Influence of the primary ion incidence angle on secondary ion emission in SIMS with nitric oxide as reactant gas

Summary Secondary ion emission has been investigated for Ti, V, Cr and for Co, Ni and Cu under 9 mPa of NO as reactant gas with dynamic SIMS conditions. Using pivoted targets the relative intensities of various positive secondary ions were measured for varied incidence angles of the primary Ar⁺ ions (2 keV; 32 A·cm^–2). The axis of the PI beam and the axis of the SI detector were fixed rectangular to each other. The targets could be rotated about an axis perpendicular to both the PI and the detector axis. From the directional change of the emission of the metal ions Me⁺ a geometric shift parameter P_s could be deduced which proved to be related to the relative secondary ion yield and may therefore be used for surface characterization.     

An lonophoretic study of the interactions between metal lons and 1-phenyl-3-pyrazolidinone

Summary The ionic behaviour of 1-phenyl-3-pyrazolidinone (phenidone) at different pH values and its complexes with a selected group of metal ions such as Mg(II), Al(III), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) were investigated in the pH range of 1–13 by paper electrophoresis. pH-mobility curves were determined for phenidone, the nine metal ions and 21 metal-ligand systems with 1, 110 and 1100 metal: ligand ratios. The effect of the pH on complex formation and the influence of the phenidone concentration on the metal ion mobilities are discussed.Presented at the XXII International Conference on Coordination Chemistry, August 23–27, 1982, Budapest (Hungary).     

Crystal Structure of 1,3-Alternate 25,26,27,28-Tetra(tert-butoxyethoxy)calix[4]arene: a Selective Ag+ Extractant

Alkylation of calix[4]arene by 2-tert-butoxyethyl bromide led to the tetraalkylatedcalix[4]arene in the 1,3-alternate, the conformation of which has been established byX-ray crystallography. This spatial structure included a cavity potentially useful forhost–guest complexes achieved with metal cations, especially with Ag⁺. The titlecompound crystallizes in the monoclinic space group Cc with cell constants a = 29.901(2),b = 8.139(1), c = 22.264(3) Å, = 90°, = 117.08(1)°and = 90°. This conformer represents an example for Ag⁺-tunnelingacross an aromatic cavity. This behaviour could lead to important implications with regardto the metal cation- interaction expected for metal transport through ion channels,metal inclusion in fullerenes, intercalation of metal cations into graphites, etc.     

Determination of lead and cadmium using a polycyclodextrin-modified carbon paste electrode with anodic stripping voltammetry

This work reports the use of and -cyclodextrin-modified carbon paste electrodes (CPE_-CD and CPE_-CD) to determine simultaneously Pb(II) and Cd(II) by means of the electrochemical technique known as anodic stripping voltammetry (ASV). Both modified electrodes displayed good resolution of the oxidation peaks of the said metals. Statistic analysis of the results strongly suggests that the CPE_-CD exhibited a better analytical response that the CPE_-CD, while the detection limits obtained for Pb(II) were 6.3×10^–7 M for the CPE_-CD and 7.14×10^–7 M for the CPE_-CD, whereas for Cd(II) they were 2.51×10^–6 M for the CPE_-CD and 2.03×10^–6 M for the CPE_-CD.     

Divalent 3d metal chloride adducts with 2′-deoxyadenosine

Summary Adducts of 2-deoxyadenosine (dado) with chlorides of dipositive 3d metal ions (M=Mn, Fe, Co, Ni, Cu and Zn) were prepared by boiling, under reflux, mixtures of ligand and the metal salt in HC(OEt)₃·EtOH. The solid complexes isolated are either 21 or 11 adducts of dado and metal chloride,i.e.: M(dado)₂Cl₂ (M=Co or Cu), M(dado)₂Cl₂·2H₂O (M=Mn or Zn), Fe(dado)Cl₂ and Ni(dado)Cl₂·2H₂O. The 21 adducts are monomeric distorted tetrahedral (M=Co or Cu) or hexacoordinated (M=Mn or Zn). The 11 complexes are apparently single-bridged linear polymeric species, involving a [M-(dado)]_x backbone (M=Fe or Ni), two terminal Cl- and for M=Ni, two aqua ligands. Terminal dado is most probably N(7)-bound, while bidentate bridging dado bindsvia N(1), N(7).Presented in part at the XXVIII ICCC, see ref. 1.     

