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.     

Mixed Ligand Complex Formation of Cetirizine Drug with Bivalent Transition Metal(II) Ions in the Presence of 2-Aminomethylbenzimidazole: Synthesis,Structural, Biological,pH-Metric and Thermodynamic Studies

Mononuclear copper(II), cobalt(II) and nickel(II) complexes of cetirizine (CTZ = 2-[2-[4-[(4-chlorophenyl)phenyl methyl]-piperazine-1-yl]-ethoxy]acetic acid) in the presence of 2-aminomethyl-benzimidazole·2HCl (AMBI), as a representative example of heterocyclic bases, were synthesized and studied by different physical techniques. All mixed-ligand complexes have been fully characterized with the help of elemental analyses, molecular weight determinations, molar conductance, magnetic moments and spectroscopic data. The formulae of the isolated complexes are [M(AMBI)(CTZ)(NO₃)(H₂O)₂]·nH₂O where AMBI is the neutral bidentate 2-aminomethylbenzimidazole, CTZ the deprotonated cetirizine and n = 1 for Co(II) or 0 for Cu(II) and Ni(II) complexes. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytes. The formation equilibria of the ternary complexes have been investigated. Ternary complexes are formed by a simultaneous mechanism. Stoichiometry and stability constants for the complexes formed are reported. The concentration distribution of the complexes in solution was evaluated as a function of pH. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The synthesized metal chelates have been screened for their antimicrobial activities against the selected types of Gram-positive (G⁺) and Gram-negative (G^?) bacteria. They were found to be more active against Gram positive than Gram negative bacteria. The antimicrobial activity in terms of metal ions obeys this order: Cu(II) > Ni(II) > Co(II).     

Synthesis, crystal structure, magnetic, DSS cell, lifetime measurement, electrochemical, catecholase activity, and antimicrobial studies of mono and hetero binuclear cryptates

Mono and hetero binuclear cryptates, [GdML(DMF)] [M = VO(IV), Co(II), Cu(II)], were synthesized. The ligand L represents the deprotonated anionic cryptate obtained by the 2+3 condensation of tris-(2-aminoethyl)amine with 2,6-diformyl-4-methylphenol. The crystal structure of [GdL(NO₃)](NO₃)₂·H₂O was determined by single-crystal X-ray diffraction method. The magnetic susceptibility of the complexes was measured by SQUID. The Gd(III)Cu(II) cryptate has ferromagnetic interaction and [Gd(III)VO(IV)] cryptate has weaker intramolecular antiferromagnetic interaction. Fluorescence intensity and excited state lifetime of the cryptates increase in the following order: [GdCoL] < [GdVOL] < [GdL] < [GdCuL]. The efficiency (η) of cryptate based dye-sensitized solar cell increases in the following order: [GdL] < [GdVOL] < [GdCoL] < [GdCuL]. The reduction potential values of [Gd(M)L] M = VO(IV), Co(II), Cu(II) complexes are in the following order: Cu(II) > Co(II) > VO(IV). The catecholase activity of binuclear [GdML] complexes are relatively high compared with the mononuclear [Gd(III)L] complex in the following order: [GdL] < [GdVOL] < [GdCoL] < [GdCuL]. The antimicrobial activity of the binuclear complex Gd(III)Cu(II) is relatively higher than the mononuclear and other binuclear complexes.     

Metal chelates of salicyl-4-aminoantipyrine

The formation constants of salicyl-4-amino-2,3-dimethyl-1-phenyl-3-pyrazoline-5-one (SAAP) complexes with 3d transition metal ions [Cu(II), Ni(II), Co(II), Zn(II) and Mn(II)] have been determined in 60% ethanol-water medium ofμ = 0.1M (NaCl) at 25°C. It is observed that the formation constants for chelates with 3d transition metals follow the order Mn(II) < Co(II) < Ni(II) < Zn(II) < Cu(II). The effects of metal ions, ionic radii, electronegativities and ionization potentials on chelate formation constants are discussed. Complexes of UO₂(II) and Pd(II) have been synthesized and characterised by elemental analysis, electrolytic conductance, IR spectra and magnetic measurements. The ligand forms the complexes PdLCl and UO₂L₂,2H₂O, where L is a uninegatively charged tridentate ligand (ONO donor sets).     

