Determination of oxygen content in YBa2Cu3O6.5+x

A method for determining the oxygen content of the high-temperature superconductor YBa₂Cu₃O_6.5+x is described. The superconductor is dissolved in 4.4 M hydrobromic acid, forming bromine. The mixture is then diluted with hydrochloric acid to obtain a solution of bromine and Cu(II) in 0.44 M hydrobromic acid and 1.1 M hydrochloric acid. As(III) is added in slight excess of that required to react with the bromine and the unreacted As(III) is determined by titration with potassium bromate. Oxygen does not interfere. The results of this method are in agreement with those of other iodimetric procedures. The dissolution of the superconductor in 4.4 M hydrobromic acid is much faster than in hydrochloric acid, the medium used in one iodimetric technique. YBa₂Cu₃O_6.5+x sintered fibers and powder samples weighing from ca. 0.5 to 200 mg were analyzed for oxygen content.     

A Polarographic Method Determing Cu(II), Cu(I) and Metallic Copper Contents in Copper Oxide Samples

Abstract

A polarographic procedure was developed which permits the analysis of powdered cupric and cuprous oxides in the presence of metallic copper. To determine CuO, Cu₂O and metallic copper content in the sample two weight aliquots were used. The first aliquot was dissolved in medium of 50 % ethanol + 3 M hydrochloric acid + saturated ascorbic acid solution. Insoluable metallic copper was determined polarographically after its' separation and additional dissolving in concentrated nitric acid.

The second sample aliquot was dissolved in 6 M hydrochloric acid and the ratio of Cu(I) / Cu(II) in the solution was determined from the polarographic curves. To calculate CuO, Cu₂O and Cu content in a sample the proposed procedure was applied. The developed method provides the accurate results of the determination of CuO, Cu₂O and Cu content in a powdered mixture. The reproducibility expressed as the relative standard deviation is from 1 % to 5 %.     

Locating redox couples in the layered sulfides with application to Cu[Cr2]S4

Use of LiPF₆ in EC:DEC as electrolyte has allowed electrochemical extraction of Li from LiV_1−yM_yS₂ and LiTi_1−yM_yS₂ (M=Cr or Fe). The data show access not only to the Ti(IV)/Ti(III) and V(IV)/V(III) redox couples, but also to the V(V)/V(IV) and Fe(III)/Fe(II) couples in these layered sulfides. However, the Cr(IV)/Cr(III) couple could not be accessed. The concept of redox-couple pinning is outlined and applied to the V(V)/V(IV) and Fe(III)/Fe(II) couples, which are pinned at the top of the S-3p bands. Holes associated with the “pinned” couples occupy orbitals of dominant S-3p character, but they have sufficient cation-3d character to prevent condensation of the holes into p-p antibonding states of disulfide bonds. Strong covalent bonding in the pinned couples creates itinerant-electron states in the partially occupied couples. Application to the metallic, ferromagnetic thiospinel Cu[Cr₂]S₄ favors location of the itinerant holes in states of a pinned Cu(II)/Cu(I) couple having primarily S-3p character.     

Copper-catalyzed asymmetric hydrosilylation of ketones using air and moisture stable precatalyst Cu(OAc)2·H2O

Air and moisture stable copper(II) salts can be used to catalyze the hydrosilylation of aromatic ketones. The combination of catalytic amounts of copper(II) acetate or copper(II) acetate monohydrate (Cu(OAc)₂·H₂O) and BINAP in the presence of organosilanes as the stoichiometric reducing agent generates an active catalyst for the reduction of ketones.     

Determination of Cu(III) and Cu(II) + Cu(III) in superconducting copper ceramics

Summary Copper(III) and total copper in superconducting Y-Ba-Cu oxide and related compounds can be determinated by two successive iodimetric titrations after the sample has been dissolved under Ar in HCl/KI medium. First, the iodine equivalent to copper(III) ist titrated with Na₂S₂O₃ solution at pH 4.8, copper(II) being masked with EDTA. The total copper is then determined in the same solution by demasking with acid and iodide, followed by iodimetric titration. The method is both accurate and reproducible. The relative standard deviations for 1.074% copper(III) and 23.37% total copper are 0.8% and 0.3%, respectively.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

