Catalytic reactivity of new Ni(II), Cu(II) and Sn(II) complexes for decolorization of indigo carmine in aqueous solution, high efficiency of copper complex

Article abstract of DOI:10.1002/aoc.4056

A new Ni(II), Cu(II) and Sn(II) Schiff base complexes were synthesized in this work. The characterization of the new complexes is carried out by elemental analysis, FT-IR, UV–Visible, ¹H NMR and ¹³C NMR spectroscopy, conductance analysis, magnetic measurements and thermal gravimetric analysis. It was found that the ligand behaves as a dibasic bidentate which coordinated to the metal center through two deprotonated hydroxyl groups to form tetrahedral complex with Ni(II) and octahedral complex with Cu(II). The ligand acts as neutral bidentate through azomethine nitrogen and thiazol sulfur to form octahedral complex with Sn(II). The synthesized complexes are evaluated as catalysts for oxidative degradation of indigo carmine dye using H₂O₂ as oxidant and the efficiency of the catalysts is determined. The copper complex shows the best catalytic action with efficiency 92.17% after 25?min.

Full text of DOI:10.1002/aoc.4056

Received: 3 June 2017
DOI: 10.1002/aoc.4056
Revised: 27 July 2017
Accepted: 28 July 2017
F U L L P A P E R
Catalytic reactivity of new Ni(II), cu(II) and Sn(II)
complexes for decolorization of indigo carmine in aqueous
solution, high efficiency of copper complex
1,2
Amr Mohammad Nassar
1
Chemistry Department, College of
A new Ni(II), Cu(II) and Sn(II) Schiff base complexes were synthesized in this
work. The characterization of the new complexes is carried out by elemental
Science, Aljouf University, PO Box 2014
Sakaka, Aljouf, Saudi Arabia
2
Chemistry Department, Faculty of
1
13
analysis, FT‐IR, UV–Visible, H NMR and C NMR spectroscopy, conductance
analysis, magnetic measurements and thermal gravimetric analysis. It was
found that the ligand behaves as a dibasic bidentate which coordinated to the
metal center through two deprotonated hydroxyl groups to form tetrahedral
complex with Ni(II) and octahedral complex with Cu(II). The ligand acts as
neutral bidentate through azomethine nitrogen and thiazol sulfur to form octa-
hedral complex with Sn(II). The synthesized complexes are evaluated as cata-
lysts for oxidative degradation of indigo carmine dye using H O as oxidant
Science, Al‐Azhar University, Nasr city,
118804, Cairo, Egypt
Correspondence
Amr Mohamed Nassar, Chemistry
Department, College of Science, Aljouf
University, Sakaka, Aljouf, Saudi Arabia.
Email: nassar_tanta@yahoo.com
2
2
and the efficiency of the catalysts is determined. The copper complex shows
the best catalytic action with efficiency 92.17% after 25 min.
KEYWORDS
catalysts, complexes, degradation, indigo carmine, oxidation
1
| INTRODUCTION
dyes remain unfixed and are discharged in the wastewa-
[
16]
ter.
Indigo Carmine is highly toxic, cause eye and
Schiff bases have excellent coordinative capability to form
beings irritations to human and leads to tumors at the site
[1]
[17]
stable complexes with most of metal ions. The wide
range of applications of these complexes were studied by
of application.
It makes the removal of indigo carmine
from industrial wastewater be a major concern for the
human health and environmental standpoint. Hydrogen
peroxide is environmental friendly oxidizer because it
produces H O and O as a final reduction products. Also,
[2–7]
several works.
From these applications, A large
number of Schiff base complexes exhibit remarkable cata-
lytic activity for enhancing yield and product selectivity.
Schiff base complexes show excellent homogeneous and
heterogeneous catalytic properties in various reactions
2
2
[
18]
it is available and cheap reagent. H O without catalyst
2
2
is moderate oxidizing agent of organic compounds while
in the presence of catalyst, photo, ultrasound or heat, lead
[8]
such as oxidation of organic compounds, reduction of
[
9]
[10]
alkyl and aryl halides, DNA bending,
H O decom-
to powerful oxidation and degrade many organic
2
2
[11]
[12]
[19]
position,
ester hydrolysis
from aqueous solutions.
and dyes decolonization
Indigo Carmine is one of
substrates.
