SlideShare a Scribd company logo
 Coordination chemistry is a fascinating branch of
inorganic chemistry.
 The first successful preparation of the complex was
carried out in centuries back.
 There was a welcome renaissance in coordination
chemistry after Werner, Werner’s theory has been
extended greatly and is regarded as one of the
milestones in the development of coordination
chemistry.
 In addition to the magnetic and spectral properties the
stability of complexes were well explained by the
crystal field theory developed by Van Vleck and
bethe.
 Advance in the spectroscopic and crystallographic
techniques, further fine tuned the understanding of
this class of compounds.
 It now provides new promising frontiers of research in
supra molecular chemistry, non silicon based devices,
single molecule based photonic device s and sensors.
 Non silicon based devices, single molecule based
molecular chemistry
 We have chosen hydrazine based compounds, which
contain two inter linked (>N-N<) nitrogen atom in their
structure
 Hydrazine readily react with carbonyl compounds to form
compounds like hydrazone and hydralazone
 Hydrazones contain the triatomic grouping [>C=N-N<]
with an azomethine linkage
 The two connected nitrogen atoms in these compounds are
of different nature
 The C=N bond is conjugated with the lone pair electron on
the terminal nitrogen atom.
 Hydralazones and phenyl hydrazones are some of the
important group of compounds coming under nitrogen-
oxygen donor ligands.
 The presence of heterocyclic rings in Hydrazones can
increase the number of binding sites and make them
potential chelating ligands.
 Also the ring can increases the denticity depending on
its availability for coordination and other reaction
condition.
 The presence of an additional [>C=O] group increases
the electron delocalization.
 Many of the Aryl hydrazone complexes of transition
metal ions are known to be effective model for
elucidation of mechanism of enzyme inhibition.
2-thiophene carboxylaldehyde
2,3-butanedione
Hydralazine
Phenylhydrazine
 Many hydrazones were reported to show
antimicrobial activities and anti-inflammatory activity.
 Metal complexes of pyridylhydrazones have been used
as acid base indicator.
 Phenyl hydrazones were found to be good acid base
indicators because of their ability to impart notable
changes.
 Some of the hydrazones are used as spot test reagents
for certain transition metals.
 Metal complexes of hydrazones are being used as
luminescent probes and molecular sensors.
 Hydrazones also find used as spectrofluorimetric reagents.
 Pyridine 2-aldehyde p-nitro phenyl hydrazones as an
indicator for the colorimetric pH measurements.
 N, N, N hydrazones find use as metallochromic indicators.
 A number of hydrazone complexes show remarkable
catalytic activity.
 Some hydrazones have also been used as herbicides,
insecticides, nematocides, rodenticides, plant growth
regulators as well as plasticizers and stabilizers for
polymers.
 Hydrazones are used as plasticizers and stabilizers for
polymers and as polymerization initiators, antioxidants etc.
 2-Hydroxy acetophenone aroyl hydrazone derivatives were
found to inhibit corrosion of metals like copper.
 Phenylhydrazone find application in qualitative and
quantitative analysis and some find use as insecticide and
herbicides.
 Thiophenes are used as component of organic conducting
polymers.
 Thiophene ring systems occur in some plant products and
are components of synthetic pharmaceuticals and
dyestuffs.
 Wide spectrum of applications and versatile modes of
coordination of hydrazine based heterocyclic ligands
inspired us to work on these compounds.
 Scope of our work is the synthesis, characterization of
a few hydrazine based heterocyclic ligands such as
hydralazone and phenylhydrazone and also their
metal complexes.
So in this project, my aim is
 To synthesis the ligands: 2-
thiophenecarboxylaldehydehydralazone and 2,3-
butanedione phenylhydrazone
 To characterize the synthesized hydrazones by
different physiochemical techniques.
 To synthesis Cu (II), Zn (II) and Co (II) complexes
using the synthesized hydrazones as principal ligands.
Materials Required:
 Hydralazine
 2-thiophene carboxylaldehyde
 Phenylhydrazine
 2,3-butanedione
 Ethanol
 Cu (II) acetate
 Zn (II) acetate
 Co (II) acetate
 DMF
 DMSO
 Sodium acetate
 Elemental Analysis
Micro analysis for carbon, hydrogen and
nitrogen in the synthesized hydrazones and
their metal complexes were carried out an
elemental model CHN analyzer at the
sophisticated test and instrumentation centre
STIC Cochin.
 IR Spectroscopy
The IR spectroscopy is widely used as
characterization techniques for metal complexes. The
basic theory involved is that the stretching modes
of ligands changes upon complexation due to
weakening/strengthening of the bonds involved in
the bond formation resulting in the subsequent
changes in the position of the band in IR spectrum.
The IR spectra of the components were recorded on a
FTIR spectrometer using KBr pellets at STIC, Cochin.
• Electronic Spectroscopy:
UV-Visible spectra of the ligand and complexes were recorded
using a Systronic-2210 UV-visible spectrophotometer in the 200-990
nm range, at the Department of Chemistry and Research Centre.
Solvent used for recording the spectra of complexes was mainly
ethanol.
• Conductivity studies:
Molar conductance data were obtained using Deluxe
Conductivity Meter Model 601 E at the department of chemistry and
research center. Conductivity of 10-3 M solution of the complexes in
DMF was measured at room temperature.
 To hydralazine(0.299g, 1.5m mol) dissolved in ethanol
was added with stirring an ethanol solution of 2-
thiophenecarboxylaldehyde (0.112g, 1m mol) and (1.5m
mol) sodium acetate.
 The mixture was stirred well with slight heating for 40
minutes when a yellow hydralazone precipitates out.
 The precipitate was washed with water and then with
water- ethanol mixture.
Then the precipitate was kept for some time.
 The ethanol was evaporated off.
 Yellow colored finely powdered 2-thiophene
carboxylaldehydehydralazone was obtained.
 Melting point was noted (Mp= 122 0C)
+
2-thiophenecarboxylaldehyde
hydralazone
 An ethanol solution of Cu/ Zn acetate (0.5m mol)
was added to an ethanol solution of (0.127g) 2-
thiophene carboxylaldehydehydralazone .
 Stirring continued with slight heating for 45-60
minutes.
 When an olive green / yellow precipitate of the
complexes are separated out for Cu/ Zn respectively.
 The precipitate was washed with water and then with
ethanol 2-3 times and dried.
 An ethanol solution of Cobalt acetate (0.25m mol) was
added to an ethanol solution of (0.127g) 2-thiophene
carboxylaldehydehydralazone.
 Stirring continued with slight heating for 90 minutes.
When a dark brown precipitate of the complex was
separated out.
 The precipitate was washed with water and then with
ethanol 2-3 times and dried.
Ligand /
complex
Color C% H% N% M%
TL1 Pale yellow 61.41 3.89 22.04 _
TL1C1 Brown 44.96 3.86 12.34 14.50
TL1C2 Light
brown
43.06 4.20 11.82 12.40
TL1C3 Yellow 46.61 3.65 12.79 15.00
 Solubility of ligand and complexes were noted in solvents
like ethanol and DMF.
 Both ligand and complexes are soluble in DMF and
Partially soluble in ethanol
Conductivity studies
• Molar conductance of 10-3M solution of the complexes
in DMF was found less than 20 mhocm2mol-1.
• This indicates their non electrolytic nature.
 Cu (TL1)(OAC)2 , Co(TL1)(OAC)2(H2O)2,
Zn(TL1)(OAC)2.
Compound Conductance (mhocm2mol-1)
Cu (II) complex 13
Co (II) complex 18
Zn (II) complex 14
Magnetic moment value of 1.7BM of the complex
