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.     

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.     

Phenoxo-bridged symmetrical homobinuclear complexes derived from an “end-off” compartmental ligand, 2,6- bis [5′-chloro-3′-phenyl- 1H -indole-2′-carboxamidyliminomethyl]-4-methylphenol

A compartment ligand 2,6-bis[5′-chloro-3′-phenyl-1H-indole-2′-carboxamidyliminomethyl]-4-methylphenol was prepared and homobinuclear phenol-bridged Cu(II), Ni(II), Co(II), Zn(II), Cd(II), Hg(II), Fe(III), and Mn(II) complexes have been prepared by the template method using the precursors 2,6-diformyl-4-methylphenol, 5-chloro-3-phenylindole-2-carbohydrazide and metal chlorides in 1 : 2 : 2 ratio, respectively. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, NMR, FAB mass and ESR spectra, TGA, and powder XRD data. Cu(II), Co(II), Zn(II), Cd(II) and Hg(II) complexes exhibit square pyramidal geometry whereas Ni(II), Mn(II), and Fe(III) complexes are octahedral. Low magnetic moment values for Cu(II), Ni(II), Co(II), Fe(III), and Mn(II) complexes show antiferromagnetic spin-exchange interaction between two metal centers in binuclear complexes. The ligand and its complexes were tested for antibacterial activity against Escherichia coli and Staphyloccocus aureus, and antifungal activity against Aspergillus niger and Candida albicans.     

Synthesis,characterization and antimicrobial activity of homodinuclear complexes derived from 2,6- bis [3′-methyl- 2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol,an end-off compartmental ligand

End-off compartmental pentadentate Schiff base, 2,6-bis[3′-methyl-2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol is synthesized and characterized by 2D NMR experiments and mass spectral techniques. The homodinuclear phenalato bridged end-off compartmental Schiff-base complexes Cu(II), Co(II), Ni(II), Mn(II), Fe(III), VO(IV), Zn(II), Cd(II) and Hg(II) have been prepared by the template method using the precursors 2,6-diformyl-4-methylphenol, 3-methyl(6′,7′)-2-benzindolehydrazide and metal chlorides in 1?:?2?:?2 ratio. The complexes are characterized by IR, NMR, UV-vis, FAB-mass, ESR and TGA techniques. Ni(II), Mn(II) and Fe(III) complexes have octahedral geometry, whereas the Cu(II), Co(II), VO(IV), Zn(II), Cd(II) and Hg(II) complexes have square pyramidal geometry. Low magnetic moment values for Cu(II), Co(II), Ni(II), Mn(II), Fe(III) and VO(IV) complexes indicate antiferromagnetic spin-exchange interaction between two metal centers. The metal complexes have been screened for their antibacterial activity against Escherichia coli and Staphyloccocus aureus and antifungal activity against Aspergillus niger and Fusarium oxysporum.     

New Complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with 3,3-dimethylglutaric Acid

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)3,3-dimethylglutarates were investigated and their quantitative composition, solubility in water at 293 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with general formula MC₇H₁₀O₄⋅nH₂O (n=0−2) were recorded and their thermal decomposition in air were studied. During heating the hydrated complexes of Mn(II),Co(II), Ni(II) and Cu(II) are dehydrated in one step and next all the anhydrous complexes decompose to oxides directly (Mn, Co, Zn) or with intermediate formation free metal (Ni,Cu) or oxocarbonates (Cd). The carboxylate groups in the complexes studied are bidentate. The magnetic moments for the paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II)attain values 5.62, 5.25, 2.91 and 1.41 M.B., respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

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.     

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.     

Spectroscopic investigations and physico-chemical characterization of newly synthesized mixed-ligand complexes of 2-methylbenzimidazole with metal ions

Some mixed ligand complexes containing 2-methylbenzimidazole and thiocyanate ion were synthesized. Free ligands and their metal complexes were characterized using elemental analysis, determination of metal, magnetic susceptibility, molar conductivity, infrared, UV-VIS, and (¹H, ¹³C) NMR spectra, and X-ray structure analysis. The results suggest that the Ag(I) complex has linear geometry, Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have tetrahedral geometry, Pd(II) complex has square planar geometry, VO(IV) square pyramidal geometry, Pb(II) irregular tetrahedral geometry, and that the Cr(III) and Mn(II) complexes have octahedral geometry. The following general formulae were proposed for the prepared complexes: [AgBX], [CrB₃X₃], (HB)₂[MnB₂X₄] · 2B and [MB₂X₂], where B = 2-methylbenzimidazole, HB = 2-methylbenzimidazolium, X = thiocyanate ion, and M = VO(IV), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), and Pb(II). Molar conductance of a 10⁻³ M solution in N,N-dimethyl formamide (DMF) indicates that all the complexes are non-electrolytes except the Mn(II) complex which is an electrolyte because the molar conductivity of its solution in DMF is high.     

