Synthesis and Crystal Structure of a Novel Polymeric Thiocyanato-Bridged Heteronuclear Complex of Copper(II) and Cadmium(II)

The title polymeric complex of Cu(II) and Cd(II) bridged by thiocyanate, Cu(en)₂[Cd(SCN)₃]₂, has been prepared and its structure determined by X-ray diffraction (XRD) methods. The crystal structure reveals that the Cu(II) atom is in an elongated octahedral coordination formed by two SCN^– anions and two en molecules. The Cd(II) atom is in a distorted octahedral coordination formed by six bridging SCN^– anions. Two different bridging thiocyanate anions exist in the complex. Both 1,1--SCN^– and 1,3--SCN^– anion act a role of bridge ligand and link Cu(II), Cd(II) atoms, and adjacent Cd(II). Cd(II) atoms form the three-dimensional (3-D) network polymeric structure. The IR and UV-Vis spectra have also been investigated.     

Extending the dynamic range of the determination of copper by adsorption differential pulse stripping method using a principal component artificial neural network

A principal component artificial neural network (PC-ANN) has been applied for the analysis of the voltammogram data of Cu(II) and Cu(II)–PAN complex for extending the dynamic range of the determination of Cu(II) (5–550 μg/l). A three layer back-propagation network (6:5:1) was used with learning rate (r=0.09) and momentum (m=0.9), with sigmoidal transfer function in the hidden layer and one bias node in the input layer. Overall, the application of PC-ANN enables the extension of the dynamic range of the determination of Cu(II) from its narrow linear range (5–50 μg/l) to the high dynamic range (5–550 μg/l).     

Extractive photometric determination of palladium with o-mercaptobenzoic acid

A procedure is described for the extractive photometric determination of palladium(II) with o-mercaptobenzoic acid. The reagent forms a yellow complex having maximum absorption at 365–370 mμ. The complex is quantitatively extractable with chloroform in the presence of pyridine at pH 5.2–7.2. The color develops immediately at room temperature and is very stable. Beer's law conforms over the range of 0.37–5.86 ppm of palladium. Most of the cations do not interfere in the presence of ascorbic acid and EDTA. Gold and silver are effectively masked with excess of thiocyanate prior to the addition of ascorbic acid and EDTA. Many common anions do not interfere. The molar absorptivity and Sandell sensitivity are 16.7 × 10³ and 0.0065 μg/cm². The reagent forms a 2:1 complex with palladium. The proposed method is simple, rapid, and selective for the determination of palladium(II).     

Preconcentration and XRF-determination of heavy metals in hair from Sudanese populations

Energy-dispersive X-ray fluorescence analysis was applied for the analysis of hair. The hair samples were digested in a mixture of nitric and perchloric acid and the heavy metals were precipitated with ammonium pyrrolidine dithiocarbamate. The accuracy, precision and recovery of the method for the elements Fe, Ni, Cu, Zn and Pb were evaluated through the analysis of a standard hair sample. The procedure was applied to the analysis of hair from an occupationally exposed group of Sudanese workers and a control group. The hair of the exposed group showed a range of 80–550 ppm Fe, 6–12 ppm Cu, 57–190 ppm Zn and 70–3700 ppm Pb, while that of the control group had a range of 60–310 ppm Fe, 7–22 ppm Cu, 89–170 ppm Zn and 3–17 ppm Pb.     

Study of a bis-furaldehyde Schiff base copper(II) complex as carrier for preparation of highly selective thiocyanate electrodes

