bluuebunny/crossref_metadata_2025 huggingface dataset:
The nature and composition of the outer layers of the cuticle of Acanthosentis oligospinus n.sp. (Acanthocephala) from the fish Macrones gulio
Authors: Anantaraman Sita
Published: March 2015

The nature and composition of the outer layer of the cuticle of Acanthosentis oligospinus n.sp., were investigated. The outermost layer is formed of lipids and the one internal to it is constituted of lipoprotein. In staining reactions, in possession of resistant properties, and in the absence of chitin, these two layers recall the outer and inner epicuticle of arthropods.
Zum Bindungszustand des fünf- und sechsbindigen Siliciums in kationischen und anionischen o-Arylendioxychelaten / (d ← n) π-Bonding in Anionic and Cationic o-Arylenedioxy Chelates of Hexacoordinate and Pentacoordinate Silicon Studied by Means of ESCA
Authors: Meyer Heinrich , Nagorsen Günter
Published: March 2015

The “Si-2s- and Si-2p-binding energies” of 5 o-arylenedioxy complexes containing penta- and hexacoordinate silicon have been obtained from their ESCA-spectra. The data have been compared to those of tetracovalent silicon compounds. A linear correlation between calculated Pauling charges and binding energies has been found for compounds where no (d ← n) -interaction should exist. Characteristic deviations from the linear relation were found both in tetravalent silicon compounds containing Si-O-bonds, the (d ← n)π-interaction of which is well established, and in the anionic tris(o-phenylenedioxy) siliconate and in the bis(o-phenylenedioxy) organosiliconates. No deviations were observed in case of the cationic 6-coordinate complexes of silicon with acetylacetone and 2-hydroxypyridine-N-oxide. We conclude that an additional back donation from the free electron pair (dSi ← nOo) only exists to a considerable extent in tetracovalent silicic ester derivatives, in the hexa- and pentacoordinate tris(o-phenylendioxy) siliconate and in the bis(o-phenylenedioxy) organosiliconates. A method is given to obtain crystalline tris(2-oxypyridine-N-oxy) siliconium chloride in good yield.
Conductometric Pulse Radiolysis Study on the Reaction of the Solvated Electron with 5-Bromouracil in Aqueous Solutions at Different pH Values
Authors: Wagner Burkhard O. , Klever Herbert , Schulte-Frohlinde Dietrich
Published: March 2015

To study the reaction of the solvated electron with 5-bromouracil an aqueous solution has been examined by conductometric pulse radiolysis at pH values between 4.68 and 8.74. Alcohol was added to scavenge the hydrogen atom and the hydroxyl radical. G(Br—) = (2.64 ± 0.08)/100 eV was found to be independent of the pH. The mobility of the bromouracil mono-anion was measured to be (2.7 ± 0.2) 10-4 cm2 V-1 s-1 at 20°C, and the rate constant of reaction (3b) was determined to be k(H+ BrUr-) = (2.3 ± 0.2) 1010 I mole-1 s-1*.
Strukturbestimmungen an kleinen Molekülen, III / Das 1H-NMR-Spektrum von partiell orientiertem Cyclopentadien / Structure Determinations for Small Molecules, III.
Authors: Günther Harald , Herrig Wolfgang , Pawliczek Josef B.
Published: March 2015

The 1H NMR spectrum of cyclopenta-1,3-diene partielly oriented in a nematic phase was recorded and analysed. A proton geometry characterised by the following H,H distance ratios was determined: r12/r23 = 0.954 ± 0.007, r13/r23 = 1.596 ± 0.004, r25/r23 = 1.476 ± 0.009, r14/r23 = 1.638 ± 0.005, r15/r23 = 0.990 ± 0.001, and r55,/r23 = 0.653 ± 0.002. The molecule is found to be planar. CC bond lengths and bond angles were calculated on the basis of the proton geometry using molecular mechanics. Evidence for a possible influence of ring bending on the NMR results is discussed.
Notizen: Die Struktur von [(CH3)2Si]2S2N4 / The Structure of [(CH3)2Si]2S2N4
Authors: Ertl Gert , Weiss Johannes
Published: March 2015

The structure of [(CH3)2Si]2S2N4 has been determined from threedimensional diffractometer data and refined by least squares methods to R = 0.07. The unit cell is orthorhombic with four molecules per unit cell and a = 599,5 pm, b = 2300.9 pm, c = 841.9 pm.

Wie von ROESKY und WIEZER1 gezeigt werden konnte, lassen sich im achtgliedrigen Ringsystem des S4N4 2 Schwefelatome durch Si(CH3)2-Gruppen ersetzen. Die Struktur dieser Verbindung haben wir röntgenographisch bestimmt.
Notizen: Schwingungsspektren der Gold(I)-halogenide AuX (X = Cl, Br und I); Strukturprognosen für AuCl und AuBr / Vibrational Spectra of the Aurous Halides AuX (X= Cl, Br and I); Structural Prognoses for AuCl and AuBr
Authors: Breitinger Dietrich , Leuchtenstern Heiko
Published: March 2015

Chain structure, Force constants

From vibrational spectra chain structures are predicted for AuCl and AuBr; bond angles, bond lengths and force constants have been estimated for these aurous halides.
Darstellung und Struktur der Phase Li7Sn3 / Preparation und Crystal Structure of Li7Sn3
Authors: Müller Wiking
Published: March 2015

The intermetallic compound Li7Sn3 has been prepared and its crystal structure determined. It crystallizes monoclinic, space group P 21/m—G2h
2, a = 9.45 ± 0.01 A, b = 8.56 ± 0.01 Å, c = 4.72 ± 0.01 Å, γ = 105.95° ± 0.05 in a variant of the cubic I-lattice.
Kernresonanzspektroskopische Untersuchungen an Organophosphorverbindungen des Typs [R2P(X)]2Y / NMR Spectroscopic Investigations on Organophosphorus Compounds of Type [R2P(X)]2Y
Authors: Hagele Gerhard , Kuchen Wilhelm , Steinberger Helmut
Published: March 2015

Various methods for the synthesis of [R,P(X)]2Y are described. High-resolution NMR spectra were analyzed on the basis of [AXn]2 spinsystems and simulated by computer programs.
Darstellung und Komplexierungsverhalten von 2.4.6-Tri(4-pyridyl)-s-triazin / Preparation and Complex Behaviour of 2,4,6-Tri(4-pyridyl)-s-triazine
Authors: Biedermann Hans-G. , Wichmann Klaus
Published: March 2015

2,4,6-Tri(4-pyridyl)-s-triazine is prepared from 4-cyanopyridine by a cationic and anionic mechanism. It forms with transition metal chlorides in toluene or benzene the complexes: (FeCl3)3(TPyT)2, and (MeCl2)3(TPyT)2 with Me = Ni, Co, Cu.

