Die halbquantitative Bestimmung von Cl?, Br?, J?, SCN?, AsO43?, Cr2O72? und [Fe(CN)6]3?

Ohne Zusammenfassung     

Zum schnellen Nachweis der Kationen Cu++, Ni++, Co++, Fe++ und Mn++, der AnionenSCN?,OCN?,CN?,S2O82?,J?und Br? sowie tert.aliphatischer Amine und Pyridine

Ohne Zusammenfassung     

Bestimmung von Halogenidionen (Cl?, Br?, J?) in Halogenidgemischen

Zusammenfassung Es wird über eine Methode zur Bestimmung von Halogenidionen in Halogenidgemischen berichtet. Die Endpunktindikation erfolgt nach dem Prinzip der Polarisationsspannungstitration und liefert scharf ausgeprägte Titrationsendpunkte in der Reihenfolge der Schwerlöslichkeit der Ag-Halogenide. Insbesondere wird auch der für Serienanalysen erforderlichen Einfachheit und geringen Störanfälligkeit Rechnung getragen. Das Verfahren eignet sich für die Analyse anorganischer Halogenidgemische, für die Bestimmung von CN^–- und SCN^– -Ionen und für die Analyse organischer Halogenverbindungen im Makro- und Halbmikromaßstab nach deren Aufschluß. Die Meßanordnung kann außerdem für die Bestimmung von Kalium und für die Endpunktindikation einiger chelatometrischer Titrationen eingesetzt werden.

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Summary A method is described for the determination of halogenide in mixtures of halogenides. End points are sharply indicated by the polarisation titration technique in the order of solubility of the silver halogenides. The method is suitable for the analysis of mixtures of inorganic halogenides, for the determination of CN^– and SCN^–ions, and for the analysis of organic halogen compounds in macro and semimicro scale after decomposition. For routine analyses it offers the advantage of being simple and only slightly liable to interferences. Moreover, the assembly can be used for the determination of potassium and for the end point indication in some chelatometric titrations.

     

Die Reaktion zwischen Thioglykols?ure (TGA) und Zn2+, Hg2+, Cd2+, Pb2+ und Ag+

Ohne Zusammenfassung     

Synthesis of a water purification reagent based on the Fe(II), Fe(III), Al(III), Cl−-H2O-OH-system

Formation kinetics of a water purification reagent based on the Fe(II), Fe(III), Al(III), Cl^?-H₂O-OH^? system was studied in relation to the nature and state of the surface of dispersed aluminum, initial concentration of iron(III) ions, and pH value. The chemical composition of heteronuclear coordination compounds of iron and aluminum was determined by potentiometry, nuclear magnetic resonance, and X-ray phase analysis.     

Ionophoretische Trennung von ReCl62?, ReBr62? und ReO4?

Zusammenfassung Es wurde die ionophoretische Trennung von ReCl₆ ^2–, ReBr₆ ^2– und ReO₄ ^– unter Verwendung verschiedener Papiersorten untersucht. Am geeignetsten erwies sich das Papier 2045 b Gl von Schl. & Sch.

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Summary The ionophoretic separation of ReCl₆ ^2–, ReBr₆ ^2–, and ReO₄ ^– has been examined using different kinds of paper. Best results have been obtained with the paper 2045 b Gl from Schleicher & Schüll.

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Herrn Prof. G. Brauer danke ich für Förderung. Für die Überlassung von Rheniumverbindungen bin ich der Fa. W. C. Heraeus, Hanau, verpflichtet. Die Neutronenaktivierung wurde freundlicherweise von den Herren Dr. Marth und Dr. Köhler von der Reaktorstation in Garching bei München vorgenommen. Das Bundesministerium für Atomkernenergie und Wasserwirtschaft unterstützte die Untersuchung durch eine Sachbeihilfe.     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

Magnetic properties of fullerene salts containing d- and f-metal cations (Co2+, Ni2+, Fe2+, Mn2+, Eu2+, Cd2+). Specific features of the interaction between C60·? and the metal cations

