Synthesis and Characterization of Metal Complexes of Novel Schiff's Base Ligands Derived From 4-Carboxy Hydrazide-5,6-Diphenyl-3 (2-H) Pyridazone

SCHOLEDGE INTERNATIONAL JOURNAL OF MULTIDISCIPLINARY & ALLIED STUDIES
Vol. 1, Issue 1(October 2014)
www.scholedge.org
ISSN- (2394-336X)
Synthesis and Characterization of Metal Complexes

of Novel Schiff's Base Ligands Derived from
4-Carboxy Hydrazide-5,6-Diphenyl-3[2-H]Pyridazone
Author
Dr. William Rodes
NY, United States of America.
ABSTRACT
new
ligand,
4-[carboxy--(2-hydroxyphenyl)
ethylidene
hydrazide-5,6-diphenyl-3(2H)
pyridazinone (CHDP), were synthesized and characterized by 1H-NMR, IR spectra and C, H, N

elemental analysis.
The dissociation equilibrium constant of CHEDP as well as the equilibrium constant for
different M+n-CHEDP complexes were reported at different temperatures in 75% (v/v) dioxanewater media and constant ionic strength.
The values of the stability constants of CHDP complexes with transition and non-transition
ions were evaluated. The thermodynamic parameters were also calculated and discussed. A series
of mono nuclear protic M(HL), M(HL)2, ML(HL) and non-protic ML2 complex species were
formed in solutions.
The structure of the solid complexes formed between CHEDP and cobalt (II), copper (II)
and iron (III) are substantiated by elemental analysis, mass spectra, thermal studies (TG and
DSC) and IR spectra.
Key words: CHEDP ligand, Potentiometric titration, Solid complexes, Spectrophotometric
studies of Fe(III)-CHEDP complexes.
1. Introduction
SCHOLEDGE PUBLISHING WORLDWIDE- SCHOLARLY INTERNATIONAL JOURNAL
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Pyridazines are compounds act as complexing agents, 2-hydrazino pyridazine and their
metal complexes have many analytical application and also of a great interest in various
biological systems.
The synthesis of pyridazine hydrazines may lead to prepare several interesting chelating
agents. The condensation reaction takes place between hydrazine group and carbonyl group to
give ligand with chromophoric group (1). These classes of compound are structurally related to
the corresponding azo-pyrazolone dyes (II) [4,5] and different only on the position of azo- or
hydrazo- group relative to the nitrogenous nucleus.
N
R
HN
A A
N
(I)
(II)
In the present communication, the metal complexes formed with 4-[carboxy-2hydroxybenzylidene]-5,6-diphenyl-3-(2H)-pyridazinone

