Preparation of an efficient catalyst through injection of CuI on modified poly (styrene-co-maleic anhydride) and theoretical investigation of the structural and electronic properties of catalyst

Article abstract of DOI:10.1002/aoc.5435

A novel polymer supported [poly (styrene-co-maleic imide) (SMI)]Cu(I) nano-particles was prepared via in situ reaction of 4-amino-5-methyl-4H-1,2,4-triazole-3-thione with [poly (styrene-co-maleic anhydride)] (SMA) along with immobilization of CuI. These nano-particles were fully characterized by using scanning electron microscopy (SEM), energy dispersive spectroscopy analysis, Xray (EDAX), inductively coupled plasma (ICP) analysis, ¹H NMR and FT-IR techniques. Moreover, the structural and electronic features of metal–ligand interactions in the complex model of polymer-supported copper nanocatalyst were assessed using density functional theory calculations. The catalytic activity of these supported Cu(I) nonoparticles was examined in one of the classiest name reaction so–called “click reaction” which is coined K. B Sharpless for the regioselective synthesis of 1,2,3-triazole derivatives using a multicomponent reaction (MCR) involving benzyl halides, sodium azide and terminal alkynes in water as a green solvent. This heterogeneous catalyst showed excellent catalytic activity and was separated by simple filtration and was used at least in five consecutive runs without a significant decrease in its activity.

Full text of DOI:10.1002/aoc.5435

Received: 6 July 2019
DOI: 10.1002/aoc.5435
Revised: 14 October 2019
Accepted: 2 December 2019
F U L L P A P E R
Preparation of an efficient catalyst through injection of CuI
on modified poly (styrene-co-maleic anhydride) and
theoretical investigation of the structural and electronic
properties of catalyst
Rozita Zoghi1 | Majid M. Heravi2
| Naser Montazeri1
|
Masoud Mohammadi Zeydi1 | Tayebeh Hosseinnejad2
1Department of chemistry, Tonekabon
A novel polymer supported [poly (styrene-co-maleic imide) (SMI)]Cu(I) nano-
particles was prepared via in situ reaction of 4-amino-5-methyl-4H-1,-
2,4-triazole-3-thione with [poly (styrene-co-maleic anhydride)] (SMA) along
with immobilization of CuI. These nano-particles were fully characterized by
using scanning electron microscopy (SEM), energy dispersive spectroscopy
Branch, Islamic Azad University,
Tonekabon, Iran
2Department of Chemistry, Alzahra
University, Vanak, Tehran, Iran
Correspondence
1
Majid M. Heravi, Department of
Chemistry, Alzahra University, Vanak,
Tehran, Iran.
analysis, Xray (EDAX), inductively coupled plasma (ICP) analysis, H NMR
and FT-IR techniques. Moreover, the structural and electronic features of
metal–ligand interactions in the complex model of polymer-supported copper
nanocatalyst were assessed using density functional theory calculations. The
catalytic activity of these supported Cu(I) nonoparticles was examined in one
of the classiest name reaction so–called “click reaction” which is coined K. B
Sharpless for the regioselective synthesis of 1,2,3-triazole derivatives using a
multicomponent reaction (MCR) involving benzyl halides, sodium azide and
terminal alkynes in water as a green solvent. This heterogeneous catalyst
showed excellent catalytic activity and was separated by simple filtration and
was used at least in five consecutive runs without a significant decrease in its
activity.
Email: mmheravi@alzahra.ac.ir
Naser Montazeri, Department of
chemistry, Tonekabon Branch, Islamic
Azad University. Tonekabon, Iran.
Email: n.montazeri20@gmail.com
Funding information
Iran National Science Foundation; Alzhra
University and Islamic Azad University
K E Y W O R D S
4-amino-5-methyl-4H-1,2,4-triazole-3-thione, click reaction, density functional theory, DFT, poly
(styrene-co-maleic anhydride) [SMA]
1 | INTRODUCTION
benzyl halides, sodium azide and terminal alkynes in
the presences of catalyst.[2,3] In order to take advantages
1,2,3-Triazoles are an important class of heterocyclic
compounds with a wide range of applications. Some of
them are pharmaceutical agents, photographic mate-
rials, and agrochemicals.[1] One of the most conven-
tional methods for the regioselective synthesis of
1,4-disubstitued 1,2,3-triazoles, is the well-known,
1,3-dipolar Huisgen cycloaddition via MCR involving
of simple separation, efficient recovery and reusability
of copper species as catalyst, they usually immobilized
onto various supports, such as amine-functionalized
polymers,[4] zeolites,[5] aluminum oxyhydroxide fiber[6]
and amine-functionalized silica[7] Heterogeneous cata-
lysts are very important in large number of chemical
and energy consuming industries.[8] Applications of
Appl Organometal Chem. 2020;e5435.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.5435