The using of H O in the degradation of
2 2
[13,14]
different organic dyes and their color removal from indus-
[20–22]
the mainly dyes used in the textile dyeing. It is also used
in food, cosmetics, paper, and plastics as coloring dye,
redox indicator in analytical chemistry, and in biology
trial wastewater effluents have been studied.
Moreover, the using of transition metal complexes as het-
erogeneous catalysts in decomposition of indigo carmine
[15]
[23–25]
microscopic stain.
It is found that, the effluent from
with H O has been investigated.
In this work, the
2
2
textile dying industry contain about 30% of the applied
catalytic activity of newly synthesized Schiff base
Appl Organometal Chem. 2017;e4056.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 8
https://doi.org/10.1002/aoc.4056

2
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NASSAR
complexes in degradation of Indigo Carmine was
investigated. To the best of the author knowledge, this is
the first report for the using of Schiff base complexes in
catalytic removal of indigo carmine from aqueous
solutions. This system may be apply to color removal in
wastewater effluent stream.
45.95; H, 3.86; N, 10.72; Ni, 14.97. Found (%): C, 46.0; H,
4.0; N, 3.9; Ni, 15.0. Main IR peaks (KBr, cm ): 1601
−
1
(C¼N), 745 ν C‐S‐C, 1162 (C―O), 3421 (ν H O), 448
as
2
−
1
−1
2
(Ni―O). Λm(Ω mol cm ): 4.55. UV–visible (DMF,
nm): 671 nm (d–d transition). μ eff (BM): 3.49 B.M.
2
.3.2 | Complex. 2
2
2
| EXPERIMENTAL
Deep brown solid; m.p. > 300 °C; molecular weight
−
1
3
4
96.01 g.mol . Anal. Calcd for C H N CuO S (%):C,
15 15 3 4
5.39; H, 3.81; N, 10.95; Cu, 16.01. Found(%): C, 45.40;
.1 | Materials and methods
Indigo Carmine dye was obtained from Sigma‐Aldrich and
used as received. Hydrogen peroxide (30%, w/v) was used
as an oxidizer. All the chemical reagents were analytical
grade and were used as received. All the experiments were
done using MQ water. The solvents used in this work were
extra‐pure grades and were used as received.
−1
H, 3.75; N, 10.66; Cu, 16.02. Main IR peaks (KBr, cm ):
1
4
601 (C¼N), 746 ν C‐S‐C, 1177 (C―O), 3423 (ν H O),
as
2
−1 −1 2
52 (Cu―O). Λm(Ω
mol
cm ): 5.02. UV–visible
(
DMF, nm): 433, 471, 580 and 822 nm (d–d transition).
μ eff (BM): 2.15 B.M.
2.3.3 | Complex. 3
2.2 | Instrumentation
Greenish yellow solid; m.p. > 300 °C; molecular weight
Elemental analysis was detected using a CHNS‐932
LECO) Vario elemental analyzer. Room temperature
−
1
7
4
88 g.mol . Anal. Calcd for C H Cl N O S Sn (%): C,
30 26 2 6 4 2
(
5.68; H, 3.30; N, 10.65; Sn, 15.06. Found (%): C, 45.55;
magnetic susceptibility measurements were conducted
with a Sherwood Scientific magnetic balance. UV–visible
spectra in the range (195–1100 nm) were recorded using
labomed Spectro UV–VIS Double PC 8 Auto cell scanning
spectrophotometer.IR spectra were carried out using KBr
pellets with a PerkinElmer 1430 spectrometer in the
−
1
H, 3.35; N, 10.77; Sn, 15.10. Main IR peaks (KBr, cm ):
588 (C¼N), 700 ν C‐S‐C, 1183 (C―O), 3469 (ν OH), 452
1
−
1
−1
2
(
Cu―O). Λm(Ω mol cm ): 4.75. UV–visible (DMF,
nm): 490 (charge transfer). μ (BM): Diamagnetic. Main
eff
1
HNMR signals, δ = 8.2 ppm (HC = N), 9–10.5 PPM
13
−
1
(OH). Main
CNMR signals δ = 146,148 (C‐OH),
region 4000–200 cm . The instrument used for
158(Ph‐C = N).
performing the thermal gravimetric analysis (TGA) was
1
TGA‐50 Shimadzu thermogravimetric analyzer. H NMR
13
and C NMR spectra were recorded with a GEMINI‐
00BB NMR 500 MHz spectrometer.