hydroxyphenyl)
ethylidene
(CHDP)
hydrazine-5,6-diphenyl-3(2H)
and
pyridazinone
4-[carboxy--(2(CHEDP)
were
discussed.
2. Experimental
2.1. Materials
All chemicals were commercial product of analytical grade. Solvents were purified by
conventional methods. The parent compound 4-carboxy hydrazide-5,6-diphenyl-3-(2H)
pyridazinone was synthesized as previously described [6].
2.2
Preparation of ligands:
CHEDP was obtained by mixing 100 ml of ethanolic solution of 0.01 mole of 4-carboxy
hydrazide-5,6-diphenyl-3-(2H) pyridazinone and 0.012 mole of o-hydroxy acetophenone. The
reaction mixture was refluxed for three hours. Then the formed solid was crystallized from
ethanol to give CHEDP, m. p. 255oC.
CHDP was prepared as in case of CHEDP but o-hydroxy-acetophenone was replaced by ohydroxy salicylaldehyde. Finally, the solid obtained was washed, dried and collected to give
CHDP, m. p. 167.7oC.
2.3. Synthesis of the complexes
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Copper (II), Co(II) and Fe(III) chelating were prepared by adding ethanolic solution of CHDP
ligand ( 0.01 moles) to aqueous solution of metal nitrate (0.01 moles). The mixture was
refluxed for one hour. The solid obtained has filtered off, washed and dried, the elemental
analysis for C, H and N of the complexes are given in Table 1. The complexes were analyzed for
their metal content by EDTA titrations using suitable indicator. The elemental analysis obtained
for both ligands and formed complexes are listed in Table 1.
2.4. Measurements
Potentiometric studies were done with WTW digital pH-meter with a combined glass
electrode. Solutions were adjusted to 0.10M ionic strength by addition of KNO3 and maintained
at constant temperature (0.05oC) with constant temperature water circulated through a sealed of
jacketed cell. The ligand solution in 75% (v/v) dioxane-water reached with standard carbonatefree KOH in 75% (v/v) dioxane-water and the pH had recorded after addition of each increment
of base. Metal-chelate formation equilibriums were measured with 3:1 molar ratios of the ligand
to metal ion (0.001 M). The correction of pH value in 75% (v/v) dioxane-water was taken as
+0.28 [7].
Infrared spectra (KBr discs) were recorded on a Perkin-Elmer 437 spectrometer (4000-400
cm-1). The electronic spectra were measured at 25oC with Jasco V-550 UV-visible spectrometer,
with 1 cm matched quartz cells. 1H-NMR spectra were recorded on Varian EM-390, 90 MHZ.
NMR-spectrometer with TMS as an internal standard.
Conductance of 1x10-3 M solution of the solid complex in DMF was measured using
WTW D-812 Weil heium conductivity meter model LBR, fitted with cell model LTA 100.
Magnetic moments were measured by the Gouy method at room temperature using
Johnson Matthey A/80 Product, model no. M KI, magnetic susceptibility balance with Hg
[Co(CNS)4] as celibrant. Diamagnetic correction was calculated from Pascal's constants. The
effective magnetic moment Meff was determined according to: M eff 2.828( X Mcorr .T )
, where
XM being the corrected molar magnetic susceptibility in e. m. u, mol-1 and T in K.

Thermal analysis (TG-DSC) was carried out on Shim adzu-5O thermal analyzer at heating
rate 10oC/min in nitrogen atmosphere using TA-SO WSI program. Mass spectra were recorded
on a Hewlett-Packard mass spectrometer; model MS 5988, electron energy 70 eV.
3. Results
3.1. Ligand Protonation Constant:
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The protonation constants ( pK nH , n = 1,2,3,)
ISSN- (2394-336X)
of the ligand CHDP and CHEDP are
determined by direct poteniometric measurements. A representative titration curves for CHDP in

the absence and presence of some metal ion is plotted in Fig. 1. No conclusion about the protic
nature or the stepwise dissociation of OH and NH protons could be drowned from the titration
curves of the free ligands. The protic nature of the ligands is substantiated from the metal-ligand
titration curves, only two protons were liberated as indicated by the inflection point at m = 2 (m
is the number of moles of base added per mole of metal). This indicates that under these
conditions the ligand behaves as a diprotic species. For general protonation equilibrium:
H H n1L H n L
(n= 1 or 2)
(1)
The constants ( K nH ) were determined from hydrogen ion concentration of the ligand solution for
each increment of the base added. The absence of any inflection point in the titration curves of
the free ligand indicates that the protonation constants of OH and NH groups are close to each
other (less than 2.8). The values of K1H (-OH) and K 2H (-NH) are calculated from potentiometric
data using the following relationship [8].
1
[ H ]2
(1 F )
x
x( F K 2H ) [ H ]x
H
K1 (2 F )
(2 F )
Where, F (C A [ H ] [OH ]) / C1
and,
(2)
(3)
TxN
Wx103
CA
; C1
(V VT )
M (V VT )
where W is the weight taken, M is the molecular weight, V is the volume of water used for
dissolving the substance, VT is the volume of titrant added, CA is the concentration of K+ and N
is the normality of the alkali added. Since, the value of the ionic product of water in 75% (v/v)
dioxane-water medium is 18.7 [9], both hydrogen ion and hydroxide ion concentration term in
equation (3) are negligible in the dissociation region.
In addition to pH-metric method, spectrophotometric method is further assessed for the
calculation of protonation constants. The electronic absorption spectra of CHDP in 75% (v/v)
dioxane-water display three absorption bands at 321, 275 and 220 nm and having molar
absorptivities 2.00x104, 3.75x104 and 1.30x105 mol-1.cm-1 respectively, like those reported for
pyridazine ring at 245 and 295 nm [10]. The two bands at 275 and 321 nm in CHDP spectra are
attributed to enhanced * transition (K-band) over the whole conjugation system and an
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enhanced n* transition (R-band) respectively. At fixed lignd concentration, the absorbance

