Synthesis and Thermal Decomposition of the Macrocyclic Dinuclear Ni(II) Complex

Crystal of the complex Ni₂L (ClO₄)₂ was obtained by reaction of Ni(ClO₄)₂ and macrocyclic ligand H₂L, where L^2– is the dinucleating macrocycle with two 2,6-di(aminomethyl)-4-methyl phenolate entities combined by the same two lateral chains, –(CH₂)₂–NH–(CH₂)₂–, at the amino nitrogens. The thermal decomposition processes of the title complex were studied in a dynamic atmosphere of dry argon using TG-DTG. The kinetic analysis of the first and second thermal decomposition steps were performed via the TG-DTG curves, and the kinetic parameters were obtained from analysis of the TG-DTG curves with integral and differential methods. The most probable kinetic function was suggested by comparison of the kinetic parameters.This revised version was published online in November 2005 with corrections to the Cover Date.     

大环金属铜(II)、镍(II)配合物的模板合成与晶体结构

用模板法合成了1个大环金属铜(II)配合物[CuLCl₂]·3H₂O (1)和3个大环金属镍(II)配合物[NiLCl₂] (2)，[NiL](ClO₄)₂ (3)和[NiLH₂](ClO₄)₄ (4)(L=3,10-二乙基-1，3，5，8，10，12-六氮杂十四烷)，通过X-射线衍射单晶结构分析测定了它们的晶体结构。晶体结构显示：配合物1和2的金属离子与大环配体的4个氮原子及大环平面轴向的2个氯离子以八面体配位方式配位；配合物3和4的金属离子与大环配体的4个氮原子以平面正方形配位方式配位，配合物4的侧链氮原子的质子化导致侧链结构翻转，使得其侧链与大环平面共面。     

Characterization and TG-MS studies of lactato and bipyridine-lactato complexes of Co(II) and Ni(II)

Two lactates and four new mixed ligand complexes with formulae Co(lact)₂·2H₂O, Ni(lact)₂·3H₂O, Co(4-bpy)(lact)₂, Co(2,4'-bpy)₂(lact)₂, Ni(4-bpy)(lact)₂·2H₂O and Ni(2,4'-bpy)₂(lact)₂ (where 4-bpy=4,4'-bipyridine, 2,4'-bpy=2,4'-bipyridine, lact=CH₃CH(OH)COO^-) were isolated and investigated. The thermal behaviour of compounds was studied by thermal analysis (TG, DTG, DTA). In the case of hydrated complexes thermal decomposition starts with the release of water molecules. The compounds decompose at high temperature to metal(II) oxides in air. A coupled TG-MS system was used to analyse the principal volatile products of thermolysis and fragmentation processes of obtained complexes. This revised version was published online in July 2006 with corrections to the Cover Date.     

New Ni(II)Cu(II)Ni(II) trinuclear complexes with an 5=3/2 high-spin ground

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)₂]₂[Cu(opba)]}(ClO₄)₂, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO₂-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me₂bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)₂]₂[Cu(opba)]}(ClO₄)₂3H₂O has been studied in the 4–300 K range, giving the exchange integral J—109 cm^?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Syntheses,structural characterizations and microbial activities of Ni(II) and Zn(II) 5-aminoisophthalate coordination polymers