Spectrophotometric,potentiometric, and conductometric studies of binary complex formation between copper(II) and three forms of vitamin B6 in aqueous solutions

This article reports the detailed study concerning the mode of binding of three forms of vitamin B₆, pyridoxamine (pm), pyridoxine (pn), and pyridoxal (pl), with Cu(II) in aqueous solutions using three independent methods: potentiometry, conductometry, and UV–vis spectroscopy. The stability constants of complexes formed between copper(II) and vitamin B₆ were investigated by potentiometric titration in 0.1 M KNO₃ ionic medium at 25 °C. While drawing the relations between molar conductance and the ratio of metal to ligand concentrations, different types of lines were obtained indicating the formation of 1 : 1 and 1 : 2 stoichiometric compounds. The stability constants have been determined using EQUID and CVEQUID computer programs and the obtained results were in agreement. The relatively high values of stability constants of Cu(II)-vitamin B₆ complexes obtained from three independent methods in comparison to those with other competing cations suggest that the complexes studied are relatively stable in aqueous solutions.     

Novel complexes of Co2+, Ni2+, and Cu2+ with N-(phosphonomethyl)aminosuccinic acid

Complexes of Co²⁺, Ni²⁺, and Cu²⁺ with N-(phosphonomethyl)aminosuccinic acid (H₄PMAS) of general formula Na₂MPMAS·nH₂O [M=Co(II), Ni(II), Cu(II), n—number of water molecules] were synthesized. Based on interpretation of diffusion reflectance spectroscopy, structure of all complexes is based on distorted octahedral. Analysis of IR spectra of Co(II), Ni(II), and Cu(II) N-(phosphonomethyl)aminosuccinates demonstrated that metal ions are coordinated to the ligand through nitrogen atom of the imino group, oxygen atoms of the α- and β-carboxyl groups as well as oxygen atom of the phosphonic group of the H₄PMAS. We demonstrated that thermal stability of complexes increases in sequence Cu(II) < Ni(II) < Co(II), obviously as a result of change over from the dimeric to polymeric character of the initial complex. Complete decomposition of ligand occurs at these temperatures and is accompanied by release of H₂O, CO₂, and NO₂. The final products of thermal decomposition of the complexes are mixtures of oxides and phosphates of respective metals.     

Metallation of tetradentate N<Subscript>2</Subscript>O<Subscript>2</Subscript> Schiff base with Mn(II), Co(II), Cu(II) and Zn(II): synthesis,characterization and formation constants measurement

Four Schiff base ligands, salabza-H₂ = N,N′-bis(salicylidene)-2-aminobenzylamine, were synthesized by condensation of one mole of 2-aminobenzylamine and two moles of salicylaldehyde and/or two moles of substituted salicylaldehyde (5-OMe, 5-Br, 5-NO₂). All the four Schiff bases and their Mn(II), Co(II), Cu(II) and Zn(II) complexes are characterized by UV-Vis, FT-IR, ¹H NMR spectroscopy, mass spectrometry and elemental analysis. The formation constants and the Gibbs free energies were measured spectrophotometrically for 1:1 complexes in methanol in constant ionic strength (I = 0.1 mol dm⁻³ NaClO₄) and at 25°C. The data refinement was carried out with the SQUAD program. The trend of formation constants of H₂L¹ with M(II) follows the order: Mn(II) (3.97) < Zn(II) (4.30) < Co(II) (4.89) < Cu(II) (5.73)     

Synthesis,characterization, DFT modeling and biological studies of new Co(II), Ni(II) and Cu(II) 4,6-bis(4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile complexes

Three new metal complexes of 4,6-bis(4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile (L) with Co(II), Ni(II) and Cu(II) were synthesized and characterized with physicochemical and spectroscopic techniques. The data suggest that (L) acts as a bidentate ligand bound to the divalent metal ions through amino N and carbinitrile N atoms having [M(L)₂(H₂O)₂]²⁺ formula (M = metal ions). The theoretical parameters, model structures, charges and molecular orbitals of all possible complexes have been determined using density functional theory. The energy gap of free ligand is ?E = 0.12565 eV, and this value is greater than energy gap of complexes, which indicates that the complexes are more reactive than free ligand. Also, ?E of Co(II) complex is lower than other complexes, which indicates that Co(II) complex is more reactive than Ni(II) and Cu(II) complexes. The antibacterial and antifungal activities of the ligand, metal salts and its complexes were tested against some microorganisms (bacteria and fungi). The complexes showed increased antibacterial and antifungal profile in comparison with the free ligand.     