Dicarboxylate assisted synthesis of the monoclinic heterometallic tetrathiocyanato bridged copper(II) and mercury(II) coordination polymer {Cu[Hg(SCN)4]}n: Synthesis, structural, vibration, luminescence, EPR studies and DFT calculations

The synthesis of the monoclinic polymorph of {Cu[Hg(SCN)₄]}_n is reported. The compound, as determined by X-ray diffraction of a twinned crystal, consists of mercury and copper atoms linked by μ_1,3-SCN bridges. The crystal packing shows a highly porous infinite 3D structure. Diagnostic resonances for the SCN^- ligand and metal-ligand bonds in the IR, far-IR and Raman spectra are assigned and discussed. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that the compound is an indirect band gap semiconductor. The DFT calculations show that the observed luminescence of the compound arises mainly from an excited LLCT state with small MLCT contributions (from the copper to unoccupied π^? orbital of the thiocyanate groups). The X-band EPR spectrum of the powdered sample at room temperature reveals an axial signal with anisotropic g factors consistent with the unpaired electron of Cu(II) ion in the d_x²−y² orbital.     

X-ray emission spectra of vanadium atoms in a new series of (Cu,V)-based high-Tc superconductors

Non-resonant V L_2,3 and OKα X-ray emission spectra of a new series of (Cu,V)Sr₂Ca_n−1Cu_nO_y (n=3-7) superconductors are presented. We have found that oxygen atoms surround V-atoms in the given compounds, form a (VO₄)³⁻ tetrahedrons and have a pentavalent state. This induces holes due to the substitution of divalent copper by pentavalent vanadium ions providing a hole-doping mechanism of superconductivity in this series of compounds. A spectral estimation of the oxygen concentration shows that the oxygen content under high-pressure/high-temperature synthesis conditions is not changed considerably from the start to the final product.     

ICP-AES determination of trace elements after preconcentrated with p-dimethylaminobenzaldehyde-modified nanometer SiO2 from sample solution

A new method that utilizes p-dimethylaminobenzaldehyde-modified nanometer SiO₂ (SiO₂-p-DMABD) as a solid phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The preconcentration conditions of analytes were investigated, including the pH value, the shaking time, the mass of sorbent, the sample flow rate and volume, the elution condition and the interfering ions. The adsorption capacity of nanometer SiO₂-p-DMABD was found to be (mg g^− 1) Cr(III): 6.2, Cu(II): 18.6, Fe(III): 4.7 and Pb(II): 6.0 at pH 4. The adsorbed metals were quantitatively eluted with 4 mL of 1.0 mol L^− 1 HCl. According to the definition of IUPAC, the detection limits (3σ) of this method for Cr(III), Cu(II), Fe(III) and Pb(II) were 0.79, 1.27, 0.40 and 1.79 ng mL^− 1, respectively. The proposed method achieved satisfied results when it was applied to the determination of trace Cr(III), Cu(II), Fe(III) and Pb(II) in biological and water samples.     

Synthesis,structure and magnetism of a one-dimensional silicotungstate array: K3H4Cu0.5{Cu[Cu7.5Si2W16O60(H2O)4(OH)4]2} · 9H2O

A structurally distinct, multi-copper(II)-substituted silicotungstate K₃H₄Cu_0.5{Cu[Cu_7.5Si₂W₁₆O₆₀(H₂O)₄(OH)₄]₂} · 9H₂O (1) has been synthesized and characterized by FT-IR spectroscopy, elemental analysis, variable-temperature magnetic measurements, electron spin resonance, and X-ray diffraction. Green crystalline plates of 1 were obtained by the reaction of K₈[γ-SiW₁₀O₃₆] · 12H₂O with 8 equiv. of Cu(II) in a 50% ethylene glycol solution. A cationic copper center connects the terminal oxygen atoms of neighboring polyanions, resulting in a one-dimensional structure. Magnetic susceptibility measurements indicate weak ferromagnetic superexchange between the Jahn–Teller-distorted S = 1/2 Cu(II) centers.     

