Studies on some Metal Complexes of Dithio Ligands

The thesis deals with our studies on the synthesis and elucidation of structure of some metal complexes of dithio ligands, such as the dithiocarbamates, xanthates and 2-aminocyclopent-1-ene-1-dithiocarboxylate and its N-alkyl derivatives.2-Aminocyclopent-1-ene-1-dithiocarboxylate (ACDA) is an interesting ligand, because of its potential dual capability of bonding between the metal and the ligand. Since the earlier reports on the complexes of ACDA contain contradictory ideas on the nature of its bonding, it was thought worthwhile to undertake a detailed and systematic study of these type of complexes. As the ACDA complexes have very low solubilities in solvents like chloroform, we have used the isopropyl derivative of ACDA as the ligand. The increased solubility of these complexes have made it possible to investigate their NMR and solution electronic spectra.The complexes of this ligand have not yet been reported in the literature.We have synthesised some new mixed ligand complexes of dithiocarbamates by reacting bis(dithiocarbamato)-µ-dichloro dicopper complexes (obtained by the reaction of mixed benzoic dithiocarbamic anhydride and copper(II) chloride) with ACDA or its N-alkyl derivatives.Interactions of metal halides with the mixed anhydrides formed from benzoylchloride and xanthates have also been investigated. Novel complexes of the type, [Cu2(RXant)CI] (R=i-Bu, i-Pr, n-Bu or n-Pr)) have been isolated from the reaction of copper(II) chloride and the mixed anhydride, and these reactions appear to be like the clock reactions reported in the literature.It also deal with the characterisation of the complexes of the type [Hg(R2d t c )X] (X=Cl, Br or 1),[Cu3(R2dtc)6][Cu2Br6] and [Cu(R2dtc)Cl2](R2=Me2,Et2,Pip,Morph or Pyrr)respectively, synthesised by simple and novel routes, different from those reported earlier.

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.

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.

Synthesis and spectral investigations of vanadium(IV/V) complexes derived from an ONS donor thiosemicarbazone ligand

Four oxovanadium and one dioxovanadium complex with 2-hydroxyacetophenone N(4)- phenylthiosemicarbazone (H2L) which are represented as [VOLphen]·2H2O (1), [VOLbipy] (2), [VOLdmbipy] (3), [VOL]2 (4) and [VO2HL]·CH3OH (5) have been synthesized and characterized by elemental analyses, electronic, infrared and EPR spectral techniques. In all the complexes 1–4 the ligand coordinates through phenolic oxygen, azomethine nitrogen and thiolate sulfur. But in complex [VO2HL]·CH3OH, coordination takes place in thione form instead of thiolate sulfur. All the complexes except [VO2HL]·CH3OH are EPR active due to the presence of an unpaired electron. In frozen DMF at 77 K, all the oxovanadium(IV) complexes show axial anisotropy with two sets of eight line patterns

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors

Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene

Co(II), Ni(II) and Cu(II) complexes of dimethylglyoxime and N,N-ethylenebis(7-methylsalicylideneamine) have been synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. The hybrid materials obtained have been characterized by elemental analysis, SEM, XRD, surface area, pore volume, magnetic moment, FTIR, UV-Vis and EPR techniques. Analysis of data indicates the formation of complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activities for hydrogen peroxide decomposition and oxidation of benzyl alcohol and ethylbenzene of zeolite complexes are reported. Zeolite Cu(II) complexes were found to be more active than the corresponding Co(II) and Ni(II) complexes for oxidation reactions. The catalytic properties of the complexes are influenced by their geometry and by the steric environment of the active sites. Zeolite complexes are stable enough to be reused and are suitable to be utilized as partial oxidation catalysts.

Studies on Some Transition Metal Complexes of Schiff Bases Derived from Quinoxaline-2-carboxaldehyde

Two series of transition metal complexes of Schiff bases derived from quinoxaline-2-carboxaldehyde with semicarbazide (QSC) and furfurylamine (QFA) were synthesised and characterised by elemental analyses, molar conductance and magnetic susceptibility measurements, IR, electronic and EPR spectral studies. The QSC complexes have the general formula [M(QSC)Cl2]. A tetrahedral structure has been assigned for the Mn(II), Co(II) and Ni(II) complexes and a square-planar structure for the Cu(II) complex. The QFA complexes have the formula [M(QFA)2Cl2]. An octahedral structure has been assigned for these complexes. All of the complexes exhibit catalytic activity towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) to 3,5-di-tert-butylquinone (DTBQ) using atmospheric oxygen. The cobalt(II) complex of the ligand QFA was found to be the most active catalyst.