Stability of Copper(II), Nickel(II) and Zinc(II) Binary and Ternary Complexes of Histidine,Histamine and Glycine in Aqueous Solution

The binary and mixed-ligand complexes formed between ligands (histidine (His), histamine (Him) and glycine (Gly)) and some transition metals (Cu(II), Ni(II) and Zn(II)) were studied potentiometrically in aqueous solution at (25.0 ± 0.1) C and I = 0.10 M KCl in order to determine the protonation constants of the free ligands and stability constants of binary and ternary complexes. The complexation model for each system has been established by the software program BEST from the potentiometric data. The most probable binding mode for each binary species of histidine and for all mixed species was also discussed based upon derived equilibrium constants and stability constants related to the binary species. The ambidentate nature of the histidine ligand, i.e. the ability to coordinate histamine-like, imidazolepropionic acid-like and glycine-like modes was indicated from the results obtained. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters, log K, log X and ₁₁₁₀. The concentration distributions of various species formed in solution were also evaluated. In terms of the nature of metal ion, the complex stability follows the trend Cu(II) > Ni(II) > Zn(II), which is in agreement with the Irving-Williams order of metal ions. Thus, the results obtained were compared and evaluated with those in the literature.     

The phase equilibria in some binary systems containing stearic alcohol

The liquid — liquid and liquid — solid equilibrium temperatures are taken for the binary systems octadecanol + A (A=dicarboxylic acids, biphenyl or (K, Na) stearate). The results are discussed and a relation connecting the composition of the eutectics with the thermodynamic properties of fusion of the components is derived from the ideal equation and compared with the experimental one.

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Zusammenfassung Die Flüssig-Flüssig- und Flüssig-Fest-Gleichgewichtstemperaturen der binÄren Systeme Octadecanol + A (A=DicarboxylsÄuren, Diphenyl oder (K, Na/ Stearat) wurden ermittelt. Die Ergebnisse werden diskutiert und ein Zusammenhang zwischen der Zusammensetzung der Eutektika und den Thermodynamischen Eigenschaften der Schmelze der Komponenten wird aus dem Vergleich der idealen und der auf dem Versuchswege erhaltenen Gleichungen abgeleitet.

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Résumé On a mesuré les températures des équilibres liquide-liquide et liquide-solide des systèmes binaires octadécanol + A (A=acides dicarboxyliques, diphényle ou stéarate de potassium, sodium). On discute les résultats et l'on établit une relation entre la composition des eutectiques et les propriétés thermodynamiques de fusion des constituants, dérivée de l'équation initiale et comparée avec la relation expérimentale.

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- - + A (A = , (K, Na) ). , .

     

Extraction-spectrophotometric determination of traces of copper(II), zinc(II), cadmium(II) and mercury(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Summary Sensitive extraction-spectrophotometric procedures are described for the complexes of Cu(II), Zn(II), Cd(II) and Hg(II) with 5-Br-PADAP using chloroform as solvent. Optimal conditions have been established for the quantitative extraction of the metal chelates and their composition and optical characteristics have been determined as well. The conditional extraction constants amount logK _ex=10, the molar absorptivities of the complexes being 10⁵ l·mole^–1·cm^–1. Job's method and equilibrium shift method indicate the molar ratios M5-Br-PADAP=12.

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Spektralphotometrische Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)

Zusammenfassung Einfache und empfindliche Methoden zur extraktionsspektralphotometrischen Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 5-Br-PADAP wurden beschrieben. Chloroform wurde als Extraktionsmittel verwendet. Die optimalen Bedingungen für die quantitative Extraktion der Metallchelate wurden ermittelt und deren Zusammensetzung bestimmt. Die Stabilitätskonstanten haben hohe Werte (logK _ex=10), die molare Absorption der Komplexe beträgt 10⁵1·mol^–1·cm^–1. Das Molarverhältnis der Komplexe beträgt M5-Br-PADAP=12.

