Analytische Anwendung der Di-(4-phenyl)thiosemicarbazone von 1,2-Diketonen

Zusammenfassung 1,2-Diketo-bis-(4-phenyl)thiosemicarbazone können als vierzähnige Liganden mit Metallionen der I, II. und VII. Nebengruppe und einigen Metallionen der Hauptgruppen gefärbte Chelate bilden. Die Chelate sind mit organischen Lösungsmitteln extrahierbar und erlauben spektralphotometrische Metallbestimmungen bis in den 1 ppm-Bereich (E _M=1,0–2,3·10⁴).Eine Trennung der Chelate läßt sich neben einer pH-abhängigen Extraktion durch Dünnschicht-Chromatographie erreichen. Variation der Substituenten erlaubt es, dem Reagens gewünschte Eigenschaften zu geben, ohne die Neigung zur Chelatbildung wesentlich zu beeinflussen. Untersucht wurden 1,2-Diketo-bis-(4-phenyl thiosemicarbazone mit verschieden substituierten Phenylresten.Chromatographie von Metallchelaten: IV. Mitteilung.     

Spektralphotometrische Bestimmung von Eisen(III) und Chrom(VI) mit Helasolviolett 4R

Ohne Zusammenfassung

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Spectrophotometric determination of iron(III) and chromium(VI) by means of helasol violet 4R

     

Steuerung metallkatalysierter reaktionen: XIV. kontrolle der nickel(0)-katalysierten cooligomerisation von 1,3-butadien mit vinylsilanen durch konzentration und eigenschaften von zugesetzten p-liganden

The effects of substituents X (X = OR, SPh, CMe₃ and SiR₃) in CH₂=CHX olefins on the nickel(0)-catalyzed co-oligomerization with 1,3-butadiene were investigated. Only the vinylsilanes reacted by co-oligomerization with butadiene. The yields and product selectivities are controlled by the concentration and property (the latter characterized by Tolman's χ and θ parameters) of the added P ligands. The results are discussed in connection with the reaction mechanism. Electron-withdrawing substituents at silicon lower the reactivity of the vinylsilanes.     

Synthesis,Characterization, Antimicrobial Activities,and Structural Studies of Lanthanide (III) Complexes with 1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone

Twelve coordinate lanthanide (III) complexes with the general composition [Ln L₃X_n(H₂O)_n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl^?1, NO₃ ^?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Beiträge zur Chemie des Phosphors. 237. Reaktion von Diphosphan(4) mit Peroxoverbindungen: Bildung von Phosphinophosphinsäure,H2PPH(O)OH,und Bis(phosphino)phosphinsäure, (H2P)2P(O)OH

Contributions to the Chemistry of Phosphorus. 237. On the Reaction of Diphosphane(4) with Peroxo Compounds: Formation of Phosphinophosphinic Acid, H₂PPH(O)OH, and Bis(phosphino)phosphinic Acid, (H₂P)₂P(O)OH Diphosphane(4) reacts with peroxo compounds such as hydrogen peroxide, tetraline hydroperoxide, trifluoroperoxyacetic acid, and cumene hydroperoxide (which is particularly suited for preparative work) at ?30°C to furnish phosphino-phosphinic acid, H₂PPH(O)OH ( 1 ), as the primary product. Compound 1 disproportionates to a major extent in statu nascendi to give phosphanes (above all PH₃) and monophosphorus acids of various oxidation states as well as some bis(phosphino)phosphinic acid, (H₂P)₂P(O)OH ( 2 ). The acids 1 and 2 can be trapped and stabilized as their triethylammonium salts. The structures of these salts have been determined by spectroscopic investigations.     