suggested distorted square planar geometry to Cu (II)
complex.
Cobalt (II) complex showed a magnetic moment 4.8
corresponding to high spin octahedral geometries.
Compound Magnetic moment
Cu (II) complex 1.7
Co (II) complex 4.8
Zn (II) complex _
 IR spectra of the ligands and complexes were recorded
using Brucker IFS66V IR spectrometer using KBr pellet
method.
 A sharp peak of medium intensity at 3319 cm-1 in the IR
spectrum of the ligand TL1 can be assigned to ν (N-H)
stretching.
 An intense sharp band at 1596 cm-1 for ν(C=N) and a
band at 1078 cm-1 to ν(N-N) vibration.
 Sharp and intense band at 705 cm-1 can be assigned to
the C-H out-of-plane bending vibration.
 In the spectra of the zinc complex, a broad band around
3207 cm-1 can be assigned to ν(N-H) stretching vibration.
 The sharp and intense band due to C=N shifts downward
by 1589 cm-1 indicating coordination through the
azomethine nitrogen.
 Band in the range 1280-1250 cm-1 in the complexes can be
assigned to the symmetric ν(C-O) stretching vibration of
coordinated acetate ion.
 Weak band at 599 and 455cm-1 in the complexes can be
assigned to the ν (M-O), ν (M-N) modes respectively.
 Electronic spectra of the ligand indicate their hydrazone
structure.
 Absorption bands of TL1 were at 272 nm (π-π*) and 382 nm (n-
π*).
 Electronic spectral bands of the ligands corresponding to π-π*
and n-π* has shifted in the complexes indicating coordination
through azomethine nitrogen.
 Electronic spectra of the complexes in the solid state were
recorded and the main absorption obtained and the
corresponding transition and geometries are determined.
 The spectra of Cu (II) complexes showed bands at ~538 nm
corresponding to 2B1g
2A1g transition in a square planar
geometry.
 The ligand has coordinated to the copper ion through
azomethine nitrogen and one hetero nitrogen atom or
acting as bidentate ligand .
 Third and fourth coordination sites of the metal are
occupied by acetate ion.
 From CHN analysis and metal estimation, it is clear
that only one molecule of ligand coordinated to the
copper ion in the complex.
 It is a four coordinated structure and the geometry
may be square planar
 For the cobalt complex, the ligand coordinated to the metal
through the azomethine nitrogen and one hetero nitrogen.
 Thus the ligand act as a bidentate ligand.
 Two molecules of water and acetate ions also coordinated
with the central cobalt metal and form a six coordinated
cobalt complex having octahedral geometry.
 For the zinc complex, one molecule of ligand is
coordinated to the central zinc ion through azomethine
nitrogen and one hetero nitrogen.
 Thus a four coordinated tetrahedral geometry is obtained.
 To phenyl hydralazine (0.24g) dissolved in ethanol was
added with stirring an ethanol solution of 2,3-
butanedione (0.086g, 1m mol) and sodium acetate.
 Ligand was prepared by refluxing ethanol solution of
phenyl hydrazine and 2,3-butanedione taken in 2:1
molar ratio.
 The mixture was stirred well with slight heating for
90 minutes when a brown phenyl hydralazone
precipitates out.
 The precipitate was washed with water and then with
water-ethanol mixture.
 Then the precipitate was kept for some time.
 Then ethanol was evaporated off.
 Brown colored finely powdered 2,3-
butanedionephenylhydazone was obtained.
 Melting point was noted (mp= 168 o C).
2
phenylhydrazine + 2,3-butanedione 2,3-butanedionephenylhydrazone
 0.5m mol of Cu(II)/ Zn (II) was dissolved in 10 ml of
ethanol.
 Then it was added drop by drop to 1m mol [0.26g] of
2,3-butanedione phenylhydrazone dissolved in 10ml of
ethanol.
 It was then mixed for 90 minutes using magnetic
stirrer.
 Brown/ white creamy complexes separated out of the
solution.
 Then it was filtered and washed with water containing
ethanol and finally with ethanol
Ligand /
complex
color C% H% N% M%
BPh Reddish
brown
72.18 6.76 21.0 _
BPhCI brown 60.51 5.88 15.69 9.0
BPhC2 Pale yellow 60.36 5.86 9.27 9.27
Compound Conductance (mhocm2mol-1)
Cu (II) complex 150
Zn (II) complex 145
• From conductivity studies of the complexes in DMSO,
the molar conductivity of the complexes were greater
than 20 mhocm2mol-indicating their electrolytic in nature.
• From elemental analysis and conductivity studies
the following formula were proposed for the
Cu(II) and Zn(II) complexes. [Cu (BPh)2 ](CH3COO)2 ,
[ Zn (BPh)2 ] (CH3COO)2.
 IR spectrum of BPh , a sharp peak of medium intensity
at 3344 cm-1 can be assigned to ν(N-H) stretching
vibration.
 An intense sharp band at 1596 cm-1 for ν(C=N) and a
band at 1066 cm-1 to ν (N-N) vibration.
 A weak band at 3025 cm-1 can be assigned to aromatic
ν(C-H) stretching .
 sharp intense bands at 687 and 745 cm-1 can be
assigned to the aromatic C-H out-of-plane bending
vibrations.
 The sharp band of medium intensity at 3344 cm-1 in the
ligand that can be assigned to ν(N-H), become
broadened, increased in intensity and shifted to 3427 cm-
• In the acetate complexes also, there is broadening of this
band which may be due to the H-bond formed between
(N-H) hydrogen with the coordinated acetate groups.
• The ν(C=N) of the ligand is shifted to lower frequency
indicating coordination through azomethine nitrogen.
• Bonding by the azomethine nitrogen is further
corroborated by the upward shift of ν (N-N) in the ligand to
1100 cm-1 in complexes.
• Weak band at 546 and 490 cm-1 in the complex are
assignable to the ν (M-N), ν(M-O) respectively
 Electronic spectra of the complexes depend on
energies of metal d-orbitals , their degeneracy and the
number of electrons distributed in them.
 These features are in turn controlled by the oxidation
state of the metal, number and type of ligand and the
geometry of the complexes.
 So valuable information regarding the structure,
geometry and the splitting of d-orbital can be
obtained from their electronic spectra.
 The spectra of BPh showed peaks at 300 nm and 351
nm which can be assigned to the π- π* and n-π*
transitions.
 Various analysis results indicate that the ligand BPhC1 has
coordinated to the metal through both the azomethine
nitrogen atoms.
 from CHN analysis and metal estimation, it is clear that
two molecules of the ligand coordinate to the copper ion in
the complex.
 Therefore it is a four coordinated structure and the
geometry may be square planar
 For zinc complex, two molecules of ligand coordinated to
the central zinc through both the azomethine nitrogen
atoms.
 Thus a four coordinated square planar geometry is
obtained.
 C. Serbutoviez, C. Bosshard, G. Knopfle, P. Pretre, P. Gunter,
K.Schenk, E. Solari, G. Chapu, Chem. Matter. 7 (1995) 1198.
 G.A. Al-Hazmi, A.A. EI-Asmy, J.Coord. Chem. 62 (2009)337.
 K.M. Ibrahim, I.M. Gabr, R.R Zaky, J. Coord. Chem. 62
(2009)1100.
 V. Getuatis, M. Daskevicience, T. Malinauskas, V. Gaidelis, V.
Jankauskas, Z.
 Tokarski, Synthetic Metals 155 (2005)599
J.P.Tandon and A.Garg, Trans.Met.Chem., 1987,12,526.
 V.K Varshney, J.Ambwni and R.C.Sharma.,
J.Inst.Chemists(India),
 B.Singh and H.Misra, J.Indian Chem. Soc.,1986, 63,1069.
 D.K. Misra, R. Rai, P.Om Pandey and K.S.Sengupta, Trans. Met.
 Chem., 1992, 17,127.
 B.Singh and H.Misra, J.Indian Chem. Soc.,1986,
63,1069.
• D.K. Misra, R. Rai, P.Om Pandey and K.S.Sengupta,
Trans. Met. Chem., 1992, 17,127.
• A.P.Mishra,S.K.Srivastava and V.Srivastava., J.Indian
Chem.Soc.,1997,74,487.
• A.P.Mishra, R.Rai, P.Om.
Z.I.Kamal, A.Ei-Dissouky and Z.S.Azizia, 1997,16,2909.
 B.N.Harikumar, M.R.P Kurup and T.N.Jayaprakash,
Tras.Met.Chem., 1997, 27,507.
 M.Sathpathy, B.Pradan, J.Indian Chem, 1991, 3, 45.
synthesis and characterization of hydrazone ligand and their metal complexes