Two coordination polymers with 5-aminoisophthalic acid (H₂aip), [Ni(μ-aip)(H₂O)₂(tmeda)]_n (1) and {H₂dap[Zn₂(μ-aip)(μ₃-aip)₂]?9H₂O}_n (2) (H₂aip = 5-aminoisophthalic acid, tmeda = N,N,N′-N′-tetramethylethylenediamine, dap = 1,3-diaminopropane) have been synthesized. Elemental and thermal analyses, magnetic susceptibilities, IR, AAS, mass and UV–vis spectroscopic studies have been performed to characterize the compounds. Nickel(II) has octahedral geometry by two oxygens of different carboxylates, bidentate, tmeda as bidentate chelating and two water ligands. Zn(II) has tetrahedral geometry by three oxygens of different carboxylate groups and one nitrogen by amine of aip. 1 crystallizes in the orthorhombic crystal system with space group Pccn and 2 in monoclinic crystal system with space group P2₁/c. Complex 2 exhibits photoluminescence properties in the solid state at room temperature. This study determined the susceptibility patterns of 1 and 2 against bacterial, yeast and mold micro-organisms. Antimicrobial activities were done on 12 different micro-organisms using the micro-dilution method. Tested microbial species were inhibited by 1 with a Minimum inhibitory concentrations (MIC) of 375–3000 μg mL^?1. Compound 2 showed antimicrobial activities against tested micro-organisms with a MIC of 188–1500 μg mL^?1. Compound 2 showed antibacterial activity against Legionella pneumophila sg1 375 μg mL^?1 (MIC value).     

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.     

Thermal Decomposition Kinetics of the Zn(II) Complex with Norfloxacin in Static Air Atmosphere

The thermal decomposition of Zn[NFA]₂5H₂O (NFA=C₁₆H₁₈FN₃O₃, norfloxacin) and its kinetics were studied under non-isothermal conditions in air by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from the TG curve. The non-isothermal kinetic data were analyzed by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the second stage can be expressed as d/dt=Aexp(–E/RT)(1–).This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis,Crystal Structure,Theoretical Calculations,Antibacterial Activity,Electrochemical Behavior,and Molecular Docking of Ni(II) and Cu(II) Complexes with Pyridoxal-Semicarbazone

New Ni (II) and Cu (II) complexes with pyridoxal-semicarbazone were synthesized and their structures were solved by X-ray crystallography. This analysis showed the bis-ligand octahedral structure of [Ni(PLSC-H)₂]·H₂O and the dimer octahedral structure of [Cu(PLSC)(SO₄)(H₂O)]₂·2H₂O. Hirshfeld surface analysis was employed to determine the most important intermolecular interactions in the crystallographic structures. The structures of both complexes were further examined using density functional theory and natural bond orbital analysis. The photocatalytic decomposition of methylene blue in the presence of both compounds was investigated. Both compounds were active toward E. coli and S. aureus, with a minimum inhibition concentration similar to that of chloramphenicol. The obtained complexes led to the formation of free radical species, as was demonstrated in an experiment with dichlorofluorescein-diacetate. It is postulated that this is the mechanistic pathway of the antibacterial and photocatalytic activities. Cyclic voltammograms of the compounds showed the peaks of the reduction of metal ions. A molecular docking study showed that the Ni(II) complex exhibited promising activity towards Janus kinase (JAK), as a potential therapy for inflammatory diseases, cancers, and immunologic disorders.     

Kinetics And Mechanism of The Non-isothermal Decomposition. Some Ni(II)-carboxylate-imidazole ternary complexes

The thermal decomposition of some Ni(II)-carboxylate-imidazole complexes in a nitrogen atmosphere was studied non-isothermally. From the non-isothermal thermoanalytical data, it was found that these complexes decompose through a stepwise release of imidazole molecules and/or CO ones forming unstable intermediates which produce metal oxide or the metal as a final decomposition product. TG in conjunction with DTG were used to evaluate the kinetic and thermodynamic parameters of the decomposition reaction. The kinetic studies were performed employing a computer-oriented kinetic analysis of each set of W-T data obtained under constant heating rate. The diffusion processes are the decisive mechanisms for the decomposition. The values of ΔE, A, ΔH, ΔS and ΔG for activation were calculated for the complexes and correlated to variation in their structure. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and characterization of Co(II), Ni(II), Zn(II) and Cu(II) complexes with a new tetraazamacrocyclic Schiff base ligand containing a piperazine moiety: X-ray crystal structure determination of the Co(II) complex