The IR spectra, magnetic and electrical conductivity measurements are discussed.
Zur Ringöffnung von Spirobipyranen / About the Ringopening of Spirobipyranes
Authors: Paal Gabor
Published: March 2015

The structure of pyryliumsalts derived from spiropyranes by reaction with acids was investigated. The structure found spectroscopically could be verified by synthesis.
Zur Kenntnis einer neuen SrSi-Modifikation und der Phase SrGe0,76 / On a New SrSi-Modification and the New Compound SrGe0,76
Authors: Eisenmann B. , Schäfer H. , Turban K.
Published: March 2015

A new SrSi-modification and the new phase SrGe0,76 were prepared and their structures determined. In these compounds the elementlVatoms form planar hexagons substituted in the 1, 2, 4, 5-positions by four additional Si(Ge)atoms. In the compound SrGe0,76 there are defects in this unit in the positions 1, 2, 4, 5, while in SrSi no indications of such defects could be found.
The Polarographic Reduction of Diazoacetone
Authors: Paliani Giulio , Sorriso Salvatore , Murgia Sandro Maria
Published: March 2015

The electrochemical reduction of diazoacetone in 10 % water: ethanol solution, between pH = 3 and pH = 9, has been studied. Two waves have been observed in acid solution: the first is attributed to the reduction of diazoacetone to aminoacetone and the second one to the reduction of 2,5-dimethyldihydropyrazine (formed by dimerization of the aminoacetone) to 2,5-dimethylpiperazine. In neutral and alkaline media the first wave splits into two waves corresponding to a reduction of diazoacetone to hydrazone and aminoacetone.
Substituentenaustauschreaktionen zwischen Tris(trimethylsilyl)phosphan und Trimethylgermanium- und Trimethylzinnchlorid / Scrambling Reactions Between Tris(trimethylsilyl)phosphane and Trimethylgermanium- and Trimethyltinchloride
Authors: Schumann Herbert , Kroth Heinz-Jürgen , Rösch Lutz
Published: March 2015

Tris(trimethylsilyl)phosphane reacts with trimethylgermaniumchloride and trimethyltinchloride with redistribution of the trimethylelement-IVb groups. All 10 possible compounds are detected by 31P NMR.
Zur Existenz neuer Verbindungen zwischen Alkalimetallen / On the Existence of New Compounds Between Alkali Metals
Authors: Simon Arndt , Ebbinghaus Gebhard
Published: March 2015

Compound formation is found in the systems Na/K (Na2K), Na/Cs (Na2Cs) and K/Cs (K2Cs, K7Cs6).

Due to modified GUiNIER-photographs Na2Cs crystallizes with the hexagonal LAVES-type structure (a0 = 7.861 ± 0.001, c0 = 13.062 ± 0.002 Å at —50°C). The structure is discussed in terms of VEC- and geometrical arguments.
Notizen: Synthesis and Crystal Data of the Bismuth Sulphide Chloride B19Si27Cl3
Authors: Krämer Volker
Published: March 2015

The title compound was synthesized by a sinter technique at 560°C. X ray powder data are listed, the hexagonal lattice parameters are a = 15.403 (3) and c = 4.015 (2) Å; possible space groups are P63 and P63/m.
Notizen: Die Phase Li2CeGe / The Phase Li2CeGe
Authors: Schuster Hans-Uwe , Czybulka Axel
Published: March 2015

The phase Li2CeGe has been prepared and investigated by X-ray diffraction. The spacegroup was found to be C mcm (orthorhombic). The relations to other ternary lithium compounds are discussed.
Notizen: Li5Fe7Ge8, eine monoklin bzw. hexagonal kristallisierende neue ternäre Phase / Li5Fe7Ge8, a Monoclinic resp. Hexagonal Crystallizing New Ternary Phase
Authors: Schuster Hans-Uwe , Welk Erwin
Published: March 2015

The phase Li5Fe7Ge8 has been prepared and investigated by X-ray diffraction. Two modifications - monoclinic and hexagonal - have been found, the crystal data were determined.
Reactions of Aromatic Amines on 5-Arylidene-4-methylmercapto-hydantoin and 5-Arylazo-2-methylmercapto-hydantoin
Authors: Shalaby A. F. A. , Daboun H. A. , Boghdadi S. S. W. , Abdel-Aziz M. A.
Published: March 2015

Treatment of 5-arylidene-4-methylmercapto-hydantoin (1a,b) and 1-phenyl-4-thiohydantoin (3) with aromatic amines gave 5-arylidene-4-arylimino hydantoin (2 a-h) and 4-arylimino- l -phenyl-hydantoin (4a-c) respectively. 2 a and 4 a were hydrolysed with concentrated hydrochloric acid and gave 5-benzylidene-hydantoin and 1-phenyl-hydantoin respectively. N2-phenylglycocyamidine (7) was found to condense with aromatic aldehydes yielding (6a-c). Compound 6a was also obtained from 5-benzylidene-2-methylmercaptohydantoin (5) and aniline. Treatment of 5-arylazo-2-methylmercapto-hydantoin (8a-e) with aromatic amines gave the products 9 a-k. The compound 9 a was hydrolysed with a mixture of concentrated hydrochloric acid and acetic acid yielding (10).
Notizen: Thiol Ester Aminolysis in Acetonitrile
Authors: Kömives T. , Márton A. F. , Dutka F.
Published: March 2015

The kinetics of the reactions of p-nitrophenyl thiolacetate with several amines in acetonitrile was studied. Hydrazine exhibits considerably greater nucleophilicity than expected from its pKa value. Common mechanism is suggested for the aminolysis of the thiol ester and its oxygen analogue.
Notizen: Zur Synthese von 4-Formyl-chinolin-2-carbonsäuren / Synthesis of 4-Formyl-quinoline-2-carboxylic Acids
Authors: Schmut Otto , Kappe Thomas
Published: March 2015

The reaction of o-aminophenylglyoxal dimethylacetales with sodium pyruvate in the presence of sodium ethoxide yields 4-dimethoxymethyl-quinoline-2-carboxylic acids which give the title compounds on acid hydrolysis.
Die pH-abhängige Wirkung von Molybdat- und Wolframationen auf Hefezellen und Ehrlich-Krebs-Ascites-Zellen / pH Dependent Cytostatic Effect of Molybdat- and Tungstate Ions on Yeast Cells and Ehrlich-Krebs-Ascites Cells
Authors: Schönfeld Bernd , Glemser Oskar
Published: March 2015

Molybdate and tungstate ions have an pH dependent cytostatic effect on yeast S. cerevisiae and Ehrlich-Krebs-Ascites cells.
Ein Makroheteropolyanion1 mit antiviraler Wirkung: [Sb8W20O80] 16- / A Macroheteropolyanion with Antiviralic Effect: [Sb8W20O80]16-
Authors: Schönfeld Bernd , Bähr Wolfgang , Buss Bruno , Glemser Oskar
Published: March 2015

