Synthesis,characterization and biocidal activities of some metal(II) complexes with diacetyl salicylaldehyde acyldihydrazones

Complexes of diacetyl salicylaldehyde oxalic acid dihydrazone, CH₃COC(CH₃)= NNHCOCONHN=CHC₆H₄(OH),(dsodh) and diacetyl salicylaldehyde malonic acid dihydrazone CH₃COC(CH₃)=NNHCOCH₂CONHN=CHC₆H₄(OH), (dsmdh) of general compositions [M(L)]Cl, [M′(L)Cl], [M(L′)]Cl and [M′(L′)Cl] (where M?=?Co(II), Cu(II), Zn(II), Cd(II) and M′?=?Ni(II); HL?=?dsodh and HL′?=?dsmdh) were prepared and characterized by elemental analyses, molar conductance, magnetic moments, electronic, ESR and infrared spectra and X-ray diffraction data. The magnetic moments and electronic spectra indicate six-coordinate octahedral geometry for Co(II) and square planar geometry for Ni(II) complexes. The ESR spectral data of Cu(II) complexes in DMF solution reveal a tetragonally distorted octahedral geometry. Both ligands bond through >C=O, >C=N and deprotonated phenolate groups in all octahedral complexes and through >C=N and deprotonated phenolate groups in Ni(II) square planar complexes. The lattice parameters for Cu(dsodh) and Co(dsmdh) correspond to an orthorhombic and Ni(dsodh) corresponds to a tetragonal crystal lattice.

The complexes show significant antifungal activity against a number of pathogenic fungi viz. Stemphylium, Myrothecium and Alternaria. The antibacterial activity was studied against Pseudomonas fluorescence (gram ?ve) and Clostridium thermocellum (gram +ve).     

Synthesis, spectral, and biological studies of some metal(II) complexes with benzil salicylaldehyde acyldihydrazones

Complexes of the general formula [M(Bsodh)]Cl and [M(Bsmdh)]Cl, where M = Co(II), Ni(II), Cu(II), Zn(II,) and Cd(II) (HBsodh = benzil salicylaldehyde oxalic acid dihydrazone and HBsmdh = benzil salicylaldehyde malonic acid dihydrazone) were synthesized and characterized by elemental analyses, molar conductance, magnetic moments, electronic, ESR, infrared spectra, and X-ray diffraction studies. The complexes are stable solids insoluble in common organic solvents and 1: 1 electrolytes. The magnetic moments and electronic spectra reveal a square-planar geometry for [M(Bsodh)]Cl and a six-coordinate octahedral geometry for [M(Bsmdh)]Cl. The HBsodh ligand bonds to the metal ion via one >C=O, two >C=N−, and one deprotonated phenolate group, whereas HBsmdh bonds through three >C=O, two >C=N−, and one phenolate group. The lattice parameters for [Co(Bsodh)]Cl and [Ni(Bsmdh)]Cl correspond to tetragonal and orthorhombic crystal lattices, respectively. ESR spectral data indicate the presence of an unpaired electron in of the Cu²⁺ ion. The ligands, as well as their metal complexes, show significant antibacterial activity against Bacillus subtilis and Pseudomonas fluorescens. The text was submitted by the authors in English.     

Synthesis and physico-chemical studies of metal(II) complexes with diacetyl benzaldehyde acyldihydrazones and their bio-activity

Complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with diacetyl benzaldehyde oxalic acid dihydrazone (dbodh), CH₃COC(CH₃)=NNHCOCONHN=CHC₆H₅ and diacetyl benzaldehyde malonic acid dihydrazone (dbmdh), CH₃COC(CH₃)=NNHCOCH₂CONHN=CHC₆H₅ of general composition [M(dbodh)Cl]Cl and [M(dbmdh)Cl]Cl were synthesized and characterized by microanalyses, molar conductance, magnetic susceptibility, UV–Vis, ESR and IR spectra and X-ray diffraction studies. The complexes are 1 : 1 electrolytes in DMF and are insoluble in water and common organic solvents. The dbodh and dbmdh are neutral tridentate ligands in most complexes and coordinate via one >C=O and two >C=N–groups. In Cu(II) complexes the ligands are pentadentate coordinating through three >C=O and two >C=N–groups. The magnetic moment values and UV–Vis spectra suggest square-planar geometry for Co(II) and Ni(II) complexes and distorted octahedron for both Cu(II) complexes. The ESR spectra of Cu(II) complexes show well-defined copper hyperfine lines in DMSO solution at 120 K and exhibit d _{x ² ?y ²} as the ground state. The X-ray diffraction parameters for [Ni(dbodh)Cl]Cl and [Co(dbmdh)Cl]Cl correspond to a tetragonal crystal lattice. The complexes show significant antifungal activity against Alternaria sp., Curvularia sp. and Colletotrichum sp. and fair antibacterial activity against Bacillus subtilis and Pseudomonas fluorescence.     