     

Effect of complexation on electrical conductivity in system consisting of an anion-radical salt and a crown ether

Various experimental methods have been used in a study of the effect of complexation on the electrical conductivity in systems consisting of an anion-radical salt of an alkali metal, a crown ether (CE), and a polar solvent. The electrical conductivity of solutions of M⁺TCQDM (TCQDM = tetracyanoquinodimethane) in the presence of the CE is determined by the ratio () of the radius of the CE cavity to that of the metal ion. The equilibrium constants of the processes taking place in these systems have been determined. It has been established that the electrical conductivity of the systems is determined by the following: a) electrostatic interaction (with = 0–0.8 and > 2); b) formation of complexes {M⁺...CE (with }- 1); c) formation of ternary associates {A...M⁺...CE (with }- 1.4). In the last case, the symmetry of the environment of the M⁺ ion is increased and the potential barrier to the transition of ions between the equilibrium positions is lowered, which is responsible for the observed increase in mobility of the ions in solution.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 2, pp. 188–196, March–April, 1986.     

Electronic structure of the Fe3S4 cluster and its quasi-aromaticity

The localized molecular orbitals and their energy levels for the clusters [Fe₃S₄(SH)₃]^2–, [(HS)₃Fe₃S₄·Ni(PH₃)]^2–, [Mo₃S₄(OH₂)₉]⁴⁺, and [Mo₃S₄·Ni]⁴⁺ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe₃S₄]⁺ and [Mo₃S₄]⁴⁺ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M ₃(₃-S)(-S)₃} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M₃S₃} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo₃S₄]⁴⁺ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe₃S₄]⁺ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo₃S₄]⁴⁺ cluster.     

Some remarks on the periodical change of the stability constants of the lanthanide complexes

The correlations between the values of the lgK (K = stability constant of the lanthanide complex) and the reciprocal of the ionic radius 1/r or the sum of the ionization potentials ₁ ³ I for the lanthanide ions were reviewed for different ligands. A straight-line relationship (lgK – lgK)/lgK vs. (1/r – 1/r)/(1/r) or vs. ( ₁ ³ I – ₁ ³ I)/ ₁ ³ I was found within the tetrads La-Nd, Gd-Ho, and Er-Lu.

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Bemerkungen zum periodischen Wechsel der Stabilitätskonstanten von Lanthaniden-Komplexen

Zusammenfassung Es wurde eine Übersicht der Korrelationen zwischen den Werten von logK (K = Stabilitätskonstante der Lanthanidenkomplexe) und den reziproken Ionenradien 1/r oder der Summe der Ionisierungspotentiale ₁ ³ I für die Lanthanidenionen für verschiedene Liganden gegeben. Dabei wurde eine lineare Korrelation für (lgK – lgK)/lgK gegen (1/r – 1/r)/(1/r) oder gegen ( ₁ ³ I – ₁ ³ I)/_1/3 I innerhalb der Tetraden La-Nd, Gd-Ho und Er-Lu aufgefunden.

     

Interaction of PM12?nVnO40?(3+n) (M=Mo, W) heteropoly complexes with nitrogen oxide

In aqueous solution, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) hetero-polyanions provide a much faster oxidation of NO than mononuclear VO ₂ ⁺ ions, yielding HNO₂, NO ₃ ^– and reduced HPA.

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, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) , VO ₂ ⁺ , NO HNO₂ NO ₃ ^– .