2 of 13
ZOGHI ET AL.
various forms of polymer-supported CuI as recoverable
catalyst for the click synthesis of 1,2,3-triazoles from
azides and alkynes have been well established and
reported.[9,10]
recorded using a TeScan-Mira III model instrument.
Melting points were recorded on Electrothermal 9100 s
apparatus in open capillary tubes. X-ray diffraction
(XRD) measurements were performed at room tempera-
ture on an X'Pert PRO MPD model of PAN analytical
Company in Netherlands. The chemical composition was
obtained using energy dispersive X-ray spectroscopy
(EDX) on Leica Cambridge S 360. All products were
known and identified by comparison of their melting
points and spectroscopic data with those of authentic
samples and found being identical.
Nowadays, the use of metal nano-particles (NPs) has
been considered as competitive alternative to conven-
tional catalysts. Such NPs possess very large surface area,
giving them high activity under the gentle conditions, at
the same time maintaining the essential advantageous
features of a heterogeneous catalyst.[11] The immobiliza-
tion of copper (I) salts as NPs on high surface area sup-
ports such as polymers[12] allow higher stability, better
dispersion of the particles, and good recycling properties
of the catalyst. Poly (styrene-co-maleic anhydride) [SMA]
is a market purchasable co-polymer with reactive anhy-
dride moiety, which can be modified using various nucle-
ophiles, providing an attractive support for the design of
different reagents and as well as heterogeneous active
nano catalysts.[13]
In continuation of our previous interest in the appli-
cation of polymers and preparation of nanocatalysts,[14,15]
we have investigated the reaction of SMA with 4-amino-
5-methyl-4H-1,2,4-triazole-3-thione and examined the
capability of this novel-modified support for the prepara-
tion of a novel metal NPs as a catalyst. This Cu(I) NPs
supported onto modified SMA was successfully used in a
one-pot, three-component synthesis of 1,4-disubstituted-
1H-1,2,3-triazoles from α-haloketones or alkyl haides,
sodium azide, and terminal alkynes in water as a green
reaction, via click reaction.
2.3 | The synthesis of catalyst
2.3.1 | Preparation of SMI
The chemical SMA (1) was prepared according to the
reported method in authoritative sources.[16] SMA
(1.00 g) and 4-amino-5-methyl-4H-1,2,4-triazole-3-thione
(2.54 g, 16 mmol) in 15 ml dry DMF were added in to a
100 ml glass reactor and then N2 gas was charged in to
the reactor and then it was sealed. The reactor was placed
into the thermostatic oil-bath on the oscillator and the
reactive mixture was oscillated until the reagents were
ꢀ
dissolved in DMF and kept oscillating at 35 C for 4 hr.
Then, acetic anhydride (0.6 ml, 6 mmol), sodium acetate
(0.33 g, 4 mmol) and triethylamine (0.3 ml, 2 mmol) were
added to reaction mixture by syringe.ꢀThen, the tempera-
ture of the reaction was raised to 75 C and stirring was
continued for further 4 hr. The reaction mixture was
cooled to ambient temperature and was added slowly to
stirring MeOH (30 ml). The precipitated polymer was
washeꢀd for several times with methanol and dried under
at 70 C. In order to further purification, the SMI poly-
mer (3) was re-precipitated twice. The amine content of
SMI polymer was measured via back titration using
NaOH (0.2 N).[17]
2 | EXPERIMENTAL
2.1 | Materials
All chemicals were purchased from Aldrich and Merck
companies and used as received. The general formula of
SMA (KARABOND SAM), applied in this research in this
research,
is
[(C8H8)0.6(C4H2O3)0.4 n
]
with
Mn
(g/mol) = 86.666, Mw = 182.000, and Mw/Mn = 2.1.
2.3.2 | Preparation of nano cu
(I) immobilized catalyst onto SMI (SMI–
CuI)
2.2 | Equipment
CuI (1 mg, 5 mmol) was dissolved in CH3CN (2 ml) and
exposed to ultrasonic irradiation, after a while a transpar-
ent pale yellow solution was obtained. Then, DMF
(20 ml) was added at room temperature to provide CuI
solution.[18] Then, dry aforementioned SMI polymer (1 g)
was added, and the mixture was magnetically stirred at
reflux temperature for 5 hr under a nitrogen atmosphere.
After completion of the reaction, the precipitated brown
polymer was filtered and washed with acetonitrile
1H NMR and 13C NMR spectra were recorded using a
Bruker Ultra shield 400 and 100 MHz, respectively. The
FT-IR spectra of the samples were recorded in the range
of 400–4000 cm−1 on an FT-IR spectrometer (Shimadzu)
using KBr pellet technique. Copper content was mea-
sured by Inductively Coupled Plasma (ICP) on a Varian,
730-ES model analyzer. The scanning electron micro-
graphs (SEM) of the catalyst external surface were