Synthesis,structural studies and bio-activity of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with p -amino acetophenone salicyloyl hydrazone

Complexes of the type [M(pash)Cl] and [M(Hpash)(H₂O)SO₄] (M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpash = p-amino acetophenone salicyloyl hydrazone) have been synthesized and characterized by elemental analyses, molar electrical conductance, magnetic moments, electronic, ESR and IR spectra, thermal studies and X-ray powder diffraction. All the complexes are insoluble in common organic solvents and are non-electrolytes. The magnetic moment values and electronic spectra indicate a square-planar geometry for Co(II), Ni(II) and Cu(II) chloride complexes and spin-free octahedral geometry for the sulfato complexes. The ligand coordinates through >C=N–,–NH₂ and a deprotonated enolate group in all the chloro complexes, and through >C=N–, >C=O and–NH₂ in the sulfato complexes. Thermal analyses (TGA and DTA) of [Cu(pash)Cl] show a multi-step exothermic decomposition pattern. ESR spectral parameters of Cu(II) complexes in solid state at room temperature suggest the presence of the unpaired electron in d _{x ² ? y ²} . X-ray powder diffraction parameters for [Cu(pash)Cl] and [Ni(Hpash)(H₂O)SO₄] correspond to tetragonal and orthorhombic crystal lattices, respectively. The complexes show a fair degree of antifungal activity against Aspergillus sp., Stemphylium sp. and Trichoderma sp. and moderate antibacterial activity against E. coli and Clostridium sp.     

Asymmetric Schiff Base (N 2 O 3 ) Complexes as Ligands Towards Mn(II), Fe(III) and Co(II), Synthesis and Characterization

Heterobi- and tri-nuclear complexes [LMM'Cl] and [(LM) 2 M'](M=Ni or Cu and M'=Mn, Fe or Co) have been synthesised. The heteronuclear complexes were prepared by stepwise reactions using two mononuclear Ni(II) and Cu(II) complexes of the general formula [HLM]·1/2H 2 O, as ligands towards the metal ions, Mn(II), Fe(III) and Co(II). The asymmetrical pentadentate (N 2 O 3 ) Schiff-base ligands used were prepared by condensing acetoacetylphenol and ethylenediamine, molar ratio 1 1, to yield a half-unit compound which was further condensed with either salicylaldehyde or naphthaldehyde to yield the ligands H 3 L 1 and H 3 L 2 which possess two dissimilar coordination sites, an inner four-coordinate N 2 O 2 donor set and an outer three-coordinated O 2 O set. 1 H NMR and IR spectra indicate that the Ni(II) and Cu(II) ions are bonded to the inner N 2 O 2 sites of the ligands leaving their outer O 2 O sites vacant for further coordination. Different types of products were obtained according to the type of metal ion. These products differ in stoichiometry according to the type of ligand in the parent compound. Electronic spectra and magnetic moments indicate that the structures of the parent Ni(II) and Cu(II) complexes are square-planar while the geometry around Fe(III), Mn(II) and Co(II) in their products are octahedral as elucidated from IR, UV-visible, ESR, 1 H NMR, mass spectrometry and magnetic moments.     

Synthesis and characterization of some pyrimidine, purine, amino acid and mixed ligand complexes

Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of barbital, thiouracil, adenine, amino acids (methionine, lysine and alanine) and some mixed ligands were prepared and characterized by elemental analyses, IR, electronic spectra, magnetic susceptibility and ESR spectra. Coordination of the metallic centre to the oxygen and nitrogen atoms of barbital, thiouracil, amino acids and coordinate to amino group and nitrogen atom of adenine occurred. Electronic spectra and magnetic susceptibility measurements were utilized to infer the structure of the complexes which are octahedral for Mn(II), Fe(III), Co(II), Ni(II) and Cd(II) and tetrahedral for Mn(II), Cu(II), Zn(II) complexes. ESR spectra were observed for copper complexes with a d(x2)-(y2) ground state with small g(||) values indicating strong interaction between the ligands and their metal ions.     