Design and development of several polymeric metal–organic frameworks,spectral characterization,and their antimicrobial activity

Coordination polymers were obtained by the reaction of metal acetates, M(CH₃COO)₂·xH₂O {where M = Mn(II), Co(II), Ni(II) and Cu(II)} with AFP ligand (AFP = 5,5'-(piperazine-1,4-diylbis(methylene))bis(2-aminobenzoic acid). The AFP ligand was prepared by the one-pot, two-step reaction of formaldehyde, 2-aminobenzoic acid, and piperazine. Structural and spectroscopic properties have been studied by elemental, spectral (FT-IR, ¹H NMR, ¹³C NMR, and UV–vis), and thermogravimetric analysis. UV–vis spectra and magnetic moment values indicate that Mn(II), Co(II), and Ni(II) polymer–metal complexes are octahedral, while Cu(II) and Zn(II) polymer–metal complexes are distorted octahedral and tetrahedral, respectively. The analytical data confirmed that the coordination polymers of Mn(II), Co(II), Ni(II), and Cu(II) are coordinated with two water molecules, which are further supported by infrared spectra and thermogravimetric analysis data. The prepared polymer–metal complexes showed good antibacterial activities against all tested microorganisms; however, the AFP ligand was also found to be effective, but relatively less than their polymer–metal complexes. Along with antibacterial activity, all the polymer–metal complexes exhibit significant antifungal activity against most of the tested fungal strains. The results of antimicrobial activity reveals that the AFP–Cu(II) showed the highest antibacterial and antifungal activity than other polymer–metal complexes.     

Complex formation of cetirizine drug with bivalent transition metal(II) ions in the presence of alanine: synthesis,characterization, equilibrium studies,and biological activity studies

Mononuclear cobalt(II), nickel(II), and copper(II) complexes of cetirizine·2HCl (CTZ = 2-[2-[4-[(4-chlorophenyl)phenyl methyl]piperazine-1-yl]-ethoxy]acetic acid) in the presence of alanine (Ala) as a representative example of amino acids were synthesized and elucidated by different physical techniques. All complexes have been characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments, and spectroscopic data. The measured molar conductance values in DMSO indicate that the complexes are nonelectrolytes. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of complexes. The metal–oxygen bond length in the synthesized complexes obeys the order M–OH₂ > M–O_CTZ > M–O_Ala. Formation equilibria of the ternary complexes have been investigated. Ternary complexes are formed by a simultaneous mechanism. Stoichiometry and stability constants for the complexes formed are reported. The concentration distributions of various species formed in solution were also evaluated as a function of pH. CTZ and its metal chelates have been screened for their antimicrobial activities against some selected types of gram-positive (G⁺) and gram-negative (G^?) bacteria. They were more active against (G⁺) than (G^?) bacteria.     

Novel repaglinide complexes with manganese(II), iron(III), copper(II) and zinc(II): Spectroscopic,DFT characterization and electrochemical behaviour

Novel transition metal complexes with the repaglinide ligand [2-ethoxy-4-[N-[1-(2piperidinophenyl)-3-methyl-1-1butyl] aminocarbonylmethyl]benzoic acid] (HL) are prepared from chloride salts of manganese(II), iron(III), copper(II), and zinc(II) ions in water-alcoholic media. The mononuclear and non-electrolyte [M(L)₂(H₂O)₂]?nH₂O (M = Mn²⁺, n = 2, M = Cu²⁺, n = 5 and M = Zn²⁺, n = 1) and [M(L)₂(H₂O)(OH)]?H₂O (M = Fe³⁺) complexes are obtained with the metal:ligand ratio of 1:2 and the L-deprotonated form of repaglinide. They are characterized using the elemental and molar conductance. The infrared, ¹H and ¹³C NMR spectra show the coordination mode of the metal ions to the repaglinide ligand. Magnetic susceptibility measurements and electronic spectra confirm the octahedral geometry around the metal center. The experimental values of FT-IR, ¹H, NMR, and electronic spectra are compared with theoretical data obtained by the density functional theory (DFT) using the B3LYP method with the LANL2DZ basis set. Analytical and spectral results suggest that the HL ligand is coordinated to the metal ions via two oxygen atoms of the ethoxy and carboxyl groups. The structural parameters of the optimized geometries of the ligand and the studied complexes are evaluated by theoretical calculations. The order of complexation energies for the obtained structures is as follows:

$$Fe(III) complex < Cu(II) complex < Zn(II) complex < Mn(II) complex.$$

The redox behavior of repaglinide and metal complexes are studied by cyclic voltammetry revealing irreversible redox processes. The presence of repaglinide in the complexes shifts the reduction potentials of the metal ions towards more negative values.

