Solvent extraction of copper(II) from sulfate medium with N -(2-hydroxybenzylidene)aniline

Solvent extraction of copper(II) from sulfate medium with N-(2-hydroxybenzylidene)aniline is studied with the following parameters: pH, concentration of the extractant, nature of diluent, and temperature. The extraction of copper(II) proceeds by a cation exchange mechanism and the extracted species are CuL₂ in cyclohexane and toluene and CuL₂ with some CuL₂HL in chloroform. The equilibrium constants have been calculated as well as thermodynamic parameters ΔH°, ΔS°, and ΔG°. The temperature effect on the solvent extraction of copper(II) with N-(2-hydroxybenzylidene)aniline in cyclohexane is discussed.     

Solvent extraction studies of cobalt(II) by capric acid from sodium sulfate solution

The extraction of cobalt(II) from sulfate medium of ionic strength 0.33?mol dm^?3 by capric acid dissolved in chloroform has been carried out at 25°C. By using the slope analysis method, the stoichiometry of the organometallic complex extracted was determined. Cobalt(II) complex exists as a mononuclear species CoL₂.2HL in the lower concentration region of capric acid and a binuclear ones (CoL₂.2HL)₂ in the higher concentration region. Extraction constants for each species were given. UV–visible and FTIR spectroscopy have also been used for the investigation of the extractant and their complexes. Electronic spectrum of cobalt(II) caprate species indicates the octahedral structure.     

Coordination compounds of Co(II), Ni(II) and Cu(II) with capric acid hydrazide

The reaction of aquo-ethanolic solutions of Co(II), Ni(II) and Cu(II) salts and ethanolic solution of capric acid hydrazide (L) yielded paramagnetic, high-spin bis- and tris(ligand) chelate complexes. The tris(ligand) complexes, [ML ₃]X ₂·nH₂O [M=Co(II), Ni(II);X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ], have an octahedral structure formed on account of the bidentate (NO) coordination of three neutral hydrazide molecules. In the bis(ligand) complexes,ML ₂(NCS)₂ [M=Co(II), Ni(II)] and CuL ₂ X ₂·nH₂O (X=NO ₃ ^– , ClO ₄ ^– and 1/2SO ₄ ^2– ), the oxoanions and NCS^– take also part in coordination. The complexes have been characterized by elemental analysis, IR spectra, magnetic measurements, molar conductivity and TG analysis.

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Caprinsäurehydrazid-Komplexe von Co(II), Ni(II) und Cu(II)

Zusammenfassung Durch die Reaktion von wäßrig-ethanolischen Lösungen von Co(II)-, Ni(II)-und Cu(II)-Salzen mit einer ethanolischen Lösung von Caprinsäurehydrazid (L) wurden paramagnetische high-spin Bis- und Tris-Ligand-Chelatkomplexe erhalten. Tris-Ligand-Komplexe des Typs [ML ₃ X ₂·nH₂O [M=Co(II), Ni(II);X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ], die eine oktaedrische Struktur besitzen, entstehen durch die Koordination von drei neutralen zweizähnigen (NO)-Hydrazidmolekülen. Bei den Bis-Ligand-KomplexenML ₂(NCS)₂ [M=Co(II), Ni(II)], sowie bei den Bis-Ligand-Komplexen CuL ₂ X ₂·nH₂O (X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ) nehmen bei der Koordination außer Hydrazid auch die Säurereste teil. Die Komplexe wurden durch Elementaranalyse, IR-Spektren, magnetische Messungen, molare Leitfähigkeit und TG-Analysen charakterisiert.

     

Interaction of copper(II) and palladium(II) with linked 2,2′-dipyridylamine derivatives: Synthetic and structural studies