The interaction between the radical anions C₆₀ ^·− and divalent d- and f-metal (Co, Fe, Ni, Mn, Eu, Cd) cations in DMF and acetonitrile-benzonitrile (AN-BN) mixture was studied. Black solid polycrystalline salts (C₆₀ ^·−)₂{(M²⁺)(DMF) _x } (x = 2.4–4, 1–6) containing the radical anions C₆₀ ^·− and metal(ii) cations solvated by DMF were prepared for the first time and their optical and magnetic properties were studied. The salts containing Co²⁺, Fe²⁺, and Ni²⁺ are characterized by antiferromagnetic interactions between the radical anions C₆₀ ^·−, which result in unusually large broadening of the EPR signal of C₆₀ ^·− upon lowering the temperature (from 5.55–12.6 mT at room temperature to 35–40 mT at 6 K for Co²⁺ and Ni²⁺). The salts containing Mn²⁺ and Eu²⁺ form diamagnetic dimers (C₆₀ ⁻)₂, which causes a jumpwise decrease in the magnetic moment of the complexes and disappearance of the EPR signal of C₆₀ ^·− in the temperature range 210–130 K. A feature of salt 6 is magnetic isolation of the radical anions C₆₀ ^·− due to the presence of diamagnetic cation Cd²⁺. The salts prepared are unstable in air and decompose in o-dichlorobenzene or AN. Reactions of C₆₀ ^·− with metal(ii) cations in AN-BN mixture result in decomposition products of the salts that contain neutral fullerene dimers and metals solvated by BN. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1909–1919, September, 2008.     

Spuren von Eisen (4 ? 10?6%), Kupfer (2 ? 10?6%), Nickel (2 ? 10?6%), Zinn (10?5%), Arsen (4 ? 10?6%), Thallium und Antimon (10?5 bis 5 ? 10?5%) in metallischem Cadmium hoher Reinheit

Ohne Zusammenfassung     

Eine titrimetrische Bestimmung von ClO?, ClO2? und ClO3? aus einer Probe

Ohne Zusammenfassung     

X@(HAlNH)12和X(HAlNH)12 (X＝F－, Cl－, Br－, O2－, S2－, Se2－)复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)₁₂及其内含式X@(HAlNH)₁₂和外接式X(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, O^2－, S^2－, Se^2－)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有T_h对称性的X@(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, S^2－, Se^2－)复合物和具有C₃对称性的O^2－@(HAlNH)₁₂复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.     

X@(HAlNH)12和X(HAlNH)12 (X＝F－, Cl－, Br－, O2－, S2－, Se2－)复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)₁₂及其内含式X@(HAlNH)₁₂和外接式X(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, O^2－, S^2－, Se^2－)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有T_h对称性的X@(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, S^2－, Se^2－)复合物和具有C₃对称性的O^2－@(HAlNH)₁₂复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.     

Trinuclear {M1}CN{M2}2 complexes (M1 = Cr(III), Fe(III), Co(III); M2 = Cu(II), Ni(II), Mn(II)). Are single molecule magnets predictable?

The reaction of the hexacyanometalates K3[M(1)(CN)6] (M(1) = Cr(III), Fe(III), Co(III)) with the bispidine complexes [M(2)(L(1))(X)](n+) and [M(2)(L(2))(X)](n+) (M(2) = Mn(II), Ni(II), Cu(II); L(1) = 3-methyl-9-oxo-2,4-di-(2-pyridyl)-7-(2-pyridylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; L(2) = 3-methyl-9-oxo-7-(2-pyridylmethyl)-2,4-di-(2-quinolyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; X = anion or solvent) in water-methanol mixtures affords trinuclear complexes with cis- or trans-arrangement of the bispidine-capped divalent metal centers around the hexacyanometalate. X-ray structural analyses of five members of this family of complexes (cis-Fe[CuL(2)]2, trans-Fe[CuL(1)]2, cis-Co[CuL(2)]2, trans-Cr[MnL(1)]2, trans-Fe[MnL(1)]2) and the magnetic data of the entire series are reported. The magnetic data of the cyanide bridged, ferromagnetically coupled cis- and trans-Fe[ML]2 compounds (M = Ni(II), Cu(II)) with S = 3/2 (Cu(II)) and S = 5/2 (Ni(II)) ground states are analyzed with an extended Heisenberg Hamiltonian which accounts for anisotropy and zero-field splitting, and the data of the Cu(II) systems, for which structures are available, are thoroughly analyzed in terms of an orbital-dependent Heisenberg Hamiltonian, in which both spin-orbit coupling and low-symmetry ligand fields are taken into account. It is shown that the absence of single-molecule magnetic behavior in all spin clusters reported here is due to a large angular distortion of the [Fe(CN)6](3-) center and the concomitant quenching of orbital angular momentum of the Fe(III) ((2)T2g) ground state.     

Heterometallic complexes of Co2+, Ni2+, and Zn2+ with the [RuNO(NO2)4OH]2? anion and pyridine: Synthesis, crystal structure, and thermolysis

Three new heteronuclear complexes [Ru(NO)(NO₂)₄(OH)M(Py)₃] (M = Co²⁺, Ni²⁺, Zn²⁺) were synthesized and structurally characterized. In all compounds, the [Ru(NO)(NO²)⁴(OH)] fragment is coordinated to the M atom by a bridging OH and two bridging NO₂ groups. The coordination environment of the metal also includes three pyridine nitrogen atoms. Thermal decomposition of cobalt and nickel complexes in an inert atmosphere yields bimetallic solid solutions. Original Russian Text ? G.A. Kostin, A.O. Borodin, Yu.V. Shubin, N.V. Kurat’eva, V.A. Emelyanov, P.E. Plyusnin, M.R. Gallyamov, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 1, pp. 57–64.     