The formula of the ammonium salt (NH4)16[Sb8W20O80] · 32 H2O is proved by chemical analysis, Raman-spectra, determination of the molecular weight by ultrazentrifuge technique and X-ray structural analysis.
Über Isopolywolframatfeststoffe und deren Beziehung zu Isopolywolframationen in wäßriger Lösun / Concerning Solid Isopolytungstates and their Relation to Isopolytungstate Ions in Aqueous Solutio
Authors: Cordis Vasile , Tytko Karl-Heinz , Glemser Oskar
Published: March 2015

A classification and characterization of the solid isopolytungstates obtainable from acidified aqueous solutions is given and the relation of the solid isopolytungstates to the isopolytungstate ions in the corresponding solutions is studied. As distinguished from the molybdate system all the polytungstate ions forming a solid exist in solution as well. The reasons for the non-occurrence of insoluble solids of species absent from solution are discussed. For setting up a reaction scheme on the polytungstates only very few of the large number of papers on this subject give evidentiary informations.
57Fe- und 119Sn-Mößbauer-Untersuchungen an Tetracarbonyl(organoelement IV a-phosphin)eisen(0)-Komplexen / 57Fe and 119Sn Mössbauer Studies on Tetracarbonyl(organoelement IV a-phosphine)iron(0) Complexes
Authors: Ensling Jürgen , Gütlich Philipp , Rösch Lutz
Published: March 2015

57Fe and 119Sn Mössbauer effect measurements were performed on a series of complexes of the type (CO)4FeL with L being organoelement(IV a)-phosphine, [(CH3)3C]3-nP[E(CH3)3]n(n = 0,1,2,2; E = Si, Sn), to gain some insight into the nature of the phosphorous-element(IV a) bond as well as the iron-nearest neighbour bond. The results of the Mössbauer measurements are in contradiction with the widely discussed presence of (p → d)π interaction in the phosphorous-element(IVa) bond. In accordance with NMR and vibrational spectroscopic studies they rather suggest that (p → d)π interaction be of little importance.
Photoelectron Spectra and Molecular Properties, XLVIII Carbonates and Thiocarbonates
Authors: Wittel K. , Astrup E. E. , Bock H. , Graeffe G. , Juslén H.
Published: March 2015

Photoelectron (PE) spectra of ethylene and vinylene carbonates and thiocarbonates as well as of methylene trithiocarbonate and some open-chain derivatives are reported.

The low energy bands, well separated in the unsaturated compounds, are assigned to lone pair and π type ionizations. The assignment is based on comparison of PE spectra, modified CNDO calculations, and sulfur Κβ emission spectra. The pronounced substituent effects due to which the first ionization potential varies from 8.4 eV to 11.1 eV are discussed.
Hochdruckmodifikationen der Lanthaniden(III)sulfide Ln2S3 (Ln = Lu-Ho, Y) mit U2S3-Struktur / High Pressure Modifications of the Rare Earth Sulfides Ln2S3 (Ln = Lu-Ho, Y) with U2S3-Structure
Authors: Range Klaus-Jürgen , Leeb Richard
Published: March 2015

New modifications of the rare-earth sesquisulfides Ln2S3 (Ln = Lu-Ho, Y) were found after high pressure, high temperature treatment and quenching to ambient conditions. The crystal structure of the prototype Tm2S3-III was determined from singlecrystal data. Tm2S3-III and the other members of the isotypic series Ln2S3-III are isostructural with U2S3. Some relations between the U2S3 structure and other structures with trigonal prismatic anion configurations are discussed.
N-Triäthylsilyl-triorganophosphinimine / N-Triethylsilyl-triorganophosphine Imines
Authors: Wolfsberger Werner
Published: March 2015

Some N-triethylsilyl-phosphine imines have been prepared by transsilylation of the corresponding N-trimethylsilyl compounds with triethylsilicon halides. All new compounds are characterized by elemental analysis and spectral data.
Notizen: Synthesis and Crystal Structure of 2-Chloro-4-dimethylamino-6-triphenylphosphazen-1′-y1-1,3,5-triazine
Authors: Cameron T. Stanley , Mannan Kh. , Biddlestone Malcolm , Shaw Robert A.
Published: March 2015

The title compound was synthesized and its structure determined by X-ray crystallography. The NPPh3 substituent adopts a type I conformation with its nitrogen and phosphorus atoms coplanar with the ring. The compound, the first asymmetric 1,3,5-triazine to be crystallographically investigated, shows significant variations in ring bond lengths and angles; these are discussed.
Notizen: LiZnSb, eine weitere ternäre Phase mit Wurtzitgerüst / LiZnSb, an Additional Ternary Phase with a Wurtzit-type Lattice
Authors: Schroeder Gerhard , Schuster Hans-Uwe
Published: March 2015

X-ray investigations on the ternary phase LiZnSb showed that this phase crystallizes in a Wurtzit-type lattice with an ordered arrangement of the positions of Zn and Sb.
Notizen: Reaktivität und spektroskopische Eigenschaften von Acylisocyanidpentacarbonylchrom Komplexen / Reactivity and Spectroscopic Properties of Acylisonitrile Chromium Pentacarbonyls
Authors: Höfle Gerhard
Published: March 2015

The title compounds react with nucleophiles similar to activated carboxylic acid derivatives. There is no indication of acylisonitrile fragments on either thermolysis or mass spectrometry.
Notizen: Synthesis of Poncimarin, a New Cumarin from Poncirus trifoliata L.
Authors: Rodighiero P. , Guiotto A. , Manzini P. , Pastorini G.
Published: March 2015

Poncimarin[7-(2′,3′-epoxy-3′-methylbutyloxy)-8-(2″,3″-epoxy3″methylbutyl)coumarin], a coumarinic derivative isolated from unripe fruits of Poncirus trifoliata L., was synthetized by isoprenylation and diepoxidation of osthenol. Analitical and spectral properties of synthetic product superimposes with that of natural coumarin.
Spectroscopic Behaviour of Quasi-One-Dimensional Linear Chains in MgPt(CN)4 · 7 H2O Single Crystals
Authors: Yersin Hartmut , Gliemann Günter
Published: March 2015

In the direction of the crystallographic c-axis MgPt(CN)4 · 7 H2O has a relatively low Pt-Pt-distance (3.15 Å at 300°K). Thus the optical behaviour shows inter-molecular interactions. Single crystal polarized emission and absorption spectra were measured between 300°K and 5°K. In this temperature range the emission peaks shift to the red by about 1,100 cm-1. This is attributed to a decrease in Pt-Pt-distance. MgPt(CN)4 · 7 H2O undergoes phase transitions at about 166°K and 60°K. To interprete the solid state emission and absorption behaviour the Davydov theory is applied. The two lowest excited bands of electronic origin are assigned to the symmetries Γ2u(κ) and Γ5u(κ) in the double group D′8h·
29Si-Kernresonanzmessungen an Siliciumhalogeniden / 29Si NMR Studies on Silicon Halogenides
Authors: Niemann U. , Marsmann H. C.
Published: March 2015