A new highly selective thiocyanate electrode based on N,N-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD] as neutral carrier is described. The electrode has an anti-Hofmeister selectivity sequence: SCN^–>I^–>Sal^–>ClO₄ ^–>Br^–>NO₂ ^–>Cl^–>NO₃ ^–>SO₄ ^2–>SO₃ ^2–>H₂PO₄ ^– and a near-Nernstian potential linear range for thiocyanate from 1.0×10^–1 to 5.0×10^–6 mol L^–1 with a detection limit 2.0×10^–6 mol L^–1 and a slope of 57.5 mV decade^–1 in pH 5.0 of phosphate buffer solution at 20 °C. The response mechanism is discussed on the basis of results from A.C. impedance measurement and UV spectroscopy. The anti-Hofmeister behavior of the electrode results from a direct interaction between the central metal and the analyte ion and a steric effect associated with the structure of the carrier. The electrode has the advantages of simplicity, fast response, fair stability and reproducibility, and low detection limit. The selectivity of electrodes based on [Cu(II)-BFPD] exceeds that of classical anion-sensitive membrane electrodes based on ion exchangers such as lipophilic quaternary ammonium or phosphonium salts. Application of the electrode for determination of thiocyanate in waste water samples from a laboratory and a gas factory, and in human urine samples, is reported. The results obtained were fair agreement with the results obtained by HPLC.     

The rotating ring-disk electrochemistry of the copper(II) complex of thyrotropin-releasing hormone

Thyrotropin-releasing hormone (TRH) forms an electroactive Cu(II) complex in aqueous solution. Rotating ring-disk electrochemistry reveals oxidation at the disk electrode and reduction at the ring electrode. The plot of limiting current vs. square root of rotation frequency deviates from the Levich equation, indicating both preceding and following chemical reactions. The reaction following the oxidation is a multiple-electron ECE-type of process that has been seen before in Cu(II)–peptide electrochemistry. The preceding reaction is unusual. The deviation from diffusion-controlled behavior is more pronounced at higher initial concentration of Cu(II) and peptide. We propose that a non-electroactive dimer, Cu(II)₂–TRH₂, is in a slow equilibrium with the electroactive Cu(II)–TRH. Simulation of the RRDE behavior of the postulated Cu(II)–TRH system has succeeded in matching experimental data. Capillary electrophoresis indicates that there is a negative charge on the dimer. It is suggested that a hydroxo-bridge may link the two Cu(II) centers. Calculations verify that bi-nuclear Cu(II)₂–TRH₂ complexes are possible.     

Spectrophotometric microdetermination of copper(II), silver(I), and gold(III) using azastyrene Schiff bases

A new method for the spectrophotometric microdetermination of Cu(II), Ag(I), and Au(III) using β-2-hydroxybenzyl-5-bromo- (I_a), 5-chloro- (I_b), and 3-methoxy-2-hydroxyazastyrene (I_c) is given. The optimum conditions favoring the formation of the colored complexes are extensively studied. The molecular structure was found to be (1:1) and (1:2) (M:L). Beer's law is obeyed up to 5.00, 8.64, and 11.82 ppm for Cu(II), Ag(I), and Au(III), respectively, while the optimum concentration ranges using the Ringbom method are 0.6–5.00, 1.00–8.60, and 2.00–11.80 ppm for the same metal ions, respectively.     

Adsorptive accumulation voltammetry of copper(II) using complex formation reaction with salicylideneamino-2-thiophenol

Summary The cathodic stripping voltammetry of copper(II) was investigated with a method, based on the adsorptive accumulation of the Cu(II)-salicylideneamino-2-thiophenol (SATP) complex on a hanging mercury drop electrode. The copper(II)-SATP complex could be accumulated on the electrode at –0.20 V in 0.01 mol/l nitric acid. The reduction peak of the copper complex was observed by scanning the potential in a negative direction in the differential pulse mode. The calibration curve for copper was linear over the range 5×10^–9–1×10^–7 mol/l. This method was applied to determine copper(II) in GSJ (Geological Survey of Japan) standard rock reference materials.     