     

Mixed metal hydroxycarboxylic acid complexes. Spectrophotometric study of complexes of U(VI) with In(III), Cu(II), Zn(II) and Cd(II)

The formation of mixed metal complexes between uranium (VI), as the central metal ion, and aluminium (III), indium (III), copper (II), zinc (II) and cadmium (II), as the additional metal ions, with a hydroxycarboxylic acid chosen between citric, tartaric or malic, has been studied using spectrophotometric methods.The effect of pH has been examined, and the results show that at pH=4 stable complexes are formed for most of the systems. At this pH the method of mole ratio and Job's method of continuous variations, were employed to determine the stoichiometry of the mixed metal complexes. Al(III), In(III) and Cu(II) showed a high tendency to form mixed metal complexes with U(VI), while the formation of complexes is uncertain for Cd(II) and Zn(II). The ratio of the ligand to the total metal ion has been found to be 21 and metal:metal ratios of 11 and 12 have been observed.Represents part of the Ph.D. thesis submitted by Emanuel Manzurola to Ben Gurion University of the Negev.     

Triterpene glycosides of alfalfa. III. Medicoside I

On the basis of chemical transformations and with the aid of physicochemical results, the structure of glycoside I isolated from the roots of the plantMedicago sativa has been established as hederagin 3-O-[O--L-arabinopyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinopyranoside] 28-O--D-glucopyranoside. Compound (I), C₅₂H₈₄O₂₂, mp 210–212°C, [] _D ²¹ +38.4° (c 1.48; methanol). Acid hydrolysis of (I) led to hederogenin (II) — C₃₀H₄₈O₄, mp 326–330°C, [] _D ²³ +84.2° (c 0.19; pyridine. The Hakomorimethylation of glycoside (I) yielded the permethylate (IV) — C₆₅H₁₁O₂₂ [] _D ²³ +41.6° (c 1.79; methanol). The GLC analysis of the products of the methanolysis of compound (IV) showed the presence of 3,4,6-tri-O-methyl-D-glucopyranose, 2,3,4,6-tetra-O-methyl-D-glucopyranose, 3,4-di-O-methyl-L-O-arabinopyranose, and 2,3,4-tri-o-methyl-L-arabinopyranose. The alkaline hydrolysis of glycoside I gave compound (III) with mp 230–233°C, [] _D ²¹ +35.2° (c 0.21; methanol), which was identified as medicoside C. Details of the PMR spectrum are given for compound (IV) and of the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1986.     

Determination of Aqueous Nickel-Carbonate and Nickel-Oxalate Complexation Constants

An ion-exchange method was used to determine complexation constants for the Ni-oxalate and Ni-carbonate systems in a NaClO₄ background electrolyte. The Ni-oxalate data were interpreted in terms of a single Niox(aq) complex having log K ₁ values for Ni²⁺ + ox^2– Niox(aq) of 3.9 ± 0.1 (I.S. = 0.5 mol-L^–1 p[H] = 7.1) and 4.4 ± 0.1 (I.S. = 0.1 mol-L^–1 p[H] = 8.6) at 22 ± 1C. Specific ion-interaction theory (SIT) was used to obtain log K ₁ = 5.17 ± 0.05 (95% confidence level and = –0.23 ± 0.15) at I.S. = 0. The Ni-carbonate studies were carried out at p[H] values of 7.5, 8.5, and 9.6 in 0.5 mol-L^–1 NaClO₄/NaHCO₃ solutions. The NiCO₃(aq) species was the dominant complex in the [CO₃ ^2–] concentration ranges studied at all three p[H] values. A log K ₁ value for Ni²⁺ + CO₃ ^2– NiCO₃(aq) of 2.9 ± 0.3 was deduced at I.S. = 0.5 mol-L^–1. Extrapolating this value to zero ionic strength using the SIT approach yielded log K ₁ = 4.2 ± 0.3 (95% confidence level and = –0.26 ± 0.04). The data allowed upper bound values for the complexation constants for NiHCO₃ ⁺ and Ni(CO₃)₂ ^2– to be estimated, i.e., log K < 1.4 for Ni²⁺ + HCO₃ ^– NiHCO₃ ⁺, and log K ₂ < 2 for NiCO₃(aq) + CO₃ ^2– Ni(CO₃)₂ ^2–, respectively.     