     

Photometric determination of aqueous cobalt (II), nickel (II), copper (II) and iron (III) with 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt in gelatin films

Photometric determination of aqueous Co(II), Cu(II), Ni(II) and Fe(III) was performed using indicator films prepared by immobilization of 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt (NRS) into hardened photographic film. Immobilization was based on electrostatic interaction of reagent and metal complexes with the gelatin. The isoelectric point pH of hardened gelatin (4.46±0.04) was evaluated by viscometry. Co(II), Fe(III), Ni(II) form 1:3 complexes with NRS in gelatin at pH 2 and Cu(II) forms 1:2 complexes. Their log β′ values were: Co-6.7, Fe-8.6, Cu-8.0, and Ni-6.4. The absorption maxima were: 370nm for NRS, and 430nm, 470nm, 495nm and 720nm for complexes of Co(II), Ni(II), Cu(II) and Fe(III). An algorithm for their simultaneous determination using the indicator films was developed. The detection limits were: c_lim(Co²⁺) = 0.45×10⁻⁵ M, c_lim(Fe³⁺) = 0.50×10⁻⁵ M, c_lim(Cu²⁺) = 0.67×10⁻⁵ M, c_lim(Ni²⁺) = 0.75×10⁻⁵ M,; and their sum c_lim(ΣMn⁺) = 0.82×10⁻⁵ M.      

Potentiometric Studies on Complexation of Cu(II) Ion with Methyl/Nitro-Substituted 1,10-Phenanthrolines and Selected Amino Acids

Protonation constants of methyl/nitro substituted 1,10-phenanthrolines {(m/n-sphen): 4-methyl-phenanthroline (4-mphen), 5-methyl-1,10-phenanthroline (5-mphen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10-phenanthroline (5-nphen)] and the amino acids (aa) l-tyrosine (tyr) and glycine (gly), and their corresponding binary and ternary stability constants with Cu(II), were determined in aqueous 0.1 mol·L^?1 KCl ionic media at 298.15 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. The species distribution diagrams were obtained using the “SPE” software package under the experimental conditions described. The order of stability of the ternary complexes in terms of the primary ligands is [Cu(tmphen)(aa)]⁺ > [Cu(dmphen)(aa)]⁺ > [Cu(4-mphen)(aa)]⁺ > [Cu(5-mphen)(aa)]⁺ > [Cu(5-nphen)(aa)]⁺. The stability constants of the ternary complexes decrease in the following order: [Cu(m/n-sphen)(gly)]⁺ > [Cu(m/n-sphen)(tyr)]⁺, which is identical to the sequence found for the binary complexes of Cu(II) with gly and tyr.     

Ternary and binary copper(II) complexes: synthesis,characterization, ROS-inductive,proteasome inhibitory,and anticancer properties

Three ternary copper(II) complexes, [Cu(phen)(L-phe)Cl]·2H₂O, [Cu(phen)(L-leu)Cl]·4½H₂O, and [Cu(phen)(L-tyr)Cl]·3H₂O, and four binary copper(II) complexes, [Cu(phen)Cl₂]_, Cu(L-phe)₂·½H₂O, Cu(L-leu)₂·½H₂O, and Cu(L-tyr)₂·H₂O (where phen = 110-phenanthroline, L-phe = L-phenylalanine, L-tyr = L-tyrosine, L-leu = L-leucine and Cl^- = chloride), were synthesized and characterized by elemental analysis, spectroscopic techniques (FTIR, UV–visible, fluorescence spectroscopy), magnetic susceptibility, molar conductivity, and lipophilicity measurement. X-ray diffraction determination of a single crystal of [Cu(phen)(L-tyr)Cl] showed two independent molecules in the asymmetric unit, each with the same distorted square pyramidal geometry about copper(II). p-Nitrosodimethylaniline assay revealed that the three ternary complexes were better inducers of reactive oxygen species over time than binary complexes, CuCl₂, and free ligands. All the copper(II) complexes in this series inhibited the three proteolytic activities in the order Trypsin-like > Caspase-like > Chymotrypsin-like. In terms of anticancer properties, the copper(II)-phen complexes had GI50 values of less than 4 μM against MCF-7, HepG2, CNE1 and A549 cancer cell lines, more potent than cisplatin.     

