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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 (21 Tables) and represented in (62 Figures), (10 Schemes) as well as (161 References). The First Chapter: Introduction This chapter concerned with a scientific literature survey on dehydroacetic acid derivatives, pyrazolopyridine compounds and 2-thiobarbituric acid and their chelates as well as their biological activity.The Second Chapter: Experimental This part describes the preparation of Schiff base ligand (HL1), (Z)-3-(1- ((4,6-dimethyl-1H-pyrazolo[3,4-b]pyridin-3-yl)imino)ethyl)-4-hydroxy- 6-methyl-2H-pyran-2-one which is prepared from condensation of 4,6- dimethyl-1H-pyrazolo[3,4-b]pyridin-3-amine with dehydroacetic acid with (1:1) molar ratio. Also, it describes synthesis of azodye ligand (H3L2), (E)-5-((4,6-dimethyl-1H-pyrazolo[3,4-b]pyridin-3-yl)diazenyl)-2-thioxo dihydropyrimidine-4,6(1H,5H)-dione which is resulted from coupling of diazotization of 4,6-dimethyl-1H-pyrazolo[3,4-b]pyridin-3-amine with 2- thiobarbituric acid with (1:1) molar ratio. HL1 ligand reacts with Co(II), Pd(II), Fe(III) chloride and Cu(II) salts (chloride, bromide, sulphate and perchlorate) with different molar ratios. Also, (H3L2) ligand reacts with Co(II), Ni(II), Cu(II), Pd(II), Fe(III), Ru(III). The structure of ligands and their metal complexes were elucidated by elemental analyses, spectral techniques (IR, UV–Vis, 1H NMR, ESR, Xray diffraction and mass spectra for the ligands), magnetic susceptibility, molar conductivity and thermogravimetric studies. Finally, the biological activity (antioxidant and antibacterial) of the prepared ligands and some of their metal complexes was investigated. The Third Chapter: Results and Discussion This chapter concerned to discuss the obtained results illustrating the chemical formula, mode of bonding and geometrical structure for all systems. (I) Part (A) concerning Schiff base ligand )HL1( The date proved that: The complexes are formed with different stoichiometries (1:1), (1:2) and (2:3) (M:L). The ligand HL1 coordinates in Co(II), Cu(II), Pd(II) chloride and CuSO4 complexes as a monobasic tridentate ONN moiety via the oxygen atom of the deprotonated phenolic OH, the nitrogen atoms of the azomethine and the imine groups in pyrazolopyridine ring. While, it behaves as a neutral/monobasic bidentate in CuBr2, Cu(ClO4)2 and FeCl3 complexes, chelates via oxygen and nitrogen atoms of enolic OH and azomethine groups. The complexes separated from CuCl2, CuBr2 and FeCl3have octahedral structure. While, CoCl2 and CuSO4 complexes have triagonal bipyramidal and square pyramidal geometries, respectively. However, Cu(ClO4)2 and PdCl2 complexes have square planar structure. (II) Part (B) concerning azodye ligand (H3L2) The results showed that: The complexes derived from azodye ligand (H3L2) have mononuclear structure with (1M:2L) molar ratio for all complexes except Pd(II) complex has (1M:1L) molar ratio. The molar conductivity values reveal that all complexes have nonelectrolytic nature. The azodye ligand coordinated with all metal ions (except Fe(III) and Ru(III)) in neutral keto-thione form via oxygen and nitrogen atoms of thiobarbituric acid carbonyl and azo groups. But, in Fe(III) and Ru(III) complexes one of the ligands behaved as neutral bidentate in ketothione form and the other one acted as monobasic bidentate species. All complexes of H3L2 ligand have octahedral geometry except Pd(II) complex possess square planar structure. TG/DTG studies confirmed the chemical formula for all prepared metal complexes of HL1 and H3L2 ligands and established the thermal decomposition processes ended with the formation of metal or metal oxides contaminated with carbon residue. An axial electron spin resonance spectra were suggested for all prepared Cu(II) complexes pointing to 2B1g as a ground state. In vitro antibacterial and antioxidant activities were performed for HL1 and H3L2 ligands and some of its metal complexes. The biological studies indicate that CuBr2 and CuCl2 complexes has better antibacterial activity compared to the ligand and the other complexes. |