The 22Si NMR spectra of the mixed halides of silicon, SiWXYZ, W, X, Y, Z = Cl, Br, J, have been recorded. The chemical shift of these compounds can be rationalized in terms of substituent effects. Relations to the isoelectronic aluminium and phosphorus compounds are discussed. The 99Si spectra of the simple chloropolysilanes have been assigned. A complication arises from the fact that SiCl3- and SiCl2-groups give about the same values of the chemical shift.
Infrared Spectra of Some Er3+ β-Diketonates in the Region 4000—250 cm-1
Authors: Mathur R. C. , Surana S. S. L. , Tandon S. P.
Published: March 2015

The infrared spectra of four erbium β-diketonates have been recorded in KBr phase on Perkin -Elmer 521 grating spectrophotometer. About thirty bands in each case have been observed and assigned to different modes of vibration. Single ring analysis has been used in interpretation of the bands.
Reaktionen von Metallcarbonylen mit Poly-1-vinyl-2-pyrrolidinon / Metal Complexes with Polymeric Ligands, XI Reactions of Metal Carbonyls with Poly-1-vinyl-2-pyrrolidinone
Authors: Biedermann Hans-G. , Graf Wolfgang
Published: March 2015

Poly-1-vinyl-2-pyrrolidinone with Mn2(CO)10, Fe(CO)5, Co2(CO)8 and Ni(CO)4 in methylene chloride forms the following complexes: [Mn(C6H9NO)5]n, Fe(C6H9NO)5]n, [[Co(C6H9NO)5] [Co(CO)4]2]n and [Ni(C6H9NO)4]n. The IR spectra are discussed.
Übergangsmetallkomplexe der Liganden C6H5P(H)Li und C6H5PLi2 / Transition Metal Derivatives with C6H5P(H)Li and C6H5PLi2 Ligands
Authors: Huttner Gottfried , Müller Hans-Dieter
Published: March 2015

Transition metal derivatives of phenylphosphine, C6H5PH2ML with ML = Cr(CO)5, C5H5Mn(CO)2 and CH3C5H4Mn(CO)2 may be lithiated by lithium-n-butyl. The synthesis of CH3C5H4Mn(CO)2P(C6H5) (H)Li and CH3C5H4Mn(CO)2P(C6H5)Li2 as well as there reaction with D2O are described.
3-Formyl-4-hydroxycoumarin Derivatives Syntheses of Semicarbazone, Phenylsemicarbazone, Hydrazino(oxazolin-4-one-2-yl) Hydrazone, Urea Derivatives, and their Sulfur Analogues
Authors: Trkovnik M. , Kekić M. , Kuleš M. , Gorenc A.
Published: March 2015

Considering certain kinds of pharmacologic activity previously found in semicarbazide derivatives of a number of compounds we decided to synthesize molecules containing a semicarbazide or thiosemicarbazide moiety for subsequent pharmacological testing. For a start we combined the semicarbazide grouping with another potentially active component, the 4-hydroxycoumarin ring system.
Zur Reaktivität von C=N Doppelbindungssystemen, II / The Reactivity of the C=N Double Bond Systems, II
Authors: Uray Georg , Ziegler Erich
Published: March 2015

The adducts from carboxylicacid chlorides and -anhydrides of aromatic Schiff-Bases differ fundamentally in their spectroscopic behavior compared with the hydrochlorides. A real addition on the azomethine double-bond is shown by 1H NMR, 13C NMR and UV spectroscopy.
Ein neuer Weg zu symm. Octahydroacridin-1.8-dionen / To the Chemistry of Enaminoketones, X / A Novel Route to Symm. Octahydroacridin-1,8-diones
Authors: Wolfbeis Otto S. , Junek Hans
Published: March 2015

A novel route to octahydroacridine-1,8-diones, starting from cyclohexane-1,3-dionemonoimines and triethylorthoformate is described. The method is superior to former ones. The obtained octahydroacridines can be transformed into several derivatives.
Darstellung und Struktur der Phase Li13Sn5 und die strukturelle Verwandtschaft der Phasen in den Systemen Li-Sn und Li-Pb / The Preparation and Crystal Structure of Li13Sn5 and the Structural Relations Between the Phases of the Systems Li-Sn and Li-Pb
Authors: Frank Ursula , Müller Wiking
Published: March 2015

A new compound Li13Sn5 has been prepared and its crystal structure has been determined, It crystallizes trigonal, α = 4.70 ± 0.01 Å, c = 17.12 ± 0.04 Å, c/α = 0.2745, space group P3̅ml-D3
3d, in an ordered bcc derivative structure. Structural relations to other compounds of the systems Li—Sn and Li—Pb with similar atomic arrangements are shown. The Sn—Sn and Pb—Pb-distances are discussed in connection with the valence rule18.
Elektrochemische Synthesen, II / Electrochemical Syntheses, II
Authors: Bockmair Georg , Fritz Heinz P.
Published: March 2015

It was shown by cyclovoltammetry that carbon-monoxide dissolved in organic electrolyte can be reduced irreversibly at Ni-, Co-, and Ti-electrodes. A dependance of the potential on the metal was evident, corresponding to chemisorption and subsequent reduction of CO.
Beiträge zur Chemie des Bors, LXXII / Contributions to the Chemistry of Boron, LXXII
Authors: Goetze Riceard , Nöth Heinrich
Published: March 2015

The study of a series of arsine boranes reveal that (C6H5)3As is a stronger base than (C6H5)2AsH and that the Lewis acidity of some boranes towards these bases decreases in the series BBr3 > BH3 > CH3BBr2 > (CH3)2BBr > (CH3)2BSCH3. The borane adducts of (CH3)4As2, (CH3)3SiAs(C6H5)2, (CH3)3SiAs(CH3)2 and (CH3)3SnAs(CH3)2 are thermally unstable. (CH3)3SiAs(C6H5)2 · BBr(C6H5)2 yields (CH3)3SiBr, B(C6H5)3 and [AsC6H5]n on decomposition.
Photoaquation of Carbonylpentacyanoferrate(II)
Authors: Vogler Arnd , Kunkely Horst
Published: March 2015

Upon ligand field excitation (300 nm-370 nm irradiating wavelengths) aqueous Fe(CN)5CO3- underwent a photosubstitution under release of CO and formation of Fe(CN)5H2O3- with the quantum yield 0.9.
Radiation Chemistry of Carbohydrates, VI: γ-Radiolysis of Glucose in Deoxygenated N2O Saturated Aqueous Solution
Authors: Dizdaroglu Miral , Henneberg Dieter , Schomburg Gerhard , Sonntag Clemens von
Published: March 2015

