Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

Thermal behaviour of Cu(II)-urea complex

The urea complex of copper was synthesized and its structure was established by Fourier transform infrared (FTIR), electron spin resonance (ESR) and atomic absorption spectroscopy and elemental analysis to be Cu(urea)₄Cl₂. The thermal behaviour of this complex has been studied by thermogravimetry and differential thermal analysis and FTIR and ESR. Thermal analysis shows that the decomposition of the complex occurs in four stages of weight loss of different intermediates followed by three endothermal effects. The complex is thermally stable up to 428 K. The ESR and FTIR behaviour of the Cu(II)-urea complex during thermolysis was studied between 428 and 633 K. The experimental results suggest that in this temperature range the complex decomposition occurred forming thermodynamically stable regions of Cu(II) which are ferromagnetically coupled.

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Zusammenfassung Der Harnstoffkomplex von Kupfer wurde hergestellt, seine Zusammen-setzung ergab sich anhand von FTIR-, ESR- und Atomabsorptionsspektroskopie-Untersuchungen sowie Elementaranalyse mit der Formel Cu(Harnstoff)₄Cl₂.Mittels TG, DTA, FTIR und ESR wurde auch das thermische Verhalten dieser Komplexe untersucht. Die Thermoanalyse zeigte, daß der Zersetzungsprozeß über verschiedene Zwischen-produkte in vier Stufen mit Massenverlust verläuft, gefolgt von insgesamt drei endothermen Effekten. Bis 428 K ist der Komplex thermisch stabil. Das ESR- und FTIR-Verhalten des Cu(II)-harnstoffkomplexes bei der Thermolyse wurde im Temperaturbereich 428–633 K untersucht. Die experimentellen Ergebnisse lassen darauf schließen, daß bei der Zersetzung des Komplexes in diesem Temperaturbereich thermodynamisch stabile Regionen von ferromagnetisch gekoppeltem Cu(II) gebildet werden.

     

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.     

Structural investigation of dibromobis(benzimidazole)Zn(II) complex

The molecular structure of the title complex [ZnBr₂(C₇H₆N₂)₂] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å³. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br⁻ anions and two benzimidazole ligands. Intramolecular steric repulsions between Br⁻ anions and benzimidazole groups have been caused to cis configuration around the central metal atom.     

联合处理电位法和极谱法得到的实验数据确定金属配合物稳定常数(英)

The cadmium(Ⅱ)-glycinamide system was modeled and its stability constants were calculated by a unified mathematical treatment for experimental data obtained from ion selective electrode (ISE) and differential pulse polarography (DPP). It has been shown that very much the same experimental complex formation curve (ECFC) and theoretical complex formation curve (TCFC) could be given from both experimental techniques for the same experimental conditions, such as the same total ligand c(L_T) and metal ion c(M_T) concentrations. The combination of the two techniques is of many advantages as ISE can be performed at low a c(L_T)∶c(M_T) ratio and significantly higher c(M_T), whereas DPP could be used well at larger the c(L_T)∶c(M_T) ratio and very low c(M_T). This makes it possible to study a metal-ligand system in much broader range of experimental conditions that, in turn, provides us more data and information about the metal-ligand system of interest. Application of the unified mathematical treatment to the cadmium-glycinamide system in this paper, three new complexes MHL, ML₃ and ML₃(OH) as well as two complexes ML and ML₂, reported in literatures, could be modeled and all their stability constants have been refined.     

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。     

Stabilities of mixed ligand complexes of Cu(II) with ligands coordinating through O and N : ESR studies

Mixed ligand complexes of Cu(II) with 8-hydroxy-quinolinate (Hy) as one ligand and acetylacetonate (ac.ac) or salicylaldehydate (Sal) as the second ligand have been prepared in reaction mixtures of Cu(Hy)₂ + Cu(ac.ac)₂ and Cu(Hy)₂ + Cu(Sal)₂ in chloroform. Ligand hyperfine structures and the minimum ESR linewidth associated withm = − 3/2 hyperfine component have been used to detect and identify the mixed ligand complexes. The ligands in these complexes coordinate through O or N. The constantsK associated with the ligand exchange equilibriums are ~ 2 at −20°C and are close to the value expected from the empirical relation obtained in an earlier work from a study of Cu(II) complexes in which S also participates in the coordination.     

