Synthesis and characterization of some Ni(II) and Cu(II) complexes with 2-[(4-aminophenyl)imino]-1, 2-diphenyl-1-ethanone

Article abstract of DOI:10.1155/2010/293904

The present work deals with synthesis and characterization of the ligand 2-[(4-aminophnyl)imino]-1,2-diphenyl-1-ethanone and their complexes with Ni(II) and Cu(II) ions. The synthesized ligand and its complexes have been characterized by elemental analysi

Full text of DOI:10.1155/2010/293904

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2010, 7(1), 49-54
http://www.e-journals.net
Synthesis and Characterization of Some
Ni(II) and Cu(II) Complexes with
2-[(4-Aminophenyl)imino]-1, 2-diphenyl-1-ethanone
K.M.KHALIFA, A.M.HAMIL* A.GASEM and A.ABDULSALAM
,
Chemistry Department, Faculty of Science,
Sebha University, Sebha, Libya.
abdsalam_1956@maktoob.com
Received 28 March 2009; Accepted 14 May 2009
Abstract: The present work deals with synthesis and characterization of the
ligand 2-[(4-aminophnyl)imino]-1,2-diphenyl-1-ethanone and their complexes
with Ni(II) and Cu(II) ions. The synthesized ligand and its complexes have
been characterized by elemental analysis, infrared, electronic, nuclear
magnetic resonance and mass spectra. The metal ligand ratio was found to be
1:1. Square planer geometry for both complexes was suggested.
Keywords: Synthesis, Characterisation studies, Spectral, Copper coplexes.
Introduction
Many complexes of the type 4-dimethylaminobenzaldehyde, G-atyle-5-hexene-2-4-diones with
transition metal ions have been synthesized and characterized and a square planar geometry was
suggested for Ni(II) and Cr(III) and Pd(II) complexes1. Several complexes of different ligands
derived form salicylaldehyde and o-aminophenol or o-aminobenzoic acid have been synthesized
and characterized using different techniques. A square planar geometry was predicted
for the metal complexes2. Ternary complexes of Ni(II) with 1,2-diaminopropanoecysteine,
o-penicillamine and L-cysteic acid have been synthesized and characterized3.
Experimental
All chemicals used were of laboratory pure. All organic solvents were obtained as pure
grade materials from BDH.
Preparation of the ligand
2-[(4-Aminophnyl)imino]-1,2-diphenyl-1-ethanone was prepared by mixing an ethanolic
solution of 0.01 mol of benzil (2.0 g) with another ethanolic solution of 0.01 mol of 1,4-
diaminebenzene (Scheme 1). The reaction mixture was refluxed for two hours. The formed
precipitate was filtered, washed several times with ethanol and dried in a desiccator over
calcium hydroxide. The yield of the reaction was 73%.

50
A. M. HAMIL et al.
NH
2
NH
2
O
C
O
C
N
C
O
C
+
H
O
2
+
NH
2
Scheme 1
Preparation of the complexes
Complexes of Ni(II) and Cu(II) ions with 2-[(4-aminophenyl)imino]-1,2-diphenyl-1-ethanone
were prepared by mixing ethanolic solutions (50 mL) of 0.01 mole (3.0 g) of the synthesized
ligand with an ethanolic solution (50 mL) of the 0.01 mol (2.38 and 1.71 g) of NiCl2.6H2O,
CuCl2.2H2O, respectively and few drops of ammonia solution were added to adjust the pH
until the complexes isolated. The reactions mixtures were refluxed for three hours and left to
cool and filtered by suction. The precipitates were washed several times with chloroform,
then ether. The complexes were dried in desiccators over anhydrous calcium chloride under
vacuum. The yield was 73 and 78% respectively. Some physical properties of the ligand and
its complexes are listed in Table 1.
Table 1. Some physical properties of the ligand and its complexes with Ni(II) and Cu(II) ions.
Solubility
H2O C2H5OH CCl4 CH3Cl CH3COOH
Ligand/ Complexes
C20H16N2O
Color
M. P cC
Brown 140-142
I.S
I.S
I.S
S
S
S
I.S
I.S
I.S
P.S
P.S
I.S
I.S
I.S
[Ni(C20H16N2O)OH] Black
[Cu(C20H16N2O)OH] Black
S = Soluble
>250
>250
I.S
I.S = Insoluble
P.S = Partial soluble
Measurements
The ligand and its complexes with Ni(II) and Cu(II) ions were subjected to CHN elemental
analyses using 2400 elemental analyzer at Micro-Analytical Center, Cairo University, Giza,
Egypt. Infrared spectra were obtained by KBr disc technique by using IFS-25DPUS/IR
Spectrometer (Bruker). Electronic absorption spectra were measured in nujol mull using a
Perkin-Elmer-Lambda β-Spetrophotometer. The proton NMR spectra were recorded using a
Varian Gemini 400 MHz Spectrometer using d6-DMSO solvent.
Results and Discussion
The reactions of benzil with 1, 4-diaminobenzene in ethanol yields one compound of 2-[(4-
amino-phenyl)imino]-1,2-diphenyl-1-ethanone. The reaction of the prepared ligand with
Ni(II) and Cu(II) metal ions leading to the formation of complexes.
Microanalysis
The elemental analyses (C, H and N) of the ligand and its complexes are listed in Table 2 and
show a good agreement with the calculated values and display the formation of 1:1 [M:L] ratio.
Table 2. Elemental analysis data of the ligand and its complexes.
Complex
C%
Calc. Found Calc. Found Calc. Found
75.69 75.41 6.03 6.17 13.24 13.20
H%
N%
C20H16N2O
[Ni(C20H16N2O)OH] 63.88 63.20 4.52 4.32
[Cu(C20H16N2O)OH] 63.00 62.59 4.46 4.33
7.45
7.36
7.34
7.08

