الفهرس 
Chapter I. IntroductionOnly 14 pages are availabe for public view
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Abstract
The present thesis comprises of three main chapters in addition to Arabic and English summaries. The data are collected in (17 Tables) and represented in (81 Figures), (15 Schemes) as well as (132 References).
The First Chapter: Introduction This chapter concern with a comprehensive study of thiosemicarbazone,
pyrazolone, isonicotinic hydrazone derivatives and their chelates as well as their biological activity against human Hepatic Cancer Cell Line Hep-G-2.
The Second Chapter: Experimental
This chapter consists of:
1- Synthesis of Schiff base ligand (H2L1), {(5-hydroxy-1,3-diphenyl)-1H-pyrazol-4-yl)(phenyl)methan-oneN-allylthiosemicarbazide}. It was prepared from the condensation of 4-benzoyl-1,3-diphenyl-5-pyrazolone (Start 1) with allylthiosemicarbazide with (1:1) molar ratio. Also, it describes the preparation of some chelates obtained from the reaction of Schiff base ligand (H2L1) with copper(II) salts (chloride, nitrate and perchlorate), nickel(II) nitrate and chloride salts of Co(II) and Pd(II) ions (1:1:1) molar ratio in absolute ethanol.
2- Preparation of some metal chelates obtained from the template reaction of 4-benzoyl-1,3-diphenyl-5-pyrazolone (Start 1) with isonicotinic acid hydrazide (INH) and different metal salts {chloride, nitrate and perchlorate of Cu(II) ion, Ni(II) nitrate and Co(II) chloride and Pd(II) chloride} with (1:1:1) molar ratio in absolute ethanol.
English Summary
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3- Synthesis of Schiff base ligand (H2L2), ((Z)-N’-((5-oxo-1,3diphenyl-4,5-dihydro-1H-pyrazol-4 yl)(phenyl)methylene)isonicotinohydrazide) derived from the condensation of 4-benzoyl-1,3-diphenyl-5-pyrazolone (Start 1) with isonicotinic acid hydrazide (INH) in absolute ethanol with a molar ratio (1:1). Then, this ligand (H2L2) reacted with Cu(II) perchlorate salt with a molar ratio (1:1) in absolute ethanol.
4- The chemical and geometrical structure of the ligands and their metal chelates were characterized using elemental analyses (C, H, N, M and Cl), spectral methods including (IR, UV–Vis, 1H NMR, ESR, X-ray diffraction and mass spectra), magnetic susceptibility, molar conductivity and thermogravimetric measurements.
5- The biological activity of the prepared Schiff bases and some of their metal chelates was investigated against human Hepatic Cancer Cell Line Hep-G-2.
The Third Chapter: Results and Discussion
This chapter focuses on explaining the results acquired by clarifying the chelates’ geometrical structures, bonding modes, and chemical formulas.
(I) Part (A) characterization of Schiff base ligand) H2L1( and its metal chelates
The recent arguments demonstrated that:
The elemental analysis of the metal chelates confirmed that the Schiff base ligand (H2L1) coordinated with the previously mentioned bivalent metal salts with different stoichiometries (1M:1L) chelates (3) and (6)}; (1M:2L) chelate (1) and (2M:1L) {chelates (2), (4) and (5)}.
According to molar conductivity measurements, all chelates are electrolytes (1:1) with the exception of palladium (II) chelate.
The Infrared (IR) spectral studies proved that the Schiff base ligand (H2L1) achieved as monobasic bidentate species (NS), coordinates with
English Summary
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the metal (II) ion through the nitrogen atom of azomethane group and sulfur atom of thione group, in CoCl2 and PdCl2 chelates (1 and 6). In addition, the results in chelates (3 and 4) clarified that the Schiff base ligand (H2L1) behaved as monobasic tridentate (NNO) with the metal(II) ions and coordinated through the two nitrogen atoms of azomethane group and imine group (-C-NHR) together with the oxygen atom of the deprotonated hydroxyl group (enolic OH), located in pyrazolone ring. Moreover, the infrared (IR) spectral studies confirmed that the ligand (H2L1) binded with the metal (II) ion as monobasic tridentate (ONS) in Ni(II) nitrate and Cu(II) perchlorate chelates (2 and 5), coordinated with the ion through the oxygen atom of the deprotonated hydroxyl group (enolic OH) of pyrazolone ring and the nitrogen atom of azomethane group together with the sulfur atom of thione group of thiosemicarbazone.
The electronic absᴏrptіᴏn spectra ᴏf (H2L1) metal chelates and magnetic mᴏment measurements showed that Ni(II) and Cu(II) chelates (2 and 3-5) possess square pyramidal geometry while Co(II) and Pd(II) chelates (1 and 6) have square planar structure.
(II) Part (B) characterization of Schiff base ligand )H2L2( and its metal chelates
The results illustrated that:
The molar conductivity measurements confirmed that all chelates are non-electrolytes except Ni(II) nitrate chelate (2`) and cu(II) nitrate chelate (3`), demonstrating electrolytic nature with (1:1).
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The elemental analysis confirmed that the template reaction using CoCl2, PdCl2 and Cu(ClO4)2 salts led to the formation of binuclear metal chelates (1`, 6`and 5`). In addition, this type of reaction afforded mononuclear chelates (2` and 3`) with Ni(II) nitrate and Cu(II) nitrate salts, respectively.
The direct reaction of Schiff base ligand (H2L2) with Cu(II) perchlorate occurred with (1:1), giving a binuclear metal chelate (7`).
The Infrared (IR) spectral studies ascertained the formulas of Schiff base ligand (H2L2) in the presence of the metal ion during the template reaction.
The Infrared (IR) spectral studies confirmed that the Schiff base ligand (H2L2) coordinated with the metal(II) ion as a tridentate species (ONO) in CoCl2, Cu(NO3)2, CuCl2, Cu(ClO4)2 chelates (1`, 3`, 4` and 5`, 7`) and attached with these ions through the oxygen atom of the protonated hydroxyl group (enolic OH) located in pyrazolone ring, the nitrogen atom of azomethane group and oxygen atom of the carbonyl group (amidic C=O). In addition, the Schiff base ligand (H2L2) coordinated with the metal(II) ion as a tridentate moiety (ONO) in Ni(II) chelate (2`) through the two oxygen atoms of the carbonyl groups in pyrazolone ring and (amidic C=O) along with the nitrogen atom of azomethane group.
The electronic absᴏrptіᴏn spectra ᴏf (H2L2) metal chelates and magnetic mᴏment measurements showed that Cu(NO3)2 and CuCl2 chelates (3` and 4`) possess square pyramidal geometry while Cu(ClO4)2 and PdCl2 chelates (5`, 7` and 6`) have square planar structure. Additionally, trigonal bipyramidal and octahedral geometrical structures were concluded for CoCl2, Ni(NO3)2 chelates (1`and 2`).
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TG/DTG studies confirmed the chemical formula for all prepared metal chelates of H2L1 and H2L2 ligands and interpreted the thermal decomposition processes which ended with the formation of metal or metal oxides contaminated with carbon residue as final products.
An axial electron spin resonance spectra were suggested for all prepared Cu(II) chelates of H2L1 pointing to 2B1g as a ground state corresponding to the electron configuration (dX2-Y2) 1.
In vitro antitumor activities against Hep-G-2 were performed for H2L1 and H2L2 ligands and some of its metal chelates. The biological studies indicate that Cu(II) chelates have better antitumor activity compared to the H2L1 and H2L2 ligands and the other chelates.