was found to be pH-dependent Fig. 2. The results were analyzed for the calculation of the
protonation constants of CHDP in 75% (v/v) dioxane-water using the following equation [8].
( M )
[ H ] ( C )
x
K 2H [ H ]x
H
K1
( A )
( A )
(4)
where, C , Aand M are the molar absorptivities (extinction coefficient) for the analytical
wavelength at given pH for di-protonated, mono-protonated and non-protonated species
respectively.
The plot of [ H ]
( C )
( M )
versus [ H ]
gives straight line of slope equals to ( 1 / K1H )
( A )
( A )
and intercept equal ( K 2H ) . The values of K1H andK 2H are refined using least square method. The
obtained values are found to be 9.70 and 10.87 for K1H andK 2H respectively compared to 9.71 and
10.82 obtained potentiometrically.
3. 2. Ligand-metal ion interactions:
The protonation equilibrium curve for Co-CHDP at 40oC is shown in Fig. 1. The shapes of
these curves clearly indicate the formation of simple mononuclear chelate as well as various
protonated species. The complex equilibrium in the first buffer region may be represented by:
M z H 2 L M ( HL) ( z 1) H
(5)
M ( HL) ( z 1) H 2 L M ( HL) (2z 2) H
(6)
Further addition of base results the subsequent dissociation of two protons as indicated by the
amount of base required per metal chelate. The reaction involved may be described by the
equilibriums:
M ( HL) (2z 2) ML( HL) ( z 3) H
and
ML( HL) ( z 3) ML(2z 4) H
K MH ( HL )2
[ M ( HL) (2z 2 ) ]
[ ML( HL) ( z 3) ][ H ]
(7)
H
K ML
( HL )
[ ML( HL) ( z 3) ]
[ ML(2z 4 ) ][ H ]
(8)
Computer assisted algebraic method use to solve the overlapping complex protonation constants
involved in the second buffer regions. Calculation of the constants K MM( HL ) andK MM( HL )2 was
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carried out using standard procedures based on the calculation of the average number of the
ligand bound per metal ion (n HL

) and the free ligand concentration [ HL ] using the first buffer
region of the titration curve. Values of the constants are obtained from the intercept and slope of
the linear relationship:
nHL
(2 nHL
)
xK MM ( HL )2 K MM ( HL )
(1 n HL )[ HL] (1 n HL )
(9)
The best straight line is obtained by the method of least squares. In a similar way, the second
M
M
buffer region in the titration curves is used to calculate the constants K ML
( HL ) andK ML as well as
H
H
the constants K ML
( HL ) andK ML2 . The values of stability constants as well as thermodynamic
parameters were summarized in Tables 2, 3, 4, 5 and 6.