Preparation and characterization of a new SNO ligand derived from ethanebis(thioamide) and 2-hydroxybenzaldehyde, and its Cu(II), Co(II), and Rh(III) metal complexes

A new Schiff base N-[(E)-(2-hydroxyphenyl)methylidene]-N’-[(Z)-(2-hydroxyphenyl)methylidene]ethanebis(thioamide) (L_C) containing sulfur, nitrogen, and oxygen atoms has been synthesized by condensation of ethanebis(thioamide) with 2-hydroxybenzaldehyde. Metal complexes were synthesized by reaction of the new ligand with copper(II) and cobalt(II) as nitrate salts and with rhodium(III) as chloride salt, using hot absolute ethanol as solvent. All the new compounds were characterized by use of different physicochemical techniques including UV–visible spectroscopy, magnetic susceptibility, IR spectroscopy, molar conductance, and determination of metal content. It is proposed the paramagnetic copper and cobalt complexes adopt octahedral geometry whereas the diamagnetic rhodium complex has octahedral geometry.     

Synthesis, crystal structure and thermal decomposition of a new copper propionate [Cu(CH3CH2COO)2]·2H2O

A new copper propionate complex was synthesised and characterized for application as precursor for CuO based oxide thin films deposition. The FT-IR and X-ray diffraction analyses have revealed the formation of a cooper propionate complex [Cu(CH₃CH₂COO)₂]·2H₂O. The crystal and molecular structure of a new copper propionate complex was determined by XRD on the copper propionate single crystal. The copper propionate complex has a binuclear structure, connected by bridging bidentate carboxylates groups and a Cu?Cu bond of 2.6 Å. The thermal decomposition of copper propionate has been investigated by thermal analysis using thermogravimetric (TG) and differential thermal analysis (DTA), differential thermal analysis coupled with quadrupole mass spectrometry-QMS, X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR) techniques. TG and XRD data indicate the reduction of Cu(II)-Cu(I,0) during the decomposition of copper propionate.     

Electrochemical and electrocatalytic properties of meso-triphenylcorrole and its complexes with Mn(III), Co(III), Cu(III), and Zn(II)

The method of cyclic voltammetry (CV) was used to compare electrochemical and electrocatalytic properties of meso-triphenylcorrole [H₃(ms-Ph)₃Cor] and also its complexes with Mn(III), Co(III), Cu(III), and Zn(II) in 0.1M KOH. Metal-localized redox transitions are detected in the complexes of Mn (III ?? IV) and (III ?? II), Co (III ?? II), Cu (III ?? II). It is shown that the manganese complex features most effective catalytic properties in the reaction of molecular oxygen electroreduction.     

Synthesis and Properties of Colored Copper-Containing Apatites of Composition Ca5(PO4)3CuyO y + δ(OH)0.5 − y − δX0.5 (X = OH,F, Cl)

Ca₅(PO₄)₃Cu_yO _{y + δ}(OH)_{0.5 ? y ? δ}X_0.5 compounds (for X = OH, y = 0.01–0.3; for X = F, y = 0.01–0.1; for X = Cl, y = 0.1) have been synthesized by heat treatment of oxide-carbonate mixtures at 1150°C in air and have been characterized by X-ray diffraction, electronic spectroscopy, and magnetic measurements. The compounds have an apatite structure in which copper atoms substitute for part of the hydroxyl hydrogen atoms in hexagonal channels. The electronic spectrum shows two main absorption bands due to d-d transitions in copper(II) linearly coordinated to two oxygen atoms, as well as extra, weaker bands, whose contribution to the overall spectrum decreases with decreasing y. The latter are assignable to copper atoms occupying other sites in the crystal lattice. The temperature dependence of the magnetic susceptibility of the compounds obeys the Curie-Weiss law with a Curie constant close to zero. The Weiss constant characterizes the copper(II) content of the compounds and correlates qualitatively with the intensity of the main absorption bands in the visible spectrum. The fraction of copper(II) in the total amount of copper in the apatites increases in the substituent order X: Cl, OH, F, as well as upon the low-temperature annealing of the compounds in air. At the same time, copper(II) fraction depends only slightly on the total copper content. As the copper(II) content increases, the color of apatite changes from pink to dark claret.     

