الفهرس | Only 14 pages are availabe for public view |
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. |