The poteniometric equilibrium curves of the Fe(III)-CHDP and Fe(III)-CHEDP systems
show a curve similar to strong acid titration Fig. 3. The formation of iron chelate is so nearly
complete even at low pH, that the stability constant can not be accurately calculated from
poteniometric data. For this reason, the values of stability constants for Fe(III)-CHDP and
Fe(III)-CHEDP have been determined by spectrophotometric method.
On mixing a solution containing Fe(III) ions with the solution of CHDP in 75% (v/v)
dioxane-water, coloured complexes are formed. At constant metal ion concentration [Fe3+] and
varying ligand concentration, the absorbance increasing effectively at low concentrations of
ligand but tends to attain a limiting value at higher concentrations Fig. 4. Multiple band spectra
indicate the probable formation of complexes with varying stiochiometry. The intensities of
peaks observed are function of both pH of the medium and the molar ratios of metal to ligand.
As seen from Fig. 5, the absorbance increases rapidly with increase pH from 2 to 4, followed by
a plateau in pH region 4.0 - 9.0. From the absorbance-pH diagram, it can be concluded that the
optimum pH values are 3.0 for the formation of Fe(III)-CHDP complex systems. In addition, it
could be concluded that more than one species are formed. At pH 2.0, the formation of
protonated complexes [Fe(HL)]2+ and [Fe(HL)2]1+ are formed through the replacement of
phenolic proton. On increasing the pH from 2.0 to 4.0, the ionization of NH proton could take
place and this leads to the formation of different species. These different absorbing species in the
pH range from 2.0 to 9.0 is substantiated applying Coleman's graphical method [11]. Typical
plots are given in Fig. 6 "a &b". The analysis revealed that only one absorbing species exists in
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the acidic region (pH below 4.0), which probably formed between Fe(III) and acidic ligand Fig.
6a. Above pH 4.0 two absorbing species (protonated and non-protonated) are found as indicated
by the linear plots shown in Fig. 6b. Above pH 6.0, the absorbance is nearly constant indicating
that both the protonated [ML(HL)] and non-protonated [ML2] are absorbing to the same extent
( ML( HL ) ML ) .
The composition of complexes formed in this study is determined using Job's and molar
ratio methods [12]. All of these spectrophotometric methods indicate the formation of 1:1 and 1:2
(M:L) complexes. In molar ratio method Fig. 7, a sharp break in the line at 1:1 and 1:2 (M:L),
molar ratios indicating formation of 1:1 and 1:2 complex types. In Jobs method the curve shows
maximum absorbance at 0.5 mole fraction Fig. 8 indicating the presence of 1:1 (M:L) complex
type.
For studying the validity of Beer's law, a series of solutions containing constant excess
concentration of ligand (CHDP or CHEDP) and variable concentration of Fe(III) ions all in 75%
(v/v) dioxane-water are prepared. The absorbance of these solutions is measured at fixed
wavelength (usually max) the linear relation obtained between C Fe 3 and absorbances satisfy
Beer's law for iron in certain concentration range. Values of are 1309.5 and 601.5 mol-1 cm-1 at
625 nm and optimum range for accurate measurement are 1x10-4 1.2x10-3 and 1x10-4 2.6x103
for CHDP and CHEDP complex systems respectively. These ranges had obtained from
Ringbom plots and Sandell's sensitivity index [13], S% = 2.14x10-3 and 4.65x10-3 for Fe(III)CHDP and Fe(III)-CHEDP complex system respectively. The reproducibility of the method is
checked by testing three series of solutions and the relative standard deviation is found to be less
than 2%.
Since iron chelates have intense colors and absorb in the region 500-600 nm, the
formation constants of these species were calculated spectrophotometrically. In the region of
overlapping spectrograms of the free metal ion and its complex, assuming that only 1:1
complexes are formed (CL / CM 0.3) , the following relationship holds for Fe(III)-CHEDP
complex system [14]:
[ HL1 ]1 (1 A / Ao )( K MM( HL ) ) K MM( HL )
(10)
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where, A, Ao are the absorbance in the absence and presence of the ligand.
K MM( HL ) x( C / M ) where, C and M are the molar extinctions of the complex and metal ion
respectively. Plots of [ HL1 ] vs. (1 A Ao ) gives a straight line its intercept is K MM( HL ) .
The free ligand concentration were calculated at any particular pH using the following equation:
CHL [ HL ](1 K1H [ H ]
(11)
A sample set of these calculations are shown in Fig. 9. In the region of overlapping spectrograms
of Fe(III)-CHEDP complex and assuming that 1:1 complex is formed another equation is used to
calculate the stability constant [15]:
log K MM( HL ) log( A / ) log[ HL] log[ M ]
(12)
where, A and are the absorbance and molar extinction of the complex. The value of log K MM( HL )
for Fe(III)-CHEDP complex obtained by this method is 11.310.16 which is higher than the
corresponding value for Fe(III)-CHDP complex system ( log K MM( HL ) = 10.200.15). This
difference is consistent with the structure of the two ligands. In CHEDP, the methyl group
increases the basicity of the ligand, which in turns increases its stability constant.
4. Discussion
4.1. The ligand:
The analytical and spectral data prove that each ligand is a mixture of two tautomeric
isomers is shown in the following diagram:
(1)
(2)
[R = -H CHDP], [R = CH3 CHEDP].