In the γ-radiolysis of deoxygenated N2O-saturated aqueous solutions of D-glucose (10-2 M, 1 · 1019 - 4 · 1019 eV/g, dose rate 4.3 · 1018 eV/g · h at 25°C), the following products have been identified: Gluconic acid (1), 2-deoxy-gluconic acid (2), arabinose (3), 2-deoxy-ribose (4), 5-deoxy-gluconic acid (5), glucosone (6), 3-deoxy-glucosone (7), 3-keto-glucose (8), [2-deoxy-3-keto-glucose (9), 4-deoxy-3-keto-glucose (10)]3, 4-ketoglucose (11), 3-deoxy-4-keto-glucose (12), 5-deoxy-4-keto-glucose (13), 5-keto-glucose (14), 2-deoxy-5-keto-glucose (15), 4-deoxy-5-keto-glucose (16), 6-deoxy-5-keto-glucose (17), gluco-hexodialdose (18), 5-deoxy-xylo-hexodialdose (19), ribose (20), xylose (21), erythrose (22), threose (23), 3-deoxy-pentulose (24), 2-butanone-(1,4)-diol (25), and dihydroxyacetone (26). G-values were also determined.

In the primary processes OH radicals and H atoms from the radiolysis of the solvent water abstract carbon bound hydrogen atoms from D-glucose to give all six possible primary glucosyl radicals. The observed products are formed in disproportionation reactions of the primary glucosyl radicals (1, 6, 8, 11, 14, 18) or of sugar radicals which originate from the primary glucosyl radicals by water elimination (2, 4, 7, 9, 10, 12, 13, 15, 16, 17, 19), rearrangements (5, 14, 15), or loss of carbon monoxide (3, 4, 20).

Products 1-5 and probably 20 have primary glucosyl radicals with the odd electron at C-1 as precursors. Radicals with the free spin at C-2 give rise to the products 6 and 7. Attack at C-3 yield products 8-10, at C-4 products 11-13, at C-5 products 14-17, and an attack at C-6 products 18 and 19. Products 21-26 are formed in very low yields and hence are of minor importance. Their mechanism of formation has not been investigated.
Furoquinolines, VIII.
Authors: Lakshminarayana P. , Kanakarajan K. , Shanmugam P.
Published: March 2015

Syntheses of 2,3-dihydro-3-methoxyfuro(2,3-b)quinolines starting from the respective 3-vinyl-2-quinolones are described.
Notizen: Hydrierung von Acrylsäureäthylester mit dem Katalysatorsystem NiCl2 + NaB4 in Dimethylformamid / Hydrogénation of Acrylic Acid Ethyl Ester with Catalyst-System NiCl2 + NaBH4 in Dimethylformamide
Authors: Strohmeier Walter , Steigerwald Hannelore
Published: March 2015

By reaction of NiCl2 or NiCl2 · 6 H2O with NaBH4 in dimethylformamide an active hydrogenation catalyst, working under mild conditions is produced. Methods for preparation of catalyst, using acrylicethylester as an unsaturated compound are described. Reaction rates r up to 26 (mMol · I—1 ·ܨ min—1) were found.
Organozinnverbindungen als Reagenzien, II. Neue Synthese von CF3E-Verbindungen des Zinns (E = P, As)2 / Organotin Compounds as Reagents, II: New Synthesis of CF3E Compounds of Tin (E = P, As)2
Authors: Ansari Salman , Grobe Joseph
Published: March 2015

The organotin compounds Me3SnE(CF3)2, Me3SnE(H)CF3 and (Me3Sn)2ECF3 (Me = CH3, E = P, As) are obtained in good yield by the reaction of E2(CF3)4 and (CF3E)n (n = 4,5), respectively, with trimethylstannane.
Synthesis and 1H NMR Spectra of Thiophenoyl-, Furoyl- and Pyrroylureas with Antiviral Properties
Authors: O’Sullivan D. G. , Wallis A. K.
Published: March 2015

N-(2-Thiophenoyl)urea, its 5-chloro and 5-methyl derivatives, N-ethyl-N′-(2-thiophenoyl)urea, N-phenyl-N′-(5-methyl-2-thiophenoyl)urea, N-(2-furanoyl)urea, N-(1-methyl-2-pyrroyl)urea and 5-methyl-2-thiophene-carboxamide have been prepared. The 1H NMR spectra of the ureides have been analysed. These ureides show antiviral activity.
Radiation Chemistry of DNA-Model Compounds, VIII Dephosphorylation Products from Reactions of OH Radicals with Ribose-5-phosphate in Aqueous Solution. The Effect of Oxygen
Authors: Stelter Lothar , von Sonntag Clemens , Schulte-Frohlinde Dietrich
Published: March 2015

The reaction of hydroxyl radicals with ribose-5-phosphate in oxygenated aqueous solution leads to the following phosphate free products (G-values): Erythrodialdose (0.4), formic acid (0.4) and ribodialdose (0.1). In addition, inorganic phosphate (0.6) and some minor phosphate free products (total G≈ 0.08) are formed.

Within the limits of experimental error material balance between dephosphorylation products and inorganic phosphate is obtained. A mechanism is proposed which can account for the main products. The primary steps of the dephosphorylation are H atom abstraction from C-5 of ribose-5-phosphate by OH radicals and subsequent addition of O2. The peroxy radicals formed decompose to ~80% by C-C bond cleavage followed by elimination of inorganic phosphate and only to ~20% by direct dephosphorylation. The relevance of these results with respect to the radiolysis of DNA is discussed.
Notizen: Notiz über einfache Synthesen von Tris(methylthio)-, Tris(methylseleno)- und Tris(dimethylamino)boran / Note on convenient Syntheses of Tris(methylthio)-, Tris(methylseleno)- and Tris(dimethylamino)borane
Authors: Siebert Walter , Ruf Werner , Full Roland
Published: March 2015

The reaction of in situ generated LiAlX4, (X = SCH3' SeCH3', N(CH3)2) with (C2H5)2O BF3 leads to BX3 in good yields.
Neue intermetallische Verbindungen im anti-PbCl2Typ / New Intermetallic Compounds of the anti-PbCl2-Structure Type
Authors: Eisenmann Brigitte , Schäfer Herbert , Turban Karlheinz
Published: March 2015

The intermetallic compounds Sr2Ge, BaCaSi, BaCaGe, BaCaSn, BaCaPb, CaLiBi and SrLiBi crystallize in the anti-PbCl2-structure. They belong to the Co2P-subgroup of this structure type.
Photochemisch initiierte Telomerisation von Äthylen mit Formamid / Photo-Initiated Telomerization of Ethylene with Formamide
Authors: Rath H. P. , Saus A. , Dederichs B.
Published: March 2015

