Synthesis,spectral and antimicrobial studies of transition metal complexes with novel macrocyclic ligand containing C=N and CO–NH group

This article reports synthesis of Co(II), Ni(II), Mn(II), Cu(II), and Zn(II) complexes with a new macrocyclic ligand 1,4,11,14-tetraazacyclonanodeca-5,10-dioxo-1,14-diene (H₂L). The ligand (L₁) was prepared by reaction of adipic acid and ethylenediamine in 1 : 2 ratio while the macrocycle was derived from 1,4-bis-(2′-amino-ethanamide)butane and glutaraldehyde. The synthesized complexes were characterized by elemental analysis, molar conductance, spectral analyses (¹H NMR spectra, FT-IR spectra, electronic spectra, and mass spectra), magnetic susceptibility measurements, and thermogravimetric studies. On the basis of electronic spectral studies and molar conductance measurements, octahedral geometry was confirmed for Ni(II), Mn(II), and Co(II) while tetrahedral for Zn(II) and square planar for Cu(II) complexes. The TGA results revealed that the complexes exhibited higher thermal stability than the macrocycle. All the complexes were screened against bacterial and fungal strains and preliminary antimicrobial results showed that these complexes inhibited bacterial/fungal growth to a greater extent than the ligand.     

Coordination polymers of glutaraldehyde with glycine metal complexes: synthesis,spectral characterization,and their biological evaluation

Glycine metal complexes were prepared by the reaction of glycine with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) in 1?:?2 molar ratio. Thereafter their condensation polymerization was done with glutaraldehyde to obtain polymer metal complexes. All the synthesized polymer metal complexes were characterized by elemental analysis, FT-IR, ¹H-NMR, and UV-Vis spectrometry, magnetic susceptibility, and thermogravimetric studies. The analytical data of all the polymers agreed with 1?:?1 molar ratio of metal complex to glutaraldehyde and magnetic moment data suggest that PGG–Mn(II), PGG–Co(II), PGG–Ni(II), and PGG–Cu(II) have an octahedral geometry around the metal atom, whereas the tetrahedral geometry was proposed for PGG–Zn(II) polymer. The PGG–Mn(II) and PGG–Cu(II) showed octahedral geometry. Thermal behavior of the polymer metal complexes was obtained at a heating rate of 10°C?min^?1 under nitrogen atmosphere from 0°C to 800°C. The antimicrobial activities of synthesized polymers were investigated against Streptococcus aureus, Escherichia coli, Bacillus sphaericus, Salmonella sp. (Bacteria), Fusarium oryzae, Candida albicans, and Aspergillus niger (Yeast).     

Synthesis,spectral and antibacterial activity of Co(II), Ni(II) and Zn(II) complexes with 2‐hydroxy‐benzoic acid(3,4‐dihydro‐2H‐naphthalen‐1‐ylidene)‐hydrazide

A bioactive Schiff base HL i.e. 2‐hydroxy‐benzoic acid(3,4‐dihydro‐2H ‐naphthalen‐1‐ylidene)‐hydrazide was synthesized by reacting equimolar amount of salicylic acid hydrazide and 1‐tetralone. Co(II), Ni(II) and Zn(II) complexes of ligand HL was synthesized in 1:1 and 1:2 molar ratio of metal to ligand. The structure of the synthesized ligand and metal complexes was established by elemental analysis, molar conductance, magnetic susceptibility measurements, electronic, IR and EPR spectral techniques. For determining the thermal stability the TGA has been done. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6–31 + g(d,p) basis set. Spectral data reveal that ligand behave uninegative tridentate in ML complexes and uninegative bidentate in ML₂ complexes. On the basis of characterization octahedral geometry has been assigned for Co(II) and Ni(II) complexes, while tetrahedral for Zn(II) complexes. Antibacterial activity of the synthesized compounds were evaluated against Staphylococcus aureus , Bacillus subtilis, Escherichia coli , Xanthomonas campestris and Pseudomonas aeruginosa and the results revealed that metal complexes show enhanced activity in comparison to free ligand.     

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.     

New homoleptic metal complexes of Schiff bases derived from 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one

New bidentate Schiff-base ligands 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarbothioamide HL¹ and 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarboxamide HL² were synthesized from the condensation of 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one with thiosemicarbazide and semicarbazide, respectively. Homoleptic complexes of these ligands, of general formula K[Cr(L ⁿ )₂Cl₂], K₂[Mn(L ⁿ )₂Cl₂], K₂[Fe(L¹)₂Cl₂] and [M(L ⁿ )₂] (where M = Co(II), Ni(II) Cu(II), Zn(II), Cd(II), and Hg(II) ions; n = 1 or 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometry for Cr(III), Mn(II), and Fe(II) complexes, square planar for Cu(II), Co(II), and Ni(II) complexes and tetrahedral for Zn(II), Cd(II), and Hg(II) complexes.     