Polarographic Studies of the Reduction of Sn(II) in Dimethylsulphoxide and its Mixtures with Water and Acetonitrile

Abstract

The polarographic reduction of Sn(II) in DMSO, H₂O-DMSO and AN-DMSO mixtures was characterized as being reversible. When the reduction was carried out in an the process was found to be irreversible and in this case the kinetic parameters were determined by Meites and Israel's method. the effect of DMSO on the reduction of Sn(II) in an shows that the Sn(II) forms six successive complexes with DMSO, whose stability constants were determined by Deford and Hume's method.

The Walden product was determined for the mixtures under study. In AN-DMSO it decreases up to 20 vol.% DMSO, and from there remains approximately constant. In the H₂O-DMSO mixtures the Walden product passes through a broad minimum between 60 and 70 vol.% DMSO. the free energy of transfer in the hydro-organic mixture changes gradually with the increase in DMSO content, whereas in the AN-DMSO mixture this energy increases rapidly in very low DMSO content mixtures.     

Self-activated DNA cleavage of a water-soluble mononuclear Cu(II) complex with polyquinolinyl ligand

The synthesis and characterization of a water-soluble mononuclear Cu(II) complex, [CuLCl₂]·2CH₃CH₂OH, where L = bis(2-quinolinyl methyl)benzyl-amine has been reported. L is a tridentate polyquinolinyl ligand, coordinated to Cu(II) via NNN donors. The central copper ion of 1 has N₃Cl₂ donor set in a distorted trigonal-bipyramidal geometry. The dimer existing in the solid state resulted from hydrogen bonds and π–π accumulation between two mononuclear units. The interaction of 1 with CT-DNA has been explored by absorption and emission titration methods, revealing partial intercalation between 1 and CT-DNA. Moreover, 1 could make pBR322 plasmid DNA cleaved by a self-activated oxidative process; hydroxyl radical and singlet oxygen may be the main reactive oxygen species species in the process. Complex 1 may quench the intrinsic fluorescence of bovine serum albumin in a static quenching process, which has been investigated by UV–visible and fluorescence spectroscopic methods. 1 also demonstrates potent cytotoxity against Hela cells with IC₅₀ value of 2.84 μM, which shows it to be a potential candidate as an anticancer metal-based drug.     

Theoretical investigation on molecular structure of a new mononuclear copper(II) thiocyanato complex with tridentate Schiff base ligand

An asymmetrical Schiff base ligand, 4-bromo-2-(2-pyridylmethyliminomethyl)phenol (HL), and its copper(II) complex, [Cu(L)SCN] (1), have been synthesized. Complex 1 is experimentally characterized by elemental analysis, FT-IR and UV–vis spectroscopic techniques, and cyclic voltammetry. The structure of the complex has been established by single-crystal X-ray diffraction studies, which reveal a square planar geometry of the central copper(II) ion in 1. The neighboring molecules of the complex connect each other by π–π stacking interactions with centroid-to-centroid ring distance 3.653 Å. The ligand can display two possible tautomeric forms; therefore, 1 can have an alternate molecular structure. DFT calculations have been employed to investigate the structure and relative stabilities of the suggested tautomeric forms of the ligand and its corresponding copper(II) complex.     

Differential Pulse Polarographic Determination of Cd(II) and Pb(II) in Milk Samples after Solid‐Phase Extraction Using Amberlite XAD‐2 Resin Modified with 2,2′‐DPED3P

In the present paper novel column solid phase extraction procedure was developed for the determination of Cd(II) and Pb(II) in cows', goats', ewes', buffalos' and humans' milk samples using newly synthesized reagent 2,2′‐DPED₃P (2,2′‐{[1,2‐diphenylethane‐1,2‐diylidene]dinitrilo}diphenol) for preconcentration and separation prior to differential pulse polarography using amberlite XAD‐2 in the ranges of pH 4.0–5.0. The sorbed elements were subsequently eluted with 10 mL of 2 M HCl elutes were analysed by differential pulse polarography (DPP). The interference of foreign ions has also been studied. Effects of various instrumental parameters are investigated and received conditions are optimized. The total metal concentration of the milk samples in the study area were in the following ranges 0.030–0.090 μg L^?1 of Cd(II), 0.009–0.026 μg L^?1 of Pb(II) respectively. The limits of detections were found to be 0.020 and 0.024 μg L^?1 for Cd(II) and Pb(II) respectively by applying a preconcentration factor ～40. The proposed enrichment method was applied successfully for the determination of metal ions in cows', goats', ewes', buffalos' and humans' milk samples.     