More Related Content

What's hot

Metal alkyne compledes
Metal alkyne compledesMetal alkyne compledes
Metal alkyne compledesDrGeetaTewari
 
heck reaction, suzuki coupling and sharpless epoxidation
heck reaction, suzuki coupling and sharpless epoxidationheck reaction, suzuki coupling and sharpless epoxidation
heck reaction, suzuki coupling and sharpless epoxidationVISHAL PATIL
 
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)SonamVSancheti
 
Acid Base Hydrolysis in Octahedral Complexes
Acid Base Hydrolysis in Octahedral ComplexesAcid Base Hydrolysis in Octahedral Complexes
Acid Base Hydrolysis in Octahedral ComplexesSPCGC AJMER
 
Schiff base and complexe
Schiff base and complexeSchiff base and complexe
Schiff base and complexewael alharbi
 
C-C Cross Coupling Reactions in Organic chemistry by Anthony crasto
C-C Cross Coupling Reactions in Organic chemistry by Anthony crastoC-C Cross Coupling Reactions in Organic chemistry by Anthony crasto
C-C Cross Coupling Reactions in Organic chemistry by Anthony crastoAnthony Melvin Crasto Ph.D
 
C-H Activation and Functionalization
C-H Activation and FunctionalizationC-H Activation and Functionalization
C-H Activation and FunctionalizationSanjeev Kumar
 
Synthetic Reagents & Applications in Organic Chemistry
Synthetic Reagents & Applications in Organic ChemistrySynthetic Reagents & Applications in Organic Chemistry
Synthetic Reagents & Applications in Organic ChemistryAjay Kumar
 
Dicyclohexylcarbodiimide [DCC]
Dicyclohexylcarbodiimide [DCC]Dicyclohexylcarbodiimide [DCC]
Dicyclohexylcarbodiimide [DCC]Shikha Popali
 
Kumada cross coupling reaction
Kumada cross coupling reactionKumada cross coupling reaction
Kumada cross coupling reactionDrShahidRasool1
 
Effective Aatomic Number
Effective Aatomic Number Effective Aatomic Number
Effective Aatomic Number SPCGC AJMER
 
M.sc. inorganic chemistry laboratory manual complex preparations
M.sc. inorganic chemistry laboratory manual complex preparationsM.sc. inorganic chemistry laboratory manual complex preparations
M.sc. inorganic chemistry laboratory manual complex preparationsDrSSreenivasa
 
Metal alkene complexes.ppt
Metal alkene complexes.pptMetal alkene complexes.ppt
Metal alkene complexes.pptDrGeetaTewari
 

What's hot (20)

Metal alkyne compledes
Metal alkyne compledesMetal alkyne compledes
Metal alkyne compledes
 