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
3 of 13
ꢀ
(2 × 20 ml), dried under vacuum at 60 C to give the
2.4 | Synthesis of 1,4-disubstituted
immobilized SMI-CuInano-particles 4 (Scheme 1). To
estimate the Copper amount, the SMI-CuI (100 mg) was
reacted with a mixture of hydrochloric acid (10 ml) and
nitric acid (1:1, v/v) at 100 ꢀC for 4 hr. Then, the resulting
mixture was filtered and the recovered polymers were
washed with distilled water (6 × 2.5 ml). The resin beads
were diluted by 50 ml distilled water and analyzed using
ICP-atomic emission spectrometry. (Catalyst Cu loading
was 7.11% w/w).
−1,2,3-triazoles via click reaction: General
procedure
A mixture of an appropriate α-haloketones or alkyl
halides (1.0 mmol) (5a–h), alkynes (1.0 mmol) (6a–c),
sodium azide (1.10 mmol), in the presence of 0.03 g of
SMI-CuI 4 was prepared in H2O (10 ml) and heated
under reflux conditions with vigorous stirring
(Scheme 2). After the completion of the reaction [moni-
tored by thin layer chromatography (TLC) using (n-hex-
ane-EtOAc (7:3)], the solution was filtered through a
Büchner funnel to remove the heterogeneous catalyst. It
was washed with acetone several times and dried under
reduced pressured at 70 ꢀC for 4 hr. The filtrate was evap-
orated to dryness under reduced pressure and in some
cases (7e–h) the residue was washed with 10 ml of diethyl
ether. Afterward, the residue was re-crystallized from
EtOH/H2O (3:1 v/v) to give the pure crystalline products.
All triazoles (7a–k) are known compounds and their
physical data and spectral data are in agreement with
those reported authentic compounds.[6,19–22]
2.3.3 | Determination of the copper
content in SMI–CuI
In a screw-capped funnel, a sample of SMI–CuI
(100 mg) was extracted with conc. HCl and HNO3 (1:1,
10 ml) for digestion of the metal complex. Then, this
mixture was transferred into
a
volumetric flask
(100 ml), diluted and was analyzed by ICP. In this way,
the Cu content was determined as 7.11% w/w. The
same procedure was followed to measure the amount of
leaching from the supported catalyst after five succes-
sive recyclability.
The spectral (IR, 1H NMR and 13C NMR) data for the
selected compound are as follows[23]
:
SCHEME 1 Synthesis of a novel polymer supported
[poly (styrene-co-maleic imide) (SMI)]Cu(I) nano-
particles
SCHEME 2 Cu(I) NPs supported onto modified SMA catalyzed one-pot, three-component synthesis of 1,4-disubstituted-1H-
1,2,3-triazoles via click reaction

4 of 13
ZOGHI ET AL.
ꢀ
Table 3, Ent
M. P. 114–116 C. IR (KBr) ν: 3099 (C-Harom. Str.);
ry 1: 1-phenyl-2-(4-phenyl-[1,2,3] triazol-1-yl) (7a)
2980 (C-Haliph. Str.); 1655 (C=O Str.); 1650 (C=N Str.);
1500 (C=C Str.); 1229 (C-N Str.); 1216 (C-O Str.) cm−1
.
M.P. 170–171 ꢀC. IR (KBr) ν: 3078 (C-Harom. Str.);
1707 (C=O Str.); 1546 (C=N Str.); 1483 (C=C Str.); 1223
(C-N Str.) cm−1.1H NMR (400 MHz, DMSO-d6) δ 8.54 (s,
1H, CH), 8.12–7.34 (m, 10H, Ar-H), 6.28 (s, 2H, CH2)
ppm. 13C NMR (100 MHz, DMSO-d6) δ 193.0, 147.2,
135.1, 135.0, 131.6, 129.8, 129.8, 129.1, 128.7, 126.0, 123.9,
56.8 ppm.
1H NMR (400 MHz, DMSO-d6) δ 7.82 (s, 1H, Ar-H); 7.72
(s, 1H, CH, Ar-H); 7.75–7.35 (m, 5H, Ar-H); 6.28 (s, 2H,
CH2); 4.14 (s, 3H, CH3) ppm. 13C NMR (100 MHz,
DMSO-d6) δ190.2, 148.1, 140.0, 134.4, 131.5, 131.1, 130.0,
129.8, 128.7, 126.3, 123.8, 56.8 ppm.
3 | RESULTS AND DISCUSSION
Table 3, Entry 2: 2-(4-phenyl)-1H-1,2,3-triazol-1-yl)-1-p-
tolyl-ethanone (7b)
3.1 | Preparation and characterization of
the SMI
M.P. 156–159 ꢀC. IR (KBr) ν: 3127 (C-Harom. Str.);
2983 (C-Haliph. Str.); 1695 (C=O Str.); 1568 (C=N Str.);
1473 (C=C Str.); 1232 (C-N Str.) cm−1.1H NMR
(400 MHz, DMSO-d6) δ 8.52 (s, 1H, CH), 8.00–7.99 (m,
2H, Ar-H), 7.88–7.87 (m, 2H, Ar-H), 7.47–7.33 (m, 5H,
Ar-H), 6.21 (s, 2H, CH2), 2.41 (s, 3H, CH3) ppm. 13C
NMR (100 MHz, DMSO-d6) δ 192.4, 147.1, 145.7, 132.5,
131.6, 130.4, 129.8, 129.1, 128.7, 126.0, 123.9, 56.7,
22.1 ppm.
Initially, SMA (1) was successfully modified using,
4-amino-5-methyl-4H-1,2,4-triazole-3-thione
(2) (Scheme 1). The conversion of the maleic anhydride
group in SMA to the corresponding maleimide was con-
firmed by FT-IR spectroscopy. Figure 1 shows four spec-
tra; (a) is the 4-amino-5-methyl-4H-1,2,4-triazole-
3-thione before reaction, (b) is SMA before further reac-
tion, (c) is the prepared SMI and (d) is CuI/SMI (3). The
FT-IR data for pure amine shows two peaks clearly at
3288 and 3268 cm−1 attributed to primary N-H stretching
in Figure 1a. The typical doublet of anhydride units can
Table 3, Entry 9: Methyl-2-(4-phenyl-1H-1,2,3-triazol-
1-yl)acetate (7i):
FIGURE 1 FT-IR spectrum of 4-amino-5-methyl-4H-1,2,4-triazole-3-thione (a), SMA (b), SMI (c) and CuI/SMI (d)