Spectral, magnetic and biological studies of 1,4-dibenzoyl-3-thiosemicarbazide complexes with some first row transition metal ions

The ligand 1,4-dibenzoyl-3-thiosemicarbazide (DBtsc) forms complexes [M(DBtsc-H)(SCN)] [M = Mn(II), Co(II) or Zn(II)], [M(DBtsc-H) (SCN)(H₂O)] [M = Ni(II) or Cu(II)], [M(DBtsc-H)Cl] [M = Co(II), Ni(II), Cu(II) or Zn(II)] and [Mn(DBtsc)Cl₂], which have been characterized by elemental analyses, magnetic susceptibility measurements, UV/Vis, IR,¹H and¹³C NMR and FAB mass spectral data. Room temperature ESR spectra of the Mn(II) and Cu(II) complexes yield <g> values, characteristic of tetrahedral and square planar complexes respectively. DBtsc and its soluble complexes have been screened against several bacteria, fungi and tumour cell lines.     

Synthesis,Spectral Studies and Bio‐activity of Some Ligand Bridged Polymeric Transition Metal Complexes of Acetone p‐Amino Acetophenone Isonicotinoyl Hydrazone

Ligand bridged polymeric complexes of the type [M(apainh)(H₂O)X] where, M=Mn(II), Co(II), Ni(II), Cu(II), and Zn(II); X=Cl₂ or SO₄; apainh=acetone p‐amino acetophenone isonicotinoyl hydrazone have been synthesized and characterized. The complexes are stable solids, insoluble in common organic solvents and are non‐electrolytes. Magnetic moments and electronic spectral studies suggest a spin‐free octahedral geometry for all Mn(II), Co(II), Ni(II), and Cu(II) complexes. IR spectra show tridentate nature of the ligand bonding through two >C?N and a >C?O groups. X‐ray powder diffraction parameters for some of the complexes correspond to orthorhombic and tetragonal crystal lattices. Thermal studies (TGA and DTA) of [Mn(apainh)(H₂O)SO₄] complex show multi‐step decomposition pattern of both an endothermic and exothermic nature. ESR data of Cu(II) chloride complex in solid state show an axial spectra, whereas, Cu(II) sulfate complex is isotropic in nature. The complexes show a significant antifungal activity against a number of pathogenic fungal species and antibacterial activity against Pseudomonas sp. and Clostridium sp. The metal complexes are more active than the ligand.     

Metal-based antibacterial agents: synthesis,characterization, and in vitro biological evaluation of cefixime-derived Schiff bases and their complexes with Zn(II), Cu(II), Ni(II), and Co(II)

The zinc(II), copper(II), nickel(II), and cobalt(II) complexes of Schiff bases, obtained by the condensation of cefixime with furyl-2-carboxaldehyde, thiophene-2-carboxaldehyde, salicylaldehyde, pyrrol-2-carboxaldehyde, and 3-hydroxynaphthalene-2-carboxaldehyde, were synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, IR, and electronic spectral measurements. Analytical data and electrical conductivity measurements indicated the formation of M?:?L (1?:?2) complexes, [M(L)₂(H₂O)₂] or [M(L)₂(H₂O)₂]Cl₂ [where M?=?Zn(II), Cu(II), Ni(II), and Co(II)] in which ligands are bidentate via azomethine-N and deprotonated-O of salicyl and naphthyl, furanyl-O, thienyl-S, and deprotonated pyrrolyl-N. The magnetic moments and electronic spectral data suggest octahedral complexes. The synthesized ligands, along with their metal complexes, were screened for their antibacterial activity against different bacterial strains. The studies show the metal complexes to be more active against one or more species as compared to the uncomplexed ligands.     

Synthesis,physico-chemical investigations and biological studies on Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with p -amino acetophenone isonicotinoyl hydrazone

Complexes of the type [M(painh)(H₂O)₂X], where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); X = Cl₂ or SO₄; painh = p-amino acetophenone isonicotinoyl hydrazone, have been synthesized and characterized by spectral and other physico-chemical techniques. The synthesized complexes are stable powders, insoluble in common organic solvents such as ethanol, benzene, carbon tetrachloride, chloroform and diethyl ether, and are non-electrolytes. Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) studies show that the organic ligand decomposes exothermically through various steps. TGA and Infrared (IR) spectral studies indicate the presence of coordinated water in the metal complexes. Magnetic susceptibility measurements and electronic spectra suggest that Mn(II), Co(II), and Ni(II) complexes are paramagnetic with octahedral geometry, whereas Cu(II) complexes have distorted octahedral geometry. The neutral bidentate ligand bonds through >C=O and >C=N–groups in all the complexes. Electron Spin Resonance (ESR) spectra in the solid state show axial symmetry for [Cu(painh)(H₂O)₂(SO₄)] and elongated rhombic symmetry for [Cu(painh)(H₂O)₂Cl₂], suggesting an elongated tetragonally-distorted octahedral structure for both complexes. X-ray powder diffraction parameters for two complexes correspond to tetragonal and orthorhombic crystal lattices. The metal complexes show fair antifungal activity against Rizoctonia sp., Aspergillus sp., Stemphylium sp., and Penicillium sp. and appreciable antibacterial activity against Pseudomonas sp. and Escherichia coli.     