Complexes of a diacetylmonoxime Schiff base of S-methyldithiocarbazate (H2damsm) with Fe(III), Ru(III)/Ru(II), and V(IV); catalytic activity and X-ray crystal structure of [Fe(Hdamsm)2]NO3·H2O

The complexes [M(Hdamsm)₂]X·H₂O (M = Fe, X = NO₃; M = Ru, X = Cl), [Ru(Hdamsm)(PPh₃)₂X′](X′ = Cl, Br), and [VO(Hdamsm)(acac)] (H₂damsm = diacetylmonoxime Schiff base of S-methyldithiocarbazate, Hacac = acetylacetone) have been prepared and characterized by spectroscopic techniques. Their redox properties were investigated by cyclic voltammetry. The X-ray crystal structure of [Fe(Hdamsm)₂]NO₃.H₂O has been determined and shows that the complex has a distorted octahedral geometry in which the Hdamsm behaves as a monoanionic NNS tridentate ligand coordinating via oxime nitrogen, hydrazinic imine nitrogen, and thiolate sulfur. The reactivity of these complexes toward oxidation of alcohols in the presence of t-BuOOH and H₂O₂ as co-oxidants is reported.     

Die quantitative Trennung der Halogenide Cl?, Br? und J? durch Ionenaustauscn-Chromatographie

Ohne Zusammenfassung     

Synthesis, characterization, and crystal structural study of the iron(II) 4,4′-bithiazole complex [Fe(C6H4N2S2)3]2+(NO3?)2

Abstract  

The complex [Fe(C₆H₄N₂S₂)₃]²⁺(NO₃⁻)₂ was prepared from the reaction of 4,4′-bithiazole with Fe(NO₃)₃·9H₂O in methanol. It was characterized by IR, UV-Vis, luminescence, ¹H NMR and ¹³C NMR spectroscopy, and X ray crystallography. The structure was solved in the orthorhombic space group P2₁2₁2₁ with a = 12.1500(5), b = 12.8434(6), c = 16.2222(7) ?, V = 2531.43(19) ?³, Z = 4, and with wR ₂  = 0.0897.     

Crystal structure of [MnII (1,10-C12H8N2)3]2+[(B9C2H11)CoIII(B8C2H10)CoIII(B9C2H11)]2?·CH3CN

A novel compound, [MnPhen₃][(B₉C₂H₁₁)Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]· CH₃CN (Phen = 1,10-phenantroline), comprising a Co(III) dicobaltacarborane cluster anion has been prepared and characterized by single crystal X-ray diffraction. Crystal data are the following: C₄₄H₅₉B₂₆N₇Co₂Mn, M = 1139.84, triclinic, space group , unit cell parameters: a = 13.2465(11) Å, b = 14.521(2) Å, c = 15.2536(15) Å; α = 77.027(9)°, β = 88.500(8)°, γ = 77.274(9)°; V = 2788.5(5) ų, Z = 2, d _calc = 1.358 g/cm³, T = 295 K, F(000) = 1162, μ = 0.853 mm⁻¹. The structure was solved by the direct and Fourier methods and refined anisotropically (isotropically for hydrogen atoms) using the full-matrix technique to final factors R ₁ = 0.0374, wR ₂ = 0.0915 for 7397 I _hkl ≥2σ_I of 9779 I _hkl measured (diffractometer Enraf-Nonius CAD-4, λMoK _α , graphite monochromator, θ/2θ-scanning). The structure is formed from [MnPhen₃]²⁺ cations, [(B₉C₂H₁₁)×Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]₂₋ anions, and acetonitrile molecules CH₃CN. Central Mn atom in the cation has a distorted octahedral coordination environment formed by six nitrogen atoms of three bi-dentate Phen ligands, average Mn-N bond length being 2.263(2) Å. The anion has a chain-like structure built from three icosahedra sharing common vertices occupied by the cobalt atoms. The central icosahedron including ten light atoms (8B, 2C) provides two vertices for the cobalt atoms shared with the other icosahedra having 11 light atoms (9B, 2C). The arrangement of-C₂-groups in the anion corresponds to a quasi-gauche-configuration of asymmetric sandwich complexes of both cobalt atoms. Original Russian Text Copyright ? 2005 by T. M. Polyanskaya, V. V. Volkov, and M. K. Drozdova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.730–740, July–August, 2005.     

Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb] 2+ [PtCl6]2?, [Ph4Sb]+[AuCl4]?, and [Ph4Sb] 2+ [SnCl6]2?: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph₄Sb]⁺ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.