Synthesis and Characterization of Ni (II) Complex …textroad.com/pdf/JAEBS/J. Appl. Environ. Biol....
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J. Appl. Environ. Biol. Sci., 3(8)75-80, 2013 © 2013, TextRoad Publication ISSN: 2090-4274 Journal of Applied Environmental and Biological Sciences www.textroad.com *Corresponding Author: Roghayeh Fekri, Department of Chemistry, Ardabil branch, Islamic Azad University, Ardabil, Iran. Synthesis and Characterization of Ni (II) Complex with Tridentate Ligand of Schiff’s Bases of Salicylaldehyde with Thiocyanate Ligand Roghayeh Fekri 1 , Behrooz Shaabani 2 1 Department of Chemistry, Ardabil branch, Islamic Azad University, Ardabil, Iran. 2 Department of Inorganic Chemistry, Faculty of Chemistry, Tabriz University, Tabriz, Iran. ABSTRACT A group of combinations which have more importance in biological studies, biochemistry and also catalytic applications are Schiff base complexes. They have been considered by the chemists. IN this work, we reported the synthesis and characterization of tridentate Schiff base ligand from the reaction of isonicotinohydrazide with salicylaldehyde. Metal complex of the Schiff base was prepared from salt of Ni(II) on 1:1(ligand: metal).Thiocyanate ligand was used in addition to coordinate to transition metal ion, which presents a novel in transition metal complex .The obtained ligand and complex were investigated using techniques such as IR, 1 HNMR, 13 CNMR,UV/Vis,CV, measurement of electrical conduction, and melt point. The comparison of spectroscopic results for the ligand and complex an also visible absorption spectra for complex suggest that ligand act as tridentate .In UV/Vis spectrum ,the observed transfers in ligand include the transfer between n-π * and π- π * orbitals, and in the transfer is related to d-d in complex. KEY WORDS: Schiff base, Ni (II) complex, Salicylaldehyde, Thiocyanate INTRODUCTION Considerable interest has been shown in metal complexes of thiocarbazate derivatives especially those having NNS donor sequences. These compounds warrant further study because they provide an interesting series of ligands whose properties can be greatly modified by introducing different organic substituents, thereby giving variation in donor properties. These ligands interact with metal ions to give structures of different geometry and properties and they are often biologically active [1]. Ligand, a metal surrounded by a cluster of ions or molecule, is used for preparation of complex compounds named as Schiff’s bases, which are condensation products of primary amines and aldehydes or ketones (RCH=NR’, where R & R’ represents alkyl and/ or aryl substituents)[2]. Molecular recognition due to non- covalent intermolecular interactions between two different molecules has become an important subject in areas of chemistry, biology and physiology. In particular, the selective binding via interactions such as hydrogen bonding and π- π aromatic stacking between the receptor and the neutral guest molecule has been known as the basis of the main concept in molecular recognition. [3].The preparation of macrocyclic polyamine ligands bearing functional pendant donor groups and their subsequent ligation to various metal ions has been an active area of research in recent years. Macrocyclic ligands containing a heteroatom are important complexing agents for cations, anions and molecules [4]. The complexes of azo compounds also exhibits bacteriostatic and other biochemical activities, heterocyclie azo Schiff base and their complexes with transition metal ions are also of importance due to their complexing, catalytieal biological properties[5]. Studies of a new kind of chemotherapeutic Schiff bases are now attracting the attention of biochemists. Earlier work reported that some drugs showed increased activity, when administered as metal complexes rather than as organic compounds [6]. Molybdenum has been found to be an important element in biological systems.It possesses a large number of stable and variable oxidation states as well as coordination numbers which can vary from four to eight. Although only a minor constituent of the earth’s crust, molybdenum is readily available to biological systems because of the solubility of molybdate salts in water [7]. Studies of new kinds of chemotherapeutic Schiff bases are now attracted the attention of biochemists. Schiff bases of o-phenylenediamine and its complexes have a variety of applications including biological, clinical and analytical [8]. The signals of the H NMR spectra as well as the important bands in the IR spectra are considered and discussed in relation to molecular structure [9]. Arylazo derivatives of 1, 3-diketones have gained considerable importance in recent years because of their application in the laboratory as acid- base, redox, metallochromic and other indicators[10]. The transition metal complexes having oxygen and nitrogen donor Schiff bases possess unusual configuration, structural lability and are sensitive to the molecular environment [11]. Tetradentate Schiff base ligands were synthesized by the reaction of diamines with the corresponding salicylaldehyde derivative [12]. A large number of Schiff bases and their complexes have been studied for their interesting and important properties, their ability to reversibly bind oxygen, catalytic activity in hydrogenation of olefins and transfer of an amino group3, photochromic properties, and complexing ability towards some toxic metals [13]. In principle, the central transition metal atoms of different soft and hard Lewis acidity usually need to be satisfied in the most suitable fashion [14]. The coordination chemistry of hydrazones is an intensive area of study and numerous transition metal complexes of these ligands have been investigated [15]. Lanthanide complexes typically exhibit high coordination numbers and structural 75
Transcript of Synthesis and Characterization of Ni (II) Complex …textroad.com/pdf/JAEBS/J. Appl. Environ. Biol....