Struktur und thermischer Abbau von Bis (1,3-diketonato) cobalt-bisimidazolen

Structure and Thermal Degradation of Bis(1,3-diketonato)cobaltbisimidazoles The crystal structure of Co(bzac)₂(HIm)₂. 2MeOH ( I ) and Co(acac)₂(HIm)₂ ( II ) were determined by x-ray diffraction. II : triclinic, space group P1 , Z = 2, a = 746.3(1), b = 948.2(1), c = 1396.7(2)pm, α = 85.18(1)°, β = 88.96(1)°, γ = 80.72(1)°, R = 3.0% for a total of 2194 observed reflections. I : monoclinic, P2₁/c, Z = 2, a = 964.2(3), b = 864.5(2), c = 1769.8(4)pm, β = 98.87(2)°, R = 4.7% for a total of 967 observed reflections. In both compounds centrosymmetric molecules with two bidentate diketonato groups and two imidazole ligands in trans-position are present. The molecules of II are linked by N? H…?O-bridges within layers, while in the lattice of I by the interaction with methanol molecules N-H…?O-H…?O-bridges are formed. The nature of the H-bridges is the deciding factor for the first step of the thermal degradation of the complexes. The N-H…?O-bridges of II relieves the change of the acidic protons of the imidazole to the acetylacetonato ligands. Therefore in the first step acetylacetone is eliminated. No such bridges are present in the complex I . Therefore, in the first step, imidazole and methanol are removed. On heating in O-donor solvents the reaction of I is quite analogous, and this is the reason for the application of this complex as a latent initiator of the epoxide polymerisation.     

Bestimmung von Antithrombin (Heparin-Cofaktor) mit einem chromogenen Peptid-Substrat: Methodik und klinische Anwendung

Ohne Zusammenfassung

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Determination of antithrombin (heparin cofactor) with a chromogenic peptide substrate: Method and clinical application

     

Nachweis von Hydroxyphenylalkylaminen mit 7-Chlor-4-nitrobenzo-2-oxa-1,3-diazol (NBD-Chlorid). Identifizierung der Reaktionsprodukte

Zusammenfassung Hydroxyphenylalkylamine werden bei alkalischer Reaktion mit NBD-Chlorid (7-Chlor-4-nitrobenzo-2-oxa-1,3-diazol) derivatisiert und die entstandenen Produkte dünnschicht-chromatographisch aufgetrennt. R_f-Werte für drei Laufmittel sind angegeben. Die Identifizierung der Reaktionsprodukte wird mittels spektroskopischer Methoden (NMR, UV und Fluorescenz) durchgeführt und in Tabellenform angegeben.

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Detection of hydroxyphenylalkylamines using 7-chloro-4-nitrobenzo-2-oxa-1,3-diazol. Identification of the reaction products

Summary Hydroxyphenylalkylamines are derivatised using NBD-chloride (7-chloro-4-nitro-benzo-2-oxa-1,3-diazol) in alkaline medium. The derivatives are separated by TLC, and R_f-values in three eluents are given. Identification of the reaction products has been carried out by NMR spectroscopy as well as UV-spectroscopy and fluorimetry. Tables are given.

Dem Verein Österreichischer Chemiker sei an dieser Stelle für seine großzügige Unterstützung im Rahmen des Karl-Schröder-Forschungsförderungsfonds herzlichst gedankt.     

Beiträge zum thermischen Verhalten von Sulfaten. VIII. Zum chemischen Transport von FeSO4 mit NH4Cl und von von Fe2(SO4)3 mit Cl2 oder NH4Cl. Experimente und Modellrechnungen

Contributions on the Thermal Behaviour of Sulfates. VIII. The Chemical Vapour Transport of FeSO₄ with NH₄Cl and Fe₂(SO₄)₃ with Cl₂ or NH₄Cl. Experiments and Calculations Well shaped crystals of FeSO₄ and Fe₂(SO₄)₃ can be grown by CVT (T₁? 650°C). We investigated the dependence of the transport rate on the concentration of the transport agent (Fe₂(SO₄)₃/Cl₂ and Fe₂(SO₄)₃/NH₄Cl) as well as on the temperature (FeSO₄/NH₄Cl and Fe₂(SO₄)₃/Cl₂). Using Δ_fH(FeSO₄) = ?220 kcal/ mol, C^p(T) = 30.1 + 9.9 · 10^?3 ×T and Δ_fH(Fe₂(SO₄)₃) = ?615.4 kcal/mol a satisfying agreement between thermodynamical calculations and experimental results can be reached     