Ion-Pair High-Performance Liquid Chromatographic Retention Behavior of Copper(II)–1-Oxa-4,7,10,13- tetraazacyclopentadecane Complex

The ion-pair high-performance liquid chromatographic retention behavior of copper(II)–1-oxa-4,7,10,13-tetraazacyclopentadecane (Cu(II)–OTACP) complex is discussed with data from indirect spectrophotometric detection on the μBondapak CN column. The mobile phase was acetonitrile solution (MeCN:H₂O 20:80) containing sodium dodecyl sulfate (SDS) as ion-pairing reagent and sodium 1-naphthalenesulfonate (SNS) as detection reagent. The effects of the concentration of SDS and OTACP added to the sample solution to form the Cu(II)–OTACP complex on the capacity factor of the complex, k′, are illustrated. As a consequence of the study, it was found that two peaks anticipated for the 1:1 and 1:2 mole ratio complexes appeared, and the peak anticipated for the 1:2 mole ratio complex could be used to determine the Cu(II) ion. The method has been applied in the determination of Cu(II) ion in waste water and serum.     

Homo and heteronuclear complexes of dioxime ligands

The mononuclear fragments [Cu(HDopn)(OH)2]+ and [Cu(HPopn)(OH)2]+, [H2Dopn=3,3-(trimethylene- dinitrilo)-dibutan-2–one dioximate and H2Popn, = 3, 3-(phenylenedinitrilo)-dibutan-2–one dioximate] were used to prepare four binuclear complexes [(OH2)Cu (Dopn)Cu(ditn)]2+, [(OH2)Cu(Dopn)Ni(ditn)(H2O)]2+ (ditn=diethylenetriamine) and [(OH2)Cu(Popn)Cu(L) (H2O)]2+ (L=2,2-bipyridine or 1,10–phenanthroline). Two trinuclear complexes, [{Cu(Popn)(OH2)}2M (H2O)n]2+ (when M=CuII, n=1; M=ZnII, n= 2), have been synthesised and characterised by elemental analyses, f.a.b. mass, i.r., electronic, e.s.r. spectroscopy and variable temperature (5–300K) magnetic susceptibility measurements. A strong antiferromagnetic interaction (J=–545cm–1 to –700cm–1) has been found for the binuclear copper(II) complexes. The X-band e.s.r. spectra of these complexes at 300K and for trinuclear complexes at 120K indicate square-pyramidal geometry for the copper centres with a (dx2–y2)1 ground state. The binuclear complex of copper(II)–nickel(II) centres with antiferromagnetic interaction (J=–107 cm–1) is described, and moderately strong zero-field splitting within the quartet state leads to Kramers doublet, as indicated by X-band e.s.r. spectra of this complex. The trinuclear copper(II) complex with an antiferromagnetic interaction (J= –350cm–1) is also described. The heterometallic trinuclear copper(II)–zinc(II)–copper(II) system shows a very weak interaction (J–1cm–1).     

Crystal structure and magnetic properties of the 1D bimetallic thiocyanate bridged compound: {(CuL1)[Co(NCS)4]}(L1 = N-rac-5,12-Me2-[14]-4,11-dieneN4)

The synthesis, crystal structure and magnetic properties are reported for the new bimetallic compound {(CuL₁)[Co(NCS)₄]} where L₁ = N-rac-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The complex forms a one-dimensional zig-zag coordination polymer along the crystallographic c axis, with Co(II) and Cu(II) ions connected via thiocyanate bridges. The Co(II) centre in the [Co(NCS)₄] fragment approximates a distorted tetrahedral symmetry. The Cu(II) geometry is a distorted tetragonal bipyramid with the apical position occupied by the bridging thiocyanate ligand and the basal ones by the four nitrogen atoms from the macrocyclic ring. The polymer chain nearest Cu(1)?Co(1) distances are 6.4152(9) and 6.0988(9) Å and the nearest Cu(1)?Co(1) interchain distances are 6.8609(9), 6.9628(9) and 6.0336(10) Å. The magnetization measurements for the examined compound have been carried out over the range 1.8–300 K. This data suggest ferromagnetic interactions through the thiocyanate bridge.     

