Structure and spectral characterisation of copper(II) meclofenamate complexes

The synthesis and characterisation of Cu(meclof)₂H₂O and Cu(meclof)₂L₂ (meclof = meclofenamate; L = 2-pyridylcarbinol (2-pyca), 3-pyridylcarbinol (3-pyca), nicotinamide (na), N,N-diethylnicotinamide (dena) are reported. The characterisation of the compounds were based on elemental analyses, electronic, IR and EPR spectra. The carboxyl group of the meclofenamate anions coordinates to the Cu(II) atom as an unidentate or as a chelating ligand. The crystal and molecular structures of one of the products, namely Cu(meclof)₂(2-pyca)₂ were measured. The EPR spectra of the studied complexes show they are monomeric, except for Cu(meclof)₂ · H₂O which shows triplet state feature. On the basis of the spectroscopic parameters observed, a monomeric structure with a tetragonally Jahn–Teller distorted octahedron around the Cu(II) atom is deduced for Cu(meclof)₂L₂ and for Cu(meclof)₂ · H₂O a dimeric structure is proposed. The degree of distortion in the series of the Cu(meclof)₂L₂ complexes increases in the order of L: na < 2-pyca < 3-pyca < dena.     

Synthesis,characterization and biological applications of new copper(II) complexes of aryl hydrazones

On treatment of copper(II) acetate with aryl hydrazone ligands, four new solid derivatives of copper(II) were produced in appreciable yields. Various characterization techniques including infrared, UV–visible, NMR, electron paramagnetic resonance and mass spectroscopies, elemental analysis, scanning electron microscopy, powder X‐ray diffraction and thermogravimetric analysis revealed a tetra‐coordination in all the mononuclear crystalline complexes with high thermal stability. Further, significant interaction of these novel complexes with calf thymus DNA via intercalative mode of binding was revealed by electronic absorption spectroscopy. The chemical nuclease activity of the complexes on pBR322 DNA was investigated in the presence and absence of oxidizing agent (H₂O₂). A potent nuclease activity was observed only in the presence of H₂O₂. Further, antibacterial and antifungal studies of the new ligands and complexes revealed that the latter possessed comparatively better activity.     

Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones

This paper describes the preparation of [Cu(bh)(2)(H(2)O)(2)](NO(3))(2)], [Cu(ibh)(2)(NO(3))(2)], [Cu(ibh)(2)(H(2)O)(2)](NO(3))(2) and [Cu(iinh)(2)(NO(3))(2)] (bh=benzoyl hydrazine (C(6)H(5)CONHNH(2)); ibh=isonicotinoyl hydrazine (NC(5)H(4)CONHNH(2)); ibh=isopropanone benzoyl hydrazone (C(6)H(5)CONHN=C(CH(3))(2); iinh=isopropanone isonicotinoyl hydrazone (NC(5)H(4)CONHN=C(CH(3))(2)). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77K in DMSO solution. The trend g(||)>g( perpendicular)>g(e,) observed in all the complexes suggests the presence of an unpaired electron in the [Formula: see text] orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >CO and NH(2) groups whereas, ibh and iinh bond through >CO and >CN groups. The IR spectra of bh and ibh complexes also show HOH stretching and bending modes of coordinated water.     

Magnetic properties of copper(II) complexes with some hydrazones of substituted salicylaldehydes

A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H₂L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO₄)(CH₃OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment.     

New complexes of Ni(II) and Cu(II) with Schiff bases functionalised with 1,3,4-thiadiazole: spectral,magnetic, biological and thermal characterisation

Schiff bases obtained by the condensation of 2-amino-5-mercapto-1,3,4-thiadiazole with 2,4-pentandione or 1-phenyl-1,3-butandione were synthesized and characterized in order to obtain polydentate ligands HL¹ and HL², respectively. The complexes with these ligands of the type M(L)Cl·nH₂O [(1) M:Ni, L:L¹, n = 0.5; (3) M:Ni, L:L², n = 0.5]; [(2) M:Cu, L:L¹, n = 1; (4) M:Cu, L:L², n = 0] were also synthesized and characterized. The modifications evidenced in IR spectra of complexes were correlated with the presence of monodeprotonate Schiff bases. The electronic spectra display the characteristic pattern of square-planar stereochemistry. The in vitro qualitative and quantitative antimicrobial activity assays showed that the new complexes exhibited variable antimicrobial activity. The thermal analyses have evidenced the thermal intervals of stability and also the thermodynamic effects that accompany them. Schiff bases and complexes have a similar thermal behaviour. Processes as water elimination, melting, chloride anion removal as well as oxidative degradation of the organic ligands were observed.     

Novel copper(II) homobinuclear macrocyclic complexes: cyclic voltammetry, biological properties and spectral studies

A series of five new copper(II) macrocyclic complexes have been synthesized by template condensation. The bonding and stereochemistry of the complexes have been characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, UV-visible, EPR spectral studies and electrochemical properties. g-Values are calculated for all of the complexes in polycrystalline form as well as in DMSO solution. The magnetic and spectral data indicate square planar geometry for all the complexes. Cyclic voltammograms for all the complexes are similar and involve two quasi-reversible redox processes. Cu(II)Cu(II)<=>Cu(II)Cu(I)<=>Cu(I)Cu(I). Their biological properties have also been studied. The macrocyclic complexes show more anti-bacterial than controlled one. The anti-bacterial activities of the compounds were tested against Streptococcus fecalis and Escherichia coli with different concentrations.     