Two macrocyclic Schiff base ligands, L¹ [1+1] and L² [2+2], have been obtained in a one-pot cyclocondensation of 1,4-bis(2-formylphenyl)piperazine and 1,3-diaminopropane. Unfortunately, because of the low solubility of both ligands, their separation was unsuccessful. In the direct reaction of these mixed ligands (L¹ and L²) and the appropriate metal ions only [CoL¹(NO₃)]ClO₄, [NiL¹](ClO₄)₂, [CuL¹](ClO₄)₂ and [ZnL¹(NO₃)]ClO₄ complexes have been isolated. All the complexes were characterized by elemental analyses, IR, FAB-MS, conductivity measurements and in the case of the [ZnL¹(NO₃)]ClO₄ complex with NMR spectroscopy.     

Syntheses,characterizations, crystal structures,and biological activities of two new mixed ligand Ni(II) and Cu(II) Schiff base complexes

Two mixed-ligand complexes, [Cu(L)(2imi)] (1) and [Ni(L)(2imi)]·MeOH (2) [L = 2-(((5-chloro-2-oxyphenyl)imino)methyl)phenolato) and 2imi = 2-methyl imidazole], have been prepared by the reaction of appropriate metal salts with H₂L and 2-methyl imidazole. Their structures were characterized by microanalysis, FT-IR, UV–vis, molar conductivity, and ¹H NMR for [Ni(L)(2imi)]·MeOH. The structures were determined using single crystal X-ray diffraction. Each four-coordinate metal center, Cu(II) in 1 and Ni(II) in 2, is surrounded by donors of Schiff base (L^2?) and N of 2-methyl imidazole in square planar geometries. α-Amylase activities of these compounds have also been investigated. The experimental data showed that α-amylase was inhibited by Ni(II) complex while the Cu(II) complex causes a 1.3-fold decrease in K_m value. Antimicrobial results show that these compounds, especially the Cu(II) complex, have potential for antibacterial activity against Gram negative and Gram positive bacteria and antifungal activity against Aspergillus fumigatus.     

Synthesis,characterization and antimicrobial activity of pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with 2,6-diacetylpyridine bis(trimethylammoniumacetohydrazone)

Pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with condensation product of 2,6-diacetylpyridine and trimethylammoniumacetohydrazide (Girard’s T reagent) were synthesized and characterized by elemental analyses, IR and UV–vis spectra, molar conductivity, and magnetic susceptibility. Crystal structures of the Co(II) and Ni(II) complexes were also determined. Antimicrobial activities of the ligand and metal complexes were examined.     

Synthesis, Crystal Structure and Kinetic Mechanism of Thermal Decomposition of a Zinc(II) Complex with N-Salicylidene-p-toluidine

1 INTRODUCTION Over the past decades, considerable attention has been devoted to the synthesis, characterization and property studies of Schiff bases and their com- plexes because of their potential and developed appli- cations in the fields of conducting and magnetic ma- terials, dyes, non-linear optics, catalysis, analytical chemistry, biochemical research, agriculture and so on[1～7]. A large number of reports are available in the chemistry and biologic activities of transition metal co…     

Synthesis and Crystal Structure of μ_(1,1,3) Formic Bridging 3D Microporous Ni(II) Complex

A μ1,1,3 formic bridging Ni2+ complex [Ni3(HCOO)6·H2O]]n 1 has been synthesi- zed under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 exhibits a 3D open microporous tube formed by covalent and coordination bonds. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.1487(13), b = 9.7763(11), c =17.9685(17) , β = 126.948(6)o, C6H6Ni3O13, Mr = 462.02, V = 1565.2(3) 3, Z = 4, Dc = 1.961 g/cm3, μ = 3.630 mm-1, F(000) = 917.7, Rint = 0.0234, the final R = 0.0234 and wR = 0.0734 for 3469 observed reflections (I>2σ(I)).     