Thus the IR-spectrum of the ligands CHDP and CHEDP could be associated with both
tautomeric isomers 1 and 2. The N-H, C=N and C=O of tautomeric isomer 1 are detected at 3200,
1680 and 1620 cm-1 respectively (Table 8). The phenolic OH is observed at 3450 and 3500 cm-1
as broad bands for CHDP and CHEDP respectively. The broadness of such band could be related
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to hydrogen bonding with C=N group. Evidence for tautomeric structure 2 is derived from IR
bands related to N-N and C-O which appeared at 980-960 and 1275-1280 cm-1 respectively.
The 1H-NMR spectrum (DMSO-d6) of CHEDP shows at 2.2 (s, 3H, CH3); 6.5-7.4 (m,
15H, Ar-H phenolic OH). 10.7 (s, 1H, exocycllic CONH) and 12.9 ppm (s, 1H, cyclic CONH).
The structure of CHEDP compound was further confirmed by the mass spectrum which
exhibited peaks at m/e 424 (78.34%) [M+C25H20N4O3]; 409 (34.28%) [C24H17N4O3]; 378
(13.24%) [C25H18N2O2]; 290 (40.72%) [C18H14N2O2]; 275 (100%) [C17H11N2O2]; 247 (83.17%)
[C16H11N2O2]; 219 (25%) [C16H11O] and 203 (13.12%) [C16H11]. The base peak at m/e 275
(100%) is formed due to loss of (C17H12N2O2) from the parent ion peak of CHEDP, and the base
peak at m/e 122 (100%) is formed due to loss of (C7H8NO) from the parent peak for CHDP.
Furthermore, the proposed structure of the ligands were optimized and structure
parameters were evaluated by means of semi-empirical molecular obtained calculations of MP3
level provided by hyper Chem. release 7.5. The calculated structural parameters data are
summarized in Table 7. The heat of formation (Hf), dipole moment, HOMO and LUMO
entropies and Egap= (EHOMO - ELOMO) as well as bond length. Analysis of the data indicates
that the calculated heat of formation (Hf) as well as Egap values of the present ligand, suggest
that the more favorable toutomeric forms are shown in the following diagram
CHDP.H
CHEDP...CH3
4.2. Solid complexes:

