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العنوان
Synthesis, Structural characterization and Biological
Evaluation of Novel Metal Complexes Containing
Azamacrocyclic Ligands /
المؤلف
El-Gammal, Ohylla Ahmed Abd-Elatif.
هيئة الاعداد
باحث / اهيلة احمد عبد اللطيف الجواد
مشرف / ابراهيم الطنطاوي السيد
مناقش / خالذ صلاح ابو شربينى
مناقش / هناء عبداللطيف البرعى
الموضوع
Spectrum analysis. Chemistry, Physical and theoretical.
تاريخ النشر
2015.
عدد الصفحات
ill. ;
اللغة
الإنجليزية
الدرجة
الدكتوراه
التخصص
Analytical Chemistry
الناشر
تاريخ الإجازة
6/5/2015
مكان الإجازة
جامعة المنوفية - كلية العلوم - الكيمياء
الفهرس
Only 14 pages are availabe for public view

from 215

from 215

Abstract

The present thesis comprises three main chapters in addition to arabic and english summaries as well as relevant references.
The First Chapter: Introduction
This chapter includes a scientific literature survey related to macrocycles and their coordination compounds regarding their types, design, synthesis, stability of their metal complexes and their chemical and biochemical importance.
The Second Chapter: Experimental
This chapter includes:
1- A detailed method for synthesis of the starting material (A) from the reaction of isatoic anhydride and 1,8-diaminonaphalene.
2- A detailed method for synthesis the novel tetraaza-15-membered macrocyclic ligand and its corresponding macrocyclic metal complexes with different Fe(III), Co(II), Ni(II), Cu(II), Ru(III), and Pd(II) ions.
3- The template synthesis of the novel tetraaza-16-membered macrocyclic Fe(III), Co(II), Ni(II), Cu(II) and Pd(II) metal complexes of 2-amino-N-[2-(2-amino-benzoylamino)-naphthyl]-benzamide (A) and 1-benzoylacetone.
4- Different standardized instruments were used for characterization of the structure of the prepared compounds as spectral {1H NMR, UV-Vis, mass (MS), IR and EPR} methods, magnetic susceptibility, molar conductivity measurements and thermal technique (TG/DTG).
The Third Chapter: Results and Discussion
This chapter covers the results obtained and their discussion and comprises three main parts:
Part I
The novel 15-membered (N4) macrocyclic ligand obtained from cyclization reaction of diethyloxalate and 2-amino-N-[2-(2-amino-benzoylamino)-naphthyl]-benzamide (A) as well as its tetraaza-15-membered macrocyclic Fe(II), Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) complexes have been prepared. Their structure has been inferred through different analytical and spectral methods. The thermal behavior of the investigated complexes has also been studied. The kinetic and thermodynamic activation parameters of decomposition processes, namely activation energy (ΔE*), enthalpy (ΔH*), entropy (ΔS*), and Gibbs free energy (ΔG*), were evaluated graphically from TG curve by employing the Coats-Redferm relation. The results obtained can be summarized as follows:
1. The analytical and spectral data (IR, mass (MS) and 1H NMR) confirm the formation of the macrocyclic ligand (L).
2. The results of elemental analyses show that all complexes present in 1L:1M molar ratio.
3. The ligand and its complexes are air stable, non-hygroscopic and partially soluble in common organic or mixed solvents; they are soluble in polar solvents such as DMF/DMSO.
4. The molar conductivity value for all complexes indicates that they are non-electrolytes.
5. The IR spectra show that the ligand (L) behaves as a neutral quatridentate one in complexes (1-5,7,8), binding to the M(II) via four amide nitrogens, while in complexes (6,9-12) the ligand behaves as a bidentate one with the electron pairs of two amide nitrogen atoms only.
6. On the basis of electronic, EPR spectra and magnetic susceptibility measurements distorted octahedral geometry has been proposed for complexes (1-5,7,8) , while complexes (6,9-12) have distorted square planar geometry.
7. The thermal behavior of the ligand and its complexes show good agreement with the formula suggested from the analytical, spectral and magnetic data.
8. 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.
Part II
In this part, the template condensation reaction of 1-benzoylacetone with compound (A) in presence of transition metal ions gives new type of 16-membered N4 macrocyclic complexes. Their structures were investigated by different analytical and spectral methods. The thermal behavior of the investigated complexes has also been studied, kinetic and thermodynamic activation parameters for decomposition reaction for some complexes were determined. The results obtained can be summarized as follows:
1. The results of elemental analyses show that all the macrocyclic complexes are found in 1L:1M molar ratio.
2. The complexes are air stable, non-hygroscopic and partially soluble in common organic or mixed solvents; they are soluble in polar solvents such as DMF/DMSO.
3. The molar conductivity value indicates that complexes (1-4, 6-8) are non-electrolytes, and complexes (5,9-11) are 1:1 electrolyte.
4. The IR spectra show that the ligand behaves as neutral quatridentate one in all complexes, except complex (11), binds to the M(II) via two amide and two imine nitrogens. In complex (11) it behaves as neutral bidentate one with the electron pairs of two imine nitrogen atoms only.
5. The electronic, EPR spectra and magnetic susceptibility measurements show that all complexes have distorted octahedral geometry, while complex (9) has square pyramidal structure and complex (11) has square planar geometry.
6. The thermal studies of the macrocyclic metal complexes confirmed their suggested structures.
7. Kinetic and thermodynamic activation parameters data for some complexes indicate that the thermal decomposition of the desolvated complexes is endothermic and follows first order kinetic.
Part III
This part includes the pharmacological properties of some of the obtained compounds against two tumor cell lines as anticancer agents. The results obtained show that:
1. The 15-membered N4 macrocyclic ligand L and its tested complexes are potent anticancer agents.
2. The measured cytotoxicity of the studied complexes is higher than that of their macrocyclic ligand, which implies an increase in the antitumor activity with coordination.
3. Also, the 16-membered N4 macrocyclic metal complexes are potent anticancer agents.