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
5 of 13
be observed at 1860 and 1775 cm−1 in Figure 1b. After
the reaction of SMA with 4-amino-5-methyl-4H-1,-
2,4-triazole-3-thiol, a new imide band at 1738–1780 cm−1
and SH band at 1993 cm−1 was observed, and no band at
3500 cm−1 for amino groups was observed. This indicated
that the imidization of SMA was completed and no resid-
nanoparticle catalyst (Scheme 1). Morphology and loca-
tion of metallic species on the surface of the catalyst and
SEM images of the obtained catalysts were recorded. The
crystallite size of particles and immobilization on SMI
were clearly shown for the NPs. The scanning electron
micrographs (SEM) of the SMI–CuI-NPs (Figure 3)
showed that the average size of copper NPs were about
18–29 nm and homogeneously immobilized on the modi-
fied surface.
Energy-dispersive spectroscopy analysis of X-rays
(EDAX) data for the SMI–CuI catalyst is given in
Figure 4. The EDX data vividly reveals the attachment of
copper metal on to the surface of the polymer matrix.
To evaluate the Cu content, the polymer-supported
NPs were treated with conc. HCl-NHO3 for digestion of
the Cu species. The Cu content was determined to be
7.11% w/w by ICP analysis. (for the details, see “Experi-
mental” section). The efficiency of this catalyst was
examined for the preparation of triazoles by a click-
reaction as described below. The principle advantages of
this immobilization technique are the experimental sim-
plicity of polymer-support preparation together with the
fact that no pre-activation step is required before the cat-
alyst usage.
ual
4-amino-5-methyl-4H-1,2,4-triazole-3-thiol
was
observed in the resulting SMI.
Moreover, the 1H NMR spectrum of this SMI
(Figure 2) showed a pattern similar to SMA; in addition
to the expected aromatic protons for the thiazole group of
the 4-amino-5-methyl-4H-1,2,4-triazole-3-thionemoiety,
It shows [12.13 (s, SH), 7.92 (2H, Ar-H), 7.1 (2H, Ar-H),
6.61 (1H, Ar-H), 2.85 (s, 3H), 2.47 (m, 1H), 2.14 (s, 1H),
1.93 (s, 1H), 1.88 (m, 2H)].[24,25]
3.2 | Preparation and characterization of
the catalyst
The high reactivity of the cyclic anhydride groups of
SMA makes this polymer as an ideal support for the cata-
lyzed organic transformations.[13] CuI-NPs were
immobilized on the obtained novel SMI. In order to sup-
press agglomeration of the CuI-NPs, they were prepared
in situ and then refluxed with SMI under N2 atmosphere
in DMF (the Molar ratio of amine to Cu was 2.4:1.0).[13]
This procedure afforded the polymer-supported CuI
On the other hand, due to our recent interests,[14,15]
we investigated the coordination behavior of CuI with
this new SMI polymeric support, modified with 4-amino-
5-methyl-4H-1,2,4-triazole-3-thione, based on DFT
FIGURE 2 1H NMR spectrum
of SMI

6 of 13
ZOGHI ET AL.
FIGURE 3 SEM image of SMI–CuI
FIGURE 4 EDAX data of SMI–CuI
calculations.[26] More clearly, we designed an effective
model for modified SMI ligand and SMI-CuI complex
with different active nitrogen and oxygen coordinating
sites (as were displayed in Scheme 1). It should be noted
that the proposed structural model for modified SMI
polymeric surface can be regarded as an effective model
for comparative assessment of metal–ligand interaction
strength, with a reliable comprise between accuracy and
time saving efficiency of computational process.[27,28] In
this line, we firstly determined the optimized structure of
SMI ligand and SMI-CuI complex model at
FIGURE 5 The optimized structure of SMI ligand and SMI-
CuI complex calculated at M08-HX/6-311G** level of theory