Interaction of copper(II) salts with 2,2′-dipyridylamine (1), N-cyclohexylmethyl-2,2′-dipyridylamine (2), di-2-pyridylaminomethylbenzene (3), 1,2-bis(di-2-pyridylaminomethyl)-benzene (4), 1,3-bis(di-2-pyridylaminomethyl)benzene (5), 1,4-bis(di-2-pyridylaminomethyl)benzene (6), 1,3,5-tris(di-2-pyridylaminomethyl)benzene (7) and 1,2,4,5-tetrakis(di-2-pyridylaminomethyl)benzene (8) has yielded the following complexes: [Cu(2)(μ-Cl)Cl]₂, [Cu(3)(μ-Cl)Cl]₂ · H₂O, [Cu₂(4)(NO₃)₄], [Cu₂(5)(NO₃)₄] · 2CH₃OH, [Cu₂(6)(CH₃OH)₂(NO₃)₄], [Cu₄(8)](NO₃)₄] · 4H₂O while complexation of palladium(II) with 1, 4, 5 and 6 gave [Pd(1)₂](PF₆)₂ · 2CH₃OH, [Pd₂(4)Cl₄], [Pd₂(4)(OAc)₄], [Pd₂(5)Cl₄], [Pd₂(6)Cl₄] and [Pd₂(6)(OAc)₄] · CH₂Cl₂, respectively. X-ray structures of [Cu(2)(μ-Cl)Cl]₂, [Cu(3)(μ-Cl)Cl]₂ · 2C₂H₅OH, [Cu₂(6)(CH₃OH)₂(NO₃)₄], [Pd(1)₂](PF₆)₂ · 2CH₃OH, [Pd₂(4)(OAc)₄] · 4H₂O and [Pd₂(6)(OAc)₄] · 2CH₂Cl₂ are reported. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a diverse range of coordination geometries and lattice arrangements, with the structures of [Pd₂(4)(OAc)₄] · 4H₂O and [Pd₂(6)(OAc)₄] · 2CH₂Cl₂, incorporating the isomeric ligands 4 and 6, showing some common features. Liquid–liquid (H₂O/CHCl₃) extraction experiments involving copper(II) and 1–3, 5, 7and 8 show that the degree of extraction depends markedly on the number of dpa-subunits (and concomitant lipophilicity) of the ligand employed with the tetrakis-dpa derivative 8 acting as the most efficient extractant of the six ligand systems investigated.     

Influence of the solvent on the extraction of copper(II) from nitrate medium using salicylideneaniline

Different solvents including cyclohexane, dichloromethane, chloroform, toluene, 1-octanol, and methyl isobutyl ketone (MIBK) have been evaluated in extracting copper(II) from nitrate medium by salicylideneaniline. Extracted species differs from solvent to solvent: CuL₂ in cyclohexane, toluene, 1-octanol, and methyl isobutyl ketone. However, in dichloromethane or chloroform, there are two complexes of the type CuL₂ and CuL₂(HL). The extraction constants and percentage of extraction (%E) are calculated for different solvents. Solvent played an important role in recovering copper(II) from the aqueous solution, thus affecting the extraction equilibrium and extraction efficiency. The nonpolar solvent showed better performance than the polar solvent. The maximum extraction efficiency was 85.75% at pH?=?4.5, which was from cyclohexane.     

Mononuclear and homobinuclear cobalt(II), nickel(II) and copper(II) complexes with mono and bis-azocompounds derived from 2,7-dihydroxynaphthalene and anthranilic acid or o-aminophenol

Two new series of mononuclear and homobinuclear Co(II), Ni(II) and Cu(II) complexes with mono- and bis-azo compounds derived from 2,7-dihydroxynaphthalene and anthranilic acid or o-aminophenol are prepared and characterized by elemental and thermal analyses, conductance, IR, electronic, ESR spectra and magnetic moment measurements. The ligand field splitting parameters and Racah constant are calculated. The spectral and magnetic results obtained are utilized to determine the geometries around the metal(II) ion. The geometry of the complex formed depends on the structure of the ligand and the type of metal(II) ion. The mode of bonding of the ligand with the metal ions is deduced from IR spectra.     

Extraction of cobalt(II) from aqueous thiocyanate and chloride solutions with alamine, alamine oxide and tri-n-octylphosphine oxide

Summary The extraction of Co(II) from KNCS, HNCS, LiCl and HCl solutions with Alamine 336-S, Alamine oxide and tri-n-octylphosphine oxide has been studied. For acid-deficient systems, the extraction efficiency decreases in the order AlamO > TOPO > Alamine, while the sequence is Alamine > AlamO > TOPO for extraction from acid solutions. Under acid-deficient conditions, extraction invariably proceeds through solvation. On the other hand, in the systems Alamine-HCl and -HNCS as well as AlamO-HCl, extraction is governed by anion-exchange. A mixed extraction mechanism occurs with the AlamO-HNCS, TOPO-HCl and TOPO-HNCS systems. The conclusions reported for liquid-extraction also appear to apply to reversed-phase thin-layer chromatography.