On the use of bis(1,5-dimethyl-2-phenyl-3-pyrazolone)perchlorate as a standard for non-aqueous titrations

Summary Titration curves and data are presented for the standardization of perchloric acid in glacial acetic acid and for tetrabutylammonium hydroxide solutions vs. antipyrine perchlorate. In the standardization of the basic titrant this compound yields a single potentiometric break only in the highly basic solvent 1,1,3,3-tetramethylguanidine. In methanol, pyridine, acetonitrile, N,N-dimethylformamide, and dimethylsulfoxide two breaks are obtained. Only the second break is analytically useful and corresponds to a monobasic acid.Work performed under the auspices of the U.S. Energy Research & Development Administration, contract No. W-7405-Eng-48     

Koordinationseigenschaften von Carbaboranylchlorophosphanen: Synthese und Molekülstruktur von cis-rac-Molybdäntetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaboran(12)}

Coordination Properties of Carbaboranylchlorophosphines: Synthesis and Molecular Structure of cis-rac -Molybdenumtetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaborane(12)} Rac-1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaborane(12) ( 1 ) reacts with [Mo(CO)₄(NBD)] (NBD = norbornadiene) after several hours at 50–55 °C to yield cis-rac-[Mo(CO)₄{1,2-(PPhCl)₂C₂B₁₀H₁₀}] ( 2 ). 2 was characterised spectroscopically (¹H, ¹³C, ¹¹B and ³¹P NMR) and by crystal structure determination.     

Untersuchungen und Strukturanalyse von Eisen(II)-, Cobalt(II)- und Nickel(II)-Komplexen nach synergistischer Extraktion

Zusammenfassung Die synergistische Extraktion von Eisen(II)-, Cobalt(II)- und Nickel(II)-Komplexen wird untersucht. Verwendet wurden fluorierte Diketone (A) (Hexafluoroacetylaceton und Derivate des Thenoyltrifluoracetons) und Abkömmlinge des Pyridinal(2)-phenylimins und des Bis-(pyridinal-2-)-diimines (B). Aus den Extraktionskurven nach der Job- und der Molar-Ratio-Methode, der Elementaranalyse und aus Molmassenbestimmungen werden Komplexverbindungen der Zusammensetzung [MA₂B¹], [M₂A₄B²] und [M₃A₆B³] nachgewiesen. Aus den Elektronen- und IR-Spektren und aus magnetischen Messungen wird für die Ni(II)-Komplexe eine octaedrische Struktur vorgeschlagen.

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Investigation and structure analysis of iron(II), cobalt(II) and nickel(II) complexes after synergistic extraction

Summary The synergistic extraction of iron(II), cobalt(II) and nickel(II) complexes was investigated. Fluorinated diketones (A) (hexafluoroacetylacetone and derivatives of thenoyltrifluoracetones) and derivatives of pyridinale(2)-phenylimine and bis(pyridinale-2-)diimine (B) were used. By Job and molar-ratio investigation on the extraction curves, by elementary analysis and molar mass detection complex compounds of the composition [MA₂B¹], [M₂A₄B²] and [M₃A₆B³] could be proved. Electron and infrared spectra and magnetical measurements led to an octahedral structure proposal for the Ni(II)-complexes.

Wir danken Herrn Dr. Bodo Plewinsky, Institut für Anorganische Chemie der FU Berlin, sehr herzlich für die Bestimmung der Molmassen mit der Ultrazentrifuge.     

