DNA Interaction and Catalytic Activity Studies of Some New Transition Metal Complexes of Schiff Bases Derived from Quinoxaline

In this thesis we report the synthsis and characterisation of new transition metal complexes of Pd(II),Cu(II),Ru(II) and Ir(III) of Schiff bases derived from quinoxaline-2-carboxaldehyde/3-hydroxyquinoxaline-2-carboxaldehyde and 5-aminoindazole.6-aminoindazole or 8-aminoquinoline.The complexes have been characterised by spectral and analytical data.Pd(II) and Cu(II) form square planar complexes and Ru(III) and Ir(III) form ctahedral complexes with these Schiff bases.The DNA binding properties of theses synthesised complexes have been studied by various methods including electronic absoption spectroscopy,cyclic voltammetry,different pulse voltammetry and circular dichroism spectra were used.Gel electrophoresis experiments were also performed to investigate the DNA cleavage of theses complexes.Furthermore Ru(III) and Ir(III) complexes find application as oxidation and hydogenation catalsts. The studies on catalytic activities has been presented.The metal complexes presented in this thesis assure significance as they contribute to the development of new DNA binding agents and antibacterial and anticancer drugs.

Spectral studies and crystal structures of some transition metal complexes of N4-substituted semicarbazones

The present work is concentrated on the studies of two novel semicarbazones, di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL1) and quinoline-2-carboxaldehyde-N4-phenyl-3-semicarbazone (HL2). The compositions of these semicarbazones were determined by the CHN analyses. For the characterization of these compounds we have used IR, UV and NMR spectral studies. The molecular structure of quinoline-2-carboxaldehyde-N4-phenyl-3- semicarbazone (HL2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Zn(II), Cd(II), Cu(II), Ni(II), Co(II) and Mn(II) complexes of these semicarbazones, HL1 and HL2. These complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some Zn(II) and Cd(II) compounds suitable for X-ray diffraction studies. For other complexes we could not isolate single crystals of good quality for single crystal X-ray diffraction studies.

Transition metal complexes of some bis(thiosemicarbazones) derived from 2,6-diacetylpyridine and N4-substituted thiosemicarbazides:Synthesis, spectral and structural studies

Coordination chemistry of pentadentate 2,6-diacetylpyridine bis(thiosemicarbazone) Schiff base ligands has been intensively studied due to the versatility of the molecular chain in order to obtain very different geometries as well as their broad therapeutic activity. Metal complexes of thiosemicarbazone with aldehydes and ketones have been widely reported. But there have been fewer reports on potential pentadentate bis(thiosemicarbazones) formed from 2,6-diacetylpyridine. Keeping these in view, we have synthesized four bis(thiosemicarbazone) systems with 2,6-diacetylpyridine. In the present work, the chelating behavior of bis(thiosemicarbazones) are studied, with the aim of investigating the influence of coordination exerts on their conformation and or configuration, in connection with the nature of the metal and of the counter ion. The selection of the 2,6-diacetylpyridine as the ketonic part was based on its capability to form polynuclear complexes with different coordination number. The doubled armed bis(thiosemicarbazones) can coordinate to a metal centre as dianionic ligand by losing its amide protons or it can coordinate as monoanionic ligand by losing its amide proton from one of the thiosemicarbazone moiety or it can also be coordinate as neutral ligand. Hence it is interesting to explore the coordinating capabilities of these ligands whether in neutral form or anionic form and to study the structural variations occurring in the ligands during complexation such as change in conformation.

Studies on Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Diaminonaphthalene

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.In the present study we have synthesized some new Mn(II),Co(II) and Cu(II) complexes of Schiff bases derived from 1,8-diaminonaphthalene.Even though we could not isolate theses Schiff bases (as they readily cyclise to form the perimidine compounds),we were able to characterize unequivacally the complexes synthesized from these compounds as complexes of Schiff Bases. We Synthesized three perimidine derivatives ,2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine,2-(2,3-dihydro-1H-perimidin-2-yl)-6-methoxyphenol and 4-(2,3-dihyro-1H-perimidin-2-yl)-2-methoxyphenol by the condensation of 1,8-diaminonaphthalene with quinoxaline-2-carboxaldehyde,2- hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively.Theses compounds were used as precursor ligands for the preparation of Schiff base complexes.The complexes were characterized by using elemental analysis ,conductance and magnetic susceptibility measuremets ,infrared and UV-Visible spectroscopy ,thermogravimetric analysis and EPR spectroscopy .We also encapsulated the complexes in zeolite Y matrix and these encapsulated complexes were also characterized. We have also tried theses complexes as catalysts in the oxidation of cyclohexanol and decomposition of hydrogen peroxide.

Studies on metal complexes of some tridentate acylhydrazones

Studies on transition metal complexes have achieved a great interest due to their versatile applications.The convenient route for synthesis,the nature of ligands and stability of metal complexes has significant contributions in their applications in medicine,biology,catalysis and photonics.The present work deals wth the synthesis and characterization of metal complexes of some tridentate acylhydrazones .Hydrazones are promising ligands in coordination chemistry with interesting binding modes and applications.The acylhydrazones chosen for the current study are capable of forming complexes in different forms through tautomerism.

Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Quinoxaline-2-Carboxaldehyde and Diamines: Biological and Catalytic Activity Studies

This thesis is mainly concerned with the synthesis and characterisation of new simple and zeolite encapsulated transition metal (manganese(II),nickel(II),and copper(II)complexes of quinoxaline based double Schiff base ligands.Theses ligands are N,N'-bis(quinoxaline-2-carboxalidene)hydrazine,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminoethane,N,N'-bis(quinoxaline-2-carboxalidene)-1,3-diamonopropane,N,N'-bis(quinoxaline-2-carboxalidene)-1,4-diaminobutane,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminocyclohexane and N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminobenzene.The Schiff base ligands have been characterised by spectral and single crystal XRD studies.Theses ligands provide great structural diversity during complexation.Mn(II) and Ni(II) form octahedral with these Schiff bases,whereas Cu(II) forms both octahedral and tetrahedral complexes.Studies on the biological and Catalytic activity of the copper(ll) complexes are also presented in this thesis.

Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The unusual coordination modes of semicarbazones when bound to metals, the wide applications and structural diversity of metal complexes of semicarbazones provoked us to synthesize and characterize the tridentate ONO and NNO-donor semicarbazones and their transition metal complexes. This work is focused on the studies on complexes of three N4-phenylsemicarbazones synthesized by changing the carbonyl compounds. This work is concerned with the studies of two new semicarbazones, 2- formylpyridine-N4-phenylsemicarbazone (HL1) and 3-ethoxysalicylaldehyde- N4-phenylsemicarbazone (H2L2) and a reported semicarbazone 2-benzoylpyridine-N4-phenylsemicarbazone (HL3) [29]. The compositions of these semicarbazones were determined by the CHN analyses and IR, UV and NMR spectral studies were used for the characterization of these compounds. The molecular structure of 3-ethoxysalicylaldehyde-N4-phenylsemicarbazone (H2L2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Cu(II), Cd(II), Zn(II) and Ni(II) complexes of these three semicarbazones. The complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some complexes of all metals suitable for X-ray diffraction studies. This thesis is divided into six chapters.

Ligation properties of N4-phenylsemicarbazones towards transition metals: Synthesis and spectral studies

Semicarbazones and their transition metal complexes have been receiving considerable attention because of their biological relevance and applications in the field of analysis and in the field of organic NLO materials. Their structural diversity also attracted inorganic chemists. A good deal of work has been reported on the synthesis and structural investigation of semicarbazones and their complexes. This is due partially to their capability of acting as multidentate, NO, NNO, ONO and ONNO donors with the formation of either mono or bi or polynuclear complexes. Their chemistry and pharmacological applications have been extensively investigated. Appreciable biological applications as well as diverse stereochemistry of their metal complexes prompted us to synthesize two new tridentate ONO donor N4-phenyl semicarbazones derived from 2-hydroxy-4-methoxyacetophenone and 2-hydroxy-4-methoxybenzophenone and their transition metal complexes. These ketones were selected since they can provide a further binding site from phenolic–OH and can thus increase the denticity. Introduction of heterocyclic bases like 1,10-phenanthroline, 2,2′-bipyridine, 4,4′-dimethyl- 2,2′-bipyridine and 4-picoline and some pseudohalides like azide and thiocyanate ion can result in mixed ligand metal chelates with different geometries in coordination compounds In the present study, oxovanadium(IV), manganese(II), cobalt (II/III), nickel(II), copper(II) and zinc(II) complexes of 2-hydroxy-4- methoxyacetophenone-N4-phenylsemicarbazone (H2ASC) and 2-hydroxy-4- methoxybenzophenone-N4-phenylsemicarbazone (H2BSC) were synthesized and characterized.

Waste Water Treatment Using Low Cost Natural Adsorbents

Heavy metals are major toxic pollutants with severe health effects on humans. They are released into the environment from a variety of industrial activities. Cadmium, lead, zinc, chromium and copper are the most toxic metals of widespread use in industries such as tanning, electroplating, electronic equipment manufacturing and chemical processing plants. Heavy metals contribute to a variety of adverse health environmental effects due to their acute and chronic exposure through air, water and food chain. Conventional treatment methods of metal removal are often limited by their cost and ineffectiveness at low concentrations. Adsorption, the use of inactivated biomass as adsorbents offers an attractive potential alternative to their conventional methods. Mango peel and Alisma plantago aquatica are naturally occurring and abundant biomass can offer an economical solution for metal removal.The Cd(II), Pb(II), Zn(II), Cr(III) and Cu(II) adsorption by milled adsorbents of mango peel and Alisma plantago aquatica were evaluated in batches.

Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

Eight new transition metal complexes of benzaldehyde-N(4)–phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL)2(OAc)2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL)2(OAc)2] in DMF solution at 77K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL)2SO4] complex in frozen DMF, indicate the presence of unpaired electron in the dx2−y2 orbital. The metal ligand bonding parameters evaluated showed strong in-plane bonding and in-plane bonding. The ligand and complexes were screened for their possible antimicrobial activities.