Transition Metal Complexes of an Antipyrine Derivative

The stepwise formation constants of N-antipyrinyl-N′-3-phenyl-2-propenoyl-thiourea (I) complexes with metal ions of the first transition series, Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been determined in 70% (V/V) ethanol-water medium. The formation constants for the chelates follow the Irving-Williams series: Zn(II)<Cu(II)>Ni(II)>Co(II)>Mn(II) The effect of ionic radius and electronegativity on the chelate formation are discussed. Complexes of Cu(II) and Ni(II) have been synthesised and characterised by elemental analysis, electrolytic conductance, IR spectra and magnetic susceptibility measurements. The ligand forms bis-complexes with Cu(II) and Ni(II). The binding sites are oxygen and sulphur atoms.     

Potentiometric Studies of Some Bivalent Metal Ion Complexes of a New Ligand,o-(2-Thiazolylazo)-4-Ethylphenol

Abstract

The complexations of a new ligand, o-(2-thiazolylazo)-4-ethylphenol(TAEP) with Ca(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hq(II) and Pb(II) have been studied by potentiometric titrations, at 25.0 ± 0.2°C and an ionic strength of 0.1 in 30% v/v dioxane-water mixture. The dissociation constant and spectral data of TAEP and formation constants of the complexes containing various molar ratios of metal ion to ligand, are reported. It is observed that Ca(II) forms only an ML complex in any molar ratios, whereas other metal ions react in two steps forming ML and ML₂ complexes in a 1:3 molar ratio. In the case of 1:1 and 1:2 molar ratios, Mn(II), Co(II), Cd(II) and Hg(II) seemed to form bi- or poly-nuclear complexes because of slightly different formation curves from those of 1:3 molar ratio. The sequence of the first successive formation constant is Cu > Hg > Ni > Pb > Co > Zn > Cd > Mn > Ca, showing Mellor-Maley's order. Further correlation is shown between the formation constants and the second ionization potentials of the metals.     

Synthesis,characterization, speciation and biological studies on metal chelates of 1-benzoyl(1,2,4-triazol-3-yl)thiourea

Proton-ligand association constants of 1-benzoyl(1,2,4-triazol-3-yl)thiourea (BTTU) and its complex formation constants with some bivalent metal ions Ni(II), Co(II), Mn(II), Zn(II), and Cu(II), have been determined potentiometrically in 50% EtOH–H₂O and 0.1 M NaNO₃. The complexes formed in solution have a stoichiometry of 1:1 and 1:2 [M:L], where M represents the metal ion and L the BTTU ligand. The corresponding thermodynamic parameters are derived and discussed. The complexes are stabilized by enthalpy changes and the results suggest that complexation is an enthalpy-driven process. The effects of metal ion, ionic radius, electronegativity, and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3d transition metals follow the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺. The metal complexes were synthesized and characterized by elemental analyses, conductance, IR, ¹H NMR, and magnetic measurements. The low magnetic moment of 0.11 BM for the Cu(II) complex is suggestive of dimerization through Cu–Cu interaction. The concentration distribution diagrams of the complexes were evaluated. The ligands and their metal complexes have been screened in vitro against some bacteria and fungi.     

Complexation behaviour of benzilmono(Iepidyl)hydrazone (BLH) toward bivalent metal ions: A potentiometric study

Potentiometric investigations on metal complexes of various bivalent metal ions, viz. UO₂(II), Cu(II), Ni(II), Co(II), Cd(II), Pb(II), Zn(II) and Mn(II) with benzilmonol(lepidy!)hydrazone (BLH) have been carried out at different ionic strengths and at different temperatures in order to determine stability constants of the complexes. Thermodynamic parameters ΔC, ΔH and ΔS have also been evaluated from temperature coefficient data. The effect of varying the dielectric constant of the medium on the stability constants of complexes has also been investigated at 30±0.5°C and μ = 0.1MNaCl. Thermodynamic stability constants and thermodynamic stabilization energies for the first transition metals have also been discussed.     

Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) ions: synthesis, structural characterization and biological activity studies

Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO₂(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV–vis, ¹H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25 ± 1 °C and at 0.1 M KNO₃ ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO₂(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats–Redfern and Horowitz–Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H₂O)₄]·Cl₂ and [Zn(LFX)(H₂O)₄]·Cl₂ were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had been found to be inactive at lower concentration than 100 μg/ml.     

Spectroscopic and thermodynamic studies of complexation of some divalent metal ions with isatin-<Emphasis Type="Italic">β</Emphasis>-thiosemicarbazone

Metal complexes of some divalent metal ions (Co, Ni, Cu, Zn, Hg, and Pd) with isatin-β-thiosemicarbazone (ITS) as the Schiff base have been investigated potentiometrically and spectrophotometrically. The dissociation constants of the ligand and formation constants of the metal complexes, as well as the corresponding thermodynamic functions (ΔG, ΔH and ΔS) have been determined at different temperatures in ethanol—water solution. The full stability constants were also evaluated spectrophotometrically by the Job method. The experimental results indicate that Cu(II), Zn(II), Pd(II), and Hg(II) form one-to-one molecular complexes (ML) with the studied ligand, whereas Co(II) and Ni(II) form both ML and ML₂ species.     

Thermodynamics,formation constants,spectrophotometry and infrared spectroscopy of complexes between some divalent metal ions and 3-hydrazino-6-phenylpyridazine and related ligands

The stepwise formation constants of complexes of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Cd(II) and UO₂(II) ions with 3-hydrazino-6-phenylpyridazine (HPP) and its condensation products with benzil (BHPP) and p-methoxyacetophenone (p-MeOAHPP) were determined in a 75% (v/v) dioxane-water mixture at μ = 0.05 M (KNC₃). The effect of temperature (at 10, 20, 30 and 40 °C) was also examined for Cu(II) and UO₂(II)-BHPP complexes. The overall changes in ΔG, ΔH and ΔS have been calculated. The solid complexes of Cu(II)-, Co(II)- and Ni(II)-BHPP were prepared and examined by elemental analysis and IR spectroscopy. Analysis of the data indicates chelation of the BHPP ligand through the nitrogens of both hydrazone and the pyridazine ring and the carbonyl oxygen group. The spectrophotometric studies were performed on solutions of Cu(II), Ni(II) and Co(II) with BHPP in order to obtain the optimum pH values for complex formation. The compositions of the chelates formed were determined. Analytical determinations of the micro amounts of Cu(II), Ni(II) and Co(II) were also done using BHPP as the complexing agent.     

The potentiometric and thermodynamic properties of some divalent metal ions with biologically active 2-phenyl-3-(2′-hydroxy-5′-methylbenzylidine)-quinazoline-4-(3h)-one Schiff’s base

The formation constants of 1: 1 and 1: 2 complexes between Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Pb(II), Cu(II), Ba(II), Mg(II), Mn(II), Th(IV), and UO₂ (II) metal ions and 2-phenyl-3-(2′-hydroxy-5′-methylbenzylidine)-quinazoline-4-(3H)-one [PHBMeQ] were determined potentiometrically at 30 ± 0.1 °C and different ionic strengths (0.025, 0.05, 0.10, 0.15, and 0.20 M NaNO₃) in 60: 40 (v/v) alcohol-water solutions. The proton-ligand and metal-ligand formation constants were determined pH-metrically by the Calvin-Bjerrum titration technique. The order of stability constants was found. The negative ΔG° values suggest that the reactions occur spontaneously. Correlations between the log K ₁ values and some fundamental central metal ion properties are discussed.     

Complexes of 2,3-Dihydroxypyridine with Bivalent Metals. Crystal Structure of 2,3-Dihydroxypyridine

Crystal structure of 2,3-dihydroxypyridine (H₂L) is determined. Mn(HL)Cl · H₂O, Co(HL)Cl · 2H₂O, Cu(HL)Cl, Ni(HL)OH · H₂O, and Zn(HL)OH · H₂O complexes are synthesized by reacting Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) chlorides with H₂L in ethanol solutions and identified. In these complexes, 2,3-dihydroxypyridine is involved in coordination as a monoanion. Spectral parameters of neutral and anionic forms of a ligand are determined and the acidity and complex formation constants are calculated. The compositions of complexes are established.     

