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I - Materials:
All chemicals were of analytical grade and were used with out
further purification.

II - Measurements:
1- The electronic absorption spectra.

The electronic absorption were recorded within the range 200-900

nm by the aid of Jasco V-530 uv/vis spectrophotometer and Shimadzu
UV-160A uv/vis spectrophotometer using 1cm matched quartz cells at
room temperature.

2- Infrared absorption spectra:

The ir absorption spectra of the organic ligands as well as those of

the corresponding complexes were recorded in the solid state on Basic
Vector 22 FT-IR infrared spectrophotometer using the KBr disc

3- 1Hnmr spectra:

The proton nmr spectra were recorded with a (?) using tetramethyl
silane ( TMS ) as an internal standerd and dimethyl sulphoxide was used
as a solvent.

4- The thermogravimetric analysis of the solid metal complexes:

These were carried out in an inert atmosphere (nitrogen) in a

platinum cell by using Shimadzu TGA-50H instrument.

5- The magnetic susceptibility:

The magnetic susceptibility of the solid complexes were recorded

by using Johnson Matthey magnetic susceptibility balance.

6- Partial elemental analysis (C,H,):

Partial elemental analysis (C,H,) were performed by Heraeus


7- Partial elemental analysis (Zr, Hf):

Partial elemental analysis (Zr, Hf) were performed by Perkin Elmer

OPTIMA3000.I.C.P. equipment.

III – Preparation of the organic ligands;

The dehydroacetic acid 4N-substituted, 4N-disubstituted and
3-azacyclothiosemicabazones were prepared from 0.01 mol of
dehydroacetic acid and the desired substituted thiosemicarbazide
(0.01 mol) by refluxing for two hours in 40 cm3 of absolute ethanol with
two drops of concentrated sulfuric acid. After reducing the volume by
slow evaporation, the resulting solids were filtered, washed with cold
isopropyl alcohol and anhydrous ether to apparent dryness(51). The
thiosemicarbazides were prepared following the literature procedure(52).

preparation of 4N-dimethyl thiosemicarbazide:

4.5 gm (0.1 mol) equal to 12.65 ml of 40% aqueous dimethyl amine was
added to a sodium hydroxide solution (4gm of NaOH dissolved in 125 ml
of bidistilled water to contain 0.1 mols) and stirred at room temperature
for 30 minutes. 7.6 gm (0.1 mol) equal to 6 ml of 99.9 % of carbon
disulfide was then added drop wise and the mixture was stirred for more
than 12 hours which allowed the organic layer to disappear. A solution
containing 0.1 mol of sodium chloroacetate freshly prepared by
dissolving 9.45 gm (0.1 mol) of chloroacetic acid and 4 mg (0.1 mol ) of
sodium hydroxide in 40 ml bidistilled water was then added with stirring
of room temperature for one hour, then 10 ml of concentrated hydroloric
acid was added drop wise and S-carboxymethyl N.N-dimethyl


dithiocarbamate [50] was precipitated out as white solid. The product was
collected by vacuum filtration and washed with cold isopropyl alcohol
and dried at 35ْ c overnight. 8.95 gm (0.05 mol) of S-carboxymethyl
N.N-dimethyl dithiocarbamate was dissolved in 30 ml of hydrazine
monohydrate (98% pure) and warmed to 40ْ c for about 20 minutes with


continuous stirring. The resulting 4N-dimethyl thiosemicarbazide [51]

was diluted with 15 ml of water and then dried at 35ْ c overnight and
being ready for condensation with dehydroacetic acid to produce
dehydroacetic acid 4N-dimethylthiosemicarbazone [49-a]. The other
substituted thiosemicarbazides were prepared in the same manner except
the 4-methyl thiosemicarbazide which was commercial available of
analytical grade.