Thermal analysis study of some transition metal complexes by TG and DSC methods

The thermodynamic and thermal properties of [Cu(L)₂·Cl₂], [Ni(L)₂]·Cl₂, [Co(L)₂·Cl₂]; L=1,2-bis(o-aminophenoxy)ethane (BAFE), complexes have been investigated. The thermal decomposition of the complexes took place in two distinct steps in endothermic reaction up to 700°C. The activation energy E, the entropy change S ^#, enthalpy H change and Gibbs free energy change G ^# were calculated from the results of thermogravimetry analysis (TG) and heat capacity from the results of differential scanning calorimetry (DSC). It was found that the thermal stabilities and activation energies of the complexes follow the order Ni(II)>Cu(II)>Co(II) and E _Co<E _Ni<E _Cu, respectively.This revised version was published online in November 2005 with corrections to the Cover Date.     

A Highly Efficient Chelating Polymer for the Adsorption of Uranyl and Vanadyl Ions at Low Concentrations

A new polymer containing double amidoxime groups per repeating unit was synthesized to enhance the metal ion uptake capacity. The adsorption properties of this new polymeric adsorbent, amidoximated poly(N,N-dipropionitrile acrylamide), for U(VI), V(V), Cu(II), Co(II) and Ni(II) ions were investigated by batch and flow-through processes at very low concentration levels (ppb). The chelating polymer showed high adsorption capacity for uranyl as well as vanadyl ions. In selectivity studies from a mixture of metal ions in aqueous solutions, the adsorbent showed high selectivity for uranyl and vanadyl ions in the following order: U(VI) > V(V) Co(II) = Cu(II) Ni(II) as determined by calculating the distribution coefficients D, of corresponding ions. The adsorption of uranyl and vanadyl ions from natural seawater by the new adsorbent was also examined in flow through mode.     

Copper(II) halide reactions with the - NH · CS - group in heterocyclic pentaatomic rings

Summary White crystalline complexes of general formula Cu₂L₄X₂ (where X = Cl, Br and L = 1, 3-oxazolidine-2-thione, pyrrolidine-2-thione,N-methyl-1,3-imidazolidine-2-thione andN-ethyl-1,3-imidazolidine-2-thione) and CuLX (where L = 1,3-imidazolidine-2-thione) were prepared by reduction of copper(II) halides and studied by i.r. spectroscopy in the 4000–200 cm^– range. Evidence for ligand coordination to the metal through sulphur was found in each case. The(CuCI) vibration in all the chloro derivatives falls atca. 240 cm^–.     

Determination of pentachlorophenol residues in wine and corks by solvent extraction methodology and specific gas chromatography detection

Summary A gas chromatographic methodology with selective detection is presented for the analysis in wines and corks of pentachlorophenol residues, which are suspected to be the most likely precursors of some off-flavours described in several wine samples. After derivatisation, pentachlorophenol acetate residues were monitored by electrolytic conductivity detection and/or mass spectrometric detection in the selective ion mode at m/z 264 and 266. Recoveries varied from 80 to 96% for wine samples fortified with 5 to 100 g l^–1 and from 83 to 91% for corks (fortified at 25 to 100 g kg^–1). The proposed methodology allowed for a determination limit of g l^–1 for wine and 10 g kg^–1 for corks.     

Reactions of pennogenin and related compounds. IV. Formation of (25R,22′R,25′R)-3β,3′β-diacetoxy-26,22′-epoxy-16,16′-bifurosta-5,20(22),5′,17′(20′)-tetraen-26′-ol from pennogenin diacetate under the action of BF3·Et2O

A new direction of the reaction of pennogenin diacetate with BF₃·Et₂O has been discovered in which a previously unknown dimeric steroid is formed — (25R,22R,25R)-3,3-diacetoxy-26,22-epoxy-16,16-bifurosta-5,20(22), 5,17(20)-tetraen-26-ol, the structure of which has been established as the result of an analysis of IR, UV,¹H and¹³C NMR, and mass spectra. A probable mechanism for the formation of the title compound from pennogenin diacetate is suggested.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Institute of Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 202–208, March–April, 1990.