Bioactive Co(II), Ni(II), and Cu(II) Complexes Containing a Tridentate Sulfathiazole-Based (ONN) Schiff Base

New Co(II), Ni(II), and Cu(II) complexes were synthesized with the Schiff base ligand obtained by the condensation of sulfathiazole with salicylaldehyde. Their characterization was performed by elemental analysis, molar conductance, spectroscopic techniques (IR, diffuse reflectance and UV–Vis–NIR), magnetic moments, thermal analysis, and calorimetry (thermogravimetry/derivative thermogravimetry/differential scanning calorimetry), while their morphological and crystal systems were explained on the basis of powder X-ray diffraction results. The IR data indicated that the Schiff base ligand is tridentate coordinated to the metallic ion with two N atoms from azomethine group and thiazole ring and one O atom from phenolic group. The composition of the complexes was found to be of the [ML₂]∙nH₂O (M = Co, n = 1.5 (1); M = Ni, n = 1 (2); M = Cu, n = 4.5 (3)) type, having an octahedral geometry for the Co(II) and Ni(II) complexes and a tetragonally distorted octahedral geometry for the Cu(II) complex. The presence of lattice water molecules was confirmed by thermal analysis. XRD analysis evidenced the polycrystalline nature of the powders, with a monoclinic structure. The unit cell volume of the complexes was found to increase in the order of (2) < (1) < (3). SEM evidenced hard agglomerates with micrometric-range sizes for all the investigated samples (ligand and complexes). EDS analysis showed that the N:S and N:M atomic ratios were close to the theoretical ones (1.5 and 6.0, respectively). The geometric and electronic structures of the Schiff base ligand 4-((2-hydroxybenzylidene) amino)-N-(thiazol-2-yl) benzenesulfonamide (HL) was computationally investigated by the density functional theory (DFT) method. The predictive molecular properties of the chemical reactivity of the HL and Cu(II) complex were determined by a DFT calculation. The Schiff base and its metal complexes were tested against some bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis). The results indicated that the antibacterial activity of all metal complexes is better than that of the Schiff base.     

The Synthesis,Characterization and Conductance Studies of New Cu(II), Ni(Ii) And Zn(II) Complexes with the Schiff Base Derived from 1,2-Bis-(o-Aminophenoxy)Ethane and Salicylaldehyde

Cu(II), Ni(II) and Zn(II) complexes with the Schiff base derived from 1,2-bis-(o-aminophenoxy)ethane with salicylaldehyde have been prepared. The complexes have been characterized by elemental analysis, magnetic measurements, ¹H NMR, ¹³C NMR, UV, visible and IR spectra as well as conductance measurements. The ligand is coordinated to the central metal as a tetradentate ONNO ligand. The four bonding sites are the central azomethine nitrogen and aldehydic OH groups. The ligand was used for complexation studies. Stability constants were measured by a conductometric method. Furthermore, the stability constants for complexation between ZnCl₂ and Cu(NO₃)₂ salts and N,N′-bis(salicylidene)-1,2-bis-(o-aminophenoxy)ethane (H₂L) in 80% dioxane/water and pure methanol were determined from conductance measurements. The magnitudes of these ion association constants are related to the nature of the solvation of the cation and the complexed cation. The mobilities of the complexes are also dependent, in part, upon solvation effects.     

Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L)(2)(SO(4)) and Cu(L)(2)(SO(4)) [where L=L(1) and L(2)] which are of five coordinated square pyramidal geometry.     

CHROMOTROPIC CHANGES OF Cu(II) AND Ni(II) COMPLEXES WITH N2O2 AND N3O2 SCHIFF-BASE LIGANDS IN THE SOLID PHASE

Abstract

Four new Schiff-base ligands have been prepared from the condensation of 3-formyl-4-hy-droxy-1,8-naphthyridin-2-one with different diamines and a triamine, H₂L_a-H₂L_d. Two series of Ni(II) and Cu(II) complexes with the four ligands were also prepared. The ligands and their metal complexes were characterized by chemical analyses, IR, Far-IR, electronic, ESR and mass spectra as well as magnetic measurements and X-ray diffraction patterns.