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
7 of 13
M08HX/6-311G** level of theory.[29] It is important to
mention that harmonic frequency analysis was per-
formed to confirm the found structures locate to minima.
In the case of copper and iodine atoms, LANL2DZ effec-
tive core potentials (ECPs) were used together with the
accompanying basis sets to describe the valence electron
density.[30,31] All DFT computations were performed
using GAMESS suite of programs.[32] In Figure. 1, we
have presented the optimized geometries of SMI ligand
nano-particles with nitrogen of 1,2,4-triazole ring is
slightly stronger than the interaction of copper with car-
bonyl oxygen with larger bond order.
with these promising results and our previous
experiences,[34] it is worthwhile to examine this
immobilized Cu(I) NPs in one of the classist organic
transformation, 1,3-dipolar Huisgen cycloaddtion reac-
tion via click reaction.
To optimize the reaction conditions, a mixture of
2-bromoacetophenone (1.0 mmol), sodium azide
(1.5 mmol), and phenyl acetylene (1.0 mmol) was
selected as a model reaction and studied under a variety
of conditions. Initially, it was conducted in water and
other solvents (Table 2). As shown in Table 2, the most
appropriate solvents for entries 4 and 5 (solvent
EtOH/H2O and water). Although this reaction can be
performed in the both solvents, water is chosen in this
work, which addresses several features of green chemis-
try such as availability and safety (Scheme 2).
The desired reaction For the optimization of the
amount catalyst was studied on a model reaction
(Table 3). The best result was achieved by carrying out
the reaction of 2-bromoacetophenone, phenyl acetylene,
and sodium azide (in 1:1:1.1 mol ratio) in the presence
of 0.03 g of SMI–CuI under reflux in water (Table 3,
entry 3).
and
SMI-CuI
complex
model
calculated
at
M08-HX/6-311G**level of theory with the atomic num-
bering that demonstrate the geometrical deformation in
SMI ligand through the complexion. Moreover, in order
to present a quantitative description for immobilization
behavior of copper nanoparticles on modified polymeric
surface, we concentrated on the bond order analysis of
key bonds in different coordination modes of SMI-CuI
complex model and their variations in SMI ligands. In
this respect, we have listed M08-HX/6-311G** calculated
values for bond order of some key bonds in SMI ligand
and SMI-CuI complex together with their corresponding
bond lengths in Table 1. It should be mentioned that the
presence of DMF as solvent was also considered by the
employment of polarized continuum model (PCM) via a
continuum representation of the solvent surrounding the
substances.[33] It should be noticed that from the experi-
mental viewpoint, effective immobilization and smaller
size of copper NPs on modified SMI polymeric surface
have been observed in the presence of DMF as solvent.
The reported results of Table 1 demonstrate that the bond
order of N-N in 1,2,4-triazole ring and also C-O carbonyl
bond decrease via the complexation that mainly attribute
to the donation of shared electrons from this chemical
bond to copper through coordination that is in confirma-
tion with our FT-IR spectroscopic observations. Further-
more, it can be deduced that the interaction of copper
Next, using these optimized conditions, various ter-
minal alkynes and α-halo ketones or alkyl halides were
TABLE 2 Effect of the solvent in the synthesis of 7a in reflux
condition and 0.03 g of SMI–CuI catalyst
Entry
Solvent
CH3CN
CH2Cl2
EtOH
Time (min)
Yielda (%)
1
2
3
4
5
55
50
30
20
20
81
74
80
90
87
TABLE 1 The calculated values of some selected bond orders
in SMI ligand and SMI-CuI complex in the presence of DMF as
solvent, obtained at M08-HX/6-311G** level of theory via PCM
calculations. Note that numbering of atoms is in accordance with
Figure 5 and the values in the parenthesis are the corresponding
bond lengths, reported in pm
EtOH/H2O
H2O
aYield refers to isolated and pure product
TABLE 3 Effect of the amount of catalyst in the synthesis of
7a in H2O
SMI ligand
SMI-Cu complex
1.036 (139.9)
1.657 (123.7)
1.673 (123.2)
0.377 (186.6)
0.365 (189.0)
0.264 (194.1)
0.259 (193.6)
N1-N2
C-O1
1.121 (140.7)
SMI–CuI
Entry Solvent (g)
Time
(min)
Yielda
(%)
1.979 (122.2)
C-O2
1.995 (122.5)
1
2
3
4
H2O
H2O
H2O
H2O
0.05
0.04
0.03
0.01
20
20
20
30
84
86
89
74
Cu-N1
Cu-N2
Cu-O1
Cu-O2
---
---
---
---
aYield refers to isolated and pure product.

8 of 13
ZOGHI ET AL.
TABLE 4 Synthesis of 1,4-disubstituted-H-1,2,3-triazoles under optimized condition
Time
(min)/Lit.
Time
α-Bromoketone or
Entry alkyl halide (5a-h)
Acetylene
(6a-c)
Yielda (%)/
Lit.Yield
Mp(ꢀC)/Lit.Mp
[ref]
Product (7a-k)
1
88/90
20/20
170–171/169–170[25]
2
84/85
30/25
156–159/158–160[6]
3
4
85/88
82/84
25/30
25/35
104–107/106–109[6]
117–119/115–118[6]
5
78/78
65/65
113–116/115–118[6]
6
7
73/72
75/80
70/70
75/75
180–181/179–182[18]
152–154/153–155[18]
8
72/75
80/80
166–169/169–171[18]
(Continues)