Organo mercuary compounds
Organo mercuary  compoundsOrgano mercuary  compounds
Organo mercuary compounds
 
heck reaction, suzuki coupling and sharpless epoxidation
heck reaction, suzuki coupling and sharpless epoxidationheck reaction, suzuki coupling and sharpless epoxidation
heck reaction, suzuki coupling and sharpless epoxidation
 
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)
Pd catalyzed C-C Coupling reactions- a short introduction (Nobel Prize 2010)
 
Acid Base Hydrolysis in Octahedral Complexes
Acid Base Hydrolysis in Octahedral ComplexesAcid Base Hydrolysis in Octahedral Complexes
Acid Base Hydrolysis in Octahedral Complexes
 
Schiff base and complexe
Schiff base and complexeSchiff base and complexe
Schiff base and complexe
 
Coordination chemistry -1
Coordination chemistry -1Coordination chemistry -1
Coordination chemistry -1
 
C-C Cross Coupling Reactions in Organic chemistry by Anthony crasto
C-C Cross Coupling Reactions in Organic chemistry by Anthony crastoC-C Cross Coupling Reactions in Organic chemistry by Anthony crasto
C-C Cross Coupling Reactions in Organic chemistry by Anthony crasto
 
Organometallics
OrganometallicsOrganometallics
Organometallics
 
C-H Activation and Functionalization
C-H Activation and FunctionalizationC-H Activation and Functionalization
C-H Activation and Functionalization
 
Synthetic Reagents & Applications in Organic Chemistry
Synthetic Reagents & Applications in Organic ChemistrySynthetic Reagents & Applications in Organic Chemistry
Synthetic Reagents & Applications in Organic Chemistry
 
Dicyclohexylcarbodiimide [DCC]
Dicyclohexylcarbodiimide [DCC]Dicyclohexylcarbodiimide [DCC]
Dicyclohexylcarbodiimide [DCC]
 
Grignard reagents
Grignard reagentsGrignard reagents
Grignard reagents
 
Kumada cross coupling reaction
Kumada cross coupling reactionKumada cross coupling reaction
Kumada cross coupling reaction
 
Effective Aatomic Number
Effective Aatomic Number Effective Aatomic Number
Effective Aatomic Number
 
Suzuki reaction
Suzuki reactionSuzuki reaction
Suzuki reaction
 
M.sc. inorganic chemistry laboratory manual complex preparations
M.sc. inorganic chemistry laboratory manual complex preparationsM.sc. inorganic chemistry laboratory manual complex preparations
M.sc. inorganic chemistry laboratory manual complex preparations
 
Suzuki coupling reaction
Suzuki coupling reactionSuzuki coupling reaction
Suzuki coupling reaction
 
Metal alkene complexes.ppt
Metal alkene complexes.pptMetal alkene complexes.ppt
Metal alkene complexes.ppt
 
Jeevi ppt
Jeevi pptJeevi ppt
Jeevi ppt
 

Similar to synthesis and characterization of hydrazone ligand and their metal complexes

Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...IOSR Journals
 
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...IOSR Journals
 
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...IOSRJAC
 
Research Paper Presentation by Ariful Islam
Research Paper Presentation by Ariful IslamResearch Paper Presentation by Ariful Islam
Research Paper Presentation by Ariful IslamArifulIslam665
 
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...IOSR Journals
 
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...Alexander Decker
 
6593 8735-1-pb schiff base [1,
6593 8735-1-pb schiff base [1,6593 8735-1-pb schiff base [1,
6593 8735-1-pb schiff base [1,Taghreed Al-Noor
 
Synthesis and characterization of complexes of schiff base [1, 2 diphenyl -...
Synthesis and  characterization of complexes of schiff base  [1, 2 diphenyl -...Synthesis and  characterization of complexes of schiff base  [1, 2 diphenyl -...
Synthesis and characterization of complexes of schiff base [1, 2 diphenyl -...Alexander Decker
 
complexometric titration , colorimetry and spectrophotometry
complexometric titration , colorimetry and spectrophotometry complexometric titration , colorimetry and spectrophotometry
complexometric titration , colorimetry and spectrophotometry ushaSanmugaraj
 
Njc15 publication 15
Njc15 publication 15Njc15 publication 15
Njc15 publication 15dionisio31
 
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...IOSR Journals
 
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...IOSR Journals
 
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...CrimsonPublishersACSR
 
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...Synthesis, Characterization and Antibacterial Activity of New Complexes of So...
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...IOSR Journals
 

Similar to synthesis and characterization of hydrazone ligand and their metal complexes (20)

سعد النصراوي
سعد النصراويسعد النصراوي
سعد النصراوي
 
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...
 
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...
Spectral Studies of Some Transition Metal Ion complexes with 4-[(E)-(Ferrocen...
 
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...
Synthesis and characterization of some metal complexes of 2- Phenyl-3,4-dihyd...
 
5034 7127-1-pb
5034 7127-1-pb5034 7127-1-pb
5034 7127-1-pb
 
Research Paper Presentation by Ariful Islam
Research Paper Presentation by Ariful IslamResearch Paper Presentation by Ariful Islam
Research Paper Presentation by Ariful Islam
 
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...
Studies On The Cobalt(II) And Copper(II) Complexes Of 2,5-Substituted 1,3,4-T...
 
4651 6724-1-pb
4651 6724-1-pb4651 6724-1-pb
4651 6724-1-pb
 
4651 6724-1-pb
4651 6724-1-pb4651 6724-1-pb
4651 6724-1-pb
 
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...
Coordination modes of a new ligand derived from pyrazoline with cr(iii), mn(i...
 
6593 8735-1-pb schiff base [1,
6593 8735-1-pb schiff base [1,6593 8735-1-pb schiff base [1,
6593 8735-1-pb schiff base [1,
 
Synthesis and characterization of complexes of schiff base [1, 2 diphenyl -...
Synthesis and  characterization of complexes of schiff base  [1, 2 diphenyl -...Synthesis and  characterization of complexes of schiff base  [1, 2 diphenyl -...
Synthesis and characterization of complexes of schiff base [1, 2 diphenyl -...
 
Paper expo 1_2019
Paper expo 1_2019Paper expo 1_2019
Paper expo 1_2019
 
complexometric titration , colorimetry and spectrophotometry
complexometric titration , colorimetry and spectrophotometry complexometric titration , colorimetry and spectrophotometry
complexometric titration , colorimetry and spectrophotometry
 
Njc15 publication 15
Njc15 publication 15Njc15 publication 15
Njc15 publication 15
 
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...
Spectroscopic, Thermal, Magnetic and conductimetric studies on some 7-hydroxy...
 