O and N NMR studies of the Co(II), Cu(II) and Mn(II) complexes of -proline in aqueous solution

The ¹⁷O and ¹⁴N paramagnetic transverse relaxation time and chemical shift of proline as well as of water, in aqueous solutions of Co(II), Cu(II) and Mn(II) were measured as a function of pH, temperature, and metal ion concentration. The relaxation results were fitted to a theoretical equation linking the Swift-Connick equation to the stability constants of the major complexes in equilibrium. Stability constants for the major complexes of the three ions in this work were determined, along with thermodynamic parameters for some of the complexes. Two complexes of Co(II) were detected directly by ¹⁷O NMR at basic pH, and were assigned to CoPrO₂ and CoPro₃⁻. The hyperfine coupling constant for these two complexes, A/h, was determined directly from the isotropic shift and was found to be −0.63 and −0.31 MHz, respectively. CoPrO₂ could be detected in the pH range 6–12, for Co(II) concentrations greater than 0.04 M, and its chemical shift was around 700 ppm downfield from free proline, at 300 K. CoPro₃⁻ was detected only at pH 11, in the temperature range 275–284 K, with a chemical shift of 390 ppm downfield from free proline.     

Spectrophotometric determination of nickel(II), palladium(II) and copper(II) in presence of each other and other ions with 1-(o-carboxyphenyl)-3-hydroxy-3-phenyltriazene

Summary 1-(o-Carboxyphenyl)-3-hydroxy-3-phenyltriazene was found to be an excellent spectrophotometric reagent for the determination of nickel(II), palladium(II) and copper(II). At pH 6.8–8.3, 2.4–3.5 and 2.2–3.8, nickel, palladium and copper form greenish yellow, yellowish orange and light green complexes with maximum absorption at 410, 410, 400 nm, respectively. The systems obey Beer's law with optimum ranges from 0.25 to 2.0 ppm for Ni(II), 0.5–4.0 for Pd(II) and 0.5–4.0 for Cu(II); the elements form 11 complexes with the instability constants 2.1×10^–5, 1.5×10^–5 and 2.0×10^–5, resepctively. Effects of other anions and cations on the colour systems have been studied and procedures for the determination of Ni(II), Pd(II) and Cu(II) in presence of each other are described.

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Spektrophotometrische Bestimmung von Nickel(II), Palladium(II) und Kupfer(II) nebeneinander und in Gegenwart anderer Ionen mit Hilfe von 1-(o-Carboxyphenyl)-3-hydroxy-3-phenyltriazen

Zusammenfassung Ni, Pd und Cu bilden mit dem Reagens bei pH 6,8–8,3, 2,4–3,5 bzw. 2,2–3,8 grünlich-gelbe, gelblich-orange bzw. hellgrüne Komplexe mit Absorptionsmaxima bei 410, 410 bzw. 400 nm. Das Beersche Gesetz wird in den Bereichen 0,25–2,0, 0,5–4,0 bzw. 0,5–4,0 ppm befolgt. Die Elemente bilden 11-Komplexe mit den Instabilitätskonstanten 2,1 · 10^–5, 1,5 · 10^–5 bzw. 2,0 · 10^–5. Der Einfluß anderer Kationen und Anionen wurde untersucht und Arbeitsvorschriften werden angegeben.

     

Interaction of Methyl Cysteine and Nitrilotriacetate with Transition Metal Ions

In the present work, sulfur-containing amino acid methyl cysteine was studied from the point of view of their coordinating ability with two metal ions, viz. copper(II) and cobalt(II). Solution equilibria of binary (Cu(II)/Co(II)–methyl cysteine and Cu(II)/Co(II)–nitrilotriacetate (NTA)) complex systems are investigated by paper ionophoresis at 35°C, ionic strength I= 0.1 mol/l. In addition to binary complexes, ternary complexes involving nitrilotriacetate and methyl cysteine were also studied. For studying mixed-ligand complexes, the pH of background electrolyte is brought to 8.5 (this pH value is purposely chosen because amino acid and NTA form very stable complexes much ahead of this pH). The stability constants of complexes (Cu(II)–NTA–methyl cysteine and Co(II)–NTA–methyl cysteine) were found to be 4.48 ± 0.07 and 3.55 ± 0.04 (logKvalues), respectively.     