Metal complexes of azo coumarin derivative: synthesis,spectroscopic, thermal,and antimicrobial studies

Cu(II), Co(II), Ni(II), Cd(II), and Zn(II) complexes of 6-(2-phenyldiazenyl)-7-hydroxy-4-methyl coumarin (PAHC) are characterized based on elemental analyses, infrared, ¹H NMR, magnetic moment, molar conductance, mass spectra, UV-Vis analysis, thermogravimetric analysis (TGA), and X-ray powder diffraction. From the elemental analyses, it is found that the complexes have formulae [M(L)₂(H₂O) _n ] ? xH₂O (where M = Cu(II), Co(II), Ni(II), Cd(II), and Zn(II), n = 0–2, x = 1–4). The molar conductance data reveal that all the metal chelates are non-electrolytes. From the magnetic and solid reflectance spectra, it is found that the structures of these complexes are octahedral or tetrahedral. The synthesized ligand and metal complexes were screened for antibacterial activity against some Gram-positive and Gram-negative bacteria.     

Tetraaza macrocyclic complexes: synthesis,spectral and antimicrobial studies

A tetradentate nitrogen donor [N₄] macrocyclic ligand, 1,3,7,9-tetraaza-2,8-dithia-4,10-dimethyl-6,12-diphenylcyclododeca-4,6,10,12-tetraene has been synthesized by using thiourea and benzoylacetone. Complexes of Mn(II), Co(II), Ni(II), and Cu(II) have been synthesized with this ligand and characterized by element chemical analysis, molar conductance, magnetic susceptibility, mass, ¹H nuclear magnetic resonance, Fourier transform–infrared, electronic, and electron paramagnetic resonance spectral studies. The molar conductance measurements of Mn(II), Co(II), and Cu(II) complexes in dimethyformamide correspond to nonelectrolytes, whereas Ni(II) complex is a 1: 2 electrolyte. The complexes are high-spin except for Ni(II) which is diamagnetic. Octahedral geometry has been assigned for Mn(II) and Co(II) complexes, square planar for Ni(II) and tetragonal geometry for Cu(II). The ligand and its complexes were screened in vitro against two pathogenic fungi (Fusarium moniliformae and Rhizoctonia solani) and bacteria (Staphylococcus aureus and Pseudomonas aeruginosa) to assess their growth inhibiting potential.     

Studies on 2-acetylpyridineisonicotinoyl hydrazone complexes of some bivalent 3d-metal ions

2-Acetylpyridineisonicotinoyl hydrazone (Hapinh) complexes of OV(II), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) having 1:1 metal-ligand stoichiometry have been prepared and characterised by elemental analyses, molar conductance, magnetic susceptibility, electronic, infrared, ESR and NMR (¹H and¹³C) studies. Octahedral/distorted octahedral geometry has been assigned for the OV(II), Mn(II), Ni(II), Cu(II) and Zn(II) complexes while tetrahedral and trigonal bipyramidal configurations have been suggested for the Co (II) adduct and deprotonated complexes respectively. IR and NMR spectral studies suggest a tridentate behaviour of Hapinh and apinh⁻ species in the adducts and deprotonated complexes respectively.     

First raw transition metal complexes of salicylidene and 2-hydroxy-1-naphthylidene-N-cyanoacetohydrazone

Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of salicylidene-N-cyano-acetohydrazone H2L1 and 2-hydroxy-l-naphthylidene-N-cyanoacetohydrazone H2L2 have been prepared in ethanolic solution and characterized by analytical, spectral, magnetic susceptibility, molar conductivity and TGA measurements. The analytical data show that all the complexes derived from H2L1 and H2L2 are formed in molar ratios 1M:2L, except the complexes of Mn(II), Co(II) and Cu(II) acetates of H2L2 and the complexes of Mn(II), Co(II) and Ni(II) acetates and CuCl2 of H2L1 are formed in 1:1 molar ratios. The conductance data show that all metal complexes are non-electrolytes. Electronic absorption spectra and magnetic susceptibility measurements proved that the prepared complexes have octahedral configuration except [Co(HL2)OAc] which has tetrahedral structure. The ligand field parameters were calculated for the Co(II) and Ni(II) complexes and the data show that the covalent character of the metal ligand sigma-bond is low. The ESR parameters of the Cu(II) complexes at room temperature were calculated. Thermal TGA for some solid complexes are reported.     

