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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.
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.
1
6- Partial elemental analysis (C,H,):
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
2
[50]
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
[51]
``
+
Preparation of the other ligands:
a-49
The dehydroacetic acid 4N-diethyl thiosemicarbazone
[HDHA4DE][49-b] dehydroacetic acid 4N-ethyl thiosemicarbazone
[HDHA4E][49-c] dehydroacetic acid 4N-methyl thiosemicarbazone
3
[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
manner.
1-Zirconium complexes:
2- Hafnium complexes:
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
purification.
The ligands are soluble in DMF, ethanol, methanol and acetone making it
possible to prepare 10-3 M solution . Any required lower concentration is
4
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.
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rpm for five minutes. The resulting solutions were used as such or diluted
to give a measurable absorbance.
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EXPERIMENTAL