Synthesis,Spectroscopic and Magnetic Studies on Metal Complexes of 5-Methyl-3-(2-Hydroxyphenyl)Pyrazole

A tridentate ONN donor ligand, 5-methyl-3-(2-hydroxyphenyl)pyrazole; H₂L, was synthesized by reaction of 2-(3-ketobutanoyl)phenol with hydrazine hydrate. The ligand was characterized by IR, ¹H NMR and mass spectra. ¹H NMR spectra indicated the presence of the phenolic OH group and the imine NH group of the heterocyclic moiety. Different types of mononuclear metal complexes of the following formulae [(HL)₂M][sdot]xH₂O (M=VO, Co, Ni, Cu, Zn and Cd), [(HL)₂M(H₂O)₂] (M=Mn and UO₂) and [(HL)LFe(H₂O)₂] were obtained. The Fe(III) complex, [(HL)LFe(H₂O)₂] undergoes solvatochromism. Elemental analyses, IR, electronic and ESR spectra as well as thermal, conductivity and magnetic susceptibility measurements were used to elucidate the structures of the newly prepared metal complexes. A square-pyramidal geometry is suggested for the VO(IV) complex, square-planar for the Cu(II), Co(II) and Ni(II) complexes, octahedral for the Fe(III) and Mn(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes, while the UO₂(VI) complex is eight-coordinate. Transmetallation of the UO₂(VI) ion in its mononuclear complex by Fe(III), Ni(II) or Cu(II) ions occurred and mononuclear Fe(III), Ni(II) and Cu(II) complexes were obtained. IR spectra of the products did not have the characteristic UO₂ absorption band and the electronic spectra showed absorption bands similar to those obtained for the corresponding mononuclear complexes. Also, transmetallation of the Ni(II) ion in its mononuclear complex by Fe(III) has occurred. The antifungal activity of the ligand and the mononuclear complexes were investigated.     

Metal complexes of schiff's base derived from salicoylhydrazine and biacetylmonoxime

Biacetylmonoxime-salicoylhydrazone (BMSH) complexes of the types [Hg(BMSH)Cl₂] and [M(BMSH-H)₂], where M = Cu(II), Co(II), Ni(III), Mn(II), Zn(II), Cd(II) and UO₂(VI), have been prepared and characterized by conventional chemical and physical measurements. The IR spectra show that the ligand usually coordinates via carbonyl oxygen (CO), azomethine nitrogen (CNl) and phenolic OH with replacement of hydrogen by metal ions but acts as a bidentate molecule coordinating through (CO) and (CNl) in the Hg(II) complex. The magnetic and spectral data of the Co(II) and Ni(II) complexes support octahedral stereochemistry, whilst tetragonally distorted octahedral geometry is suggested for the Cu(II) complex.     

Spectral,thermal and magnetic investigations of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates were investigated and their composition, solubility in water at 295 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with molar ratio of metal to organic ligand of 1.0:1.0 and general formula: M [ CH₃C₆H₃(CO₂)₂]·nH₂o (n=1-3) were recorded and their decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Mn, Co, Ni, Zn, Cd) or two steps (Cu) and next the anhydrous complexes decompose to oxides directly (Cu, Zn), with intermediate formation of carbonates (Mn, Cd), oxocarbonates (Ni) or carbonate and free metal (Co). The carboxylate groups in the complexes studied are mono- and bidentate (Co, Ni), bidentate chelating and bridging (Zn) or bidentate chelating (Mn, Cu, Cd). The magnetic moments for paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.92, 5.05, 3.36 and 1.96 M.B., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dissociation constants of some Schiff bases and stability constants of their copper,cobalt, nickel and zinc complexes