Structural studies of metal complexes containing amide ligands

Complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Pd(II) with di-N-phenyl pyromellitic diimide (PhPMDI) and di-N-pyridyl pyromellitic diimide (PyPMDI) were prepared and characterized based on analytical, molar conductance, magnetic, IR, PMR, electronic and ESR data. Based on analytical and molar conductance, the complexes have been formulated as [M(PhPMDA)(H₂O)₂]_n (M = Mn, Fe, Co, Ni), [Cu(PhPMDA)]_n [Pd₂(PhPMDA)Cl₂(H₂O)₂], [M(PyPMDA)]_n (M = Mn, Fe, Co, Ni and Cu) and [Pd₂(PyPMDA)Cl₂] In all these complexes PhPMDA acts as a mononegative bidentate ligand whereas PyPMDA acts as a mononegative tridentate one in the form of amide rather than imide. The geometries of the complexes have been proposed based on the electronic spectra. The various bonding parameters have been calculated from the ESR spectra of Cu(II) complexes.     

Modern spectroscopic techniques in the characterization of Schiff base macrocyclic ligand and its complexes with transition metals

Mn(II), Co(II), Ni(II), and Cu(II) complexes with a new azamacrocyclic tetradentate [N(4)] ligand i.e. 2,3,9,10-tetraphenyl;l,4,8,11-tetraazacyclotetradeca;1,3,8,10-tetraene (L) have been synthesized and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, (1)HNMR, IR, electronic and EPR spectral studies. On the basis of their non-electrolytic nature, the probable formula of the complexes is proposed to be [M(L)X(2)], where M=Mn(II), Co(II), Ni(II), and Cu(II), X=Cl(-) and NO(3)(-), in dimethylformamide (DMF). All the complexes are of high-spin type and found to have six coordinated, octahedral geometry for Mn(II), Co(II), and Ni(II) complexes, and tetragonal for Cu(II) complexes. Macrocyclic ligand and its complexes have also been screened against pathogenic bacteria and fungi in vitro as growth inhibiting agent.     

Metalloantibiotics: synthesis and antibacterial activity of ceftazidime metal complexes

Ceftazidime (Hceftaz) interacts with transition metal(II) ions to give octahedral [M(ceftaz)(H₂O)Cl] complexes [M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Cd(II)] which were characterized by physicochemical and spectroscopic methods. The spectra indicated that the ligand is a multidentate chelating agent. The complexes are insoluble in water and common organic solvents and probably have polymeric structures. The antibacterial activity of the metal complexes was found to be lower than that of free ceftazidime.     

Synthesis,spectral, and antifungal studies of transition metal complexes with sixteen-membered hexadentate macrocylic ligand

A novel hexadentate nitrogen donor [N₆] macrocyclic ligand viz, 1,5,11,15,21,22-hexaaza-2,14-dimethyl-l4,12-diphenyltricyclo[15.3.1.I(7–11)]docosane[1,4,6,8,10(22)-11,14,16,18,20(21)]decaene (L), has been synthesised. The Co (II), Ni (II), and Cu (II) complexes with this ligand have been prepared and subjected to elemental analysis, molar conductance, magnetic susceptibility measurements, mass, ¹H NMR (ligand), IR, electronic, and ESR spectral studies and electrochemical investigation. On the basis of molar conductance the complexes can be formulated as [M(L)]X₂ (where M = Co (II), Ni (II), Cu (II) and X = Cl⁻ and NO₃⁻) due to their 1: 2 electrolytic nature in DMSO. All the complexes are of the high-spin type and are six-coordinated. On the basis of IR, electronic, and ESR spectral studies, an octahedral geometry has been assigned for the Co(II) and Ni(II) complexes, whereas a tetragonal geometry for the Cu(II) complexes was found. Antimicrobial activity of L and its complexes as growth inhibiting agents have been screened in vitro against two species (F. moniliformae and R. solani) of plant pathogenic fungi. The text was submitted by the authors in English.     