4.2.1. Conductivity and magnetic Properties:
The metal complexes, which were isolated in the present study, are presented in Table 1
together with some of their properties. The deprotonation of hydrazo and phenolic protons occurs
in 1:1 Fe(III)-CHDP while in cases of Cu(II)-CHDP and Co(II)-CHDP complexes only the
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phenolic group is deprotonated. The molar conductance values of 10-3M complex solution in
DMF are 15, 67.00 and 75.20 MS/cm for copper, cobalt and iron complexes respectively. This
indicates that 1:1 electrolyte for cobalt and iron complexes, while nonionic nature for copper
complex.
The magnetic moments (eff) of iron (III) and cobalt (II) complexes are 5.67 and 4.41, which are
normal and suggest octahedral geometry for them. The magnetic moment of copper (II)
complexes reported here is in the range 1.8 B.M. accepted for Cu(II) complexes [16] (one
unpaired electron).
4.2.2. IR spectra of the complexes:
The infrared spectra of these solids show a systematic shift of C=C, C=N and C=O bands to lower
frequency with the simultaneous disappearance of N-H and O-H bands. The O-H band in the free
ligand is not observed but is replaced by a broader band at 3400-3520 cm-1 in the spectrum of the
complex due to O-H of the coordinated water molecules. The participation of phenolic oxygen
and azo-methane or N-H nitrogen are substantiated from the appearance of new bands at 551-580
and 340-470 cm-1 on the spectra of the solid complexes assigned to M-O and M-N respectively.
4.2.3. Thermal analysis (TG-DSC):
The results of TG-DSC studies of CHDP ligand and its complexes Cu(II)-, Co(II)- and
Fe(III)-CHDP are summarized in Table (9) at ambient temperature up to 800oC, the rate is 20oC
per minute. The composition of intermediates proposed were the best fit of the observed weight
loss. The TG curve of the free ligand show a very rapid and big mass loss (second step) in the
range 198.86-437.62oC corresponding to the liberation of organic moiety C17H11N2O2 [found
63.74; calc. 64.25]. The exothermic peak at 400oC originates from the combustion of carbon
from the organic part. The first decomposition stage starts at 44.41oC and continues until
198.86oC, corresponding to the degradation of 2H2O molecules (one crystalline H2O and the
other from the ligand) constituting about 8.17 of the total weight loss (8.41 calc.)The third step
show the decomposition of the remaining part of the molecule C7H5N2 at 438.99-798.80oC
temperature range (found: 27.65; calc. 27.34). DSC analysis was performed in order to obtain
quantitative results for thermal effects accompanying various processes occurring during heating.
The measurements were carried out at nearly the same rate as used for TG investigation.
The composition of TG and DSC analysis is a very useful tool in the investigation and
characterization of thermal behavior of organic compound. The values of thermodynamic
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quantities with particular TG and DSC curves for [Fe(C24H16N4O3)(H2O)3]NO3.2H2O, (Table 9).
The transition enthalpy values give information about the dimensions of thermal effects, being a
sum of all processes that taking place in the particular temperature range. The thermal
parameters of conversion of 1 and 2 steps are not similar (H1= -54.36 J/g and H2 = -15.11 J/g)
because they are connected with loss of H2O and NO2 for the first step while the second step four
of coordination water molecules are lost. The transition enthalpy of steps (3) is high (H3 = -57.11
J/g), which is due to release of C6H5NO2 moiety.
In the thermo gram of the complex [Fe(C24H16N4O3)(H2O)3]NO3.2H2O, there are four
steps of weight losses from room temperature to 743.0oC. The complex lost 10.29 of its weight at
34.34-151.99oC due to the liberation of NO2 and H2O molecules (calc. 10.39). In the second step
4 molecules of coordinated water are lost (found 11.38 and calc. 11.69). The third step occurred
at 259.6-401.0oC range is due to the loss of C6H5NO2 moiety from the organic part of ligand
molecule (found 19.80, calc. 19.97). The remaining weight loss 41.68 is for organic matter
C17H11N3 obtained at 401.01-742.99oC range (calc. 41.73). The remaining weight loss above
742.99oC is corresponding to the oxide molecules FeO and CO (found 16.85, calc. 16.21).
The TG curve of copper complex shows about five steps, the first one gives a weight loss about
3.28% (calc. 2.97) due to one mole of crystalline water and is characterized by an exothermic
peak in the DSC curve at 120oC. The second step is due to loss of NO2 and 3H2O (found 16.25,
calc. 16.49) and show an endothermic peak in DSC curve at 323oC. The other remaining steps
were due to loss of C7H6ON2, C11H2O and C6H9N2O2 organic moieties. These steps are
characterized by two endothermic and one exothermic peak in DSC curve. CuO is appeared as a
final product above 565oC, (found 13.43, calc. 13.11).
In case of cobalt complex, the decomposition process was completed and cobalt oxide (CoO) is
formed above 600oC. The first three steps are due to the loss of crystalline and coordinated water
molecules.
4.2.4. Mass spectra:
The molecular formulas of the above complexes were substantiated through mass spectra. The
iron(III) complex [Fe(C24H16N4O3)(H2O)3]NO3.2H2O (F.w., 615.85) show the highest mass
peak
at
603,
which
agrees
with
the
formula
weight
of
the
complex
[Fe(C24H16N4O3)(H2O)3]NO3.1H2O (F.w., 603). The fragmentation patterns of the iron