Synthesis and Characterization of Some Ni(II) and Cu(II) Complexes
51
Infrared spectra
Infrared spectral data of the ligand (Figure 1) shows several bands at 3338, 1662 and 1606 cm-1
due to NH2, C=O and C=N, respectively4,5. The infrared spectral data of the Ni(II) and Cu(II)
complexes (Figures 2 & 3) show a disappearance of the band due to the coordination of the
NH2 with the central metal ion6 The band at 1662 cm-1 which attributed to the C=O in free
.
ligand is shifted to lower frequency 1637 cm-1 in the spectra of the complexes. Also, the
C=N band in the free ligand disappeared in the spectra of the complexes due to the
coordination with the central metal ion7 New bands at 520-500 and 700-698 cm-1 attributed
.
to the existing of υ(M-N) and υ(M-O) vibrations. The appearance of these vibrations which
are not present in the free ligand indicates the involvement of nitrogen and oxygen atoms in
chelation8
.
102
100
98
96
3785.6
2358.52
94
694.25
92
90
88
86
84
1292.08
3338.19
1606.42
1509.99
1500
82
4000
3500
3000
2500
2000
1000
500
-1
Wavenumber
Wavenumber, cm
Figure 1. IR spectrum of the free ligand.
100
80
60
40
20
0
700.03
3336.26
1508.07
1500
4000
3500
3000
2500
2000
1000
500
Wave
Figure 2. IR spectrum of Ni(II) complex.
number, c
Wavenum
mb-e1 r

52
A. M. HAMIL et al.
100
80
60
698.1
3336.26
40
1305.58
20
1511.92
1500
4000
3500
3000
2500
2000
1000
500
-1
Wavenumber
Wavenumber, cm
Figure 3. IR spectrum of Cu(II) complex.
Proton nuclear magnetic resonance spectrum of the ligand
1H NMR spectral data of the ligand was recorded in d6-DMSO show bands at 7-8 and 3.3 ppm,
assigned to phenyl protons and NH2 group, respectively9
.
Mass spectral fragmentation of the ligand
The mass spectrum of the ligand (Figure 4) exhibits some peaks illustrates the proper
fragmentations, the peak at m/e+ = 300 are corresponding to the original ligand, while the
peak at m/e+ = 195 is due to the lose of C6H5-C=N- C6H5-NH2 and the peak at m/e+ = 92 is
attributed to the presence of –C-C6H5.
Figure 4. Mass spectrum of the ligand.
3 9 8
1 .8
1 .6
1 .4
1 .2
1 .0
3 0 0
4 0 0
5 0 0
6 0 0
W e v e le n g h
Figure 5. Ultraviolet spectrum of the ligand.

Synthesis and Characterization of Some Ni(II) and Cu(II) Complexes
53
Electronic spectra
The electronic absorption spectra of the ligand (Figure 5 ) display two bands at 360 and 398
*
*
nm which are due to π→ π (phenyl ring) and n→ π (-C=N), respectively. The electronic
spectra of Ni(II) and Cu(II) complexes (Figures 6 & 7) show three bands each at 398, 465,
560 nm and 398, 530, 640 nm, respectively which could be due to d-d and charge transfer
transitions., A square planar geometry were suggested for both complexes10
.
1.55
1.50
1.45
1.40
1.35
300
400
500
600
700
800
900
Wavelength
Figure 6. Electronic spectrum of Ni(II) complex.
0.62
0.60
0.58
0.56
0.54
300
400
500
600
700
800
900
Wavelength
Figure 7. Electronic spectrum of Cu(II) complex.
Conclusion
Form the previous analyses, we can conclude that the complexes have a square planar
structure in which the ligand coordinated to the metal ion as a tridentate via two nitrogen and
one oxygen atom. The suggested geometrical structures (Scheme 2) are shown below:

54
A. M. HAMIL et al.
Scheme 2.
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Curtius T, J Prakt Chem., 1894, 52, 278.
Pitt C G and Fowler, J Am Chem Soc., 1967, 89, 6794.
M.El-Roudi, Bull Fac Sci., Assiut University, 1989, 18, 7-12.
Bellamy J, Infrared spectra of organic molecules, 1st Ed., Wiley, London, 1975.
El-zwaey R S, El-ajaily M M and Maihub A A, Asian J Chem., 2009, 21(1), 31-35.
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