Synthesis and Properties of Mononuclear and Homobinuclear Chelates of Mn(II), Co(II), Ni(II), and Cu(II) with Phthalein Purple

Summary. Mono- and homobinuclear complexes of Mn(II), Co(II), Ni(II), and Cu(II) with phthalein purple are prepared and characterized by elemental analysis, thermal studies (TGA and DTA), spectral methods (IR, UV/Vis, and ESR), magnetic moment determination, and electrochemical reduction (DC polarography at DME and CV at HMDE). Thermal degradation of the complexes was studied by TGA and DTA where some thermodynamic parameters were determined. The mode of bonding and geometry of the complexes were determined from the spectral studies. Magnetic moment values showed some antiferromagnetism in the homobinuclear complexes. The reduction of the metal ions proceeds to the metallic state along an irreversible process.     

Synthesis and Thermal Properties of 4,4'-bipyridine Adducts of Mn(II), Co(II), Ni(II) and Cu(II) Monochloroacetate

The complexes with the empirical formula M(4-bipy)(ClCH₂COO)₂ ×nH₂O (where: 4-bipy=4,4'-bipyridine, L=ClCH₂ COO^–, M (II)=Mn, Co, Ni, Cu) were prepared and characterized via the IR and electronic (VIS) spectra and conductivity measurements. Thermal decomposition of these compounds was studied. During heating in air dehydration processes occur. The anhydrous compounds decompose at high temperature to oxides. The principal volatile mass fragments correspond to: H₂O, CO₂, CH₃Cl, HCl, Cl₂ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Structure of Mn(II), Co(II), Ni(II), and Cu(II) complexes with triformylmethane

Previously unknown [ML₂(H₂O) _n ] bischelates, where M is Mn(II), Co(II), Ni(II), or Cu(II) and L is deprotonated triformylmethane, are studied by X-ray diffraction analysis. It is revealed that in the crystals of all compounds there are multiple hydrogen bonds linking bischelate molecules into polymer layers or a single framework. The character of the temperature dependence of the effective magnetic moment [ML₂(H₂O) _n ] indicates the existences of weak intracrystalline exchange interactions between the unpaired electrons of the paramagnetic centers.     

Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3-phenyl-4-(p-methoxy- phenylazo)-5-pyrazolone

Mn(II), Co(II), Ni(II) and Cu(II) chelates with3-phenyl-4-(p-methoxyphenylazo)-5-pyrazolone have been synthesized and were characterized by elemental and thermal analyses as well as by IR, UV-VIS, ¹HNMR, conductometric and magnetic measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration, the second denotes the removal of the coordinated water molecules. The final decomposition products were found to be the respective metal oxides. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) 1:1, tetrahedral for Ni(II) 1:1and 2:3; square planar for Cu(II) 1:1 and 2:3; the complexes with no coordinated water molecules (2:3) Co(II) and Mn(II) complexes are tetrahedral. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Physicochemical Properties of the Complexes of Co(II), Ni(II), and Cu(II) with Chrysin

New solid complex compounds of Co(II), Ni(II), and Cu(II) with chrysin were obtained. Their composition and some physicochemical properties were studied (thermogravimetric analysis, ultraviolet, visible and infrared spectroscopy, magnetic properties). During heating, the hydrated complexesM(C₁₅H₉O₄)₂·nH₂O lose some crystallization water molecules in one or two steps, and then decompose to the oxides. A structure for the compounds was proposed.     

Complexes of Mn(II), Co(II), Ni(II) and Cu(II) with 4,4'-bipyridine and dichloroacetates

New mixed-ligand complexes with empirical formulae M(4-bpy)L₂·1.5H₂O (M(II)=Mn, Co), Ni(4-bpy)₂L₂ and Cu(4-bpy) L₂·H₂O (where: 4-bpy=4,4'-bipyridine, L=CC L2HCOO^-) have been isolated in pure state. The complexes have been characterized by elemental analysis, ir spectroscopy, conductivity (in methanol, dimethylformamide and dimethylsulfoxide solutions) and magnetic and x-ray diffraction measurements. The Mn(II) and Co(II) complexes are isostructural. The way of metal-ligand coordinations discussed. the ir spectra suggest that the carboxylate groups are bonded with metal(II) in the same way (Ni, Cu) or in different way (Mn, Co). The solubility in water is in the order of 19.40·10^-3÷1.88·10^-3ł mol dm^-3ł. During heating the hydrate complexes lose all water in one step. The anhydrous complexes decompose to oxides via several intermediate compounds. A coupled TG-MS system was used to analyse the principal volatile products of obtained complexes. The principal volatile products of thermal decomposition of complexes in air are: H₂O₂ ⁺, CO₂ ⁺, HCl⁺, Cl₂ ⁺, NO⁺ and other. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and Study of Co(II), Ni(II), and Cu(II) Ethylenediaminetetraacetatohydroxogermanates