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...
The DNA cleavage and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(I...
 
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...
Design, Synthesis and Structural Inspection of Some Novel Di- And Tri-Azometh...
 
D0212016025
D0212016025D0212016025
D0212016025
 
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...Synthesis, Characterization and Antibacterial Activity of New Complexes of So...
Synthesis, Characterization and Antibacterial Activity of New Complexes of So...
 

Recently uploaded

Quantifying Artificial Intelligence and What Comes Next!
Quantifying Artificial Intelligence and What Comes Next!Quantifying Artificial Intelligence and What Comes Next!
Quantifying Artificial Intelligence and What Comes Next!University of Hertfordshire
 
METHODS OF TRANSCRIPTOME ANALYSIS....pptx
METHODS OF TRANSCRIPTOME ANALYSIS....pptxMETHODS OF TRANSCRIPTOME ANALYSIS....pptx
METHODS OF TRANSCRIPTOME ANALYSIS....pptxCherry
 
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Lahari
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana LahariERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Lahari
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Laharimuralinath2
 
Erythropoiesis- Dr.E. Muralinath-C Kalyan
Erythropoiesis- Dr.E. Muralinath-C KalyanErythropoiesis- Dr.E. Muralinath-C Kalyan
Erythropoiesis- Dr.E. Muralinath-C Kalyanmuralinath2
 
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243Sérgio Sacani
 
Cell Immobilization Methods and Applications.pptx
Cell Immobilization Methods and Applications.pptxCell Immobilization Methods and Applications.pptx
Cell Immobilization Methods and Applications.pptxCherry
 
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...Sérgio Sacani
 
Jet reorientation in central galaxies of clusters and groups: insights from V...
Jet reorientation in central galaxies of clusters and groups: insights from V...Jet reorientation in central galaxies of clusters and groups: insights from V...
Jet reorientation in central galaxies of clusters and groups: insights from V...Sérgio Sacani
 
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdf
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdfPests of Green Manures_Bionomics_IPM_Dr.UPR.pdf
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdfPirithiRaju
 
National Biodiversity protection initiatives and Convention on Biological Di...
National Biodiversity protection initiatives and  Convention on Biological Di...National Biodiversity protection initiatives and  Convention on Biological Di...
National Biodiversity protection initiatives and Convention on Biological Di...PABOLU TEJASREE
 
GBSN - Biochemistry (Unit 4) Chemistry of Carbohydrates
GBSN - Biochemistry (Unit 4) Chemistry of CarbohydratesGBSN - Biochemistry (Unit 4) Chemistry of Carbohydrates
GBSN - Biochemistry (Unit 4) Chemistry of CarbohydratesAreesha Ahmad
 
Hemoglobin metabolism: C Kalyan & E. Muralinath
Hemoglobin metabolism: C Kalyan & E. MuralinathHemoglobin metabolism: C Kalyan & E. Muralinath
Hemoglobin metabolism: C Kalyan & E. Muralinathmuralinath2
 
B lymphocytes, Receptors, Maturation and Activation
B lymphocytes, Receptors, Maturation and ActivationB lymphocytes, Receptors, Maturation and Activation
B lymphocytes, Receptors, Maturation and ActivationBhanu Krishan
 
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...Sahil Suleman
 
The importance of continents, oceans and plate tectonics for the evolution of...
The importance of continents, oceans and plate tectonics for the evolution of...The importance of continents, oceans and plate tectonics for the evolution of...
The importance of continents, oceans and plate tectonics for the evolution of...Sérgio Sacani
 
SCHISTOSOMA HEAMATOBIUM life cycle .pdf
SCHISTOSOMA HEAMATOBIUM life cycle  .pdfSCHISTOSOMA HEAMATOBIUM life cycle  .pdf
SCHISTOSOMA HEAMATOBIUM life cycle .pdfDebdattaGhosh6
 
Structural annotation................pptx
Structural annotation................pptxStructural annotation................pptx
Structural annotation................pptxCherry
 
Application of Mass Spectrometry In Biotechnology
Application of Mass Spectrometry In BiotechnologyApplication of Mass Spectrometry In Biotechnology
Application of Mass Spectrometry In BiotechnologyBhanu Krishan
 
GBSN - Microbiology (Unit 6) Human and Microbial interaction
GBSN - Microbiology (Unit 6) Human and Microbial interactionGBSN - Microbiology (Unit 6) Human and Microbial interaction
GBSN - Microbiology (Unit 6) Human and Microbial interactionAreesha Ahmad
 
Climate extremes likely to drive land mammal extinction during next supercont...
Climate extremes likely to drive land mammal extinction during next supercont...Climate extremes likely to drive land mammal extinction during next supercont...
Climate extremes likely to drive land mammal extinction during next supercont...Sérgio Sacani
 

Recently uploaded (20)

Quantifying Artificial Intelligence and What Comes Next!
Quantifying Artificial Intelligence and What Comes Next!Quantifying Artificial Intelligence and What Comes Next!
Quantifying Artificial Intelligence and What Comes Next!
 
METHODS OF TRANSCRIPTOME ANALYSIS....pptx
METHODS OF TRANSCRIPTOME ANALYSIS....pptxMETHODS OF TRANSCRIPTOME ANALYSIS....pptx
METHODS OF TRANSCRIPTOME ANALYSIS....pptx
 
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Lahari
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana LahariERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Lahari
ERTHROPOIESIS: Dr. E. Muralinath & R. Gnana Lahari
 
Erythropoiesis- Dr.E. Muralinath-C Kalyan
Erythropoiesis- Dr.E. Muralinath-C KalyanErythropoiesis- Dr.E. Muralinath-C Kalyan
Erythropoiesis- Dr.E. Muralinath-C Kalyan
 
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243
Constraints on Neutrino Natal Kicks from Black-Hole Binary VFTS 243
 
Cell Immobilization Methods and Applications.pptx
Cell Immobilization Methods and Applications.pptxCell Immobilization Methods and Applications.pptx
Cell Immobilization Methods and Applications.pptx
 
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...
Extensive Pollution of Uranus and Neptune’s Atmospheres by Upsweep of Icy Mat...
 