J. Appl. Environ. Biol. Sci., 3(8)75-80, 2013
© 2013, TextRoad Publication
ISSN: 2090-4274 Journal of Applied Environmental
and Biological Sciences www.textroad.com
*Corresponding Author: Roghayeh Fekri, Department of Chemistry, Ardabil branch, Islamic Azad University, Ardabil, Iran.
Synthesis and Characterization of Ni (II) Complex with Tridentate Ligand of Schiff’s Bases of Salicylaldehyde with Thiocyanate Ligand
Roghayeh Fekri1, Behrooz Shaabani2
1Department of Chemistry, Ardabil branch, Islamic Azad University, Ardabil, Iran.
2Department of Inorganic Chemistry, Faculty of Chemistry, Tabriz University, Tabriz, Iran.
ABSTRACT
A group of combinations which have more importance in biological studies, biochemistry and also catalytic applications are Schiff base complexes. They have been considered by the chemists. IN this work, we reported the synthesis and characterization of tridentate Schiff base ligand from the reaction of isonicotinohydrazide with salicylaldehyde. Metal complex of the Schiff base was prepared from salt of Ni(II) on 1:1(ligand: metal).Thiocyanate ligand was used in addition to coordinate to transition metal ion, which presents a novel in transition metal complex .The obtained ligand and complex were investigated using techniques such as IR,1HNMR,13CNMR,UV/Vis,CV, measurement of electrical conduction, and melt point. The comparison of spectroscopic results for the ligand and complex an also visible absorption spectra for complex suggest that ligand act as tridentate .In UV/Vis spectrum ,the observed transfers in ligand include the transfer between n-π* and π- π* orbitals, and in the transfer is related to d-d in complex. KEY WORDS: Schiff base, Ni (II) complex, Salicylaldehyde, Thiocyanate
INTRODUCTION
Considerable interest has been shown in metal complexes of thiocarbazate derivatives especially those having
NNS donor sequences. These compounds warrant further study because they provide an interesting series of ligands whose properties can be greatly modified by introducing different organic substituents, thereby giving variation in donor properties. These ligands interact with metal ions to give structures of different geometry and properties and they are often biologically active [1]. Ligand, a metal surrounded by a cluster of ions or molecule, is used for preparation of complex compounds named as Schiff’s bases, which are condensation products of primary amines and aldehydes or ketones (RCH=NR’, where R & R’ represents alkyl and/ or aryl substituents)[2]. Molecular recognition due to non-covalent intermolecular interactions between two different molecules has become an important subject in areas of chemistry, biology and physiology. In particular, the selective binding via interactions such as hydrogen bonding and π- π aromatic stacking between the receptor and the neutral guest molecule has been known as the basis of the main concept in molecular recognition. [3].The preparation of macrocyclic polyamine ligands bearing functional pendant donor groups and their subsequent ligation to various metal ions has been an active area of research in recent years. Macrocyclic ligands containing a heteroatom are important complexing agents for cations, anions and molecules [4]. The complexes of azo compounds also exhibits bacteriostatic and other biochemical activities, heterocyclie azo Schiff base and their complexes with transition metal ions are also of importance due to their complexing, catalytieal biological properties[5]. Studies of a new kind of chemotherapeutic Schiff bases are now attracting the attention of biochemists. Earlier work reported that some drugs showed increased activity, when administered as metal complexes rather than as organic compounds [6]. Molybdenum has been found to be an important element in biological systems.It possesses a large number of stable and variable oxidation states as well as coordination numbers which can vary from four to eight. Although only a minor constituent of the earth’s crust, molybdenum is readily available to biological systems because of the solubility of molybdate salts in water [7]. Studies of new kinds of chemotherapeutic Schiff bases are now attracted the attention of biochemists. Schiff bases of o-phenylenediamine and its complexes have a variety of applications including biological, clinical and analytical [8]. The signals of the H NMR spectra as well as the important bands in the IR spectra are considered and discussed in relation to molecular structure [9]. Arylazo derivatives of 1, 3-diketones have gained considerable importance in recent years because of their application in the laboratory as acid-base, redox, metallochromic and other indicators[10]. The transition metal complexes having oxygen and nitrogen donor Schiff bases possess unusual configuration, structural lability and are sensitive to the molecular environment [11]. Tetradentate Schiff base ligands were synthesized by the reaction of diamines with the corresponding salicylaldehyde derivative [12]. A large number of Schiff bases and their complexes have been studied for their interesting and important properties, their ability to reversibly bind oxygen, catalytic activity in hydrogenation of olefins and transfer of an amino group3, photochromic properties, and complexing ability towards some toxic metals [13]. In principle, the central transition metal atoms of different soft and hard Lewis acidity usually need to be satisfied in the most suitable fashion [14]. The coordination chemistry of hydrazones is an intensive area of study and numerous transition metal complexes of these ligands have been investigated [15]. Lanthanide complexes typically exhibit high coordination numbers and structural
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diversity. Unlike their transition metal counterparts, the solid-state coordination geometries of lanthanides are difficult to predict, particularly for complexes of simple mono- and bi-dentate ligands [16].