An integrated experimental and theoretical investigation of the vibrational modes and molecular structure of a new Cu(II)–phosphocreatine complex

A new complex of Cu(II) of stoichiometry [Cu(PCr)(H₂O)] was prepared from aqueous solution at pH 6. Its synthesis, characterization, thermogravimetric, vibrational spectroscopy, and electron paramagnetic resonance analyses were described and suggest that phosphocreatine (PCr) in solid state is acting as a tridentate ligand (the nitrogen atom of the guanidine group and the oxygen atoms of the phosphate group and the carboxylate group being the donor atoms). The fourth position is occupied by a water molecule. These results were confirmed through computational calculations (DFT/B3LYP:6-311G theoretical procedure). The tetra coordination of Cu(II) arranged in a quadratic planar geometry was found to be more stable in the DFT calculations. The calculated vibrational spectrum agrees well with the FT-IR experimental spectrum.     

Polarographic behaviour of phenyl-2-picolylketone-2-pyridylhydrazone and its copper (II) complexes

The polarographic behaviour of phenyl-2-picolylketone-2-pyridylhydrazone, PPKPyH, has been studied in aqueous-ethanol mixtures of different pH's using DC and DP polarographic method. In the pH range 3.7–6.2, the observed single irreversible reduction wave is assigned to the splitting of the N—N bond and reduction of C=N centre. In alkaline medium, a second wave appears at more negative potential due to the reduction of the phenyl-2-picolylketone which is formed from the hydrolysis of PPKPyH. The optimum conditions for the analytical determination of PPKPyH was reported. Differential pulse polarography have been used to elucidate the complexation reaction between PPKPyH and copper(II) in unbuffered solutions. Two complexes are formed with log ₁ = 4.42 and log ₂ = 8.87.     

Cu(II) complex of an abiotic receptor as highly selective fluorescent sensor for acetate

A copper complex having quinoline moiety as fluorophore has been synthesized. The anion recognition behavior of the receptor and its copper complex has been studied in acetonitrile and in acetonitrile: H₂O (95:5 v/v). The copper complex shows high selectivity toward acetate over other anions studied such as F⁻, Cl⁻, Br⁻, I⁻, OAc⁻, dl-malate, l-mandelate, benzoate, isophthalate, , and .     

Syntheses and crystal structures of nickel(II), copper(II), and zinc(II) complexes with a biphenyl-bridged bis(pyrrole-2-yl-methyleneamine) ligand

The reactions of nickel(II), copper(II), and zinc(II) acetate salts with a potentially tetradentate biphenyl-bridged bis(pyrrole-2-yl-methyleneamine) ligand yielded three complexes with different coordination geometries. X-ray crystal structural analysis reveals that in the nickel(II) complex each nickel is five-coordinate, distorted trigonal bipyramid. In the copper(II) complex, each copper is four-coordinate, between square planar and tetrahedral. In the zinc(II) complex, each zinc is four-coordinate with a distorted tetrahedral geometry and the molar ratio of the zinc and ligand is 1 : 2.     

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.     

A dinuclear diamagnetic copper(II) complex [Cu2(ophen)2]Cl2 with hydroxylated phen

A dinuclear diamagnetic copper(II) complex, [Cu₂(ophen)₂]Cl₂ (Hophen = 2-hydroxy-1,10-phenanthroline), has been synthesized and characterized, providing good structural evidence for the long-debated Gillard mechanism.     

Polarographic analysis of the reduction waves of Pt(II)-SATSC complex

A polarographic study of the Pt(II)-salicylaldehyde thiosemicarbazone complex in sodium perchlorate as supporting electrolyte is described. In addition to the reduction wave of the complex, a catalytic hydrogen wave is also recorded. The characteristics of this catalytic hydrogen wave are studied under different experimental conditions such as varying acid/complex/supporting electrolyte/surfactant concentrations and also with mercury droptime. Based on these, a probable mechanism for the electrode process has been postulated. Presented at the 12th Annual Symposium in Chemistry held at the Indian Institute of Technology, Madras in March 1987.     

Copper(II), palladium(II) and platinum(II) chloride complexes with 5-amino-2-tert-butyltetrazole: Synthesis, characterization and cytotoxicity

Complexes CuL₃Cl₂, PdL₂Cl₂ and PtL₂Cl₂, where L is a novel ligand from the series of 2-substituted 5-aminotetrazoles, namely 5-amino-2-tert-butyltetrazole (1), have been synthesized by the reaction of metal(II) chlorides with 1 and characterized by IR spectroscopy, thermal and X-ray analyses. The crystallographic structural analysis of these complexes revealed that 1 acts as a monodentate ligand coordinated to the metal via endocyclic N4 atom. Platinum complex demonstrates promising cytotoxicity against human cervical carcinoma cells with IC₅₀ value average between those of cisplatin and carboplatin.