Under the influence of UV light (high pressure HPK 125, Philips) and in presence of acetone ethylene and formamide react under elevated pressure (12.5-100 kp/cm2) to give odd-numbered n-alkane carbonic acid amides of chain lenghth C3-C19. Product yields improve with rising pressure. By increasing the concentration of aceton (0.1-8 mol-%), the reaction pressure the reaction time and at low temperatures the average mol.-weight is shifted to higher values. The chain distribution corresponds to a geometrical progression. Per 1 kwh electrical power input of the uv-equipment 0.5 kg of product is formed with chain length: 78% C3-C7, 12% C9, 10% C11-C19.
Zur Reaktivität von C =N-Doppelbindungssystemen, III Eine einfache Olefinierungs-Reaktion / The Reactivity of the C=N-Double Bond System, III A Simple Olefination Reaction
Authors: Ziegler Erich , Rüf Walter , Zwainz Johann G.
Published: March 2015

The reaction of benzylidene anilines with compounds having an activated CH,- or CH,-group in the presence of aliphatic or cyclic anhydrides (acetic anhydride, propionic anhydride or succinic anhydride) gives olefines in good yield.
Über Reaktionen mit Betain, XI Chinolone aus Triphenylphosphin-methylenen und p-Nitrophenylisocyanat / Reactions with Betaine, XI Quinolones from Triphenylphosphin-methylenes and p-Nitrophenylisocyanate
Authors: Wittmann Helga , Sobhi Djamschid
Published: March 2015

Triphenylphosphin dicarbethoxy- or dicarbophenoxy-methylene react with p-nitro-phenylisocyanate at 110 °C under the elemination of triphenylphosphinoxide yielding the quinolones (2a-b). With toluylene-2,4-diisocyanate the tetrahydropyrroloquinoline carboxylic esters (3 a-b) are formed.
13C-NMR-Spektroskopie an polycyclischen Aromaten, IV Das 13C-NMR-Spektrum von 1-Aminopyren / 13C NMR Spectroscopy of Polycyclic Aromatics, IV The 13C NMR Spectrum of 1-Aminopyrene
Authors: Ernst Ludger
Published: March 2015

In the 13C NMR spectrum of ] -aminopyrene (1) in [D6] acetone all carbon atoms are anisochronous. Most of the sixteen signals can be safely assigned by selective 13C{1H}double resonance experiments and by the interpretation of proton-coupled 13C as well as with the aid of off-resonance noise-decoupled 13C{1H} spectra. Substituent effects on chemical shifts in rings A, B, and D are compared with those of the 1- and 2-aminonaphthalenes (2, 3). Even in ring C, most distant from the substituent, relatively strong high-field shifts are observed which are ascribed to mesomerism.
Notizen: Facile Synthesis of N-Permethylspermine and N-Permethylspermidine from their Unmethylated Precursors
Authors: Giumanini Angelo G. , Chiavari Giuseppe , Scarponi Franco L.
Published: March 2015

A rapid synthesis of the title compounds employing formaldehyde and sodium borohydride in acidic aqueous solution in combination with the unmethylated amines is described. High yields and the characteristics of the methylated amines allow the application of the method to gas chromatographic and mass spectrometric analyses.
Chemical Constitution and Activity of Bipyridylium Herbicides, XI1 A Diquaternary Salt of 2,2′ -Oxydipyridine
Authors: Pirzada Nasim H. , Summers Lindsay A.
Published: March 2015

A diquaternary salt of 2,2′-oxydipyridine has been prepared using methyl fluorosulphonate as quaternising agent. It is unstable at physiological pH values and is reduced at a much lower potential than the bipyridylium herbicides, diquat and paraquat
Phenyloge Aziđo-diazoniuin-tetrafluoroborate / Phenylogous Azidodiazonium Tetrafluoroborates
Authors: Kreher Richard , Bergmann Udo
Published: March 2015

Azidodiazonium tetrafluoroborates are readily accessible by a general reaction sequence. Nitrosation of the corresponding azidoarylamines with nitrosonium tetrafluoroborate or with alkylnitrites/tetrafluoroboric acid affords crystallinic salts, which were characterized by analytical and spectroscopic methods.
Reactions with 2-Acylbenzimidazole Preparation of 2-Cinnamoylbenzimidazoles, their Reactions towards Grignard Reagents and Thiourea
Authors: Ali Mohamed I. , Abd-Elfattah Abd-Elsamei M. , Hammouda Hamdy A.
Published: March 2015

2-Acetylbenzimidazole condensed with aldehydes to afford the 2-cinnamoyl derivatives (1 a-e). Whereas 2-acetyl- and 2-benzoylbenzimidazole added Grignard reagents at the carbonyl group, the 2-cinnamoyl derivatives (1a, b) suffered addition at the olefinic double bond to give 2a, b. Condensation of amines with 2-acetyl and 2-benzoylbenzimidazole yielded the imino compounds (4a-c). 1 a reacted with thiourea to furnish the pyrimidine (5).
Proton Magnetic Resonance Spectra of Some Substituted 2-Acylamino-3-arylamino-1,4-naphthoquinones
Authors: Agarwal N. L. , Mttal R. L.
Published: March 2015

The proton magnetic resonance spectra of a number of substituted 2-acylamino-3-arylamino-1,4-naphthoquinones have been measured and discussed. The effect of various substitution pattern and hetero atoms on the chemical shift values of N-acylmethyl protons have been studied and explained.
Umsetzung von Aminoarsinen mit tri- und tetrafunktionellen Alkoholen.
Authors: Rühl Werner J. , Kober Friedhelm
Published: March 2015

The reactions of the tri- and tetrafunctional alcoholes CH3C(CH2OH)3 and C(CH2OH)4 with the aminoarsines (CH3)2As—N(CH3)2, CH3As[N(CH3)2]2, and As[N(CH3)2]3 are examined. The reactions lead by cleavage of the As—N-bond to the formation of acyclic and mono- and bicyclic arsinous acid esters.
Notizen: Configurational Assignments to 2-X-2-Y-4-methyl-1,3,2-dioxaphosphorinans
Authors: Stec W. J. , Kinas R. , Okruszek A.
Published: March 2015

It has been reported from this Laboratory that 1JPH and 1 JPSe absolute values showed the clear dependence on the spatial orientation of H and Se substituents in several pairs of ring C-substituted 2-X-2-Y-1,3,2-dioxaphosphorinans and may therefore provide information about conformation of the ring and configuration at phosphorus atom1.
1H-NMR-spektroskopische Analyse von 2-Diphenylamino- [1.3.2] oxathiaarsolan/ 1H NMR Spectroscopic Analysis of 2-Diphenylamino-[1,3,2]oxathiaarsolane
Authors: Adler Oswald , Kober Friedhelm
Published: March 2015

1H NMR spectral data of 2-diphenylamino-[1,3,2]oxathiaarsolane are presented and discussed. The protons of the CH2-groups form an AKPX-spin system. The vicinal H-C-C-H coupling constants indicate a twist-envelope conformation. A rapid inversion at arsenic does not take place.
Untersuchungen über die Wechselwirkung von Aromaten mit Antimontrichlorid, III Schmelzdiagramme der binären Systeme.
Authors: Perkampus H.-H. , Schönberger E.
Published: March 2015