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Extraktion von Kobalt(II) aus wäßrigen Thiocyanat- und Chloridlösungen mit Alamin, Alaminoxid und Tri-n-octylphosphinoxid

Zusammenfassung Die Extraktion von Kobalt(II) aus KNCS-, HNCS-, LiCl- und HCl-Lösungen mit Alamin 336-S, Alaminoxid und Tri-n-octylphosphinoxid wurde untersucht. Im Falle von nichtsauren Systemen nimmt die Extrahierbarkeit in der Reihenfolge AlamO > TOPO > Alamin ab, während für saure Systeme die Reihenfolge Alamin > AlamO > TOPO gilt. Unter nichtsauren Bedingungen erfolgt die Extraktion stets durch Solvatation, wogegen in den Systemen Alamin-HCl, Alamin-HNCS sowie AlamO-HCl Anionenaustausch maßgebend ist. Gemischte Extraktionsmechanismen herrschen in den Systemen AlamO-HNCS, TOPO-HCl und TOPO-HNCS. Die für die flüssig-flüssig-Extraktion beschriebene Schlußfolgerungen scheinen auch für die Umkehrphasen-Dünnschicht-Chromatographie zu gelten.

     

Copper(II) coordination compounds with ferulic acid

The first two molecular structures of the ferulic acid (3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid, C₁₀H₁₀O₄) coordination compounds are presented, namely, [Cu₂(C₁₀H₉O₄)₄(CH₃CN)₂] 1 and [Cu₂(C₁₀H₉O₄)₄(C₆H₆N₂O)₂]·4CH₃CN (C₆H₆N₂O = nicotinamide) 2. Both compounds were synthesised from the starting mixture of Cu₂O and CuCl upon copper oxidation in the acetonitrile solution. The single-crystal X-ray diffraction analysis of 1 and 2 reveals the binuclear structure of the ‘paddle–wheel’ type for both complexes. 1 and 2 are unstable outside mother liquid due to loosely bound acetonitrile molecules. The final products of decomposition are [Cu₂(C₁₀H₉O₄)₄] 1a and [Cu₂(C₁₀H₉O₄)₄(C₆H₆N₂O)₂] 2a, which were characterized by several physico-chemical methods. The triplet X-band EPR spectra of 1a and 2a, showing signals B_Z1  15 mT, B₂  460 mT and B_Z2  580 mT, are in agreement with the expected data for the binuclear tetracarboxylate units, found in the structures of the parent complexes 1 and 2. Together with the room temperature magnetic susceptibility data, μ_eff/B.M. 1.40 (1a), 1.48 (2a), the EPR spectra analysis confirm the antiferromagnetic interaction in 1a and 2a. This is suggesting preservation and stability of the paddle–wheel structures in 1a and 2a.     

The effect of diluents on extraction of copper(II) with di(2-ethylhexyl)phosphoric acid

The liquid–liquid extraction of copper(II) from sulfate medium with di(2-ethylhexyl)phosphoric acid (D2EHPA, HL) at 25°C is studied with the following parameters: pH, concentration of the extractant, and the nature of diluent. The effect of the diluent using polar and nonpolar solvents in the extraction of copper(II) is discussed. The extracted copper(II) species were CuL₂ in 1-octanol and methyl isobutyl ketone and CuL₂ · 2HL in toluene, carbon tetrachloride, and cyclohexane. The extraction constants are evaluated for different diluents.     

Spectrophotometric study of coproporphyrin-I complexes of copper(II) and cobalt(II)

The reagent 3,8,13,18-tetramethyl-21H,23H-porphine-2,7,12,17-tetrapropionic acid or coproporphyrin-I (CPI) was used for the spectrophotometric determination of copper(II) and cobalt(II) in the presence of pyridine and imidazole catalysts. Optimum conditions were investigated and the methods were applied to the determination of parts per billion levels of copper(II) and cobalt(II). The Sandell sensitivities of the recommended procedures were 0.568 μm cm⁻² and 0.464 μg cm⁻² (for A = 0.001) for copper and cobalt, respectively. The relative standard deviations were 2.0% for copper and 1.0% for cobalt. The kinetics of the reaction of CPI with copper(II) and cobalt(II) in the presence of the catalysts and the influence of the temperature were studied, and their kinetic constants determined.The influence of light on the photodecomposition of CPI was also studied.     