Application of ferrous-chromate and iodometric titration for the determination of copper oxidation states in the superconductor YBa2Cu3Oy

Summary Oxidation-reduction titration methods, Fe²⁺-Cr₂C ₇ ^2– and I^–-S₂O ₃ ^2– , were applied to the determination of the oxidation state of copper in the superconductor YBa₂Cu₃O _y , and related compounds. The former method presented problems in the sample dissolution and titration steps. The dissolution of the sample in low concentrations of Fe⁺-phosphoric acid and Fe²⁺-perchloric acid takes place in two steps, the oxidation of Fe²⁺ to Fe³⁺ and the liberation of oxygen gas, when the liberation results in low analytical values for Cu⁺. In addition the coexistence of cuprous ion and acids induces the oxidation of ferrous ion by dissolved oxygen and air. The problems were resolved by dissolution in 0.1 mol/l Fe²⁺-phosphoric acid and titration in an argon atmosphere. The latter method gave good results by controlling the amounts of potassium chloride, the concentration of acetic acid, and by elimination of the dissolved oxygen in acetic acid solution. The results of the two titration methods coincided with each other.

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Anwendung der Eisen(II)-Chromat- und der iodometrischen Titration zur Bestimmung der Oxidationsstufe des Kupfers im Supraleiter YBa₂Cu₃O _y

     

The interaction of polystyryl radical with Cu(DMF)2Cl2

Kinetics of 2,2′-azobisisobutyronitrile initiated polymerization of styrene in N,N-dimethylformamide (DMF) were investigated in the presence of dichloro bis(N,N-dimethylformamide)copper(II) complex. The complex was prepared in situ by mixing tetrakis(N,N-dimethylformamide)copper(II) perchlorate with LiCl in the molar ratio of 1:2. The equilibrium constant for

was calculated by the limiting logarithmic method as 1.07 × 10¹⁰ l² mol^?2. The velocity constant at 60 for the interaction of polystyryl radical with Cu(DMF)₂Cl₂ is 2.16 × 10⁴ l. mol^?1 sec^?1.     

Identification of Cu(II)/Cu(III) couples in binuclear copper(II) complexes

A new series of binuclear copper(II) complexes were synthesised and studied by magnetic, spectral, ESR and cyclic voltammetry methods. The μ_eff values per copper atom correspond to the values observed for mononuclear copper(II) complexes. ESR spectral data in solution indicate weak interactions resulting from the electron delocalisation through the ligand system. Two nearly reversible red-ox couples are identified at $\text{+}\text{?}$0.50 V and $\text{+}\text{?}$0.75 V vs SCE. They correspond to Cu(II)αCu(III) red-ox processes, successively occurring at the two copper sites in the binuclear complexes.     

Synthesis and coordination chemistry of new tetradentate N2S2 donor Schiff-base ligand ca2-dapte: Mononuclear and dinuclear copper(I) complexes [Cu(ca2dapte)]ClO4 and [{Cu(PPh3)(X)}2(ca2dapte)] (X = I and Br)

A mononuclear copper(I) complex, [Cu(ca₂dapte)]ClO₄ (1), and two dinuclear copper(I) complexes, [{Cu(PPh₃)(X)}₂(ca₂dapte)] (X = I (2) and Br (3)), of a new tetradentate N₂S₂ donor Schiff-base ligand ca₂dapte have been prepared (ca₂dapte = N,N′-bis(trans-cinnamaldehyde)-1,2-di(o-iminophenylthio)ethane). These compounds have been characterized by elemental analyses (CHN), FT-IR, UV–Vis and ¹H NMR spectroscopy. The crystal structures of these copper(I) complexes have been determined by single-crystal X-ray diffraction. The coordination geometry around Cu(I) centers in these complexes is a distorted tetrahedron. The ca₂dapte is coordinated to Cu(I) as a tetradentate ligand in 1, while it acts as a bis-bidentate bridging ligand in 2 and 3.     

Synthesis and characterization of the [Cu(Cin2bda)2]ClO4 and [Cu(Ncin2bda)2]ClO4 complexes: Crystal structure of [Cu(Ncin2bda)2]ClO4

Two copper(I) complexes [Cu(Cin₂bda)₂]ClO₄ (I) and [Cu(Ncin₂bda)₂]ClO₄ (II) have been prepared by the reaction of the ligands N²,N²′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L¹) and N²,N²′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L²) and copper(I) salt. These compounds were characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.