2.4 | Catalytic tests
3
The methods of Indigo Carmine degradation was carried
3
out in a conical flasks (250 cm ) containing a mixture of
2.3 | Synthesis of metal complexes
−
4
3
IC 1 × 10 M, 1cm H O solution and 0.02 gm catalyst
2
2
Complexes 1, 2 and 3 were synthesized by dropwise addi-
tion of 50 ml of a methanolic solution of 0.0020 mol of
each NiNO .6H O, Cu(OAC) .H O and SnCl .2H O
equipped with a magnetic stirrer. The kinetic run was
started from the addition of the catalyst. The mixture
was continuously stirred at room temperature. At the suit-
able time intervals, the descending IC concentration is
3
2
2
2
2
2
respectively to hot stirred methanolic solution of H2L
0.3 g, 0.0010 mol) (50 ml) in metal: ligand molar ratio
3
(
followed up by withdrawing a 5 cm sample and filtration
of 2:1. Complexes 2 and 3 are precipitated immediately
while complex 1 is precipitated after reflux 2 h then addi-
tion of 1.2 ml of deionized water. The metal complexes
were filtered, washed several times with hot water and
acetone then finally dried in oven at 110 °C. Below are
mentioned the most important characteristics of the
obtained complexes.
from the catalyst to stop the reaction. The absorbance of
IC is recorded at λmax using UV–VIS spectrophotometer
between 190–1100 nm with a maximum absorbance at
[
23]
λ = 610 nm.
The efficiency of IC decolorization was
determined by Equation 1.
Aο–At
Aο
IC decolorization ð%Þ ¼
×100
(1)
2.3.1 | Complex 1:
Deep green solid; m.p. > 300 °C; molecular weight
Where Aο is the value of absorbance at time 0 and At
is the value of absorbance at any time t in min.
−
1
3
92.06 g.mol . Anal. Calcd for C H N NiO S (%): C,
15
15
3
4

NASSAR
3 of 8
−
1
3
| RESULTS AND DISCUSSION
observed in the range 1162 and1177 cm which is due
to a phenolic ν C‐O stretching vibration. The shift of this
The Schiff base ligand, H L represents in Figure 1 was
prepared and characterized according to literature.
The reaction of nickel (II), copper (II) and tin (II) salts
band toward lower frequency in comparing with H
2
L is
2
[
26]
assignable to the weakness of this bond after chelation
[
29]
of phenolic oxygen with metal ions.
The spectra of complexes 1 and 2 show a strong broad-
with H L in molar ratios and 2: 1 (M: L) in methanol
2
−
1
under refluxing conditions resulted in the formation of
complexes 1 and 2 with stoichiometries 1: 1 and complex
ness band at 3421 and 3423 cm , respectively which
[
30]
assignable to νas of coordinated H
far infrared region of the complexes display new shoulder
O molecules.
The
2
3
in 1: 2 (M: L), respectively. As listed in experimental
−
1
section, the complexes melt above 350 °C. The complexes
are air stable, freely soluble in DMF and DMSO and only
complex 1 is partially soluble in MeOH, EtOH. The molar
at 448 and 452 cm which is not found in the spectrum of
the free ligand. This band is due to νM‐O
Complex 3 shows a band at 1588 cm assignable to
azomethine stretching vibration. The shift of this band to
lower frequency indicating the weakness of this group
due to participation of azomethine nitrogen with
.
−
1
−
3
conductance of 10 M solutions of the complexes in
[
27]
DMF clear that the complexes are non‐electrolytes.
2
+ [31]
−1
Sn .
Also the lower shift of ν C‐S‐C band to 700 cm
3
3
.1 | Characterization of the complexes
.1.1 | IR spectra
assignable to coordination of S atom with stannous ion.
Confirming this, the appearance of new medium inten-
−
1
sity bands at 507 and 369 cm which are due to ν
and νSn‐S, respectively. The broad band at 3423 cm is
Sn‐N
−
1
The important infrared bands of the Schiff base and its
transition metal chelates are collected in Table 1.