A POTENTIOMETRIC STUDY OF METAL CHELATES WITH TETRAETHYLENEPENTAAMINEHEPTA-ACETIC ACID

Abstract

The protonation constants of tetraethylenepentaamineheptaacetic acid, TPHA, were determined by potentiometric titration in aqueous solution at an ionic strength of 0.10 M KNO₃ and at 25°C. The formation constants of various metal-TPHA complexes were also obtained by titrating mixtures of metal to ligand in molar ratios of 1 :1 and 2:1. Calculations were performed with the computer program BEST. Individual stability constants are reported for Co(II). Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) with TPHA as well as their related pro-tonated species. The stabilities of the 1:1 complexes parallel to those of similar complexes with DTPA and TTHA. However the 2: 1 complexes have significantly larger log K _ML's than their TTHA counterparts. The extra stability of the 2:1 metal-TPHA complexes is explained in terms of ligand denticity and steric effects. Mercury(II)-TPHA complexes exhibited the highest formation constants and the copper-TPHA complexes had slightly higher log K _ML's than those for Co(II), Ni(II), Zn(II), Cd(II) and Pb(II).     

A POTENTIOMETRIC STUDY OF METAL CHELATES WITH PENTAETHYLENEHEXAAMINEOCTAACETIC ACID

Abstract

The protonation constants of pentaethylenehexaamineoctaacetic acid, PHOA, were determined by potentiometric titration in aqueous solution at an ionic strength of 0.10 M KNO₃ and at 25°C. The formation constants of various metal-PHOA complexes were also obtained by titrating mixtures of metal to ligand in molar ratios of 1:1 and 2:1. Calculations were performed with the computer program BEST. Individual formation constants are reported for Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) with PHOA as well as their related protonated species. The stabilities of the 1:1 and 2:1 complexes are similar in many respects to complexes formed with tetraethylenepentaamineheptaacetic acid (TPHA). The similarities in the stabilities of both the 1:1 and 2:1 complexes with PHOA and those with TPHA are explained in terms of ligand denticity and steric effects. Mercury(II)-PHOA complexes exhibited the highest formation constants, followed by copper(II)-PHOA complexes which had higher log K _ML's than those for Co(II), Ni(II), Zn(II), Cd(II) and Pb(II).     

Synthesis and antibacterial activity of cephalexin metal complexes

The interactions of cephalexin (Hcepha) with transition and d¹⁰ metal ions have been investigated. The complexes [M(cepha)Cl]nH₂O [M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II)] were characterized by physicochemical and spectroscopic methods. The IR and ¹H NMR spectra of the complexes suggest that cephalexin behaves as a monoanionic tridentate ligand. In vitro antibacterial activities of Hcepha and the complexes were tested.     

Synthesis and complexation of 1,4,7-oxadithiononane-5,6-dionedioxime

A new vic-dioxime 1,4,7-oxadithiononane-5,6-dionedioxime (H₂L) was prepared from reaction of 2,2-oxydiethanthiol with dichloroglyoxime. Mononuclear complexes of H₂L with Ni(II), Co(II), Cu(II), Zn(II), and Cd(II) were also prepared and their structures were determined by means of ¹H?NMR, ¹³C?NMR, IR, and mass spectroscopy. Ni(II), Co(II), and Cu(II) form square planar complexes of 1?:?2 molar ratio of metal to ligand through N,N-chelation, while Zn(II) and Cd(II) form 1?:?1 tetrahedral complexes with a N,O-chelation.     

Spectrothermal studies of 1,10-phenanthroline complexes of Co(II), NI(II), Cu(II) and Cd(II) orotates

The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and Cd(II) orotates were synthesized and characterized by elemental analysis, magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis techniques (TG, DTG and DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes [M(H₂O)₂(phen)₂](H₂Or)₂·nH₂O (M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2) are coordinated by two aqua ligands and two moles of phen molecules as chelating ligands through their two nitrogen atoms. The monoanionic orotate behaves as a counter ion in the complexes. On the basis of the first DTG_max, the thermal stability of the hydrated complexes follows the order: Cd(II), 68°C 68°C     

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, magnetic and thermal investigations of some d-electron element 3-methoxy-4-methylbenzoates