complex shows a fragment due to hydrated ligand molecule (C24H17N4O3).H2O at 423.
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For cobalt complex [Co(C24H17N4O3)(H2O)3]NO3.H2O of F.w. 601.9 the highest mass

peak is at 602, which agrees with the formula weight of cobalt complex. The fragmentation
patterns of the complex show fragment at 439 due the ligand molecule with 1 water molecules
(C24H17N4O3)1.H2O.
The mass spectrum of the copper complex [Cu(C24H17N4O3)(H2O)3(NO3]H2O shows a
peak at 603 which in agreement with molecular formula of the complex (606.55). From the
above discussion, the structure of the three investigated complexes is shown in the following
scheme:
4.3. Complexes in solution state:

The values of acid dissociation constants K1H and K 2H (phenolic OH) and (hydrazo NH)
of CHEDP and CHDP ligands are not similar Table (2). This would indicate that the total
inductive and hyper-conjugation effects of methyl group in CHEDP on the reagent basicity
( K1H + K 2H ) are mainly dependent on the presence of such methyl group. The absence of this
group in CHDP ligand could be account for the lower basicity of the ligand compared to CHEDP
under similar conditions.
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Ph
Ph
N
N
ISSN- (2394-336X)
R = H in CHDP ; R = CH3 in CHEDP

All thermodynamic parameters of the dissociation process of the ligands are given in Table (2,
3). These values reveal that:
The stepwise pKH values decreasing with increasing temperature, demonstrating that its
acidity increasing with increasing temperature.
H is positive indicating that dissociation is accompanied by absorption of heat and the
process is endothermic.
G is positive indicating that the dissociation process is not spontaneous.
S is negative due to increased order as a result of salvation process.
The values of G of protic and non-protic complexes formed between CHEDP and divalent
metal ions are listed in Table (4). The relationship between G for M(HL), M(HL)2, ML(HL)
and ML2 complexes and second ionization potential of different metals is plotted in Fig. 10. The
linear relation indicates that the two primary factors affecting the stability of the complexes
formed between these ions and CHEDP are ionic radii and atomic number.
The wide spread success of the relation between H for the protic and non-protic complex
species and second ionization potentials of the metal ions shown in Fig. 11, indicates that the
entropy of a series of chelation reaction with a given reagent will either be roughly constant or
will vary regularly. This relationship is used because H express bond strength, also the second
ionization potential may be taken as a rough estimation of the average electron attracting power
of a divalent metal ion. It will also be a measure of the attracting power of a divalent metal ion
for a source of electrons such as that formed in the chelate ligand groups. Hence, it is more
nearly related to bond energy and H of chelation than G as measured by log of chelate
formation constants. It should also be noted that since in many cases H are accompanied by
opposing charge in S. H should be a more sensitive index of bond strength than G. Fig. 11,
shows a plot of second ionization potential of the gaseous metal atom against H of chelation.
As can be seen the relationship is satisfactory.
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CHEDP forms MHL (protic) chelates as evidenced both by the titration curves and
isolation of solid complexes. Probable arrangement of the order groups is shown in structure (III)
with the M replacing H1. As more base added, the pH becomes sufficiently high to assist in the
dissociation of the second protons (H2). The basicity of this proton is not as strong as in the free
ligands and influenced by the presence of metal ion in the following order: Ni < Co Cu < Zn <
Mn < Cd, which is in a revised order of stabilities of the normal chelates.
Page 43
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ISSN- (2394-336X)
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Synthesis and Characterization of Metal Complexes of Novel Schiff's Base Ligands Derived From 4-Carboxy Hydrazide-5,6-Diphenyl-3 (2-H) Pyridazone

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SCHOLEDGE INTERNATIONAL JOURNAL OF MULTIDISCIPLINARY & ALLIED STUDIES

Vol. 1, Issue 1(October 2014)