Jet reorientation in central galaxies of clusters and groups: insights from V...
Jet reorientation in central galaxies of clusters and groups: insights from V...Jet reorientation in central galaxies of clusters and groups: insights from V...
Jet reorientation in central galaxies of clusters and groups: insights from V...
 
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdf
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdfPests of Green Manures_Bionomics_IPM_Dr.UPR.pdf
Pests of Green Manures_Bionomics_IPM_Dr.UPR.pdf
 
National Biodiversity protection initiatives and Convention on Biological Di...
National Biodiversity protection initiatives and  Convention on Biological Di...National Biodiversity protection initiatives and  Convention on Biological Di...
National Biodiversity protection initiatives and Convention on Biological Di...
 
GBSN - Biochemistry (Unit 4) Chemistry of Carbohydrates
GBSN - Biochemistry (Unit 4) Chemistry of CarbohydratesGBSN - Biochemistry (Unit 4) Chemistry of Carbohydrates
GBSN - Biochemistry (Unit 4) Chemistry of Carbohydrates
 
Hemoglobin metabolism: C Kalyan & E. Muralinath
Hemoglobin metabolism: C Kalyan & E. MuralinathHemoglobin metabolism: C Kalyan & E. Muralinath
Hemoglobin metabolism: C Kalyan & E. Muralinath
 
B lymphocytes, Receptors, Maturation and Activation
B lymphocytes, Receptors, Maturation and ActivationB lymphocytes, Receptors, Maturation and Activation
B lymphocytes, Receptors, Maturation and Activation
 
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...
Alternative method of dissolution in-vitro in-vivo correlation and dissolutio...
 
The importance of continents, oceans and plate tectonics for the evolution of...
The importance of continents, oceans and plate tectonics for the evolution of...The importance of continents, oceans and plate tectonics for the evolution of...
The importance of continents, oceans and plate tectonics for the evolution of...
 
SCHISTOSOMA HEAMATOBIUM life cycle .pdf
SCHISTOSOMA HEAMATOBIUM life cycle  .pdfSCHISTOSOMA HEAMATOBIUM life cycle  .pdf
SCHISTOSOMA HEAMATOBIUM life cycle .pdf
 
Structural annotation................pptx
Structural annotation................pptxStructural annotation................pptx
Structural annotation................pptx
 
Application of Mass Spectrometry In Biotechnology
Application of Mass Spectrometry In BiotechnologyApplication of Mass Spectrometry In Biotechnology
Application of Mass Spectrometry In Biotechnology
 
GBSN - Microbiology (Unit 6) Human and Microbial interaction
GBSN - Microbiology (Unit 6) Human and Microbial interactionGBSN - Microbiology (Unit 6) Human and Microbial interaction
GBSN - Microbiology (Unit 6) Human and Microbial interaction
 
Climate extremes likely to drive land mammal extinction during next supercont...
Climate extremes likely to drive land mammal extinction during next supercont...Climate extremes likely to drive land mammal extinction during next supercont...
Climate extremes likely to drive land mammal extinction during next supercont...
 