Liquid-membrane type diethyldithiocarbamate ion-selective electrode and its application to the potentiometric titration of metal ions

Summary A liquid-membrane type diethyldithiocarbamate ion-selective electrode (DDC-ISE) was constructed by utilizing the nitrobenzene extract of the methyltrioctylammonium-DDC ion-pair. The DDC-ISE shows Nernstian response in the concentration range of 10^–5–10^–1 M DDC in 0.1 M sodium hydroxide solution. The electrode potential is constant in the pH range of 7.6–13.0. Potentiometric titrations of Hg(II), Cu(II), Ni(II) and Zn(II) in ammoniacal solutions with NaDDC and successive titration of two binary systems, Hg(II)-Ni(II) and Hg(II)-Zn(II), were successfully carried out with this electrode.

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Diethyldithiocarbamat-ionenselektive Flüssig-Membranelektrode und ihre Anwendung zur potentiometrischen Titration von Metallionen

Zusammenfassung Eine Diethyldithiocarbamat-ionenselektive Flüssig-Membranelektrode (DDC-ISE) wurde entwickelt, die den Nitrobenzolextrakt des Ionenpaares Methyltrioctylammonium-DDC benutzt. Die DDC-ISE zeigt Nernstsches Ansprech-Verhalten im Konzentrationsbereich von 10^–5–10^–1 M DDC in 0,1 M Natriumhydroxidlösung. Das Elektrodenpotential ist im pH-Bereich von 7,6–13,0 konstant. Potentiometrische Titrationen von Hg(II), Cu(II), Ni(II) und Zn(II) mit NaDDC in ammoniakalischer Lösung sowie sukzessive Titrationen der binären Systeme Hg(II)-Ni(II) und Hg(II) — Zn(II) wurden erfolgreich durchgeführt.

     

Anodisation of copper in thiourea- and formamidine disulphide-containing acid solution.: Part I. Identification of products and reaction pathway

The anodic behaviour of copper in aqueous 0.5 M sulphuric acid containing different amounts of dissolved thiourea or formamidine disulphide was investigated at 298 K, combining data from electrochemical polarisation, chemical analysis, UV–vis spectroscopy, XPS and EDAX analysis, and structural information on copper–thiourea complexes. The main reactions depend on the applied potential and initial thiourea concentration. In the potential range −0.30≤E≤0.075 V (versus SCE), the electro-oxidation of thiourea to formamidine disulphide, the formation of Cu(I)–thiourea soluble complexes, and Cu(I)–thiourea complex polymer-like films, are the most relevant processes. The formation of this film depends on certain critical thiourea/copper ion molar concentration ratios at the reaction interface. At low positive potentials, the former reaction is under intermediate kinetic control, with the diffusion of thiourea from the solution playing a key role. For E≥0.075 V, soluble Cu(II) ions in the solution are formed and the anodic film is gradually changed to another one consisting of copper sulphide and residual copper. The new film assists the localised electrodissolution of copper. A complex reaction pathway for copper anodisation in these media for the low and high potential range is advanced.     

Spectrophotometric determination of copper(II) using oximidobenzotetronic acid

Summary Oximidobenzotetronic acid (OBTA) is proposed as a sensitive spectrophotometric reagent for the estimation of 0.5–3.0 ppm of copper(II) at 427 nm in 50% dioxan at p_H 5.3–7.5. For the estimation of 2 ppm Cu(II), 1.3 ppm Ni(II), 1.3 ppm Co(II), 3.2 ppm Fe(II), 10.3 ppm Fe(III), 9.7 ppm Ce(IV), 300 ppm acetate, 160 ppm oxalate, 95 ppm tartrate, 50 ppm citrate, as well as Zn(II), Cd(II), Hg(II)) Pb(II), Mn(II), As(III) as well as (V), Th(IV), Be(II), Ce(III), La(III), V(V) and Mo(VI), even when present in large quantities, do not interfere. The interference due to 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) and 30 ppm W(VI) can be removed by the addition of 95 ppm tartrate ions.