The IR spectrum of the ligand shows a characteristic
attributed to stretching vibration of phenolic OH. The
−
1
band observes at 308 cm in the spectrum of complex
3 is assignable to νSn‐Cl
−
1
band at 1601 cm assignable to ν C = N, indicating the
.
formation of Schiff base molecule. The weak bands
observe at 3075 and 2924 cm is attributed to stretching
Accordingly, the ligand H L acts as a dibasic bidentate
ligand coordinated to the Ni(II) and Cu(II) ions as –O in
2
−
1
−
vibration of aromatic and aliphatic C‐H, respectively. A
these complexes and a neutral bidentate ligand coordi-
nated to Sn(II) ion through N and S.
−
1
sharp band observes at 3469 cm is assignable to ν
OH
−
1
groups. A medium intensity band observes at 744 cm
[
28]
is due to ν C‐S‐C.
Also, stretching vibration of C‐O rep-
−
1
resents a sharp band at 1183 cm .
3
.1.2 | UV–vis spectra and magnetic sus-
The IR spectra of complexe 1 and 2 do not exhibits
appreciable change in position of the (C = N) band indi-
cates the not participation of azomethine nitrogen in the
chelation with metal ions. Also, the spectra of the com-
plexes show a medium intensity band at 744 and 746 cm
ceptibility measurements
The electronic spectra of the Schiff base ligand H L and its
2
metal complexes were recorded in DMF solution, Table 2.
The ligand shows bands at 324 and 390 nm due to π‐π*
transitions. In the spectra of the complexes, these bands
slightly bathchromic shift that could be attributed to the
complexation. The ligand chromophore C = N, which
absorbs at 430 nm assignable to n‐π*transition is not
shifted in the spectra of the complexes 1 and 2 but shifts
to higher wavelength at 490 nm in the spectrum of com-
plex 3 possibly due to polarization of the C = N bond pro-
−
1
which is attributed to ν C‐S‐C. No change in the posi-
tion of this band in the spectra of the ligand and the com-
plexes which supports the S atom is not included in
coordination with metal ions. Moreover, A sharp band
[
32]
duced from the metal–ligand interaction.
In addition
the spectra displays new bands above 500 nm due to d‐d
FIGURE 1 Structure of Schiff base ligand H
2
L
transition.
TABLE 1 Infrared spectral analysis of ligand(H
2
L)and its complexes
Compound
Ligand H
Complex 1 [Ni(L)(H
Complex 2 [Cu(L)(H
Complex 3 [Sn(H L)
ν
C=N
ν
C‐S
ν
C‐O
ν
OH
ν
M‐O
ν
M‐N
ν
M‐S
ν
M‐Cl
2
L
1601
1601
1601
1588
744
745
746
700
1183
1162
1177
1183
3469
‐
‐
‐
‐
2
O)
O)
Cl
2
]
3421 (H
3423 (H
2
O)
O)
448
452
‐
‐
‐
‐
‐
‐
‐
2
4
]
2
2
2
2
]
3469 (Phenolic)
507

4
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NASSAR
TABLE 2 Electronic spectral analysis and magnetic measurements of complexes
Compound
Ligand H
Bands (nm)
324,390
Interpretation
π‐π*
Magnetic susceptibility (B.M)
‐
Geometrical structure
‐
2
L
4
30
430
71
433
22
80
71
n‐ π*
Complex 1 [Ni(L)(H
2
O)
2
]
n‐ π*
3.49
2.15
Tetrahedral
Octahedral
3
3
6
T
1
(F) →
1
T (P)
2 4
Complex 2 [Cu(L)(H O) ]
n‐ π*
2
2
8
5
4
B
B
B
1g → A1g
2
2
2
1g → B2g
2
1g → E
g
Complex 3 [Sn(H
2
L)
2
Cl
2
]
490
C.T*
D**
Octahedral
*
*
Charge transfer
*Diamagnetic
The UV–Vis spectrum of complex 1 exhibits a broad
nitrogen‐metal coordination bond can formed by the
acceptance of the nitrogen lone pair of electrons.