synthesis and characterization of hydrazone ligand and their metal complexes

  • 1.
  • 2.  Coordination chemistry is a fascinating branch of inorganic chemistry.  The first successful preparation of the complex was carried out in centuries back.  There was a welcome renaissance in coordination chemistry after Werner, Werner’s theory has been extended greatly and is regarded as one of the milestones in the development of coordination chemistry.  In addition to the magnetic and spectral properties the stability of complexes were well explained by the crystal field theory developed by Van Vleck and bethe.
  • 3.  Advance in the spectroscopic and crystallographic techniques, further fine tuned the understanding of this class of compounds.  It now provides new promising frontiers of research in supra molecular chemistry, non silicon based devices, single molecule based photonic device s and sensors.  Non silicon based devices, single molecule based molecular chemistry
  • 4.  We have chosen hydrazine based compounds, which contain two inter linked (>N-N<) nitrogen atom in their structure  Hydrazine readily react with carbonyl compounds to form compounds like hydrazone and hydralazone  Hydrazones contain the triatomic grouping [>C=N-N<] with an azomethine linkage  The two connected nitrogen atoms in these compounds are of different nature  The C=N bond is conjugated with the lone pair electron on the terminal nitrogen atom.  Hydralazones and phenyl hydrazones are some of the important group of compounds coming under nitrogen- oxygen donor ligands.
  • 5.  The presence of heterocyclic rings in Hydrazones can increase the number of binding sites and make them potential chelating ligands.  Also the ring can increases the denticity depending on its availability for coordination and other reaction condition.  The presence of an additional [>C=O] group increases the electron delocalization.  Many of the Aryl hydrazone complexes of transition metal ions are known to be effective model for elucidation of mechanism of enzyme inhibition.
  • 7.  Many hydrazones were reported to show antimicrobial activities and anti-inflammatory activity.  Metal complexes of pyridylhydrazones have been used as acid base indicator.  Phenyl hydrazones were found to be good acid base indicators because of their ability to impart notable changes.  Some of the hydrazones are used as spot test reagents for certain transition metals.  Metal complexes of hydrazones are being used as luminescent probes and molecular sensors.
  • 8.  Hydrazones also find used as spectrofluorimetric reagents.  Pyridine 2-aldehyde p-nitro phenyl hydrazones as an indicator for the colorimetric pH measurements.  N, N, N hydrazones find use as metallochromic indicators.  A number of hydrazone complexes show remarkable catalytic activity.  Some hydrazones have also been used as herbicides, insecticides, nematocides, rodenticides, plant growth regulators as well as plasticizers and stabilizers for polymers.
  • 9.  Hydrazones are used as plasticizers and stabilizers for polymers and as polymerization initiators, antioxidants etc.  2-Hydroxy acetophenone aroyl hydrazone derivatives were found to inhibit corrosion of metals like copper.  Phenylhydrazone find application in qualitative and quantitative analysis and some find use as insecticide and herbicides.  Thiophenes are used as component of organic conducting polymers.  Thiophene ring systems occur in some plant products and are components of synthetic pharmaceuticals and dyestuffs.
  • 10.  Wide spectrum of applications and versatile modes of coordination of hydrazine based heterocyclic ligands inspired us to work on these compounds.  Scope of our work is the synthesis, characterization of a few hydrazine based heterocyclic ligands such as hydralazone and phenylhydrazone and also their metal complexes.
  • 11. So in this project, my aim is  To synthesis the ligands: 2- thiophenecarboxylaldehydehydralazone and 2,3- butanedione phenylhydrazone  To characterize the synthesized hydrazones by different physiochemical techniques.  To synthesis Cu (II), Zn (II) and Co (II) complexes using the synthesized hydrazones as principal ligands.
  • 12. Materials Required:  Hydralazine  2-thiophene carboxylaldehyde  Phenylhydrazine  2,3-butanedione  Ethanol  Cu (II) acetate  Zn (II) acetate  Co (II) acetate  DMF  DMSO  Sodium acetate
  • 13.  Elemental Analysis Micro analysis for carbon, hydrogen and nitrogen in the synthesized hydrazones and their metal complexes were carried out an elemental model CHN analyzer at the sophisticated test and instrumentation centre STIC Cochin.
  • 14.  IR Spectroscopy The IR spectroscopy is widely used as characterization techniques for metal complexes. The basic theory involved is that the stretching modes of ligands changes upon complexation due to weakening/strengthening of the bonds involved in the bond formation resulting in the subsequent changes in the position of the band in IR spectrum. The IR spectra of the components were recorded on a FTIR spectrometer using KBr pellets at STIC, Cochin.
  • 15. • Electronic Spectroscopy: UV-Visible spectra of the ligand and complexes were recorded using a Systronic-2210 UV-visible spectrophotometer in the 200-990 nm range, at the Department of Chemistry and Research Centre. Solvent used for recording the spectra of complexes was mainly ethanol. • Conductivity studies: Molar conductance data were obtained using Deluxe Conductivity Meter Model 601 E at the department of chemistry and research center. Conductivity of 10-3 M solution of the complexes in DMF was measured at room temperature.
  • 16.
  • 17.  To hydralazine(0.299g, 1.5m mol) dissolved in ethanol was added with stirring an ethanol solution of 2- thiophenecarboxylaldehyde (0.112g, 1m mol) and (1.5m mol) sodium acetate.  The mixture was stirred well with slight heating for 40 minutes when a yellow hydralazone precipitates out.  The precipitate was washed with water and then with water- ethanol mixture.
  • 18. Then the precipitate was kept for some time.  The ethanol was evaporated off.  Yellow colored finely powdered 2-thiophene carboxylaldehydehydralazone was obtained.  Melting point was noted (Mp= 122 0C) + 2-thiophenecarboxylaldehyde hydralazone
  • 19.  An ethanol solution of Cu/ Zn acetate (0.5m mol) was added to an ethanol solution of (0.127g) 2- thiophene carboxylaldehydehydralazone .  Stirring continued with slight heating for 45-60 minutes.  When an olive green / yellow precipitate of the complexes are separated out for Cu/ Zn respectively.  The precipitate was washed with water and then with ethanol 2-3 times and dried.
  • 20.  An ethanol solution of Cobalt acetate (0.25m mol) was added to an ethanol solution of (0.127g) 2-thiophene carboxylaldehydehydralazone.  Stirring continued with slight heating for 90 minutes. When a dark brown precipitate of the complex was separated out.  The precipitate was washed with water and then with ethanol 2-3 times and dried.
  • 21. Ligand / complex Color C% H% N% M% TL1 Pale yellow 61.41 3.89 22.04 _ TL1C1 Brown 44.96 3.86 12.34 14.50 TL1C2 Light brown 43.06 4.20 11.82 12.40 TL1C3 Yellow 46.61 3.65 12.79 15.00
  • 22.  Solubility of ligand and complexes were noted in solvents like ethanol and DMF.  Both ligand and complexes are soluble in DMF and Partially soluble in ethanol Conductivity studies • Molar conductance of 10-3M solution of the complexes in DMF was found less than 20 mhocm2mol-1. • This indicates their non electrolytic nature.  Cu (TL1)(OAC)2 , Co(TL1)(OAC)2(H2O)2, Zn(TL1)(OAC)2.
  • 23. Compound Conductance (mhocm2mol-1) Cu (II) complex 13 Co (II) complex 18 Zn (II) complex 14
