الفهرس 
Chapter one (1. IntroductionOnly 14 pages are availabe for public view
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Abstract
The present thesis comprises three main chapters in addition to
Arabic and English summaries as well as the relevant references.
The First Chapter: - Introduction
This chapter includes a scientific literature survey related to
macrocycles and their coordination compounds, regarding their types,
design and synthesis, stability of their metal complexes and their chemical
and biochemical importance.
The Second Chapter: - Experimental
This chapter includes a detailed account about the synthesis of novel
nitrogen containing macrocyclic ligands and their corresponding
macrocyclic metal complexes with different cobalt(II), nickel(II),
copper(II), ruthenium(III) and palladium(II) salts. Different standardized
instruments as spectral (1H NMR; mass (MS); UV-Vis; IR; EPR) methods,
elemental analysis, magnetic moment, molar conductivity measurements
and thermal (TG/DTG) technique were used for characterization of the
structure of the synthesized ligands as well as their corresponding metal
complexes.
The third Chapter: - Results and discussion
This chapter includes the results obtained and their discussion and
comprises three main parts.
Part I,II
These parts include:-
(i) Synthesis and characterization of the starting material (A): [2-amino-
N-{2-[(2-amino-benzoylamino) pyridine]-benzamide] which was
synthesized from the reaction of 1H-benzo [d] [1,3]oxazine-2,4-
dione (12.0 mmol, 2 gm) with 2,6 diaminopyridine (6.0 mmol, 0.66
gm).
(ii) Synthesis and characterization of 15-membered (N5) macrocyclic
ligand and 19-membered (N5) macrocyclic ligand which were
synthesized from the reaction of starting material (A) with 2,3
pentanedione LI or terphethaldehyde LII, respectively.
(iii) Synthesis and characterization of their corresponding different salts
macrocyclic Co(II) ,Ni(II), Cu(II), Pd(II) and Ru(III) metal
complexes.
(iv) characterization of new compounds was achieved by using different
analytical and spectroscopic tools such as {IR; UV/ Vis.; 1H NMR;
mass(MS); ESR (for copper(II) complexes )}, molar conductance,
magnetic measurements and thermal analysis (TG/DTG) technique.
The kinetic and thermodynamic activation parameters as ΔE*, ΔH*,
ΔS*, ΔG* of the decomposition stages of the some selected
complexes were determined from TGA thermograms using the
Coats–Redfern equation. The obtained results can be summarized
as follows:
1. The analytical and spectral data (mass, 1H NMR and IR) confirm the
formation of the macrocyclic ligands LI, LII.
2. The results of elemental analyses show that all complexes are formed
in 1M: 1L molar ratio.
3. The ligands and their complexes are air stable, non-hygroscopic and
insoluble in most common organic solvents. However, they are
soluble in DMSO solution.
4. The molar conductivity values for LI complexes show that all
complexes are non electrolyte except complexes (6,7) and (1,11)
that have 1:1and 1:2 electrolytic nature, respectively.
5. The molar conductivity values for LII metal complexes show that all
complexes are non electrolyte except complex (8) and complex (11)
that have1:2 and 1:1 electrolytic nature, respectively.
6. IR spectral studies of both ligands LI, LII show that the ligands
exhibit interesting coordinating ability to the different metal ions
and behave as neutral quatridentate or bidentate one.
7. The electronic, EPR spectra and magnetic susceptibility
measurements proved that all LI metal complexes have distorted
octahedral geometry except Co(II), Cu(II) nitrate complexes and
Pd(II) chloride complex that adopt tetrahedral, square pyramidal
and square planar geometries, respectively.
8. Also, all LII complexes have distorted octahedral geometry except
Co(II) (chloride, acetate) and copper(II) nitrate complexes, that
adopt tetrahedral and square planar geometries, respectively.
9. The thermal behavior of both ligands LI, LII and their metal
complexes show good agreement with the formula suggested from
the analytical, spectral and magnetic data. The decomposition
temperature lies in the range (153-253°C) for LI complexes and
(117-287°C) for LII complexes.
10. Kinetic and thermodynamic activation parameters data for some
complexes indicate that the thermal decomposition of the
desolvated complexes follows first order kinetic and the
decomposition reactions are endothermic.
This part includes the pharmacological properties of the ligands LI,
LII and some of their corresponding metal complexes as anticancer agents,
toward human breast cancer cell lines (MCF-7) and human
hepatocarcinoma cells (HepG2). The results obtained show that:
1. The macrocyclic ligands and their tested metal complexes
(1,3,5,10,11) for LI and (1,4,6,11) for LII
, respectively are potent
anticancer agent.
2. The cytotoxicity of the tested complexes is higher than that of their
metal free ligands, which implies an increase in the antitumor
activity with coordination.