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Zusammenfassung Oximidobenzotetronsäure wurde als empfindliches Reagens zur spektrophotometrischen Bestimmung von 0,5 bis 3,0 ppm Kupfer(II) bei 427 nm in 50%iger Dioxanlösung bei p_H 5,3 bis 7,5 vorgeschlagen. Die Anwesenheit von 1,3 ppm Ni(II), 1,3 ppm Co(II), 3,2 ppm Fe(II), 10,3 ppm Fe(III), 9,7 ppm Ce(IV), 300 ppm Acetat, 160 ppm Oxalat, 95 ppm Tartrat, 50 ppm Citrat sowie die Anwesenheit auch großer Mengen Zn(II), Cd(II), Hg(II), Pb(II), Mn(II), As(III) bzw. (V), Th(IV), Be(II), Ce(III), La(III), V(V) und Mo(VI) stören die Bestimmung von 2 ppm Cu(II) nicht. Der störende Einfluß von 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) und 30 ppm W(VI) kann durch Zusatz von 95 ppm Tartrat beseitigt werden.

     

A study of the spectrophotometric determination of traces of cadmium(II) and copper(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in the presence of polyglycol octylphenyl ether

A spectrophotometric study of the Cd(II) and Cu(II) complex of a new reagent, 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol (5-Br-PADAP) in the presence of polyglycol octylphenyl ether (OP) is presented. A reddish binary complex is formed at pH 9 and shows maximal absorbance at 560 nm with molar absorptivity of 1.16 × 10⁵ · mol⁻¹ · cm⁻¹ liter (Cd), 1.5 × 10⁵ mol⁻¹ · cm⁻¹ · liter (Cu). Beer's law is followed over the range 0.0 to 20 μg cadmium(II) and 0.0–18 μg copper(II). The continuous variation method and molar ratio method showed that the metal ligand ratio is 1:2; ordinarily, most ions do not interfere with the determination and the method can be applied for direct spectrophotometric determination of cadmium(II) and copper(II) in actual samples and the results obtained are satisfactory.     

Electrochemical and spectroscopic studies of metal cyclam complexes with thiocyanate. Evidence for mixed ligand complex formation

Complexes of Ni^II, Co^II and Cu^II containing the macrocyclic ligand, 1,4,8,11-tetraazacyclotetradecane (cyclam), and their ability to form mixed ligand complexes with thiocyanate have been studied. These complexes in a 1:2 mole ratio, exhibit new absorption peaks at 450, 538 and 512 nm respectively. Addition of thiocyanate to the nickel–cyclam complex (1:2:5 mole ratio) led to the formation of a purple complex, exhibiting three distinct new absorption peaks at 330, 455 and 662 nm. A purple complex (1:2:10 mole ratio) separated, having absorption peaks at 352, 503 and 693 nm in CHCl₃. The Co^II–cyclam complex with thiocyanate in the same mole ratio exhibits two absorption peaks at 437 and 519 nm without appearance of any precipitate. The Cu^II–cyclam complex with thiocyanate did not form a mixed ligand complex. Electrochemical studies also confirmed the complex formation of Ni^II–cyclam with the thiocyanate with the appearance of two new oxidation peaks close to 1.25 and 1.60 V versus Ag/AgCl in H₂O and CHCl₃. The Co^II–cyclam complex with thiocyanate exhibited an oxidation peak at 1.2 V versus Ag/AgCl, while no peak was observed for the Cu^II–cyclam complex with thiocyanate. Based on spectroscopic and electrochemical studies the geometry of the complex has been evaluated.     

2-[2′-(6′-Methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid as a new reagent for rapid spectrophotometric determination of copper

2-[2-(6-methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid (MBTAMB) has been synthesized and employed as a new reagent for the spectrophotometric determination of copper(II). A blue complex is formed from MBTAMB and Cu(II) in the range of pH 2.0–5.0 in aqueous ethanol. The composition of the complex is Cu(II) MBTAMB=1 1. The maximum absorption of the complex is at 660 nm, its apparent molar absorptivity is 7.0 × 10⁴ 1· mole^–1 · cm^–1. Beer's law is obeyed for copper in the range of 0–0.72 g/ml. The method has been used for the determination of micro amounts of copper in aluminium alloy. The proposed method is simple, rapid and accurate.