Synthesis, spectroscopic characterization and comparative DNA binding studies of Schiff base complexes derived from L-leucine and glyoxal

The mononuclear Schiff base complexes of the type, [ML(CH₃OH)₂] [M = Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by template condensation of l-leucine and glyoxal. The complexes have been characterized on the basis of the results of the elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz, FT-IR, Mass, ¹H NMR and ¹³C NMR spectra. The UV–vis and magnetic moment data revealed an octahedral geometry around Co(II), Ni(II) ion with distortion around Cu(II) ion complex confirmed by EPR data. The conductivity data show a non-electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that all the complexes exhibit a significant binding to calf thymus DNA.     

Spectral and thermal studies of divalent transition metal complexes with indole-2-carboxylic acid and 4-substituted hydrazinethiocarbamide

Ternary complexes of Co(II), Ni(II) and Cu(II) with indole-2-carboxylic acid (A) and 4-substituted hydrazinethiocarbamide (L) [4-phenylhydrazinethiocarbamide (L1), 4-benzylhydrazinethiocarbamide (L2) and 4-(2-propenyl)hydrazinethiocarbamide (L3)] were prepared. The structures of the complexes were proposed by molar conductance, electronic, IR, 1H NMR, mass spectra as well as thermogravimetric (TG) studies. An octahedral structure is suggested for Co(II), Ni(II) and Cu(II) ternary complexes.     

Synthesis,spectroscopic, thermal,and biological activities of mixed ligand complexes containing E-N′-(3,4,5-trimethoxybenzylidene)benzofuran-2-carbohydrazide and 2-aminothiophenol

Complexes [M(L)(L′)Cl?·?H₂O], where M?=?Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II), L?=?ligand derived from reaction between benzofuran-2-carbohydrazide and 3,4,5-trimethoxybenzaldehyde (TMeOBFC) and L′?=?2-aminothiophenol (2-atp), have been synthesized. The structures of the complexes have been proposed from analytical data, IR, UV-Vis, ¹H NMR, direct analysis in real time-mass spectra, ESR spectral data, magnetic, and thermal studies. The complexes are soluble in DMF and DMSO. Molar conductance values indicate that the complexes are non-electrolytes. Antibacterial and antifungal activities of the ligands and their metal complexes have been obtained against bacteria Escherichia coli and Staphylococcus aureus and against fungi Aspergillus niger and Aspergillus flavus.     

Synthesis, characterization and biological activity of bis(phenylimine) Schiff base ligands and their metal complexes

Metal complexes derived from 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine); L1, 2,6-pyridinedicarboxaldehydebis (o-hydroxyphenylimine); L2, are reported and characterized based on elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The complexes are found to have the formulae [MX2(L1 or L2)] x nH2O, where M=Fe(II), Co(II), Ni(II), Cu(II) and Zn(II), X=Cl in case of Fe(II), Co(II), Ni(II), Cu(II) complexes and Br in case of Zn(II) complexes and n=0-2.5. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the Schiff bases are coordinated to the metal ions in a terdentate manner with NNN donor sites of the pyridine-N and two azomethine-N. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are trigonal bipyramidal (in case of Co(II), Ni(II), Cu(II) and Zn(II) complexes) and octahedral (in case of Fe(II) complexes). The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the coordinated water, anions and ligands (L1 and L2) in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the TG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent organic ligands against one or more bacterial species.     

Synthesis and characterization of the complexes of some transition metals with 2-acetyl pyridine (N-benzoyl) glycyl hydrazone

Complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with 2-acetyl pyridine (N-benzoyl) glycyl hydrazone(2-ApBzGH) have been synthesized and characterized by elemental analyses, molar conductances, magnetic susceptibility, IR, electronic, ESR,¹H,¹³C and¹¹³Cd NMR spectral and X-ray diffraction studies. IR and NMR data suggest the tridentate nature of the ligand coordinating as a neutral species in the addition complexes and as a uninegative species in the deprotonated complexes. The presence of more than one isomer of the ligand has been established by¹H NMR spectra of the ligand and complexes recorded over the 298–396 K range. The X-ray powder diffraction patterns of [Cd(2-ApBzGH)Cl]Cl and [Cu(2-ApBzGH)Cl(H₂O)₂]Cl are indexed for orthorhombic and tetragonal crystal systems respectively.