This paper presents the results of investigations of the melting diagrams for the systems durene/SbCl3, pentamethylbenzene/SbCl3, hexamethylbenzene/SbCl3, diphenyl/SbCl3, naphthalene/SbCl3, 2,3-dimethylnaphthalene/SbCl3, phenanthrene/SbCl3 and anthracene/SbCl3; in all cases solid complexes with the composition ArH · 2 SbCl3 were formed.
Orientation of the EFG Tensor with Respect to the Heme Group of Deoxymyoglobin
Authors: Maeda Y. , Harami T. , Trautwein A. , Gonser U.
Published: March 2015

Following Zimmermann’s method of correlating intensity tensors from single crystal Mössbauer spectra with electric field gradient (EFG) tensors we are able to derive a manyfold of solutions for the orientation of the principal axis system of the local EFG

with respect to the heme coordinate system in deoxymyoglobin. Comparing these results with theoretical estimates of the asymmetry parameter η we are able to limit the range of possible orientations of

, and we find Vẑẑ to be rather close to the heme plane with a deviation from that of at most 14°.
Syntheses of Heterocycles, 191 Reactions of β-Aminocrotononitrile with Heterocyclic Phenolic Compounds
Authors: Soliman Farid S. G. , Kappe Thomas
Published: March 2015

Condensation of β-aminocrotononitrile (2 a) with 4-hydroxycoumarin (1 a, X = O, R = R2 = H, R1 = OH) afforded the tricyclic compound 7 and the bicyclic compound 11a from 4-hydroxy-6-methyl-2-pyrone (4). Analogous compounds could not be obtained from 4-hydroxy-6-methyl-2-pyridone (5) or 4-hydroxycarbostyril (6) due to the failure of the resulting condensation products 12a and 13, respectively to undergo intramolecular cyclization. The structures assigned to 7, 11a, 12a, 18, as well as to 5-cyano-4,6-dimethyl-2-pyridone (14), obtained by self-condensation of β-aminocrotononitrile, were substantiated by spectroscopic studies.
Nucleoside Derivatives of 1,2,4-Triazine Reaction of Some Derivatives of 1,2,4-Triazine with Tetra-O-acetyl-α-D-glucopyranosyl Bromide
Authors: Mansoub A. K. , Ibrahim Y. A. , Eid M. M.
Published: March 2015

4,6-Diphenyl-, 6-phenyl-4-p-tolyl- and 6-styryl-4-phenyl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines (1 a-c) react with tetra-0-acetyl-α-D-glucopyranosyl bromide (2) to give the corresponding 2-tetra-0-acetyl-B-D-glucopyranosyl derivatives (4a-c), respectively. Oxidation of 4a with H2O2 gives the 3,5-dioxo derivative (7). On the other hand deacetylation of 4a affords 2-B-D-glucopyranosyl-4,6-diphenyl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazine (8). Furfurylidene pyruvic acid condenses with 4-phenylthiosemicarbazide to give 6-furfurylidene-4-phenyl-3-thioxo-5-oxo-2, 3, 4, 5-tetrahydro-1, 2, 4-triazine (1d). 1d reacts with ethyl iodide to give the 3-ethylmercapto derivative (9), and reacts with 2 to give 4d.
Über die Anwendung von NMR-Verschiebungsreagenzien zur Strukturaufklärung von Chinazolinderivaten.
Authors: Dusemund J. , Roth K.
Published: March 2015

The 1H NMR spectra of quinazoline-disulfide (8) and some known quinazolines (8, 7a, 7b) were analyzed by the combination of spin decoupling experiments and simultaneous addition of Eu(fod)3. Under the assumption of an independent 1:1-complex formation of both quinazoline-nitrogens with the shift reagent (i.e. the 1: 2-complex concentration is negligible) there exists a linear dependence between the chemical shift of different protons within one compound. The slopes of corresponding protons of 8 differ from those of 3, 7a, 7b due to steric effects.
Notizen: Anorganische Polyederverbindungen, II. Zintls „Polyanionige Salze“: Darstellung der kristallinen Verbindungen [Na4 · 7 en] Sn9, [Na4 · 5 en]Ge9 und [Na3 · 4 en] Sb7. Die Kristallstruktur des [Na4 · 7 en] Sn9 / Inorganic Polyhedral Compounds, II. Inorganic Polyhedral Compoinds, II1 Zintl’s “Polyanionic Salts”: Synthesis of the Crystalline Compounds [Na4 · 7 en]Sn9, [Na4 · 5 en]Ge9 and [Na3 · 4 en]Sb7. The Crystal Structure of [Na4 · 7 en]Sn9
Authors: Diehl L. , Khodadadeh K. , Kummer D. , Strähle J.
Published: March 2015

Upon use of a synthetic method reported earlier by us respective alloys of Na/Sn, Na/Ge and Na/Sb are dissolved in ethylenediamine and the title compounds precipitated from the solutions in high yield. By recrystallisation well shaped, stable crystals are obtained. The crystal structure of [Na4 · 7 en]Sn9 confirms the presence of a Sn9
4---polyhedron which had been suggested by us on the basis of other investigations. The Sn9
4--polyhedron may be described as a distorted tricapped trigonal prism. Ethylenediamine is coordinated to Na+-ions exclusively.
Notizen: Das Tetramethylthiophencyclopentadienyl-eisen(II)-Kation / Cationic Tetramethylthiophene-cyclopentadienyl-iron(II)
Authors: Bachmann Paul , Singer Hellmut
Published: March 2015

Exchange of one cyclopentadienylring in different ferrocenes by tetra- or dimethylthiophene gives cationic thiophenecyclopentadienyl-iron(II)-complexes, which were characterized spectroscopically.
Notizen: Reactions of Harmaline and its Derivatives, V A one-Step Synthesis of Reserpine Analogues
Authors: Rahman Atta , Firdous Sadiqa , Basha Anwer
Published: March 2015

The reaction of harmaline with the cyclohexanone derivative (4) affords the reserpine analogue (5) in high yields, thus providing a one step approach to such pharmacologically important substances.
Kristallstruktur und Schwingungsspektrum des Tetrammingold(III) -nitrats.
Authors: Weishaupt Martin , Strähle Joachim
Published: March 2015

[Au(NH3)4](NO3)3 crystallizes in the orthorhombic space group Cmmm, α = 7.243, b = 13:805, c = 5.302 Å, Z = 2. The crystal structure is built up by NO3- anions and square planar [Au(NH3)4]3+ cations with Au-N bond lengths of 2.02 A. The vibrational spectra of the compound are discussed.
Reactions with 2-Carboxyindole-3-acetic Acid Imides, Preparation of Some Imides, their Condensations with Aromatic Aldehydes and Nitroso Compounds and their Coupling with Diazonium Salts
Authors: Ali M. I. , El-Sayed A. A. , Abdel-Fattah A. M. , El-Reedy A. M.
Published: March 2015