Synthesis of ditopic ligands for the selective extraction of copper(II) nitrate and crystal structures of their Cu(II) complexes

We have synthesized two ditopic ligands for selective extraction of copper(II) nitrate. We also synthesized one cation-only binding analog for comparison. All three ligands were characterized by conventional techniques. Competitive two-phase metal ion solvent extraction experiments were performed at 25 °C over a period of 24 h. These ligands showed significant selectivity for Cu(II) ions, having the ditopic ligands extract 81 and 73% of the Cu(II) ions in a solution of different metal ions {Ni(II), Co(II), Cu(II), Zn(II), Cd(II), Pb(II)} at pH 5.09. Competitive transport experiments (water/chloroform/water) were undertaken employing each ligand separately as the ionophore in the membrane (chloroform) phase. No metal ion transport was observed, but a large concentration of Cu(II) was present in the membrane phase. Competitive anion extraction and transport were carried out with the ditopic ligands, yielding selective extraction and transport of nitrate. Furthermore, a pH isotherm of the best ditopic ligand (H₂L²) with Cu(II) was determined from pH 1.0 to 6.0, producing a pH_½ value of approximately 2.6. Finally, crystal structures of the ditopic ligands complexed with Cu(II) were determined and refined. The coordination geometry around the metal centers are distorted square planar and the Cu(II)-donor bond lengths fall within the normal range.     

Chelating resin containing s-bonded dithizonefor the separation of copper(II), nickel(II) and zinc(II)

Analytical and physicochemical properties of a crosslinked poly (vinyl pyridine) based resin containing dithizone were examined. The resin was further used for the preconcentration of copper, nickel and zinc at batch and column level. Various conditions such as pH, equilibration time, temperature were optimised for the maximum loading of copper, nickel and zinc. The loading capacities of the resin for copper, nickel and zinc were observed to be 0.51, 0.59 and 0.65 mmol g⁻¹ of dry resin respectively. Elution of loaded copper, nickel and zinc from the resin was done by using 0.1 M HCl, 0.1 M H₂SO₄ and 0.1 M HNO₃ respectively. Separation of copper, nickel and zinc in binary and ternary mixtures was achieved without any cross contamination.     

Extraction of Co(II) and Ni(II) ammine cations from aqueous solutions into chloroform by highly lipophilic crown carboxylic acids

The proton-ionizable crown ethers, 2-[(sym-dibenzo-14-crown-4)oxy]-decanoic acid (1), 2-[sym-dibenzo-16-crown-5)oxy]decanoic acid (2), and 2-[sym-dibenzo-19-crown-6)oxy]decanoic acid (3) efficiently extract Co(II) and Ni(II) ammine cations from highly alkaline aqueous solutions (pH>10) into chloroform. For extractions of the individual metal species,2 is more efficient than1 or3. In competitive extraction systems, good selectivity for Co(II) ammine cations over Ni(II) ammine cations is observed.     

Solvent Effect on the Ligand Exchange between Bis(diethyldithiocarbamato)copper(II) and Bis(diethyldiselenocarbamato)copper(II)

EPR and spectrophotometric study on the products of ligand‐exchange taking place on mixing bis(diethyldiselenocarbamato)copper(II), [Cu(Et₂dsc)₂], and bis(diethyldithiocarbamato)copper(II), [Cu(Et₂dtc)₂], solutions is reported. EPR spectra monitored at room temperature for one month period reveal a stable equilibrium among the parents (chromophores CuS₄ and CuSe₄) and the obtained mixed‐chelate [Cu(Et₂dtc)(Et₂dsc)] complex (chromophore CuS₂Se₂) in heptane, hexane, benzene, toluene, acetone, DMFA, DMSO and dichloromethane. In CCl₄ and CHCl₃ two new additional EPR spectra appear attributed to the mixed‐chelate complexes with the chromophores CuSSe₃ and CuS₃Se which are not observed with electronic spectroscopy. The intensities of all five EPR spectra decrease with the time. It is assumed that the new mixed‐chelates observed in CCl₄ and CHCl₃ are obtained in a reaction of [Cu(Et₂dtc)(Et₂dsc)] or [Cu(Et₂dtc)₂] with the ester of diselenocarbamic acid which is formed in a parallel reaction of [Cu(dsc)₂]with CCl₄ or CHCl₃.     

A study of complex equilibria of phenylglycine with nickel(II), copper(II) and zinc(II) in water and in water - methanol solution

The complex equilibria of the systems phenylglycine — nickel(II), copper(II) and zinc(II) in water and in water — methanol solution have been studied by computer analysis of potentiometric data. The mode of coordination has been established by¹³C-NMR and IR studies.