Synthesis and spectroscopic studies of novel transition metal complexes with schiff base synthesized from 1,4-bis-(<Emphasis Type="Italic">o</Emphasis>-aminophenoxy)butane and salicyldehyde

The new Co(II), Cu(II), Ni(II) and Zn(II) complexes of potentially N₂O₂ Schiff base ligand [N,N’-bis(salicyldehydene)-1,4-bis-(o-aminophenoxy)butane] (H₂L) prepared from 1,4-bis-(o-aminophenoxy)butane and salicyldehyde in DMF. Microanalytical data, elemental analysis, magnetic measurements, ^lH NMR, ¹³C NMR, UV-visible and IR spectra as well as conductance measurements were used to confirm the structures. In all complexes, H₂L behaves as a tetradentate. The article is published in the original.     

Synthesis,characterization and antimicrobial studies of novel ONO donor hydrazone Schiff base complexes with some divalent metal (II) ions

Metal complexes of two general formulae [M(L)(Cl)(H₂O)₂] [M = Mn(II), Co(II), Ni(II) and Cu(II)] and [M(L)(H₂O)] [M = Zn(II) and Cd(II)] with pyrazine-2-carbohydrazone of 2-hydroxy-5-methylacetophenone (H₂L) are synthesized and characterized by microanalytical, thermal, magnetic susceptibility measurement, spectroscopic (IR, ¹H NMR, ¹³C NMR), mass, molar conductance, X-ray powder diffraction, ESR and SEM studies. While the molar conductance measurements in DMSO indicated their non-electrolytic nature, the spectroscopic studies confirmed a tridentate ONO donor behaviour of the ligand towards the central metal ion. Based on the physico-chemical studies monomeric octahedral geometry around Mn(II), Co(II), Ni(II) and Cu(II) ions (i.e. for the first series of complexes) whereas tetrahedral to Zn(II) and Cd(II) ions (i.e. for the second series of complexes) are suggested. Based on the thermal behavior of the complexes, various kinetic and thermodynamic parameters were evaluated using Coats-Redfern method. The ligand and its metal complexes were screened for in vitro antibacterial and antifungal activity against Gram +ve S. aureus, B. subtilis and Gram –ve E. coli and S. typhi. and fungal strains, C. albicans and A. niger. The observed data infer promising biological activity of some of these complexes compared the parent ligand against all bacterial and fungal species.     

Synthesis and Spectral Characterization of Some Complexes Derived From N-Benzoyl-N′-Carboxylmethylthiopropylidine Thiourea (Bcmt)

Abstract

New metal complexes derived from the reaction of N-benzoyl-N′-carboxyl methylthiopropylidine thiourea (BCMT) with Cu(II), Co(II), Ni(II), and Fe(III) chloride and/or acetate salts have been synthesized and characterized using elemental analyses, molar conductance, spectral (IR, UV-Vis., mass, ¹H NMR), thermal (TGA, DTG), and magnetic measurements. The IR results showed the modes of coordination in case of mononuclear and binuclear metal complexes. Different types of geometries are suggested on the basis of the spectral and the magnetic data. Also, the ligand field parameters for the metal complexes were calculated. The amounts of the solvents as well as the mechanism of decomposition were proposed using thermal measurements. The results of biological activity of the ligand give us the promise to be effective in tumors treatment.     

Transition Metal Complexes of Dis(thiosemicarbazone): Synthesis and Spectral,and Antifungal Studies

Mn(II), Co(II), Ni(II), and Cu(II) complexes have been synthesized with benzil bis(thiosemicarbazone) (L) and characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, thermogravimetric studies, infrared (IR), electronic, and electron paramagnetic resonance (eEPR) spectral studies. The molar conductance measurements of the complexes in DMF correspond to the non-electrolytic nature of the complexes. Thus these complexes may be formulated as [M(L)X₂] (where M = Mn(II), Co(II), Ni(II), Cu(II) and X = Cl^? and NO₃ ^?). On the basis of IR, electronic, and EPR spectral studies, an octahedral geometry has been assigned for Mn(II), Co(II), and Ni(II) complexes, whereas a tetragonal geometry for the Cu(II) complexes is presumed. The free ligand and its metal complexes were tested against the phytopathogenic fungi (i.e., Rhizoctonia baticola, Alternaria alternata) in vitro.     

Synthesis and spectral studies of new N2S2 and N2O2 Mannich base ligands and their metal complexes

New Mannich bases bis(thiosemicarbazide methyl) phosphinic acid H₃L¹ and bis(1-phenylsemicarbazide methyl) phosphinic acid H₃L² were synthesized from condensation of phosphinic acid and formaldehyde with thiosemicarbazide and 1-phenylsemicarbazide, respectively. Monomeric complexes of these ligands, of general formula K₂[Cr^III(L ⁿ )Cl₂], K₃[Fe^II(L¹)Cl₂], K₃[Mn^II(L²)Cl₂], and K[M(L ⁿ )] (M = Co(II), Ni(II), Cu(II), Zn(II) or Cd(II); n = 1, 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR, and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometries for the Cr(III), Mn(II), and Fe(II) complexes, square planar for Co(II), Ni(II), and Cu(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes. Complex formation via molar ratio in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M : L) as (1 : 1).     