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

Synthesis and Spectral Characterization of Lanthanide Complexes with Sulfamethoxazole and Their Antibacterial Activity

A series of nonelectrolytic lanthanide(III) complexes, [ ML 2 Cl 3 ] · 2 H 2 O, where M is lanthanum(III), praseodymium(III), neodymium(III), samarium(III), gadolinium(III), terbium(III), dysprosium(III), and yttrium(III), containing sulfamethoxazole ligand (L) are prepared. The structure and bonding of the ligand are studied by elemental analysis, magnetic susceptibility measurements, IR, 1 H NMR, TG / DTA , X-ray diffraction studies, and electronic spectra of the complexes. The stereochemistry around the metal ions is a monocapped trigonal prism in which four of the coordination sites are occupied by two each from two chelating ligands, sulfonyl oxygen, and nitrogen of the amide group and the remaining three positions are occupied by three chlorines. The ligand and the new complexes were tested in vitro to evaluate their activity against the bacteria Escherichia coli and Staphylococcus aureus.

Structural and spectral studies of novel Co(III) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde

Seven bis(ligand) Co(III) complexes {[CoL21] NO3 · H2 O (1), [CoL21] Cl · 2 H2 O (2),[CoL21] ClO4 (3), [CoL22] NO3 (4), [CoL22] Cl · 2 H2 O (5), [CoL23] Br · 2 H2 O (6), [CoL23] ClO4 · H2 O (7)} of three thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenylethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde-N(4)-(methyl),N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. All complexes are assigned octahedral geometries on the basis of spectral studies. The ligands deprotonate and coordinate by means of pyridine nitrogen, azomethine nitrogen, and thiolate sulfur atoms. The single crystal X-ray structures of HL3 and two nitrate compounds are discussed. The structural studies corroborate the spectral characterization.

Spectral and structural studies of mono- and binuclear copper(II) complexes of salicylaldehyde N(4)-substituted thiosemicarbazones

Three copper(II) complexes of salicylaldehyde N(4)-phenyl thiosemicarbazone (H2L1) and two copper(II) complexes of N(4)-cyclohexyl thiosemicarbazone (H2L2) have been synthesized and characterized by different physicochemical techniques like magnetic studies and electronic, infrared and EPR spectral studies. The complexes View the MathML source and [(CuL2)2] (4) having dimeric structure. The thiosemicarbazones bind to the metal as dianionic ONS donor ligand in all the complexes, except in the complex [Cu(HL1)2] · H2O (2). In complex 2, the ligand moieties are coordinated as monoanionic (HL−) ones. Two of the complexes [CuL1dmbipy] · H2O (3) and [CuL2dmbipy] (5) have been found to possess the stoichiometry [CuLB], where B = 4,4′-dimethyl-2,2′-bipyridine (dmbipy). The coordination geometry around copper(II) in 5 is trigonal bipyramidal distorted square based pyramidal (TBDSBP), as obtained by 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.

Transition Metal Complexes with Ring Incorporated Thiosemicarbazones: Syntheses,Structures and Spectral Properties

In the present work,the chelating behaviour of thiosemicarbazones of a heterocyclic diketone, 2,6-diacetylpyridine is studied,with the aim of investigating the influence coordination exerts on their conformation and /or configuration, in connection with the nature of the metal and of the counter ion.The various possibilities like unsubstitution,ring incorporation at terminal nitrogen and condensation of one of the ketone group alone have been tried for ligand selection.Mainly first row transition metals like manganese,iron,nickel,copper,zinc and cadmium are studied.Metals like cobalt also were studied but could not result in fruitful isolation of the compound due to solubility problems.Different spectroscopic and characterization techniques have been utilized to reveal the nature of the metal and the ligands in coordinated metal complex.