3
3
[35]
band at 671 nm corresponding to T1(F) → T1(P) indi-
cates the tetrahedral arrangement of the ligand surround-
ing Ni(II) in this complex. The magnetic moment value of
3.1.3 | Thermal gravimetric analysis
3
.49 BM is in the range of 3.2–4.0 BM expected for the
[33]
tetrahedral Ni(II) complexes.
The thermograms of Schiff base ligand shows the first
step of decomposition within the temperature range
(25‐275 °C) attributed to liberation of C H O as gases
The μeff of complex 2 is 2.15 B.M., which confirms the
octahedral structure of this complex. The electronic spec-
trum of the complex, Figure 2 shows a bands at 822, 580
7
6 2
with mass loss of 40.88% (calc: 40.80%). The remaining
steps show the complete degradation of the organic part
C H N S within the temperature range (275–700 °C)
2
2
and 471 nm, which are attributed to B1g
→
A ,
1g
2
2
2
2
B1g → B and B → E transitions, respectively. The
2g
1g
g
8
7 3
band observed at 433 nm indicating the existence of a tran-
with estimated mass loss 59.12% (calc: 59.20%).
2
2
2
sition from dxy,dxz, dyz and dz → antibonding dx ‐y
which is half‐filled level, this is consistent with an six
The TGA figure of complex 1 displays four steps of
decomposition. The first and second steps within the tem-
[34]
0
coordinated configuration.
perature range 25–180 C correspond to elimination of
The complex 3 is diamagnetic and its electronic spec-
trum shows one broad bands in the region 490 nm which
may be assigned as charge transfer. It was reported that
the metal is capable of forming dπ–pπ* bonds with
ligands containing nitrogen as the donor atom. The
d orbital of Sn atom has 5d completely vacant, so the
three NH molecules with founded mass loss 12.95% (calc:
3
13.01%). The third step of thermal decomposition
180–250 °C is corresponds to the loss of two coordinated
water molecules with a mass loss 9.10% (calc: 9.18%).
The fourth step is matching with the loss of the organic
part of Schiff base ligand C H O with mass loss 54.70%
15
2 2
(
calc: 54.59%) leaving NiS as residue 23.34% (calc: 23.19%).
Complex 2 decomposed in four decomposition steps.
The first and second decomposition steps occurred in
the range 25–225 °C assigned to loss of N molecule with
2
estimated mass loss 6.59% (calc: 6.47%). The third decom-
position stage revealed in the range 225‐315 °C which can
be attributed to loss of NH ,4H O and O and organic part
3
2
2
C H with estimated mass loss 52.89% (calc: 52.65%). The
8
11
last weight loss stage appeared in the range 315–675 °C
produced CuS as residue 22.31% (calc: 22.05%).
Complex 3 is thermally decomposed in two steps. One
molecule of Cl gas is loosed in the first step in the tem-
2
perature range 25–300 °C with estimated mass loss
8
.46% (calc: 8.84%). The second step shows the loss of
the organic moiety within the temperature range
00–570 °C corresponds to mass loss 72.30% (calc:
72.47%).
3
FIGURE 2 Electronic spectra of ligand and complex 2

NASSAR
5 of 8
[
36]
The residual part of TGA of this complex is found to
be SnS, 18.46% (calc: 18.68%).
azomethine nitrogen atom with metal ion.
The aro-
matic signals appeared slightly deshielding due to
[
37]
increased conjugation upon coordination.
The broad
1
13
and weak signals appeared in the range 9–10.5 ppm are
attributed to hydroxyl protons which indicates that the
hydroxyl groups are not participate in the coordination
with stannous ion. These signals are disappeared when
3
.1.4 | HNMR and CNMR spectra
1
13
The HNMR and CNMR spectra of complex 3 are
recorded in DMSO‐d6 and compared with that of the free
[26]
Schiff base ligand reported in previous work.
D O is added to the solution due to proton exchangeable,
2
1
In the H NMR spectrum of Sn(II) complex, Figure 3,
the azomethine proton signal is slightly shifted to down-
field and appeared at 8.2 ppm. This shift in azomethine
proton position could assignable to the coordination of
Figure 4.