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methoxy-4-methylbenzoates were investigated and their quantitative composition and magnetic moments were determined. The IR spectra and powder diffraction patterns of the complexes prepared of general formula M(C₉H₉O₃)₂·nH₂O (n=2 for Mn, Co n=1 for Ni, Cu, n=0 for Zn, Cd) were prepared and their thermal decomposition in air was studied. Their solubility in water at 293 K is of the order 10^–2 (Mn)–10^–4 (Cu) mol dm^–3. IR spectra of the prepared 3-methoxy-4-methylbenzoates suggest that carboxylate groups are bidentate bridging. The magnetic moments for the paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.50, 4.45, 3.16 and 1.79 B. M., respectively. During heating the hydrated complexes lose crystallization water molecules in one step and then the anhydrous complexes decompose directly to oxides MO and Mn3O4. Only Co(II) complex decomposes to Co₃O₄ with intermediate formation CoO.     

New complexes of some d-electron elements with 3-methyladipic acid

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) 3-methyladipates were investigated and their qualitative composition and magnetic moments were determined. The IR spectra and powder diffraction patterns of the complexes prepared of the general formula M(C₇H₁₀O₄)·nH₂O (n=0-11) were recorded and their thermal decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Co, Ni) or two steps (Mn, Zn) losing all crystallization water molecules (Co, Ni) or some water molecules (Mn, Zn) and then anhydrous (Co, Ni, Cu) or hydrated complexes (Mn, Zn) decompose directly to oxides (Mn, Co, Zn) or with intermediate formation the mixture of M+MO (Ni, Cu). The carboxylate groups are bidentate (Mn, Co, Ni, Cu) or monodentate (Zn). The complexes exist as polymers. The magnetic moments for the paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.48, 4.49, 2.84 and 1.45 B.M., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis,characterization and antimicrobial studies on metal complexes with a naphthofuran thiosemicarbazide derivatives

Complexes of the type MLCl₂, where M?=?Co(II), Cu(II), Ni(II), Zn(II), Cd(II) and Hg(II) and L is a thiosemicarbazide ligand derived from reaction between naphthofuran-2-carboxyhydrazide and p-chlorophenylisothiocynate (NCClPT)/p-bromophenylisothiocynate (NCBrPT) characterized by elemental analysis, conductance, magnetic susceptibility measurements, UV-Vis, IR, ¹H?NMR, and ESR. The thiosemicarbazide ligands are bidentate by coordinating through the oxygen of the carbonyl group and the nitrogen of the hydrazide residue. Based on the results, we propose structures for all the metal complexes. Both the ligands and their complexes have been screened for their fungicidal and bactericidal activities.     

Studies on the complexing behavior of a potentially tetradentate Schiff-base ligand with some transition metal ions

The Schiff base furfural-histidine with Co(II), Ni(II), Cu(II), and Zn(II) in solution gives M(AB), M(AB)B, or M(AB)₂. The Schiff base is tetradentate in M(AB)₂ and M(AB)B and tridentate in M(AB)₂; [M(AB)₂] · 2H₂O (M = Co, Ni and Zn) and [Cu(AB)]NO₃ were synthesized and characterized by elemental analysis, molecular weight determination, conductance, IR, UV–Vis, and CV. The electronic spectral measurements indicate that M(AB)₂ (M = Co(II) and Ni(II)) are octahedral and Cu(AB) is square planar geometry. The donor groups in the complexes have been identified by IR. The complexes undergo irreversible one step, two-electron reduction. Antibacterial activity of the complexes was screened for Escherichia coli and Staphylococcus aureus. Cu(II) complex was found to be more active than the Co(II), Ni(II), and Zn(II) complexes.     

Preparation,Properties and Thermal Decompositions of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes of 2,5-dichlorobenzoic Acid

Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 2,5-dichlorobenzoates were prepared and their compositions and solubilities in water at 295 K were determined. The IR spectra and X-ray diffractograms of the obtained complexes were recorded. The complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) were obtained as solids with a 1:2 molar ratio of metal to organic ligand and different degrees of hydration. When heated at a heating rate of 10 K min^-1, the hydrated complexes lose some (Co, Zn) or all (Ni, Cu, Cd) of the crystallization water molecules and then decompose to oxide MO (Co, Ni) or gaseous products (Cu, Zn, Cd). When heated at a heating rate of 5 K min^-1, the complexes of Ni(II) and Cu(II) lose some (Ni) or all (Cu) of the crystallization water molecules and then decompose directly to MO. This revised version was published online in July 2006 with corrections to the Cover Date.