Beiträge zum thermischen Verhalten von Sulfaten. XVI. Zum chemischen Transport von Ga2(SO4)3 mit Cl2 und mit HCl. Experimente und Modellrechnungen

Contributions on the Thermal Behaviour of Sulphates. XVI. The Chemical Vapour Transport of Ga₂(SO₄)₃ with Cl₂ and HCl. Experimental Results and Calculations Crystals of anhydrous Ga₂(SO₄)₃ can be grown by means of CVT (e. g. 525°C → 475°C) in the less hot region of a closed silica ampoule. We investigated the dependance of the deposition rate on the concentration of the transport agent (Cl₂, HCl) and the transport temperature (475°C ≤ T ≤ 750°C; T₂ > T₁; ΔT = 50°C; T = 0.5(T₁ + T₂)). Experimental results and thermodynamic calculations on the basis of Δ_FH ${}_{\text{298}}^{\text{º}}$ (Ga₂(SO₄)₃) = ?686.5 kcal/mol show a good agreement.     

Konduktometrische Bestimmung von Nickel(II)-, Kobalt(II)- und Kupfer(II)- Ionen aufgrund der Bildung von Pyridin-Rhodanid-Komplexen

Ohne Zusammenfassung

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Conduotometric determination of Ni(II), Co(II) and Cu(II) ions based on the formation of pyridine-rhodanide complexes

     

Einkristallzüchtung und Verfeinerung der Kristallstruktur von BaPb(1-x)BixO3 (x = 0, 15)

Crystal Growth and Structure Determination of BaPb_(1–x)Bi_xO₃ (x = 0.15) Single crystals (0.15X0.20X0.20 mm) of BaPb_(1–x)Bi_xO₃ (x = 0.15) have been grown from a lead (II)-oxide melt. The refinement of the crystal structure (I4/mcm; a = 6.047(5), c = 8.603(8) Å; Z = 4; 281 diffractometer data, R = 0.03) resulted in Pb(Bi)? O? Pb(Bi) bonding angles of 180° (2X), and 165° (4X) within the a/b plane. The identity of single crystals and powder material was ensured by an Rietveld profile fit of the X-ray powder diagram. The compositions of the single crystals have been determined applying electron microprobe techniques. T_c of the single crystals was found to be 13.2 K (onset, S QUID-magnetometer).     

Beiträge zum thermischen Verhalten von Sulfaten. XII. Zum chemischen Transport von In2(SO4)3 mit Cl2 und mit HCl. Experimente und Modellrechnungen

Contributions on the Thermal Behaviour of Sulfates XII. The Chemical Vapour Transport of In₂(SO₄)₃ with Cl₂ and HCl. Experimental Results and Calculations By means of CVT (T₁ between 500°C and 825°C; ΔT = 50°C), well shaped crystals of anhydrous In₂(SO₄)₃ can be grown in the less hot region of a closed silica ampoule. We investigated the dependence of the deposition rate on the variation of the concentration of the transport agent (system In₂(SO₄)₃/Cl₂) and on the variation of the transport temperature (In₂(SO₄)₃/Cl₂ as well as In₂(SO₄)₃/HCl). A comparison of the experimental results with thermodynamical calculations shows a satisfying agreement. The influence of the variation of some additional parameters (H₂O from the wall of the ampoule; Δ_BH(In₂(SO₄)₃)) on the deposition rate is discussed.     

Zur Koordinationschemie des 1,3-Dithiol-2-selon-4,5-diselenolats (dsise) und des 1,3-Dithiol-2-selon-4,5-dithiolats (dmise). Kristall- und Molekülstruktur des Tetrabutylammonium-bis-(1,3-dithiol-2-selon-4,5-diselenolato)nickelat(II) und -(III), [(n-C4H9)4N]2[Ni(dsise)2] und (n-C4H9)4N[Ni(dsise)2]