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Gleichgewichtsuntersuchungen der Komplexbildung von Phenylglycin mit Nickel(II), Kupfer(II) und Zink(II) in Wasser und Wasser - Methanol-Lösung

Zusammenfassung Anhand einer Computer-Analyse von potentiometrischen Daten wurden die Bildungsgleichgewichte in den Systemen Phenylglycin — Nickel(II), Kupfer(II) und Zink(II) untersucht. Der Koordinationstyp wurde mittels¹³C-NMR und IR festgestellt. Die Lösungsmittel waren Wasser und Wasser — Methanol.

     

Characterization and biological properties of a copper(II) complex with pyruvic acid thiosemicarbazone

Summary A copper(II) complex with pyruvic acid thiosemicarbazone (PTSC) of composition Cu(PTSC) (PTSC-H)Cl was characterized by IR, UV/Vis, and EPR spectroscopy. The antifungo, herbicide, cytotoxic and antitumor activities of the complex andPTSC are reported.

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Charakterisierung und biologische Eigenschaften eines Kupfer(II)-Komplexes mit Brenztraubensäurethiosemicarbazon

Zusammenfassung Ein Kupfer(II)-Komplex mit Brenztraubensäurethiosemicarbazon (PTSC) der Zusammensetzung Cu(PTSC)(PTSC-H)Cl wurde mittels IR-, UV/Vis- und EPR-Spektroskopie charakterisiert. Es wird über die antifungalen, herbiziden, cytotoxischen und antitumoralen Aktivitäten des Komplexes und vonPTSC berichtet.

     

Studies on mononuclear chelates derived from substituted Schiff-base ligands (part 6): synthesis and characterization of a new 3-ethoxysalicyliden- p -aminoacetophenoneoxime and its complexes with cobalt(II), nickel(II), copper(II) and zinc(II)

Schiff-base complexes of cobalt(II), nickel(II), copper(II) and, zinc(II) with 3-ethoxysalicyliden-p-aminoacetophenoneoxime (HL) were prepared and characterized on the basis of elemental analyses, IR, ¹H- and ¹³C-NMR, electronic spectra, magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses (TGA). A tetrahedral geometry has been assigned to the complexes.     

Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups

The adsorption of lead(II) and copper(II) on an activated carbon (Filtrasorb 300, Chemviron) was characterized assuming that it takes place by formation of complexes with functional groups, present in the activated carbon. Their concentration and conditional adsorption coefficients were determined for each metal by titration of the carbon in suspension in aqueous phase, at constant acidity, with the metal itself. For each titration point, the concentration of the metal in the solution phase after equilibration was determined, and the data were processed by the Ruzic linearization method, to obtain the concentration of the active sites involved in the sorption, and the conditional constant. The effect of the pH was also examined, in the range 4-6, obtaining that the adsorption increases at increasing pH. The protonation and adsorption constants were determined from the conditional adsorption coefficients obtained at the different acidities. The concentration of the active sites is 0.023 and 0.042 mmol g⁻¹, and the protonation constants are 1.0×10⁶ and 4.6×10⁴ M⁻¹ for Pb(II) and Cu(II). The corresponding adsorption constants are respectively 1.4×10⁵ and 6.3×10³ M⁻¹. All the parameters are affected by a large uncertainty, probably due to the heterogeneity of the active groups in the activated carbon. Even if so, these parameters make it possible a good prediction of the adsorption in a wide range of conditions. Other sorption mechanism can be set up at different conditions, in particular at different pH, as it has been demonstrated in the case of copper(II).     

Photofunctional supramolecular solution systems of chiral Schiff base nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzenes

Preparations, crystal structures, electronic and CD spectra are reported for new chiral Schiff base complexes, bis(N-R-1-naphthylethyl-3,5-dichlorosalicydenaminato)nickel(II), copper(II), and zinc(II). Nickel(II) and copper(II) complexes adopt a square planar trans-[MN₂O₂] coordination geometry with Δ(R,R) configuration. While zinc(II) complex adopts a compressed tetrahedral trans-[MN₂O₂] one with Δ(R,R) configuration and exhibits an emission band around 21 000 cm⁻¹ (λ_ex = 27 000 cm⁻¹). Absorption and CD spectra were recorded in N,N′-dimethylformamide, acetone, methanol, chloroform, and toluene solutions to discuss relationships between spectral shifts of d–d and π–π^∗ bands by structural changes of the complexes and physical properties of the solvents. Moreover, we have attempted to investigate conformational changes of the complexes induced by photoisomerization of azobenzene, 4-hydroxyazobenzene, or 4-aminoazobenzene, in various solutions under different conditions. Weak intermolecular interactions between complexes and azobenzenes are important for the phenomenon by conformational changes of bulky π-conjugated moieties of the ligands.