Heating 2-carboxyindole-3-acetic acid anhydride (1) with primary amines, the cyclic imides 1,2,3,4-tetrahydro-9 H-2-arylpyrido[3,4-b]indole-1,3-diones (2) were obtained. Compounds 2 coupled with diazonium salts to give 4-arylazo derivatives (3), condensed with aromatic aldehydes afforded 4-arylmethylene derivatives (4). Benzylation of 2 yielded the 4,4-dibenzyl derivative (6). 2 reacted also with p-nitrosodimethylaniline to yield the azomethine derivatives (7) which were hydrolysed by hydrochloric/acetic acid mixture to give the triketo compounds (8). The structure assigned to the condensation products have been supported by NMR and IR data.
Zur Reaktivität von C=N-Doppelbindungssystemen, VIII PMR-spektroskopische Untersuchungen zur E/Z-Isomerie von α-Nitrozimtsäureestern.
Authors: Wolfbeis Otto S.
Published: March 2015

The preparation of the title compounds from aldehyd-aniles and alkylnitroacetates in acetic anhydride is described. The nitrocinnamates, which in solution are mixtures of the E- and Z-isomers, are studied PMR-spectroscopically, using Eu(fod)3 as a shift reagent. A simple method for the signal assignment is worked out, making it unnecessary to prepare pure diastereomers.
Bericht: Recent Investigations on Cyclic Sulfur-Nitrogen-Halogen Compounds
Authors: Glemser O.
Published: March 2015

Cyclic sulfur-nitrogen-halogen compounds constitute a traditional field of inorganic chemistry1-10. Established as long ago as the close of the previous century by DEMARCAY’S preparation of (NSCl)3-, S4N3Cl-, S3N2Cl2-, S3N2Cl-, S3N2Br-compounds11 whose SN cyclic structures were only recognized much later - the study of halocyclothiazenes, as these species are now called, has gained considerable impetus during the past quarter of a century.
Anorganische Fünfringsysteme auf der Basis Silicium/ Stickstoff/Heteroelement.
Authors: Wannagat Ulrich , Schlingmann Merten , Autzen Horst
Published: March 2015

Following schemes 1-22 a survey, general and special synthesis, structural proofs, properties and reactions of isolated and spiral fivemembered ring systems (and derived compounds) from silicon, nitrogen and “hetero elements” B, Ge, Sn, P, As, Sb, S, Ti and Zr are given.
Partiell fluorierte Dialkyldisulfane / Partially Fluorinated Dialkyldisulfanes
Authors: Gombler Willy
Published: March 2015

Gaseous methylsulfenylchloride, CH3SCl, reacts with active potassium fluoride at 100°C to give methyl(fluoromethyl)disulfane, CH3SSCH2F. This compound decomposes at room temperature to yield dimethyldisulfane and bis(fluoromethyl)disulfane. The new compounds have been identified by 1H and 19F NMR and mass spectra.
Tetrahalogeno-acetylacetonato-osmate(IV) / Tetrahalogeno-acetylacetonato-osmates(IV)
Authors: Schätzel G. , Preetz W.
Published: March 2015

The complexes K[OsX4acac], X = Cl, Br, I, are prepared by treatment of K2[OsX6] with acetylacetone. The new compounds are characterized by their IR resp. visible and UV spectra which are highly resolved when measured on transparent pellets of the tetraethylammonium salts with KBr at 10 K. The influence of the different halide ligands on the bonding of the acac-group is discussed.
Conformational Control in Substituted Allyl Radicals by Nonbonded Attraction
Authors: Schoeller Wolfgang W.
Published: March 2015

INDO calculations on various conformations in substituted allyl cations, anions and radicals indicate a new type of substituent effect in halogen substituted allyl radicals.
Notizen: Evidence against OH Radical Formation during Photocatalyzed Reduction of Manganese(III) in K2 [Mn(III)-2-α-hydroxyethyl-isochlorin e4]acetate in Oxygen Free Aqueous Alkaline Solutions
Authors: Vierke Gerhard , Müller Manfred
Published: March 2015

The hypothesis of GLIKMAN and ZABRODA (Biochemistry [USSR] 84,, 239 [1969]) that the primary electron donor during photoreduction of manganese(III) in Mn(III)-hydroxychlorin compounds in oxygen free aqueous alkaline solutions is the axially bound OH- ion was tested with Mn(III)-2-a-hydroxyethyl-isochlorin e4. It has been shown that

1) the primary generation of OH radicals upon irradiation of the complex is highly improbable,

2) light is not essential for the reduction reaction,

3) the kinetics of photoreduction of the Mn(III)-compound in 2 N NaOH clearly is not compatible with OH radical formation.
Notizen: Neue Verbindungen AB2X2 (A = Erdalkalimetall, B = Übergangselement, X = Element(IV)) im ThCr2Si2-Typ / New Compounds of the ThCr2Si2-Structure Type
Authors: Dörrscheidt Wolfgang , Niess Nicosia , Schäfer Herbert
Published: March 2015

New intermetallic compounds of the ThCr2Si2-structure type have been prepared and their structures determined by single crystal data.
Assoziationsreaktionen von Tetrakis(arylisonitril)kobalt(II), -Rhodium(I) und Rhodium(III)-Komplexen in Lösung.
Authors: Baumann D. , Keller H. J. , Nöthe D. , Rupp H. H. , Uhlmann Gerd
Published: March 2015

Investigations on several tetrakis(arylisonitrile)-metal complexes of general stoichiometry M(CNR)4
n+Xn
- with M = Rh(I), Rh(III), [n =1], [n = 3] or Co(II), [n = 2], R = p-tolyl, p-N,N-dimethylaminophenyl, p-nitrophenyl, e. g. and X- = iodide, ClO4
-, [B(C6H5)4]- e. g. are described. The paramagnetic complexes of stoichiometry Co(CNR)4I2 dimerize in organic solvents to yield dinuclear diamagnetic cations with linear iodide bridges. The amount of association depends on the iodide content and on experimental parameters like temperature and/or concentration and can be followed by IR, ESR and/or NMR techniques. Treating of these compounds with ions X- = ClO4- or [B(C6H5)4]- gives the dinuclear and diamagnetic complexes of stoichiometry [I-Co(CNR)4-I-Co(CNR)4I]X. The corresponding isonitrile compounds of rhodium(I) associate in solution to yield linear stacks in the crystals. The solid state properties depend strongly on the type of ligand and the counter anion and vary considerably with the conditions of crystallization. The rhodium(I) species are able to react with the corresponding tetrakis(arylisonitrile)-rhodium(III) complexes to mixed valence solids.