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العنوان
Synthesis, characterization and application on
some azo-pyrimidine metal complexes /
المؤلف
Hamad, Amira Mohammed Hussien.
هيئة الاعداد
باحث / أميرة محمد حسين حماد
مشرف / سعيدة ابو الثنا ابو العينين
مشرف / مها عبدالمجيد خضر
مشرف / فاطمة اب ا رهيم أبو ا زيد
الموضوع
heavy metals - pyrimidine derivatives. Chemistry. Physical Chemistry.
تاريخ النشر
2021.
عدد الصفحات
150 p. :
اللغة
الإنجليزية
الدرجة
ماجستير
التخصص
Physical and Theoretical Chemistry
تاريخ الإجازة
13/11/2021
مكان الإجازة
جامعة المنوفية - كلية العلوم - كيمياء فيزيائية
الفهرس
Only 14 pages are availabe for public view

from 150

from 150

Abstract

The current thesis consists of three main general chapters in addition to summaries in both Arabic and English. The data are compiled in (22 Tables) and represented in (39 Figures), (9 Schemes) as well as (128 References).
The First Chapter: Introduction
This chapter is concerned with a literature survey on azodye compounds containing barbituric acid and thiobarbituric acid metal complexes and their biological activity. Also, contains simple information about naphthalene derivatives and their metal complexes.
The Second Chapter: Experimental
This part illustrates the preparation of azodye ligand: 5-[5-(4,6-Dioxo-2-thioxo-hexahydro-pyrimidin-5-ylazo)- naphthalen-1-ylazo]-2-mercapto-1H-pyrimidine-4,6-dione (H4L1) ligand and ,5(2-Oxidaneylidene)-4,6-dioxohexahydropyrimidine-5-Yl)diazenyl)naphthalene-1-Yl)diazenyl)-2-hydroxypyrimidine-4,6(1H,5H)-dione (H4L2) those were resulted from the diazotization coupling of naphthalene 1,5 diaminne with thiobarbituric acid and and barbituric acid with (1:2) molar ratio, respectively. Also, their Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Fe(III) and Sm(III) metal complexes were synthesized. Different physicochemical techniques were used for elucidation the structure of ligands and their metal complexes as elemental analyses, spectral tools (1H NMR, IR, UV–Vis and mass spectra), magnetic susceptibility, molar conductivity and thermogravimetric studies. Finally. The biological activity (antitumor and antioxidant) of the synthesized ligands and some of their metal complexes were tested.
The Third Chapter: Results and Discussion
This chapter interested in discussion of the obtained results to arrive to the chemical formula, geometrical structure and mode of bonding for all systems. The date confirmed that:
(I) All (H4L1) and (H4L2) have binuclear structure with (2M:1L) molar ratio except Sm(III) complex of (H4L2) ligand has trinuclear structure. The molar conductivity proved that (H4L1) complexes have non-electrolytic character nature, while (H4L2) complexes have 1:2 electrolytic nature except Sm(III) complex has non-electrolyte nature .
(II) IR spectra showed that (H4L1) and (H4L2) ligands coordinated with all metal ions in neutral keto-thiol-thione and keto-enol forms, respectively.
(H4L1) ligand reacted as tridentate (SNO) with Mn(II) and Cu(II) ions through donor atoms of thiol sulphur, imine nitrogen and carbonyl C=O oxygen atoms of thiobarbituric moiety. However, it behaves as bidentate and (NO) coordinated with Ni(II) and Zn(II) ions through nitrogen atom of imine and oxygen atom of carbonyl (C=O) groups. Also, it bonded with Fe(III) and Co(II) ions through thiol sulphur and carbonyl (C=O) oxygen atoms. The azo group not participated in chelation. The octahedral geometry was considered for all complexes, except for Co(II) and Ni(II) complexes which have a tetrahedral structure.
(H4L2) ligand reacted with Ni(II) and Zn(II) ions as tridentate through carbonyl oxygen atom, enolic oxygen atom and nitrogen atom of imide group, while in case of Co(II) and Cu(II) complexes it behaved as bidentate and coordinated with two metal ions through enol oxygen atoms and imide nitrogen atoms. However, in case of Sm(III), two Sm(III) atoms binded with each side of ligand with enolic oxygen atom, imide nitrogen atom and carbonyl oxygen atom, while the third Sm(III) atom attached with azo nitrogen atom and carbonyl oxygen atom at one side of ligand. The square planar geometry was proposed for Co(III) and Cu(II) complexes and square pyramidal structure was ascertained for Ni(II) and Zn(II) complexes.
(III) The thermal decomposition behavior of all systems was studied depended on thermogravimetric analysis. The thermal decomposition process of all complexes ended with the formation of (metal oxide contaminated with carbon. The thermal stability of complexes was controlled by the metal ion and number/type of the crystallizing solvent.
The thermodynamic parameters, such as activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and Gibbs free energy (ΔG*) have been calculated using DTG curves.
(IV) The biological activity (cytotoxic and antioxidant) of the two ligands and their metal complexes were tested in vitro. The results showed that the coordinated compounds displayed higher activity rather than its particular free ligand. This was explained by ”chelation theory”