  • 24. Magnetic moment value of 1.7BM of the complex suggested distorted square planar geometry to Cu (II) complex. Cobalt (II) complex showed a magnetic moment 4.8 corresponding to high spin octahedral geometries. Compound Magnetic moment Cu (II) complex 1.7 Co (II) complex 4.8 Zn (II) complex _
  • 25.  IR spectra of the ligands and complexes were recorded using Brucker IFS66V IR spectrometer using KBr pellet method.  A sharp peak of medium intensity at 3319 cm-1 in the IR spectrum of the ligand TL1 can be assigned to ν (N-H) stretching.  An intense sharp band at 1596 cm-1 for ν(C=N) and a band at 1078 cm-1 to ν(N-N) vibration.  Sharp and intense band at 705 cm-1 can be assigned to the C-H out-of-plane bending vibration.
  • 26.
  • 27.  In the spectra of the zinc complex, a broad band around 3207 cm-1 can be assigned to ν(N-H) stretching vibration.  The sharp and intense band due to C=N shifts downward by 1589 cm-1 indicating coordination through the azomethine nitrogen.  Band in the range 1280-1250 cm-1 in the complexes can be assigned to the symmetric ν(C-O) stretching vibration of coordinated acetate ion.  Weak band at 599 and 455cm-1 in the complexes can be assigned to the ν (M-O), ν (M-N) modes respectively.
  • 28.
  • 29.  Electronic spectra of the ligand indicate their hydrazone structure.  Absorption bands of TL1 were at 272 nm (π-π*) and 382 nm (n- π*).  Electronic spectral bands of the ligands corresponding to π-π* and n-π* has shifted in the complexes indicating coordination through azomethine nitrogen.  Electronic spectra of the complexes in the solid state were recorded and the main absorption obtained and the corresponding transition and geometries are determined.  The spectra of Cu (II) complexes showed bands at ~538 nm corresponding to 2B1g 2A1g transition in a square planar geometry.
  • 30.
  • 31.
  • 32.  The ligand has coordinated to the copper ion through azomethine nitrogen and one hetero nitrogen atom or acting as bidentate ligand .  Third and fourth coordination sites of the metal are occupied by acetate ion.  From CHN analysis and metal estimation, it is clear that only one molecule of ligand coordinated to the copper ion in the complex.  It is a four coordinated structure and the geometry may be square planar
  • 33.  For the cobalt complex, the ligand coordinated to the metal through the azomethine nitrogen and one hetero nitrogen.  Thus the ligand act as a bidentate ligand.  Two molecules of water and acetate ions also coordinated with the central cobalt metal and form a six coordinated cobalt complex having octahedral geometry.  For the zinc complex, one molecule of ligand is coordinated to the central zinc ion through azomethine nitrogen and one hetero nitrogen.  Thus a four coordinated tetrahedral geometry is obtained.
  • 34.
  • 35.
  • 36.  To phenyl hydralazine (0.24g) dissolved in ethanol was added with stirring an ethanol solution of 2,3- butanedione (0.086g, 1m mol) and sodium acetate.  Ligand was prepared by refluxing ethanol solution of phenyl hydrazine and 2,3-butanedione taken in 2:1 molar ratio.  The mixture was stirred well with slight heating for 90 minutes when a brown phenyl hydralazone precipitates out.  The precipitate was washed with water and then with water-ethanol mixture.
  • 37.  Then the precipitate was kept for some time.  Then ethanol was evaporated off.  Brown colored finely powdered 2,3- butanedionephenylhydazone was obtained.  Melting point was noted (mp= 168 o C). 2 phenylhydrazine + 2,3-butanedione 2,3-butanedionephenylhydrazone
  • 38.  0.5m mol of Cu(II)/ Zn (II) was dissolved in 10 ml of ethanol.  Then it was added drop by drop to 1m mol [0.26g] of 2,3-butanedione phenylhydrazone dissolved in 10ml of ethanol.  It was then mixed for 90 minutes using magnetic stirrer.  Brown/ white creamy complexes separated out of the solution.  Then it was filtered and washed with water containing ethanol and finally with ethanol
  • 39. Ligand / complex color C% H% N% M% BPh Reddish brown 72.18 6.76 21.0 _ BPhCI brown 60.51 5.88 15.69 9.0 BPhC2 Pale yellow 60.36 5.86 9.27 9.27
  • 40. Compound Conductance (mhocm2mol-1) Cu (II) complex 150 Zn (II) complex 145 • From conductivity studies of the complexes in DMSO, the molar conductivity of the complexes were greater than 20 mhocm2mol-indicating their electrolytic in nature. • From elemental analysis and conductivity studies the following formula were proposed for the Cu(II) and Zn(II) complexes. [Cu (BPh)2 ](CH3COO)2 , [ Zn (BPh)2 ] (CH3COO)2.
  • 41.  IR spectrum of BPh , a sharp peak of medium intensity at 3344 cm-1 can be assigned to ν(N-H) stretching vibration.  An intense sharp band at 1596 cm-1 for ν(C=N) and a band at 1066 cm-1 to ν (N-N) vibration.  A weak band at 3025 cm-1 can be assigned to aromatic ν(C-H) stretching .  sharp intense bands at 687 and 745 cm-1 can be assigned to the aromatic C-H out-of-plane bending vibrations.
  • 42.
  • 43.  The sharp band of medium intensity at 3344 cm-1 in the ligand that can be assigned to ν(N-H), become broadened, increased in intensity and shifted to 3427 cm- • In the acetate complexes also, there is broadening of this band which may be due to the H-bond formed between (N-H) hydrogen with the coordinated acetate groups. • The ν(C=N) of the ligand is shifted to lower frequency indicating coordination through azomethine nitrogen. • Bonding by the azomethine nitrogen is further corroborated by the upward shift of ν (N-N) in the ligand to 1100 cm-1 in complexes. • Weak band at 546 and 490 cm-1 in the complex are assignable to the ν (M-N), ν(M-O) respectively
  • 44.
  • 45.  Electronic spectra of the complexes depend on energies of metal d-orbitals , their degeneracy and the number of electrons distributed in them.  These features are in turn controlled by the oxidation state of the metal, number and type of ligand and the geometry of the complexes.  So valuable information regarding the structure, geometry and the splitting of d-orbital can be obtained from their electronic spectra.
  • 46.  The spectra of BPh showed peaks at 300 nm and 351 nm which can be assigned to the π- π* and n-π* transitions.
  • 47.  Various analysis results indicate that the ligand BPhC1 has coordinated to the metal through both the azomethine nitrogen atoms.  from CHN analysis and metal estimation, it is clear that two molecules of the ligand coordinate to the copper ion in the complex.  Therefore it is a four coordinated structure and the geometry may be square planar  For zinc complex, two molecules of ligand coordinated to the central zinc through both the azomethine nitrogen atoms.  Thus a four coordinated square planar geometry is obtained.
  • 48.
  • 49.  C. Serbutoviez, C. Bosshard, G. Knopfle, P. Pretre, P. Gunter, K.Schenk, E. Solari, G. Chapu, Chem. Matter. 7 (1995) 1198.  G.A. Al-Hazmi, A.A. EI-Asmy, J.Coord. Chem. 62 (2009)337.  K.M. Ibrahim, I.M. Gabr, R.R Zaky, J. Coord. Chem. 62 (2009)1100.  V. Getuatis, M. Daskevicience, T. Malinauskas, V. Gaidelis, V. Jankauskas, Z.  Tokarski, Synthetic Metals 155 (2005)599 J.P.Tandon and A.Garg, Trans.Met.Chem., 1987,12,526.  V.K Varshney, J.Ambwni and R.C.Sharma., J.Inst.Chemists(India),  B.Singh and H.Misra, J.Indian Chem. Soc.,1986, 63,1069.  D.K. Misra, R. Rai, P.Om Pandey and K.S.Sengupta, Trans. Met.  Chem., 1992, 17,127.
  • 50.  B.Singh and H.Misra, J.Indian Chem. Soc.,1986, 63,1069. • D.K. Misra, R. Rai, P.Om Pandey and K.S.Sengupta, Trans. Met. Chem., 1992, 17,127. • A.P.Mishra,S.K.Srivastava and V.Srivastava., J.Indian Chem.Soc.,1997,74,487. • A.P.Mishra, R.Rai, P.Om. Z.I.Kamal, A.Ei-Dissouky and Z.S.Azizia, 1997,16,2909.  B.N.Harikumar, M.R.P Kurup and T.N.Jayaprakash, Tras.Met.Chem., 1997, 27,507.  M.Sathpathy, B.Pradan, J.Indian Chem, 1991, 3, 45.

Editor's Notes

  1. INTRODUCTION