13
The CNMR spectrum of tin complex, Figure 5,
shows two signals at 146.0 and 148.3 ppm which are due
to C‐OH. No remarkable shift in this signals when
(a)
(b)
1
1
FIGURE 3 HNMR spectrum of complex 3 in DMSO. HNMR spectrum of complex 3 in DMSO + D
2
O

6
of 8
NASSAR
1
3
FIGURE 4
CNMR spectrum of complex 3 in DMSO
compared with the spectrum of the ligand. This result
confirms that the hydroxyl groups are not included in
complexation with tin. On the other hand the signal due
to Ph‐C = N‐ is appeared at 158 ppm. This signal are
slightly shifted to down field region when compared with
that of free ligand indicating the involvement of
Consequently, the proposed structure of the synthe-
sized metal complexes are shown in Figure 6.
3.2 | Catalytic activity of the complexes
2+
azomethine nitrogen in coordination with Sn .
In this part of study indigo carmine dye (IC) was chosen
as a model to investigate its oxidative degradation by
H O as an oxidant using the synthesized metal com-
2
2
plexes as catalysts.
Figure 7 shows the behavior of 1 × 10 M solution of
indigo carmine, after 10 min from addition of H O only
−
4
2
2
without catalyst and H O + 0.02 gm of different catalysts
2
2
and the degradation is followed using UV–Vis spectropho-
tometer. When H O2 solution was added to the dye
2
FIGURE 6 Degradation of indigo carmine without and with
FIGURE 5 Proposed structure of the metal complexes
catalysts after 10 min

NASSAR
7 of 8
first order reaction with respect to dye concentration. The
−
1
observed rate constant, k = 0.093 min , calculated from
0
the slope of the straight lines from the first order kinetic
[
24]
plot using equation 2:‐
.
lnA ¼ lnA − k wt
(2)
0
0
where A is the absorbance of dye at a definite time t, A is
0
the initial absorbance at t = 0, w is the weight of the
catalyst, and t is the time of degradation.
FIGURE 7 Catalytic degradation of indigo carmine by complex 2
at different times
3.3 | Mechanism of degradation
[
40]
It was concluded
that the nitrogen donor ligands
2+
resulted on destabilization of the Cu center and hence
raise the potential of Cu –Cu reduction and the use
of π‐accepting ligand favors Cu state which is required
solution without catalysts, a little decay observed in
λmax = 625 nm in the spectrum of the dye. Also, a simple
IC degradation in case of using complexes 1 and 3 as cat-
alysts. On contrary, when the complex 2 was introduced,
the oxidative reaction was started fast and a gradual van-
ish of the color of IC is clearly marked. After 10 min from
the catalytic reaction the reactivity of catalysts showed the
following order 2 > 1 > 3 > H O with efficiencies 84.34%,
2+
1+
1+
for dye degradation by redox reaction.
It is popularly believed that the redox mechanism,
2+
1+
Scheme 1 involves the reduction of Cu to Cu which
•
facilitate the generation of OH radicals from H O to
2
2
[41]
attack and decompose the indigo carmine dye.
The catalytic removal of IC does not necessarily
produces a complete degradation and may be lead to
2
2
4
6.09%, 30.43% and 26.95%, respectively.
The catalytic reactivity of copper complex is higher
[42]
fragmentation without complete mineralization.
From
than nickel and tin complexes may be assigned to the
figure7, the absorbance increase at 334 nm and 405 nm
can be ascribed to IC is converted to isatin sulfonic
2
+
1+
higher redox potential of Cu → Cu = 0.15v than
2+
0
2+
0
[38]
Ni → Ni = −0.25v and Sn → Sn = −0.14v.
On
[43–45]
acid.
the other hand the lower catalytic activity of the stannous
complex is due to the large molecular weight of the com-
plex which reduces the number of the active sites leading
4
| CONCLUSIONS
[39]
to a decreasing of its catalytic activity.
Three new nickel, copper and tin Schiff base complexes
with different chelation modes and geometrical structures
are synthesized and characterized in this work. The cata-
lytic reactivity of the complexes are studied for the oxida-
tive degradation and removal of indigo carmine dye from
aqueous solution. The role of the complexes as catalysts
was demonstrated. The efficiency of the copper complex
is the highest between the other catalysts and its effi-
ciency in decolorization of the dye is found to be 92.17%
after 25 min.