Equilibrium and spectral studies of putrescine complexes with copper(II)

Summary It has been found that in the putrescine-copper system several types of complex compounds (MHL,ML,ML ₂,ML ₂OH) are formed. In thepH range of 7–9, despite a multiple excess of ligand, a precipitation occurs. When adenosine is introduced to the system, the ability to observe the complexation reaction in solution is largely increased, because the additional ligand prevents precipitation. On the basis of computer analysis of potentiometric titration data the stability constants of the compounds have been determined. The coordination mode of the complexes is discussed.

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Gleichgewichte und spektroskopische Untersuchungen an Putrescin-Komplexen mit Kupfer(II)

Zusammenfassung Es wurde festgestellt, daß sich im Putrescin-Kupfer System einige Typen von Komplexen bilden (MHL,ML,ML ₂ andML ₂OH). ImpH-Bereich von 7–9 tritt trotz eines mehrfachen Ligandenüberschusses ein Niederschlag auf. Bei Einführung von Adenosin in das System wird die Beobachtbarkeit der Komplexreaktion verbessert, da der zusätzliche Ligand die Niederschlagsbildung verhindert. Mittels Computeranalyse der potentiometrischen Titrationsdaten wurden die Stabilitätskonstanten der Verbindungen ermittelt. Die Art der Komplexierung wird ebenfalls diskutiert.

     

Thermal and spectral studies of palladium(II) complexes

Palladium(II) complexes of type [Pd(L)Cl₂] [where L=2-aminopyridine-N-thiohydrazide (L¹), (2-aminopyridine-N-thio)-1,3-propanediamine (L²), benzaldehyde 2-aminopyridine-N-thiohydrazone (L³) and salicylaldehyde-2-aminopyridine-N-thiohydrazone (L⁴)] have been synthesized. The thiohydrazide, thiodiamine and thiohydrazones can exist as thione-thiol tautomer and coordinate as a bidentate N-S ligand. The ligands found to act in bidentate fashion. The complexes have been characterized by elemental analysis, IR, mass, electronic, ¹H NMR spectroscopic studies, and TG/DTA study. Antifungal studies of some complexes were also carried out. Various kinetic and thermodynamic parameters like order of reaction (n), activation energy (E _a), apparent activation entropy (S ^# ) and heat of reaction (ΔH) have also been carried out for one complex.     

Thermal and spectral properties of halogenosalicylato-Cu(II) complexes

The paper presents the applicability of oxyreactive thermal analysis (OTA) for the investigation of different kinds of resins both natural (recent and fossil) and synthetic. For comparative reasons and a more precise interpretation, along with OTA infrared spectroscopy was used as a method commonly applied for the investigation of fossil resins. The results obtained prove that the OTA method may be very useful for diversification of different kinds of resins. The parameter most valuable for the preliminary characteristics of resins and the evaluation of their transformation was found to be the mass loss recorded on TG curves in three definite temperature ranges. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthetic, spectral and solution studies on imidazolate-bridged copper(II)-copper(II) and copper(II)-zinc(II) complexes

Synthesis, spectral and solution studies on 2-ethyl imidazolate-bridged (2-EtIm) homo-binuclear copper(II)-copper(II) and hetero-binuclear copper(II)-zinc(II) homologue are described. Magnetic moment values of homo-binuclear complexes indicate that the imidazolate group can mediate antiferromagnetic interactions. Optical spectra of hetero-binuclear complex at varying pH values suggest that the imidazolate-bridged complex is stable over the pH-range 7.15–10.0.     

Preparation and characterisation of copper(II) complexes with bis(1-pyrazolyl)propane

Summary The synthesis and characterisation of the coordination compounds of some copper(II) salts with bis (1-pyrazolyl)propane, Me₂Cpz₂, are reported. Coloured stable solid complexes of the type Cu(Me₂Cpz₂) X₂(X = Cl^–, Br^– or AcO^–), Cu(Me₂Cpz₂)(ClO₄)₂ · H₂O, [Cu(Me₂Cpz₂)SO₄ · 2 H₂O] · H₂O and [Cu(Me₂Cpz₂)₂X]X (X = NO ₃ ^– or ClO ₄ ^– ) have been isolated and characterised by elemental analysis, electronic, i.r. and magnetic measurements. Probable structures of the complexes are discussed on the basis of their spectral data.     

Thermal behaviour of hydrated copper(II) complexes

Dehydration steps of aquacopper(II) complexes with homogeneous and heterogeneous coordination sphere are investigated from the view point of structural changes taking place under their heating to the decomposition temperature and during the dehydration. The role of loosening of intra-and intermolecular hydrogen bonds in the decomposition reaction for the structure changes of the remainder, the structural presumptions of the reactants for lower hydrates formation are discussed. Activation parameters of dehydration were found to be the lower, the smaller are the structure differences between the reactants and products. They do not reflect the bond length central atomvolatile ligand, much more the overall structure differences between the starting and resulting compounds. From all data on crystal and molecular structures of dehydrated compounds is the reaction pathway best indicated by anisotropic temperature parameters of donor atoms corrected for the thermal movement of the central atom: the higher these values in the bond direction are, the lower the values of activation energies of dehydration are.     