Different products for Ni(II) and Cu(II) were obtained in similar reactions with the same metal salt, depending on the nature of the ligand. Different geometries were also obtained depending on the counter anion of metal salt. Thus, violet square-planar Cu(II) complexes were obtained with Cu(OAc)₂. H₂O and green octahedral ones with CuCl₂. 2H₂O, except the reaction with ligand H₂L_d which gave only an octahedral product whether the anion was acetate, chloride or perchlorate. Electronic and ESR spectra were used to differentiate between the two geometries of the Cu(II) complexes. The green octahedral Cu(II) complexes undergo irreversible thermochromism to the violet square-planar complexes except the copper complex of the ligand H₂L_d which did not not show any color change and retained its octahedral geometry. Based on the magnetic moments and thermal analyses, only one Ni(II) complex of the Schiffbase ligand H₂L_c undergoes reversible thermochromism from green (octahedral) to red (squareplanar). The reverse change of the thermal product (red) to the parent complex (green) proceeded on exposure to atmospheric air for a few minutes. On the other hand, Ni(II) complexes of ligands H₂L_a and H₂L_b have stable square-planar geometry and all efforts to add other ligands such as H₂O or pyridine to these complexes failed to yield other products. The corresponding Cu(II) complexes were easily transformed to their octahedral geometry by adding H₂O or pyridine and heating.     

Redox Properties of Novel Dinuclear Ni(II) Bis - Tetraazamacrocyclic Complex

Abstract

Dinuclear Ni(II) bis-tetraazamacrocyclic complex 1 with conjugated double bonds at deprotonated β-diimine linking group was characterized by ¹H NMR and cyclic voltammetry. Electrochemical studies indicated high stability of the mixed-valence (Ni^II- Ni^III) and (Ni^II- Ni^I) species, respectively. The main factor contributing to the stabilization of the mixed-valence states is the electronic delocalization through the system of the conjugated double bonds at the deprotonated β-diimine linking group. Complex 1 is the first example of dinuclear Ni(II) tetraazamacro-cyclic complex exhibiting two one-electron oxidation and two one electron reduction steps.     

Preparation,Characterization and Solid State Thermal Studies of Cadmium(II) Squarate Complexes ofhane-1,2-diamine and its Derivatives

[CdL₃]C₄O₄ [L=ethane-1,2-diamine (en)], [CdL₂(H₂O)₂]C₄O₄ [L=N-methylethane-1,2-diamine (meen), N-ethylethane-1,2-diamine (eten), N-propylethane-1,2-diamine (pren), propane-1,2-diamine (pn) and N-methylpropane-1,2-diamine (ibn)] and [CdL₂(C₄O₄)] [L=N-isopropylethane-1,2-diamine (ipren)] have been synthesized by the addition of the respective diamine to finely powdered CdC₄O₄×₂H₂O and their thermal studies have been carried out in the solid state. [Cd(en)₃]C₄O₄ upon heating loses two molecules of diamine in two overlapping steps yielding Cd(en)C₄O₄ which upon further heating transforms to unidentified products. The diaquabis(diamine) species, [CdL₂(H₂O)₂]C₄O₄, show thermally induced deaquation-anation reaction in the solid state and thereby produce [CdL₂(C₄O₄)], which reverts on exposure to humid atmosphere (RH =90%) for 20–24 h. All the squarato bis(diamine) species, [CdL₂(C₄O₄)], on pyrolysis in the solid state transform to unidentified products through the formation of intermediates, CdL_1.5C₄O₄, (L=meen, pren and ipren), CdLC₄O₄ (L=meen, en, pren, ipren, pn and ibn) and CdL_0.5C₄O₄ (L=eten, pn and ibn). However, amongst the intermediates only the mono diamine species, CdLC₄O₄ can be isolated in pure form and the pyrolytic process is the only way to synthesize them. The monodiamine species can be stored in a desiccator as well as in an open atmosphere and proposed to have a polymeric structure. This revised version was published online in August 2006 with corrections to the Cover Date.