The effect of the complex 2 as catalyst was studied at
different times at 10,15, 20 and 25 min. The catalytic effi-
ciency is increased with time, after 25 min from the reac-
tion start, the catalyst efficiency reached to 92.17%,
Figure 7.
Where the concentration of the oxidant H O was
2
2
high excess than that of the indigo carmine dye, the cata-
lytic decomposition of the dye is carried out with pseudo‐
II
II
-
+
Cu - Complex +H2O2
Cu - Complex-HO2 + H
I
Cu -Complex
OH + 1/2 O2
Dye
ORCID
OH
Amr Mohammad Nassar http://orcid.org/0000-0001-5366-
3535
II
Cu -Complex + OH-
Dye
H+
Intermediate
REFERENCES
[
1] W. A. Zoubi, A. A. S. Al‐Hamadani, M. Kasem, App.
Organomet. Chem. 2016, 30, 810.
H2O
Oxidation product
SCHEME 1 Mechanism of redox catalytic degradation of indigo
carmine dye
[2] E. Kadwa, H. B. Friedrich, M. D. Bala, Inorg. Chim. Acta 2017,
463, 112.

8
of 8
NASSAR
[
3] S. Packianathan, G. Kumaravel, N. Raman, App. Organomet.
Chem. 2017, https://doi.org/10.1002/aoc.3577.
[27] S. S. Kandil, A. El‐Dissouky, G. Y. Ali, J. Coord. Chem. 2004, 57,
105.
[
4] H. Zafar, A. Ahmad, A. U. Khan, T. A. Khan, J. Mol. Str. 2015,
[28] O. F. Ozturk, A. Cansiz, M. Koparir, Trans. Met. Chem. 2007, 32,
1
097, 129.
224.
[
[
5] Z. Liu, F. C. Anson, Inorg. Chem. 2001, 40, 1329.
[29] A. M. Hassan, A. M. Nassar, Y. Z. Hussien, A. N. Elkmash, App.
Biochem., Biotech. 2012, 167, 58.
6] A. M. Nassar, A. M. Hassan, A. N. Elkmash, App. Organomet.
Chem. 2017, https://doi.org/10.1002/aoc.3572.
[30] K. Nakamoto, Infrared and Raman Spectra of Inorganic and
Coordination Compounds, Wiley, New York 1986.
[
[
[
7] S. Suganya, F. P. Xavier, K. S. Nagaraja, Bull. Mat. Sci. 1998, 21,
4
03.
[31] A. M. Nassar, A. M. Hassan, S. S. Al‐Abd, Synth., React., Inorg.,
Metalorg., Nanomet., Chem. 2015, 45, 3256.
8] W. Al Zoubi, Y. G. Ko, App. Organomet. Chem. 2017, 31, https://
doi.org/10.1002/aoc.3574.
[32] A. Varshney, J. P. Tandon, Polyhedron 1986, 5, 1853.
9] A. Ourari, I. Bougossa, S. Bouacida, D. Aggoun, R. R. Rosas, E.
[33] A. C. Fellah, J. Meullemeestre, C. Spies, F. Vierling, M. A.
Morallon, H. Merazig, J. Iran. Chem. Soc. 2017, 14, 703.
Khan, Trans. Met. Chem. 1999, 24, 135.
[
[
[
[
[
[
[
[
[
[
[
10] A. K. Asatkar, M. Tripathi, S. Panda, R. Pande, S. S. Zade,
[34] A. M. A. Alaghaz, B. A. El‐Sayed, A. A. El‐Henawy, R. A. A.
Ammar, J. Mol. Str. 2013, 1035, 83.
Spectrochim. Acta. A. 2017, 171, 18.
11] K. Zhang, A. Gao, C. Zhang, K. Xie, Desalin. and Water Treatm.
[35] H. L. Singh, J. B. Singh, S. Bhanuka, J. Coord. Chem. 2015, 69,
2
016, 57, 19190.
343.
12] W. Jiang, B. Xu, F. Liu, Y. Wang, Z. Xiang, Synth., React., Inorg.,
Metalorg., Nanomet., Chem. 2015, 45, 34.