The stoichiometry and stability constant of metal complexes with 4-(3-methoxy-salicylideneamino)-5-hydroxynaphthalene-2,7-disulfonic acid monosodium salt (H₂L) and 4-(3-methoxysalicylideneamino)-5-hydroxy-6-(2,5-dichlorophenylazo)-2,7-naphthalene disulfonic acid monosodium salt (H₂L¹) were studied by potentiometric titration. The stability constants of H₂L and H₂L¹ Schiff bases have been investigated by potentiometric titration and u.v.–vis spectroscopy in aqueous media. The dissociation constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 °C and 0.1 m KCl ionic strength. The dissociation constants for H₂L were obtained as 3.007, 7.620 and 9.564 and for H₂L¹, 4.000, 6.525, 9.473 and 10.423, respectively. The complexes were found to have the formulae [M(L)₂] for M = Co(II), Ni(II), Zn(II) and Cu(II). The stability of the complexes follows the sequence: Zn(II) < Co(II) < Cu(II) < Ni(II). The high stability of H₂L¹ towards Cu(II) and Ni(II) over the other ions is remarkable, in particular over Cu(II), and may be of technological interest. Concentration distribution diagram of various species formed in solution was evaluated for ligands and complexes. The formation of the hydrogen bonds may cause this increased stability of ligands. The pH-metric data were used to find the stoichiometry, deprotonation and stability constants via the SUPERQUAD computer program.     

Synthesis and antibacterial activity of cephradine metal complexes

Cephradine (Hcephra) interacts with transition metal ions to give [Fe(cephra)Cl₂] and [M(cephra)Cl] complexes (M?=?Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)) which were characterized by physicochemical and spectroscopic methods; a tetrahedral geometry is suggested for their structures where cephradine behaves as monoanionic tridentate ligand. The complexes have been screened for antibacterial activity against several bacteria, and the results showed that all metal complexes tested had lower antibiotic activity than the free ligand.     

Spectrophotometric and potentiometric study of the complexes originated by the trisodium salt of 2-(p-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid (SPADNS) and several metal ions

A study of the complexes originated by U(VI), Cu(II), Pb(II), Ni(II), Co(II), Zn(II), Cd(II), Mn(II), Ca(II), Mg(II), Ba(II), and Sr(II), and SPADNS (trisodium salt of 2-(p-sulfophenylazo)-1, 8-dihydroxynaphthalene-3,6-disulfonic acid) has been made by means of spectrophotometric and potentiometric methods. The dissociation constants of the ligand and the formation constants of the metal ion-SPADNS complexes have been determined at 25 ± 0.1 °C and ionic strength 0.1 (NaClO₄).     

Metalloantibiotics: synthesis and antibacterial activity of cefepime metal complexes

Cefepime interacts with transition metal(II) ions to give [M(cefepime)Cl₂] complexes (M = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) which were characterized by physicochemical and spectroscopic methods. The complexes are insoluble in water and common organic solvents, and probably have polymeric structures. The spectra indicated that the ligand is a multidentate chelating agent. The complexes have been screened for antibacterial activity against several bacteria and showed activity less than that of free cefepime.     

Protonation Equilibria of Carminic Acid and Stability Constants of Its Complexes with Some Divalent Metal Ions in Aqueous Solution

The dissociation constants of carminic acid (7-D-glucopyronosyl-3,5,6,8-tetra- hydroxy-1-methyl-9,10-dioxo-anthracene-2-carboxylic acid) (CA), together with the stability constants of its Cu(II), Zn(II), Ni(II), Co(II) and Hg(II) complexes, were studied potentiometrically in aqueous medium at 25.0?(1)?°C, and at the ionic background of 0.1?mol?dm^?3 of NaCl, and determined with the SUPERQUAD computer program. It has been observed that carminic acid has five dissociation constants, and for H₅L their values are 3.39?(7), 5.78?(7), 8.35?(7), 10.27?(7), and 11.51?(7). This ligand behaves as a bi-dentate ligand, and the carboxyl and the ortho hydroxy groups of the ligand coordinate to the metal ions. Various metal complexes were produced in solution under the experimental conditions, for each metal ion used, including hydrolyzed species. The species distribution curves of the complexes formed in the solution were calculated and reviewed. The stability of the complexes was found to follow the order: Cu(II) > Zn(II) > Ni(II) > Co(II) > Hg(II).     