MATERIALS AND METHODS Synthesis of Ligand
In a 250 ml ballon we solved isonicotinohydrazide (10 mmol and 1.37 g) in 30 ml ethanol and refluxed it for half an hour. Then we added salicylaldehyde (10 mmol) and refluxed it for 3 to 4 hours on a magnetic mixer and we continued refluxion until sediment formed. Also sample electrical conduction in ethanol solvent was measured . The synthesis of H2L ligand has been illustrated in figure1.
NO
NH N
HON
O
HN NH2
isonicotinohydrazide
OH
HO
+EtOH/Reflux
Figure (1). Synthesis of the tridentate Schiff base ligand ( H2L)
Synthesis of Complex
After preparation of ligand, complex was formed in following way: With respect to this point that ligand and metal must be in the proportion 1:1to make complex. Synthesized ligand and 25 ml pure ethanol were poured into beaker and the compound was heated for 1 hour during the mixing. Metal salt was added to the solution and mixing as well as heating was continued for 1 hour. Afterwards, thiocyanate ligand was added and it was refluxed for 3-4 hour. The structure of metal complex has been illustrated in figure 2.
N
ON
N
O
M
N
O N
N
O
M
S C N
SCNK2
Figure (2). Structure of the complex
RESULTS AND DISCUSSION In IR spectrum the C=N band for synthesized ligand in 1617.41 cm-1 frequency confirms the ligand formation so
that the frequency was in 1627.68 cm-1 rang in the case of Ni metal complex .In UV/Vis spectrum the absorption band in 370 nm and 335 nm in synthesized ligand related to n-π* and π- π* indicates the presence of C=N band. In obtained Ni (II) metal complex, the observed wavelength in 700-800 nm rang is related to d-d transfer.Cyclic voltammogram synthesized complex Ni (II) with 0.1 Vs-1 scan rates in 1.5 to - 1.75 volt was studied in DMSO solvent. In comparing ligand graph with obtained complex in above graph a peak in Ea = - 1.20 V zone it is observed that it has moved, compared to ligand peak. Also a relatively high peak is seen in Ea = 0.75 V zone.In lower zone of the graph i.e in reduction zone two tiny peak Ec = 0.90 V and Ec = - .75 V are observed that hasmoved in reduction zone compared to ligand peak. In a comparison on oxidation and reduction peaks of thisgraph, it can be concluded that the appeared peak has been seen in oxidation and also reduction zones. So its electrochemical behavior shows reversible state of the complex. Since ligand and metal appear in a place close to each other, the peak of oxidation zone is relatively wide and high. Due to the movements which have been done in oxidation and reduction zones, the considered combination formation has been confirmed and the prepared complex is electroactive Figures (3-9).
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C:\Program Files\OPUS\meas\Sample description.141 Sample description Instrument t ype and / or accessory 29/05/201234
18.1
3
3174
.34
2998
.29
1684
.17
1613
.02
1562
.48
1480
.95
1399
.79
1349
.44
1283
.15
1211
.22
1151
.21
1065
.77
996.
5595
9.79
855.
94
767.
02
677.
47
464.
06
500100015002000250030003500Wavenumber cm-1
020
4060
8010
0
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smitt
ance
[%]
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Figure(5). UV- Vis Spectroscopy of the tridentate Schiff base ligand (H2L)
Figure (3). IR Spectroscopy of the tridentate Schiff base ligand (H2L)
Figure (4). IR Spectroscopy of the complex Ni (II)
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Figure(6).UV- Vis Spectroscopy of the complex Ni (II)
Figure(7). CV Spectroscopy of the complex Ni(II)
Figure(8). 1HNMR Spectroscopy of the tridentate Schiff base ligand (H2L)
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Figure(8). 1HNMR Spectroscopy of the tridentate Schiff base ligand (H2L)
Figure(8). 1HNMR Spectroscopy of the tridentate Schiff base ligand (H2L)
Figure(9). 13CNMR Spectroscopy of the tridentate Schiff base ligand (H2L)
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Figure(9). 13CNMR Spectroscopy of the tridentate Schiff base ligand (H2L)
The chemicals used in this research
Compounds Product Molecular mass Purity percent Density Isonicotinohydrazide Merck 137.14 99% -
Bromide Nickel Merck 218.52 99% - Salicylaldehyde Merck 122.12 99% 1.17
Ethanol Merck 46.07 99% 0.79 DMF Merck 73.10 99% -
DMSO Merck 78.13 99% - Thiocyanate Potassium Merck 97.18 99% -
The electrical conduction and melt point
Compound Melt point Electrical conduction Ligand 178 0c 1.63 µs.cm-1
Complex Ni (II) 320 0c 99.1 µs.cm-1
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