[36] D. Arish, M. S. Nair, J. Mol. Str. 2010, 983, 112.
[
[
[
[
[
[
[
[
[
37] Z. Hong‐Yun, C. Dong‐Li, C. Pei‐Kun, C. De‐Ji, C. Guang‐Xia,
13] A. S. Elsherbiny, H. A. El‐Ghamry, Int. J. Chem. Kinet. 2015, 47,
Z. Hong‐Quan, Polyhedron 1992, 11, 2313.
1
62.
38] A. J. Bard, R. Parsons, J. Jordan, Standard Potentials in Aqueous
Solutions, Marcel Dekker, New York 1985.
14] S. Farhadi, M. M. Amini, M. Dusek, M. Kucerakova, F.
Mahmoudi, J. Mol. Struc. 2017, 1130, 592.
39] R. G. El‐Sharkawy, A. S. Badr El‐din, S. E. H. Etaiw,
Spectrochim. Acta. A 2011, 79, 1969.
15] M. S. Secula, I. Creţescu, S. Petrescu, Desalination 2011, 277,
2
27.
40] T. K. Lal, J. R. Richardson, M. S. Mashuta, R. M. Buchanan, R.
16] C. N. Arenas, A. Vasco, M. Betancur, J. D. Martínez, Proce. Safe.
and Envirom. Protec. 2017, 106, 224.
Mukherjee, Polyhedron 1997, 16, 4331.
41] S. H. Tiana, Y. T. Tu, D. S. Chena, X. Chena, Y. Xionga, Chem.
Eng. J. 2011, 169, 31.
17] N. Barka, A. Assabbane, A. Nounah, Y. Aît Ichou, J. Hazard.
Mater. 2008, 152, 1054.
42] A. H. Gemeay, M. E. El‐Halwagy, R. G. El‐Sharkawy, A. B.
Zaki, J. Environ. Chem. Eng. 2017, 5, 2761.
18] I. A. Salem, H. A. El‐Ghamry, M. A. El‐Ghobashy, Beni ‐ Suif
University Journal Of Basic and Applied Sciences 2014, 3, 186.
43] A. J. Kettle, B. M. Clark, C. C. Winterbourn, J. Biol. Chem. 2004,
279, 18521.
19] P. Forlano, J. A. Olabe, J. F. Magallanes, M. A. Blesa, Canad. J.
Chem. 1997, 75, 9.
44] T. T. Blancas, G. R. Morales, F. U. Núñez, C. B. Díaz, A. D.
20] L. Cheng, M. Wei, L. Huang, F. Pan, D. Xia, X. Li, A. Xu, Ind.
Eng. Chem. Res. 2014, 53, 3478.
González, R. Natividad, J. Taiw. Inst. Chem. Eng. 2017, 74, 225.
45] M. Bernal, R. Romero, G. Roa, C. B. Díaz, T. T. Blancas, R.
[
[
21] M. B. Kasiri, A. R. Khataee, Env. Tech. 2012, 33, 1417.
Natividad, Int. J. Photoenergy 2013, 7.
22] Y. X. Penga, X. L. Zhaoa, D. Xua, H. F. Qianb, W. Huanga, Dyes
Pigm. 2017, 136, 559.
How to cite this article: Nassar AM. Catalytic
reactivity of new Ni(II), cu(II) and Sn(II) complexes
for decolorization of indigo carmine in aqueous
solution, high efficiency of copper complex. Appl
Organometal Chem. 2017;e4056. https://doi.org/
[
[
[
[
23] A. H. Gemeay, I. A. Mansour, R. G. El‐Sharkawy, A. B. Zaki,
J. Molec. Cat. A: Chem. 2003, 193, 109.
24] K. El‐Baradie, R. El‐Sharkawy, H. El‐Ghamry, K. Sakai,
Spectrochim. Acta. A. 2014, 121, 180.
25] H. El‐Ghamry, R. El‐Sharkawy, M. Gaber, J. Iran. Chem. Soc.
10.1002/aoc.4056
2
014, 11,379.
26] N. M. Ibrahim, H. A. A. Yosef, E. F. Ewies, M. R. H. Mahran,
M. M. Alib, A. E. Mahmoud, J. Braz. Chem. Soc. 2015, 26, 1086.