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
9 of 13
TABLE 4 (Continued)
Time
(min)/Lit.
Time
α-Bromoketone or
Entry alkyl halide (5a-h)
Acetylene
(6a-c)
Yielda (%)/
Lit.Yield
Mp(ꢀC)/Lit.Mp
[ref]
Product (7a-k)
9
80/79
65/65
114–116/116[21]
10
90/95
15/15
127–128/128–130[21]
127–129/128–130[22]
122–124/125[6]
11
87/89
71/80
20/20
12
CH3I 5 h
145/150
aYield refer to the pure and isolated products.
examined, in order to establish the generality of the
reaction (Table 4). The progress of the reaction was
monitored by TLC. Upon the completion of the reac-
tion (monitored by TLC) all the products were cleanly
isolated upon simple filtration to separate the heteroge-
neous catalyst, evaporation of solvent, and recrystalliza-
tion from ethanol. The reaction of α-haloketones or
alkyl halides (5a–h), alkynes (6a–c), and sodium azide
was performed in water in the presence of SMI-CuI
catalyst (Scheme 2) to afford the corresponding
1,4-disubstituted 1,2,3-triazoles in excellent yields, with
short reaction times and high regioselectivity (Table 4).
All the products are known, and their physical data
were found to be identical with those of authentic sam-
around 2100 cm−1, plus new triazole bond absorptions
around 1216 cm−1
and carbonyl bonds at
1655–1710 cm−1 [6,19–23]
,
.
A plausible mechanism for this reaction is supposed
to be similar to those of other copper (I)-catalyzed
azide-alkyne cycloaddition reactions that produce
1,4-disubstituted 1,2,3-triazoles[18] and suggested as
illustrated in Scheme 3. Nevertheless, in the present
system, the polymer support not only avoids more
copper(I) oxidation but also acts as an efficient ligand
for the metal center.[35,36] As shown in Scheme 3, the
proposed mechanism starts from the generation of the
copper(I) acetylide I. Density functional theory calcula-
tions have shown a preference for the stepwise addition
(B-1 ! B-2 ! B-3) over the concerted [2 + 3] cycload-
1
ples. In addition, H NMR and 13C NMR spectra of some
derivatives (7a, 7b, 7i) were recorded, which confirmed
that the corresponding triazoles were obtained in high
regioselectivity (For details see “Experimental”). The
structures of the regioisomers were confirmed by the
dition (B-direct) by approximately 12–15 kcal mol−1
,
leading to the six-membered copper containing interme-
diate III.[18]
Reusability of the catalyst was important for a true
heterogeneous catalyst, the supported catalyst should not
leach into the reaction mixture, thus, it was examined in
the selected model reaction. For investigation of these
properties, the reaction of 2-bromoacetophenone, phenyl
1
observations of a singlet around 8 ppm in their H NMR
spectra, which is attributed to the hydrogen on the
5-position of triazole ring, while the IR spectra exhibited
the absence of the azide absorption of the α-azidoketone

10 of 13
ZOGHI ET AL.
loss of weights were observed in the corresponding prod-
ucts. In addition only small difference in the copper con-
tent for the fresh and reused catalyst, after the fifth run,
was found being only 5%, confirming a low rate of
leaching (Figure 6).
4 | CONCLUSIONS
In conclusion, we prepared a new polymer-supported
CuI nanoparticle catalyst, based on modified SMA and
investigated its efficiency in the regioselective,
1,4-disubstituted-1H-1,2,3-triazoles cycloaddition reac-
tion. The results indicate that this new heterogeneous
catalyst is a good addition to a range of already reported
catalysts giving excellent yields and short reaction times
which can be reused at least over five repeated runs, with
very low leaching of the supported catalyst. At that time,
using water as the green solvent, experimental simplicity
are anther advantages of this protocol. Therefore, this
modified SMA should be considered as an attractive sup-
port for the synthesis of polymer-supported catalysts for
organic synthesis. In addition, we computationally inves-
tigated the interaction of copper NPs with modified SMI
polymeric surface via the design of four coordination
modes in SMI-CuI complex model. DFT and PCM calcu-
lated results demonstrated that copper atoms coordinate
more effectively with triazole nitrogen in comparison
with carbonyl oxygen of SMI ligand which can predict
and interpret the immobilization behavior of copper NPs
on modified SMI polymeric support.
SCHEME 3 A plausible mechanism for the synthesis of
1,4-disubstituted-1H-1,2,3-triazoles in the presence of Cu(I) NPs
supported onto modified SMA
acetylene, and sodium azide was selected again as model
(Table 5). A model reaction was conducted 5 times with
recycled catalyst under the optimal reaction conditions,
without any need to reload the catalyst. No appreciable
TABLE 5 The recyclability of the SMI–CuI in the preparation
of 7a
ACKNOWLEDGEMENTS
Entry
1
2
3
4
5
The partial support of this research by Alzhra University
and Islamic Azad University, Tonekabon Branch are
appreciated. M.M.H is also grateful to Iran National Sci-
ence Foundation (INSF) for given research chair.
Time (min)
Yield (%)
4
6
8
10
80
12
78
92
87
83
ORCID
Majid M. Heravi https://orcid.org/0000-0003-2978-1157
REFERENCES
[1] R. Huisgen, Angew. Chem. Int. Ed. Engl. 1963, 2, 565.
[2] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. 2001,
113, 2056.
[3] M. Meldal, C. W. Torne, Chem. Rev. 2008, 108, 2952.
[4] J. Albadi, M. Keshavarz, F. Shirini, M. Vafaie-nezhad, Catal.
Commun. 2012, 27, 17.
[5] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed.
2001, 40, 2004.
[6] I. S. Park, M. S. Kwon, Y. Kim, J. S. Lee, J. Park, Org. Lett.
2008, 10, 497.
[7] F. Alonso, Y. Moglie, G. Radivoy, M. Yus, Adv. Synth. Catal.
2010, 352, 3208.
FIGURE 6 The recyclability of the SMI–CuI in the
preparation of 7a