Preparation and Characterization of Sulfadiazine <Emphasis Type="Italic">Schiff</Emphasis> Base Complexes of Co(II), Ni(II), Cu(II), and Mn(II)

Summary. Complexes of Co(II), Ni(II), Cu(II), and Mn(II) containing Schiff base NOS donor ligands have been synthesised via chemical and electrochemical techniques. The structure of the complexes has been elucidated by elemental analysis, conductance, magnetic susceptibility measurements, IR, ESR, electronic spectral studies and thermal techniques (TGA and DTA). The electrochemical behaviour of the metal complexes was studied using DC polarography and cyclic voltammetry. Antimicrobial activity of the title Schiff base and its complexes has been tested against different microorganisms.     

Metal chelates of some transition and non-transition metal ions with Schiff base derived from isatin witho-phenylenediamine

Summary New Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) chelates of the Schiff base derived from isatin witho-phenylenediamine have been synthesized and characterized on the basis of elemental analyses, electronic, IR and¹H NMR spectra, and also by aid of molar conductivity and magnetic moment measurements. It has been found that the Schiff base behaves as ONNO tetradentate dibasic ligand forming chelates with 1:1 (metal:ligand) stoichiometry. Square planar environment is suggested for nickel(II) chelate. All the metal chelates show non-electrolytic behaviour.

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Metallchelate einiger Übergangs- und Nichtübergangsmetallionen mit Isatin-o-Phenylendiamin-Schiff-Basen

Zusammenfassung Es wurden neue Chelate von Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) und Pb(II) mit Schiff-Basen aus Isatin undo-Phenylendiamin hergestellt und mittels Elementaranalysen, Elektronen-, IR- und¹H-NMR-Spektroskopie, sowie durch Messung der molaren Leitfähigkeit und der magnetischen Momente charakterisiert. Es wurde festgestellt, daß sich die Schiff-Base als vierzähniger zweibasischer ONNO-Ligand verhält, wobei 1:1-stöchiometrische Metall:Ligand-Komplexe gebildet werden. Für das Nickel(II)-Chelat wird eine quadratisch-planare Geometrie vorgeschlagen. Alle untersuchten Metallchelate zeigen ein nicht-elektrolytisches Verhalten.

     

Synthesis and spectral characterization of Schiff-base complexes derived from alanine and 2-acetylpyridine with some divalent metal acetates

Schiff-base complexes [ML(H₂O)₂(Ac)]nH₂O (M?=?Co(II), Ni(II) and Zn(II); L?=?Schiff-base ligand derived from 2-acetylpyridine and alanine and n?=?1–3/2) were synthesized and characterized by elemental analysis, spectral (FTIR, UV/Vis, MS, ¹H-NMR), thermal (TGA), conductance and magnetic moment measurements. The results suggest octahedral geometry for all the isolated complexes. IR spectra show that the ligand coordinates to the metal ions as mononegative tridentate through pyridyl nitrogen, azomethine nitrogen and carboxylate oxygen after deprotonation of the hydroxyl group. Semi-empirical calculations PM3 and AM1 have been used to study the molecular geometry and the harmonic vibrational spectra to assist the experimental assignments of the complexes.     

TRANSITION METAL COMPLEXES OF 1-ISOVALERYL-4-PHENYL-3-THIOSEMICARBAZIDE

Abstract

The complexes of 1-isovaleryl-4-phenyl-3-thiosemicarbazide (IVPTS) with Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared and characterized on the basis of elemental analyses, molar conductance, magnetic moment and spectral (visible, IR, NMR) studies. Square-planar geometry have been proposed for Ni(II) and Cu(II) and octahedral for the Co(II) complex.     

Antimicrobial studies of N - N ′-dicarboxydiethyloxamide and its Co(II), Ni(II), Cu(II) and Zn(II) complexes

Neutral complexes of Cu(II), Ni(II), Co(II), and Zn(II) have been synthesized from the oxamide-based ligand derived from leucine and diethyloxalate. The structural features have been deduced from their microanalytical, IR, UV/Vis, mass, ¹H and ¹³C NMR spectral data. The Co(II) and Ni(II) chelates have octahedral geometries and the Cu(II) chelate is a square-pyramidal geometry. The non-electrolytic and monomeric nature of the complexes is shown by their magnetic susceptibility and low conductance data. The biological activities of the ligand and its metal chelates against gram-positive and negative bacteria and fungi are also reported. All the compounds are antimicrobially active and show higher activity than the free ligand.     

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.