Preparation of the other ligands:
The dehydroacetic acid 4N-diethyl thiosemicarbazone
[HDHA4DE][49-b] dehydroacetic acid 4N-ethyl thiosemicarbazone
[HDHA4E][49-c] dehydroacetic acid 4N-methyl thiosemicarbazone

[HDHA4M][49-d] dehydroacetic acid 4N-phenylthiosemicarbazone
[HDHA4Ph][49-e] dehydroacetic acid 3-piperidyl thiosemicarbazone
[HDHA3pip][49-f] and dehydroacetic acid 3-hexamethyleneiminyl
thiosemicarbazone [HDHAhexin] [49-g], were prepared in the same

IV Preparation of the solid complex:

Zirconium and hafnium complexes of dehydroacetic acid 4N-
substituted, 4N-disubstituted and 3-azacyclo thiosemicarbazones were
prepared as follows:

1-Zirconium complexes:

An absolute ethanol solution (~20 ml) containing 0.3223 gm (0.001 mol)

of ZrOCl2. 8H2O was added to an absolute ethanol solution (~20 ml)
containing 0.001 mol . of the desired ligand and 1 ml of diethyl amine the
resulting mixture was refluxed for 2 hours with continuous stirring . The
resulting crystals formed were filtered while hot, and washed with
absolute ethanol several times to remove any excess diethyl amine or
unreacted reactants.

2- Hafnium complexes:

The hafnium complexes were prepared in the same manner by reacting

0.3203 gm (0.001 mol ) of HfCl4 with 0.001 mol of the desired ligands.

V Preparation of solutions:
1- Spectral measurements of the ligands in different solvents:

The solvents used were of analytical grade and was used without further

The ligands are soluble in DMF, ethanol, methanol and acetone making it
possible to prepare 10-3 M solution . Any required lower concentration is

obtained by appropriate dilution in 10ml calibrated measuring flasks,
while the ligands are sparingly soluble in benzene and carbon
tetrachloride, hence saturated solutions were firstly prepared, left to
obtain equilibrium and insoluble portions were then filtered off so as to
obtain clear solution. The resulting solutions were used as such or diluted
to give a measurable absorbance.

2- Spectral measurement of the ligands at different pH values:

a- Preparation of buffer solutions.

Universal buffer solutions were prepared as follows:

 0.01M solution of each of phosphoric and acetic acid was prepared by

accurate dilution of a concentrated stock with bidistilled water.

 0.01M boric acid solution was prepared by dissolving the appropriate

weight of the recrystallized acid in bidistilled water.

 A stock acid mixture was prepared by mixing equal volumes of the

three acids in a large bottle.

 0.01 M sodium hydroxide stock solution was prepared.

 A series of buffer solutions of pH = 3 to pH = 11 were prepared as

recommended by Britton(53) by mixing 75 ml of the acid mixture in

250 ml measuring flask with the appropriate volume of sodium
hydroxide solution.

The pH value of the buffer solutions was checked using a pH meter.

b- Preparation of the ligands at different pH values:

An accurate volume (5ml) of the buffer solution of the desired pH value

was placed in a 10 ml calibrated measuring flask followed b 5 ml of 10-3
solution of desired ligand in absolute ethanol with constant shaking at 103

rpm for five minutes. The resulting solutions were used as such or diluted
to give a measurable absorbance.

3- Spectral measurements of Zr and Hf complexes:

2.5 ml of 10-3 M solution of Zr standerd was added to 2.5 ml of 10-3 M

solution of the desired ligand in absolute ethanol and one drop of diethyl
amine in a 5 ml measuring flask. The solutions of Hf complexes were
prepared in the same manner using 10-3 M solution of Hf stander.

4- Absorption measurements of Zr and Hf complexes :

The absorption spectra of Zr and Hf complexes were compared with the

absorption spectra of the corresponding ligands and the wave lengths
concerning Zr and Hf complexes with each ligand were assigned, then a
series of Zr and Hf standard solutions with different Zr and Hf
concentrations were mixed with the equivalent concentration of each
ligand and the absorbance recorded at the previously assigned wave
lenthes, the absorbance recrded in tables vs. Concentration and checked
for Beer's low.