Synthesis of asymmetrical tridendate Schiff bases and metal complexes and investigation of anticarcinogen effects on human colon and cervical cancers

The metal complexes of Zn(II), Ni(II), Cu(II) and Pb(II) with asymmetrical Schiff bases were synthesized. The asymmetrical Schiff base was obtained through the condensation of 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde and biphenyl-4-carbaldehyde. The new Schiff base ligands (L₁' and L₂') and their metal complexes were characterized by TG/DTG, FT-IR, ¹H-NMR, UV–Vis, ESR, powder XRD, elemental analysis, magnetic moment and fluorescence studies. The powder XRD studies indicate that Co(II) and Cu(II) complexes are amorphous, while Ni(II) and Zn(II) complexes are crystalline. The anticarcinogenic effects of L₁' and L₂' were also investigated against colon (SW-620) and cervical cancer (HeLa) cell lines and compound L₂' was found to possess the highest anticarcinogenic potential, with 16.7 µM and 27.5 µM of IC₅₀ values for HeLa and SW620 cells, respectively.     

Oligo‐Ortho‐Chloroazomethinephenol and its Metal Complexes: Synthesis,Characterization, Antimicrobial and Thermal Properties

The new Schiff base oligomer (oligo‐ortho‐chloroazomethinephenol) was synthesized by the condensation of ortho‐chloroaniline with oligosalicylaldehyde (OSA). Oligomer‐metal complexes of oligo‐ortho‐chloroazomethinephenol (OKAP) with Cu(II), Zn(II) and Co(II) were synthesized. The properties of OKAP and oligomer‐metal complexes were studied by elemental, UV‐Vis, ¹H‐NMR, FT‐IR, magnetic susceptibility analyses. The number average molecular weight and mass average molecular weight OKAP were found to be 1494 g · mol^?1 and 5418 g · mol^?1, respectively. Elemental analyses of oligomer‐metal complexes suggest that the ratio of metal to oligomer is 1∶2. The results indicate that the OKAP coordinate through azomethine nitrogen and phenolic oxygen to the metal ions. Antimicrobial activity of OKAP was tested against S. cerevisiae, B. subtilis, E. coli, K. pneumoniae, M. luteus and S. aureus. The thermal stabilities of the OKAP and oligomer‐metal complexes were compared by thermogravimetric (TG) analyses. According to TG, OKAP, and oligomer‐metal complexes were stable against temperature and thermooxidative decomposition. The weight losses of OKAP and oligomer‐metal complexes were found to be at 400 and 800°C at 20.2 and 50.0 (OKAP), 17.1 and 41.1 (Cu(II)), 13.4 and 38.5 (Zn(II)), 18.3 and 68.2 (Co(II)), %, respectively. Based on half degradation temperature (T_50%) parameters, Cu(II) and Zn(II) complexes were more resistant than the OKAP and Co(II) complex.     

Synthesis,structural, spectroscopic,biological and catalytic activity of Co(II), Ni(II) and Cu(II) complexes of benzilic hydrazide (BH)

Co(II), Ni(II) and Cu(II) chloro complexes of benzilic hydrazide (BH) have been synthesized. Also, reaction of the ligand (BH) with several copper(II) salts, including NO₃ ^?, AcO^?, and SO₄ ^? afforded metal complexes of the general formula [CuLX(H₂O) _n ]·nH₂O, where X is the anion and n = 0, 1 or 2. The newly synthesized complexes were characterized by elemental analysis, mass spectra, molar conductance, UV–vis, IR spectra, magnetic moment, and thermal analysis (TG/DTG). The physico-chemical studies support that the ligand acts as monobasic bidentate towards metal ion through the carbonyl and hydroxyl oxygen atoms. The spectral data revealed that the geometrical structure of the complexes is square planar for Cu (II) complexes and tetrahedral for Co(II) and Ni(II) complexes. Structural parameters of the ligand and its complexes have been calculated. The ligand and its metal complexes are screened for their antimicrobial activity. The catalytic activities of the metal chelates have been studied towards the oxidative decolorization of AB25, IC and AB92 dyes using H₂O₂. The catalytic activity is strongly dependent on the type of the metal ion and the anion of Cu(II) complexes.     