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
11 of 13
[8] R. Alvarez, S. Velazquez, A. San-Felix, S. Aquaro, E. De
Clercq, C. F. Perno, A. Karlsson, J. Balzarini, M. J. Carmarasa,
J. Med. Chem. 1994, 37, 4185.
[9] C. Girard, E. Onen, M. Aufort, S. Beauviere, E. Samson,
J. Herscovici, Org. Lett. 2006, 8, 1689.
[10] A. Coelho, P. Diz, O. Caamano, E. Soteloa, Adv. Synth. Catal.
2010, 352, 1179.
[11] L. Kashmiri, R. Poonam, ARKIVOC 2016, I, 307.
[12] D. Astruc, F. Lu, J. R. Aranzaes, Angew. Chem. Int. Ed. 2005,
44, 7852.
[20] M. Keshavarz, R. Badri, Mol. Diversity 2011, 15, 957.
[21] J. Vantikommu, S. Palle, P. S. Reddy, V. Ramanatham,
M. Khagga, V. R. Pallapothula, Eur. J. Med. Chem. 2010, 45,
5044.
[22] D. Kumar, V. B. Reddy, R. S. Varma, Tetrahedron Lett. 2009,
50, 2065.
[23] (a)M. M. Heravi, H. Hamidi, V. Zadsirjan, Curr. Org. Chem.
2014, 11, 647. (b)A. Fazeli, H. A. Oskooie, Y. S. Beheshtiha,
M. M. Heravi, F. M. Moghaddam, B. K. Foroushani,
Z. Naturforsch. B 2013, 68, 396. (c)L. S. Campbell-Verduyn,
L. Mirfeizi, R. A. Dierckx, P. H. Elsinga, B. L. Feringa, Chem.
Commun. 2009, 245, 2139. (d)A. Fazeli, H. A. Oskooie,
Y. S. Beheshtiha, M. M. Heravi, H. Valizadeh,
F. F. Bamoharram, Monatsh. Chem. 2013, 144, 1407. (e)
R. Sedghi, H. A. Oskooie, M. M. Heravi, M. R. Nabid,
A. H. Zarnani, J. Mater. Chem. B 2013, 1, 773.
[13] (a)B. Dervaux, F. E. Du Prez, Chem. Sci. 2012, 3, 959. (b)
R. Chinchilla, D. J. Dodsworth, C. Najera, J. M. Soriano, Tetra-
hedron Lett. 2001, 42, 4487. (c)R. Chinchilla, D. J. Dodsworth,
C. Najera, J. M. Soriano, Tetrahedron Lett. 2001, 42, 7579. (d)
R. Chinchilla, D. J. Dodsworth, C. Najera, J. M. Soriano, Bio-
org. Med. Chem. Lett. 2002, 12, 1817. (e)R. Chinchilla,
D. J. Dodsworth, C. Najera, J. M. Soriano, Synlett 2003, 2003,
809. (f)R. Chinchilla, D. J. Dodsworth, C. Najera,
J. M. Soriano, Tetrahedron Lett. 2002, 44, 463. (g)J. Gil-Molto,
S. Karlstrom, C. Najera, Tetrahedron 2005, 61, 12168.
[14] (a)S. Sadjadi, M. Malmir, M. M. Heravi, F. GhoreyshiKahangi,
Inorganica Chem. Acta. 2019, 488, 62. (b)S. Sadjadi,
M. M. Heravi, M. Malmir, F. Noritajer, Mater. Chem. Phys.
2019, 223, 380. (c)E. Hashemi, Y. S. Beheshtiha, S. Ahmadi,
M. M. Heravi, Transit. Metal. Chem. 2014, 39, 593. (d)
B. Heidari, M. M. Heravi, M. R. Nabid, R. Sedghi, Appl. Org.
Anometal. Chem. 2019, 33, 4934. (e)N. Ghalavand,
M. M. Heravi, M. R. Nabid, R. Sedghi, J. Alloys Compd. 2019,
799, 279. (f)S. Sadjadi, M. M. Heravi, M. Malmir, Appl.
Organomet. Chem. 2018, 32, 4029.
[15] (a)B. Heidari, M. M. Heravi, M. R. Nabid, R. Sedghi,
S. E. Hooshmand, Appl. Organometal. Chem. 2018, 33, 4632.
(b)S. Sadjadi, M. Malmir, M. M. Heravi, F. GhoreyshiKahangi,
Int. J. Biol.Macromol. 2018, 118, 1903. (c)S. Sadjadi,
M. M. Heravi, M. Raja, Carbohydr. Polym. 2018, 185, 48. (d)
M. M. Heravi, E. Hashemi, Y. ShiraziBeheshtiha, S. Ahmadi,
T. Hosseinnejad, J. Mol. Catal. A: Chem. 2014, 394, 74. (e)
R. Mirsafaei, M. M. Heravi, S. Ahmadi, M. H. Moslemin,
T. Hosseinnejad, J. Mol. Catal. A: Chem. 2015, 402, 100. (f)
S. Sadjadi, T. Hosseinnejad, M. Malmir, M. M. Heravi, New
J. Chem. 2017, 41, 3935. (g)N. Pourmohammad, M. M. Heravi,
S. Ahmadi, T. Hosseinnejad, Appl. Organomet. Chem. 2019, 33,
4967.
[24] R. J. Kalbasi, M. Kolahdoozan, S. Mozafari-Vanani, J. Solid
State Chem. 2011, 184, 2009.
[25] R. J. Kalbasi, M. Kolahdoozan, M. Rezaei, J. Ind. Eng. Chem.
2012, 18, 909.
[26] A. D. Becke, J. Chem. Phys. 1993, 98, 1372.
[27] F. Ebrahimpour-Malamir, T. Hosseinnejad, R. Mirsafaei,
M. M. Heravi, Appl. Organomet. Chem. 2017, 32, 3913.
[28] T. BaieLashaki, H. A. Oskooie, T. Hosseinnejad, M. M. Heravi,
J. Coord. Chem. 2017, 70, 1815.
[29] Y. Zhao, D. G. Truhlar, J. Chem. Theory Comput. 2008, 4, 1849.
[30] P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 284.
[31] P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270.
[32] M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert,
M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga,
K. A. Nguyen, S. J. Su, Comput. Chem. 1993, 14, 1347.
[33] V. Barone, M. Cossi, J. Phys. Chem. 1998, 102, 1995.
[34] M. M. Heravi, M. Tamimi, H. Yahyavi, T. Hosseinnejad, Curr.
Org. Chem. 2016, 20, 1591.
[35] V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless,
Angew. Chem. Int. Ed. 2002, 41, 2596.
[36] M. Sher, H. Reinke, P. Langer, Tetrahedron Lett. 2007, 48,
7923.
How to cite this article: Zoghi R, Heravi MM,
Montazeri N, Zeydi MM, Hosseinnejad T.
Preparation of an efficient catalyst through
injection of CuI on modified poly (styrene-co-
maleic anhydride) and theoretical investigation of
the structural and electronic properties of catalyst.
Appl Organometal Chem. 2020;e5435. https://doi.
org/10.1002/aoc.5435
[16] M. M. Heravi, A. Fazeli, H. A. Oskooie, Y. S. Beheshtiha,
H. Valizadeh, Syn. Lett. 2012, 23, 2927.
[17] S. S. Lee, T. O. Ahn, J. Appl. Polym. Sci. 1999, 71, 1187.
[18] H. Sharghi, R. Khalifeh, M. M. Doroodmand, Adv. Synth.
Catal. 2009, 351, 207.
[19] A. Fazeli, H. A. Oskooie, Y. S. Beheshtiha, M. M. Heravi,
H. Valizadeh, Lett. Org. Chem. 2013, 10, 738.