New heterometallic Ge(IV) and Co(II), Ni(II), and Cu(II) complexonates based on ethylenediaminetetraacetic acid (H₄Edta) were synthesized. The composition of the complexes was determined using elemental analysis and thermogravimetry. Comparison of the IR spectra of [Ge(OH)(HEdta)] ? H₂O, which was structurally characterized previously, with those of the new complexes provided information on the composition and structure of their inner and outer spheres. The cobalt and nickel coordination polyhedra were identified by analyzing the diffuse reflection spectra and the effective magnetic moments and that of copper was identified by EPR.     

Synthesis and Thermal Decomposition of Mixed 2,4'-bipyridine-oxalato Complexes With Mn(II), Co(II), Ni(II) and Cu(II)

The mixed 2,4'-bipyridine-oxalato complexes of the formulae M(2,4'-bipy)₂ C₂ O₄ 2H₂ O (M (II)=Mn, Co, Ni, Cu; 2,4'-bipyridine=2,4'-bipy or L ; C₂ O^2– ₄ =ox) have been prepared and characterized. IR data show that the 2,4'-bipy coordinated with these metals(II) via the least hindered (4')N atom; that oxalate group acts as bidentate chelating ligand. Room temperature magnetic moments are normal for the orbital singlet states. The thermal decomposition of these complexes was investigated by TG, DTA and DTG in air. The endothermic or exothermic character of the decomposition of ML₂ (ox)2H₂ O was discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chelation behaviour of nitroso- pyrazolones with Mn(II), Co(II), Ni(II), Cu(II) AND Zn(II)

Infrared (IR), nuclear magnetic resonance (NMR), thermogravimetric analysis (TG), derivative thermogravimetric analysis (DTG), differential thermal analysis (DTA) and molar conductivity studies have been carried out on the chelates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 3-methyl- and 3-phenyl-4-nitroso-5-pyrazolones. The solid chelates were synthesized, separated, analyzed and their structures were elucidated. The data obtained show that almost all of the prepared chelates contain water molecules in their coordination sphere. The initial stage in the thermal decomposition process of these chelates shows the presence of water molecule, the second denotes to the intermediate products. The final decomposition products were found to be the respective metal oxides. The NMR spectrum of 3-methyl-4-nitroso-5-pyrazolone ligand shows the existence of the oxime rather than the nitroso form. 3-phenyl-4-nitroso-5-pyrazolone acts as a neutral bidentate ligand whereas 3-methyl-4-nitroso-5-pyrazolone acts as monobasic bidentate ligand bonded to the metal ions through the two oxygen atoms of the carbonyl and nitroso groups. The solid chelates prepared behave as non-electrolytes in DMF solution. The coordination numbers of the obtained chelates using 3-methyl-4-nitroso-5-pyrazolone are four on applying the mole ratio 1:1 and six on using 1:2 mole ratio. In case of using the ligand 3-phenyl-4-nitroso-5-pyrazolone the coordination number is six in both cases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physico-Chemical Characteristics and Formation Constants of Mono- and Binuclear Co(II), Ni(II) and Cu(II) Chelates with Phthaleincomplexone

A series of Co(II), Ni(II) and Cu(II) complexes of the type [M(PC)]2H₂O and [M₂(PC)]4H₂O, where PC is phthaleincomplexone (metalphthalein), are synthesized. It is attempted to throw some light on (heir stoichiometry, structure and stability. The formation of 1:1 and 2:1 (M:L) complexes is confirmed by their elemental microanalysis. The compounds are characterized by IR, electronic absorption spectra, X-band ESR spectra, magnetic moments and TGA measurements. The conditional stability constants are also determined.     

Synthesis, thermal and other studies of 2,4'-bipyridine-dichloroacetato complexes of Mn(II), Co(II), Ni(II) and Cu(II)

Four new mixed ligand complexes were prepared by the reaction of title metal dichloroacetates and 2,4'-bipyridine. The general formulae of synthesized compounds are M(2,4'-bpy)₂(CCl₂HCOO)₂·nH₂O (where M(II)=Mn, Co, Ni, Cu; 2,4'-bpy=2,4'-bipyridine, n=2 or 4). The complexes have been isolated from aqueous media and characterized by chemical analysis, molar conductance (in MeOH, DMSO and DMF), magnetic, IR and VIS spectral studies. The nature of metal(II)-ligand coordination is discussed. The thermal behaviour of obtained complexes was studied by thermal analysis and TG-MS techniques in air. IR, X-ray powder diffraction and thermoanalytical data were used for the determination of solid intermediate products of the thermal decomposition. The principal volatile products of thermal decomposition of complexes were proved by mass spectroscopy: H₂O⁺, CO⁺ ₂, HCl⁺ ₂, Cl⁺ ₂, NO⁺ and other. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interaction of ampicillin with Mn(II), Co(II), and Ni(II) ions