Copper(II) and zinc(II) complexes with 2-formylpyridine-derived hydrazones

In the present work 2-formylpyridine-para-chloro-phenyl hydrazone (H2FopClPh) and 2-formylpyridine-para-nitro-phenyl hydrazone (H2FopNO₂Ph) were obtained, as well as their copper(II) and zinc(II) complexes [Cu(H2FopClPh)Cl₂] (1), [Cu(2FopNO₂Ph)Cl] (2), [Zn(H2FopClPh)Cl₂] (3) and [Zn(H2FopNO₂Ph)Cl₂] (4). Upon re-crystallization in DMSO:acetone conversion of 2 into [Cu(2FopNO₂Ph)Cl(DMSO)] (2a) and of 4 into [Zn(2FopNO₂Ph)Cl(DMSO)] (4a) occurred. The crystal structures of 1, 2a, 3 and 4a were determined.     

Thermal,spectral and biological properties of Zn(II) complex compounds with phenazone

The thermal decomposition of the complexes Zn(form)₂⋅2phen (I), Zn(ac)₂⋅2phen (II), Zn(prop)₂⋅2phen (III), Zn(but)₂⋅2phen (IV), where phen=phenazone, form=formiate, ac=acetate, prop=propionate, but=butyrate has been studied in air by TG/DTG and DTA methods. The possible mechanism of the thermal decomposition was proposed. The final product of thermal decomposition was ZnO. IR data show unidentate coordination of carboxylate group to Zn(II) ion. The complexes were tested against various strains of microorganisms and their efficiency decrease in the sequence yeasts >bacteria>filamentous fungi.     

Synthesis,characterisation, crystal structure and biological activity of metal(II) complexes with theophylline

Three metal complexes with empirical formulae [Mn(theop)₂(H₂O)₄] (1), [Co(theop)₂(H₂O)₄] (2), [Ni(theop)₂(H₂O)₄] (3), (where: theop?=?theophylline) were synthesized and characterized by elemental analysis, FTIR- spectroscopy and thermal decomposition techniques. Their crystal structures were determined by single crystal Xray diffraction analysis. Complexes are isomorphous and crystallise in the monocyclic space group P21/c. Their thermal behavior was studied by TGA methods under non-isothermal condition in air. Upon heating all compounds decompose progressively to metal oxides, which are the final products of pyrolysis. Furthermore, antimicrobial and antioxidant activity of the complexes was examined.     

Synthesis and spectral studies of copper(II) complexes with amide group ligands

Complexes of copper(II) with 2-(acetylamino)benzoic acid, 2-(benzoylamino) benzoic acid, 2-(aminocarbonyl)benzoic acid, 2-[(phenylamino)carbonyl]benzoic acid, 2-[(1-naphthalenylamino)carbonyl]benzoic acid, 2-[(2-aminophenylamino)carbonyl]benzoic acid, 2-aminobenzanilide, 2(aminobenzoyl)benzoic acid, maleanilic acid and malea-1-naphthalanilic acid have been prepared and characterized by chemical analyses, molar conductivity, magnetic susceptibility measurements, thermal data, IR, electronic and ESR spectra. The visible and ESR spectral studies of these complexes (except those of maleanilic acid and malea-1-naphthalanilic acid) indicate that they are monomeric having either square planar or distorted octahedral geometry around Cu(II). The Cu(II) complexes of maleanilic acid and malea-1-naphthalanilic acid have been tentatively assigned dimeric structures. From the ESR spectra of Cu(II) complexes various parameters have been calculated.     

Synthesis, characterisation and thermal behaviour of some thiosulfato-and sulfato copper(II) complexes

The investigation concerning the synthesis, spectrochemical and biological properties as well as thermal stability of some tiosulfato-and sulfato copper(II) complexes of type [Cuphen(S₂O₃)(H₂O)_n]·mH₂O (phen: 1,10-phenanthroline; (1): n=2, m=0; (2): n=2, m=0.5) and respectively [Cuphen(OSO₃)(H₂O)_n] ((3): n=0; (4): n=2) are presented in this paper. The bonding and stereochemistry of the complexes have been characterised by IR and electronic studies. The in vitro qualitative and quantitative assays of the antimicrobial activity of the tested compounds vs. planktonic and adherent Gram negative bacterial strains isolated from different surfaces in the hospital environment demonstrated that all compounds exhibited very good antimicrobial activity vs. Escherichia coli, Klebsiella sp. and Enterobacter sp. with very low M.I.C. values. The thermal analysis has evidenced the thermal intervals of stability and also the thermodynamics effects that accompany them both in synthetic air and argon. The thermal behaviour is complex according to DTG and DSC curves including dehydration as well as thiosulfate and phenanthroline decomposition.