12 of 13
ZOGHI ET AL.
Analysis Conditions
Accelerating Voltage (kV):
Beam Current (nA):
Magnification:
20.0
10.000
100000
30
Live Time (s):
Preset Time (s)
Nb Channels
30
1024
20
Ev/Channel
Offset (keV)
0
Width (keV)
20
Geometry
Tilt Angle (deg):
Azimuth Angle (deg):
Take Off Angle (deg):
Window
0.0
0.0
35.0
Window Type:
Window Thickness (um):
Contamination Layer (nm):
Detector
Moxtek AP1.3
0.30
0.00
Dead Layer (um)
Gold Layer (um)
Active Area (mm2)
Crystal:
0.10
20.00
10.00
Si
Crystal Thickness
Coating Type
3.00
Al
Coating Thickness (nm)
Sample
15.00
Coating Thickness (nm):
Density:
0.00
0.00
Quantitative Results
Elt
Line
Int
Error
K
Kr
W%
A%
ZAF
Formula
Ox%
Pk/Bg
Class
LConf
HConf
Cat#
C
Ka
420.9
34.1073
0.0878
0.0442
29.57
54.13
0.1494
0.00
64.85
A
29.05
30.10
0.00
N
Ka
Ka
Ka
Ka
Ka
Ka
La
La
28.9
34.1073
34.1073
9.3326
9.3326
1.4521
1.1290
1.4521
1.1290
0.0061
0.0328
0.0294
0.2732
0.1950
0.2173
0.0496
0.1089
1.0000
0.0031
0.0165
0.0148
0.1374
0.0981
0.1093
0.0249
0.0548
0.5030
3.43
5.39
0.0891
0.1383
0.8279
0.8036
0.8560
0.8477
0.7497
0.6433
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.85
8.29
4.97
10.39
8.10
10.51
3.82
6.91
B
3.20
3.67
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
O
154.6
124.3
1133.6
762.6
688.0
191.4
321.4
11.92
1.79
16.38
1.22
A
A
A
A
A
B
11.57
1.73
12.27
1.84
S
Cl
Ca
Cu
I
17.10
11.46
12.89
3.33
10.60
6.29
16.91
11.31
12.71
3.24
17.28
11.61
13.07
3.41
4.46
0.58
Au
8.51
0.95
A
8.34
8.69
100.00
100.00

INJECTION OF CUI ON MODIFIED POLY (STYRENE-CO-MALEIC ANHYDRIDE)
13 of 13
Automatic Identification Results
Elt
Line
Int
keV
Prob%
Nb
La1
1420.5
2.170
100
Cl
Rh
Te
Ca
I
Ka1
La1
La1
Ka1
La1
La1
La1
Ka1
897.4
293.6
258.4
527.5
142.8
27.2
2.620
2.690
3.760
3.680
3.930
1.480
8.140
8.070
100
100
100
100
100
100
33
Br
Ta
Cu
33.4
660.1
33