Moore, K. L. H. Cunningham, P. E. Fanwick, D. R. McMillin,
Inorg. Chem. 39 (2000) 3638-3644.
[33] F.H. Allen, Acta Cryst. B 58 (2002) 380-388.
[34] J. F. Dobson, B. E. Green, P. C. Healy, C. H. L. Kennard, C. Pakawatchai, A. H. White,
Aust. J. Chem. 37 (1984) 649-659.
15

[35] M. Amini, A. P. Anbari, S. Ramezani, S. Gautam, K. H. Chae, ChemistrySelect. 1 (2016)
4607-4612.
[36] I. Jlalia, F. Gallier, N. Brodie-Linder, J. Uziel, J. Auge, N. Lubin-Germain, J.Mol. Catal. A:
Chem 393 (2014) 56-61.
16

Graphical abstract-P
17

Highlights
1. Cu(I) complex containing 2,9-dimethyl-1,10-phenanthroline is synthesized.
2. The copper(I) complex is applied for the azide–alkyne cycloaddition.
3. Excellent yield has been achieved.
18