The interaction of ampicillin with the Mn²⁺, Co²⁺, and Ni²⁺ ions in aqueous solution at 20°C (supporting electrolyte 0.1 M KNO₃) was studied pH-metrically and spectrophotometrically. In weakly acidic and neutral media, Ni²⁺ forms with the anionic ampicillin species 1: 1 and 1: 2 complexes, whereas Mn²⁺ and Co²⁺ form only 1: 1 complexes. The stability constants of the complexes were determined, and their possible structures were discussed.     

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.     

Complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 4-chloro-2-methoxybenzoic acid anion

The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ were obtained as polycrystalline solids with general formula M(C₈H₆ClO₃)₂·nH₂O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn₃O₄, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10^–3 mol dm^–3. The plots of χ_M vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μ_B for Mn(C₈H₆ClO₃)₂·4H₂O, 3.96–4.75 μ_B for Co(C₈H₆ClO₃)₂·5H₂O, 2.32–3.02 μ_B for Ni(C₈H₆ClO₃)₂·5H₂O and 1.77–1.94 μ_B for Cu(C₈H₆ClO₃)₂·4H₂O.     

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.     

N-vinylcarbazole polymerization by 13X molecular sieve exchanged with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

The polymerization of N-vinylcarbazole by 13X molecular sieves modified by five different transition metal ions, viz. Mn(II), Co(II), Ni(II), Cu(II) and Zn(II), has been studied under various conditions. The order of reactivity follows the trend: Mn(II) ≈ Cu(II) > Co(II) > Zn(II) > Ni(II) at pH ∼ 3.55 and an exchange level of 30% of the metal ion. The polymerizations are believed to occur by a dual-ion-initiation mechanism in which both metal ions and proton centres participate. The overall energy of activation (E_a) for each system decreases with decreasing pH of the exchanging salt solution. Average activation energy on proton centre (E_H) and that on metal ion centre (E_a) have been evaluated for each system. E_a, E_H and E_c have been shown to correlate with one another. The molecular weights and their distributions are affected by the nature of the metal ion and also by the protonic centres. The possibility of a correlation of the catalytic activity of the modified 13X with ionic radius, electronegativity and normal co-ordination number has been examined.     

Mn(II), Co(II), Ni(II) and Cu(II) complexes of a tertraaza macrocyclic ligand: Synthesis, characterization and biological screening

Manganese(II), cobalt(II), nickel(II) and copper(II) complexes with 1,5,11,15-tetraaza-21,22-dioxo-tricyclo [19,3,1,I^6,10]-5,10,15-20-dicosatetraene (L), as a new macrocyclicligand, have been synthesized with and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMF correspond to non-electrolytic nature of Mn(II), Co(II) and Cu(II) complexes, while showing a 1:2 electrolyte for thew Ni(II) complexe. Thus, these complexes may be formulated as [M(L)X₂] and [Ni(L)]X₂ (where M = Mn(II), Co(II) and 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) and Co(II), a square planar for Ni(II) and tetragonal for Cu(II) complexes. In vitro ligand and its metal complexes were also screened against the growth of some fungal and bacterial species in order to assess their antimicrobial properties.     

Synthesis and characterization of Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with N-salicydene-o-hydroxymethyleneaniline

The new Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with tridentate Schiff base, the product of condensation of o-aminobenzyl alcohol with salicylaldehyde have been synthesized and characterized by elemental analysis, IR, electronic, EPR and Mössbauer spectra, thermal analysis, magnetic susceptibility and molecular weight measurements. Dimeric or polymeric structures for the investigated complexes were proposed. The interaction of the cobalt complex with dioxygen is also described.     

Complexes of Co(II), Ni(II) and Cu(II) with lapachol

Complexes of naturally occurring hydroxynaphtho-quinone, lapachol (2-hydroxy-3(3-methyl-2-buthenyl)-1,4-naphthoquinone = HL) with Co(II), Ni(II) and Cu(II) have been prepared by reaction of the corresponding acetates with the ligand (HL) in ethanol. The molecular and crystal structures were determined for [CoL₂(EtOH)₂] (1), [NiL₂(EtOH)₂] (2), and [CuL₂(py)₂] (3). In all cases the deprotonated lapachol behaves as chelating bidentate ligand. The complexes were also characterized by elemental analyses, cyclic voltammetry, and FAB-MS.