Potentiometric and Thermogravimetric Studies on Some Metal–Oxine–Sulphadrugs ternary Complexes

Formation constants (logK _MAL ^MA) of the mixed complexes of the type M–A–L (where M=Mn(II), Co(II), Ni(II), Cu(II), Ce(III), Th(IV), and UO₂(II); A=oxine and L=sulphamerazine or sulphadiazine) have been determined pH-metrically in 60% (v/v) ethanol–water mixture at 25°C and constant ionic strength (μ=0.1 M NaCl). The mode of chelation was ascertained by conductivity measurements. The stability sequence with respect to metal ions have been found to be Cu(II)>Ni(II)>Co(II)>Mn(II) and Th(IV)>UO₂(II)>Ce(III). CuAL ternary solid complexes have been prepared and characterized on the basis of elemental analysis and IR-spectroscopy. The thermal degradations of the prepared complexes are discussed in an attempt to assign the intermediate compounds formed. This revised version was published online in August 2006 with corrections to the Cover Date.     

A potentiometric investigation of complex formation between some metal ions and biologically active quinazoline-4-3(H)-one Schiff’s base

The proton dissociation constant of the ligand and the stability of the complexes of Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Pb(II), Cu(II), Ba(II), Mg(II), Mn(II), Th(IV), and UO₂(II) ions with 2-phenyl-3-(2′-hydroxy-5′-benzylidine)-quinazoline-4-(3H)-one [PBQ] were determined potentiometrically at 30 ± 0.1°C and ionic strengths of 0.025, 0.05, 0.10, 0.15 and 0.20 M NaNO₃ in a 60:40 (v/v) ethanol-water medium. The proton-ligand and metal-ligand stability constants of the complexes were determined pH metrically by the Calvin-Bjerrum titration technique. The order of stability constants obeys the Irving-Rossotti rule. The negative values of ΔG° suggest that the reactions are spontaneous. The article is published in the original.     

Synthesis,Characterization and Spectral Studies of Triethanolamine Complexes of Metal Saccharinates. Crystal Structures of [Co(TEA)2](SAC)2 AND [Cu2(μ-TEA)2(SAC)2]·2(CH3OH)

The novel transition metal saccharinate complexes of triethanolamine (TEA) have been synthesized and characterized by elemental analyses, magnetic moments, UV-Vis and IR spectra. Mn(II), Co(II), Ni(II), Zn(II), Cd(II) and Hg(II) form mononuclear complexes of [M(TEA)₂](SAC)₂, where SAC is the saccharinate ion, while the Cu(II) complex is dimeric. The TEA ligand acts as a tridentate N,O,O'-donor ligand and one ethanol group is not involved in coordination. The SAC ion does not coordinate to the metal ions and is present as the counter-ion in the Mn(II), Co(II), Ni(II), Zn(II), Cd(II) and Hg(II) complexes, but coordinates to the Cu(II) ion as a monodentate ligand. The crystal structures of the [Co(TEA)₂](SAC)₂ and [Cu₂(μ-TEA)₂(SAC)₂]·2(CH₃OH) complexes were determined by single crystal x-ray diffraction. The Co(II) ion has a distorted octahedral coordination by two TEA ligands. The Cu(II) complex crystallizes as a dimethanol solvate and has doubly alkoxo-bridged centrosymmetric dimeric molecules involving two tridentate triethanolaminate (deprotonated TEA) and two monodentate SAC ligands. The geometry of each Cu(II) ion is a distorted square pyramid. Both crystal structures are stabilized by hydrogen bonds to form a three-dimensional network.