Coordination Chemistry of 1,3-Dithiole-2-selone-4,5-diselenolate (dsise) and 1,3-Dithiole-2-selone-4,5-dithiolate (dmise). Crystal and Molecular Structure of Tetrabutylammonium bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate(II) and -(III), [(n-C₄H₉)₄N]₂[Ni(dsise)₂ and (n-C₄H₉)₄[Ni(dsise)₂] Syntheses and properties of metal(II) and metal(III) bis-chelates of 1,3-dithiole-2-selone-4,5-diselenolate (dsise), of the general type (Bu₄N)_n)M(dsise)₂] (n =2 : M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1: M = Ni, Au) are reported and compared with chelates of the isologue 1,3-dichalcogenole-2-chalcogenoe-4,5-dichalcogenolate (i. r., ¹³C-n. m. r., e. p. r., cyclovoltammetric data). The unexpected rearrangement during the syntheses of dsise and 1,3-dithiole-2-selone-4,5-diselenolate (dmise) is characterized by ab-initio SCF calculations. The x-ray structures of (Bu₄N)₂[Ni(dsise)₂] (space group P2₁/c, a = 8.5556(13) Å, b = 15.0009(12) Å, c = 19.696(3) Å, β = 96.018(7)°, V = 2513.9(5) ų, Z = 2) and Bu₄N[Ni(dsise)₂] (space group C2/c, a = 25.133(6) Å, b = 9.828(4) Å, c = 18.104(7) Å, β = 132.81(1)°, V = 3281(2) ų, Z = 4) are given.     

Substitutionsreaktionen der Bis(trimethylelement)carbodiimide des Siliciums und Germaniums mit Metallchloriden und Dimethylmetallchloriden des Sb,Al, Ga und In

Substitution Reactions of Bis(trimethylelement)carbodiimides of Silicon and Germanium with Metal Chlorides and Dimethylmetalchlorides of Sb, Al, Ga, and In The reaction of Me₃Ge? N?C?N? GeMe₃ (Me?CH₃) with SbCl₅ in a 1 : 1 molar ratio forms dimeric Cl₄SbNCNGeMe₃ in high yields. The corresponding compounds (X₂MNCNSiMe₃)_2–3 (with X?Cl, Me and M = Al, Ga), formed by reactions of X₂MCl and Me₃SiNCNSiMe₃, are less stable and tend to condensations, eliminating Me₃SiX. The carbodiimide derivates (Me₂MNCNEMe₃)_2–3 (with E = Si, Ge) are also available in aprotic solvents from polymeric LiNCNEMe₃ and Me₂MCl (M = Al, Ga, In). According to the IR and Raman spectra the low associated substitution products consists of cyclic ring skeletons and asymmetric > N? C?N? EMe₃ units with cyanamide conformation.     

Zur analytischen und präparativen Trennung von funktionellen Carbosilanen und Phosphanen mit Hilfe der SFC (Supercritical-Fluid-Chromatography)

Analytical and Preparative Separation of Functional Carbosilanes and Phosphanes by Means of SFC (Supercritical Fluid Chromatography) Analytical and preparative separations of functional silanes, carbosilanes and phosphanes by means of SFC (supercritical fluid chromatography) using CO₂ or CF₃Cl as mobile phases are reported. The detecting system (an IR high pressure cell) of the apparatus which was developed by us is depicted. The separation of mixtures containing silanes with strongly polarizing groups proceeds successfully with Nucleosil-C₁₈ and CO₂ according to the molecular weights. Large differences in the polarity of the compounds give rise to a separation according to molecular weights, smaller ones to the types of compounds. The advantages of a separation by SFC are demonstrated using a mixture of 1,3,5-trisilacyclohexanes with SiH, CCl₂ and SiF groups. The preparative separation is demonstrated using a mixture of 4 different groups of a toral 22 carbosilanes. Eight fractions were obtained each of which containing the compounds with the same number of Si atoms. The final separation was achieved by means of a pressure program (Nucleosil-C₁₈, CO₂). The preparative isolation of a cyclic phosphinoborane from a mixture of three components of the same type as well as the isolation of (Me₃Si)₃P from a mixture of P-rich silylphosphanes is reported.