Mixed-ligand metal complexes containing an ONS Schiff base and imidazole/benzimidazole ligands: synthesis,characterization, crystallography and biological activity

Salicylaldehyde-4-methylthiosemicarbazone (H₂MTSali) has been prepared via the condensation reaction of 4-methyl-3-thiosemicarbazide and salicylaldehyde. Four new mixed-ligand copper(II) and nickel(II) complexes with a general formula [M(MTSali)L] (M = Cu²⁺ or Ni²⁺; L = co-ligand) were synthesized, where L is either imidazole (im) or benzimidazole (bzim). The Schiff base and its mixed-ligand complexes were characterized by IR and UV/Vis spectroscopy, and the complexes by molar conductivity and magnetic susceptibility measurements. The spectroscopic data indicated that the Schiff base behaves as a tridentate ONS donor ligand coordinating via the phenoxide-oxygen, azomethine-nitrogen, and thiolate-sulphur atoms. Magnetic data indicate a square planar environment for the nickel(II) complexes while molar conductance values indicate that the metal complexes are essentially non-electrolytes in DMSO solution. X-ray crystallography shows Cu(MTSali)bzim (1) and Ni(MTSali)bzim (3) to be isostructural, with the metal(II) ions being coordinated by a N₂OS donor set that defines an approximate square planar geometry; in both cases, the benzimidazole is splayed with respect to the coordination plane. The copper(II) complexes were active against MDA-MB-231 and MCF-7 breast cancer cell lines, more so than H₂MTSali, whereas the nickel(II) complexes were inactive.     

Synthesis,characterization, potentiometry,and antimicrobial studies of transition metal complexes of a tridentate ligand

Complexes of Cu(II), Ni(II), Co(II), Mn(II), and Fe(III) with the tridentate Schiff base, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2H-pyran-2-one (HL) derived from 3-acetyl-6-methyl-(2H)-pyran-2,4(3H)-dione (dehydroacetic acid or DHA), o-phenylenediamine, and benzaldehyde were characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, ¹H-NMR, UV-Vis spectroscopy, and mass spectra. From analytical data, the stiochiometry of the complexes was found to be 1?:?2 (metal?:?ligand) with octahedral geometry. The molar conductance values suggest nonelectrolytes. X-ray diffraction data suggest monoclinic crystal systems. IR spectral data suggest that the ligand is dibasic tridentate with ONN donors. To investigate the relationship between formation constants of metal complexes and antimicrobial activity, the dissociation constants of Schiff base and stability constants of its binary metal complexes have been determined potentiometrically in THF–water (60?:?40) at 30?±?1°C and at 0.1?mol?L^?1 NaClO₄ ionic strength. The potentiometric titrations suggest 1?:?1 and 1?:?2 complexation. Antibacterial and antifungal activities in vitro were performed against Staphylococcus aureus, Escherichia coli, Aspergillus niger, and Trichoderma with determination of minimum inhibitory concentrations of ligand and metal complexes. The structure–activity correlation based on stability constants of metal complexes is discussed. Activity enhances upon complexation and the order of activity is in accord with the stability order of metal ions.     

Regularities of the formation of binuclear homo- and heteroleptic complexes of <Emphasis Type="Italic">d</Emphasis> metals with 3,3′-bis(dipyrrolylmethenes) in DMF

The reactions of seven symmetrically alkylated tetradentate ligands 3,3′-bis(dipyrrolylmethenes) (H₂L) with d-metal acetates (M(AcO)₂) in DMF solutions at 298.15 K were studied by spectrophotometry. Helicands H2L were found to be structurally preorganized to form stable binuclear homoleptic two-helix helicates [M₂L₂] with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) acetates. The coordination of the ligands by the metal ions included consecutive stages of formation of the heteroleptic [M₂L(AcO)₂] and homoleptic [M₂L₂] complexes. The [M₂L(AcO)₂] complexes were spectrally revealed in solutions containing a ligand excess (c _{H 2 L} / c _{M(AcO) 2} > 1). An increase in the salt concentration shifted the system of equilibria to the homoligand product [M₂L₂]. The thermodynamic constants of the reactions increased in the series of complexing agents: Cu(II) < Cd(II) < Hg(II) < Ni(II) < Co(II) < Zn(II). An analysis of the data on the thermodynamic constants of [M₂L₂] helicate formation in solutions and the earlier obtained results of the IR and ¹H NMR studies of the hydrobromic salts of the ligands (H₂L · 2HBr) showed that the key regularities of the influence of the structural factors on the coordination properties of the ligands were in an increase in the stability of the [M₂L₂] complexes with an increase in the basicity of the ligands.