bluuebunny/crossref_metadata_2025 huggingface dataset:
Photolysis of 5-Bromouracil and Some Related Compounds in Solution
Authors: Campbell J. M. , Sonntag C. von , Schulte-Frohlinde D.
Published: March 2015

The steady state photolysis of 5-bromouracil (BU) in aqueous solution has been studied as a function of wavelength, pH, temperature, and hydrogen-donor concentration. Under all conditions studied, the primary reaction is shown to be C-Br bond cleavage followed by abstraction from the hydrogen-donor to give uracil and HBr. At pH > 12 further products are formed. In deoxygenated aqueous solution at pH 6, 20°C, and 254 nm, the quantum yield of BU consumption, Φ (-BU), is 1.8 × 10-3 independent of hydrogen-donor type or concentration (e.g. 3 × 10-2 to 2 M MeOH). With increasing pH, Φ (-BU) increases stepwise to 0.012 at pH 10 and to 0.28 at pH 14. pK-values calculated from these data are the same as ground state pK values. Φ (-BU) increases with temperature with an activation energy of approx. 3.4 kcal/mol. Φ (-BU) increases with photon energy. Above 2 M MeOH Φ (-BU) increases reaching Φ (-BU) = 0.025 in neat MeOH. Similar high, solvent dependent, values are obtained for other hydrogen-donor solvents. In neat organic solvents an additional reaction with BU induced by solvent radicals was observed.

These results have been explained in terms of a homolytic dissociation of the C-Br bond of the excited BU followed by recombination or H atom abstraction by the radicals. At high hydrogen-donor concentration H atom abstraction can compete with cage recombination. A comparison has been made between BU photolysis in organic, hydrogendonor solvents and BU photolysis within the DNA of bacteria or phages. It has been concluded that the much higher quantum yields observed for chain breaks in the photolysis of DNA containing BU compared to photolysis of BU in aqueous solution is due to the high local concentration of hydrogen-donors (sugar molecules) within the DNA molecule, even in dilute aqueous solution.
Notizen: Neue Organosiliciumperoxide / Novel Organosilicon Peroxides
Authors: Brandes Dietmar , Blaschette Armand
Published: March 2015

Novel organosilicon peroxides, their preparation, properties, and 1H—NMR spectra are discussed.
Notizen: Supraleitung in zweidimensionalen Polyelektrolyten / Superconduction in Twodimensional Polyelectrolytes
Authors: Schöllhorn Robert , Lerf Anton , Sernetz Friedrich
Published: March 2015

The first superconducting polyelectrolytes are reported. The compounds are hydrated ternary layer chalcogenides (Ax)x+(H2O)y- [TaS2]x-; for A+= alkali metal ion the transition temperatures Tc range from 2,80°K to 5,45°K with Tc being dependent on the cation radius.
Notizen: Imidosulfenylhalogenide (CF3)2C=N-S-X aus Thiazylhalogeniden und Bis(trifluormethyl)diazomethan / Imidosulfenylhalides (CF3)2C=N-S-X from Thiazylhalides and Bis(trifluoromethyl)diazomethane
Authors: Varwig Jürgen , Steinbeisser Hartmut , Mews Rüdiger , Glemser Oskar
Published: March 2015

Imidosulfenylhalides (CF3),C=N–SX (X= Cl, F) are prepared from (CF3)2CN2, and (NSCl)3 and Hg(NSF2)2, respectively.
Schwefel-Stickstoff-Verbindungen, IV / Sulfur-Nitrogen-Compounds, IV
Authors: Golloch Alfred , Kuss Martin
Published: March 2015

The reactions of N3S3Cl3 with S7NH, (CH3)3Si—NH—Si(CH3)3, and C6F5S—NH—Si(CH3)3 were studied under a new aspect. Sulfur diimides were obtained and characterized by analysis and spectroscopic methods.
Bestimmung des nucleophilen Charakters der Zinn-Kohlenstoff-Bindung, I / Determination of the Nucleophilicity of Tin-Carbon Bond, I
Authors: Kunze Udo , Koola Johnson D.
Published: March 2015

The SO2-insertion into the tin-carbon bond of mixed tetraorganostannanes, R3SnR’ (R = alkyl, R’ = aryl, and vice versa), is determined by the nucleophilicity of the organic residue attached to metal, the ease of cleavage decreasing in the order aryl > alkenyl ⪢ alkyl. As has been proved by chemical and spectroscopic methods the reaction of triphenylmethyltin with liquid sulfur dioxide follows the above rule: Sn—CH3 bond remains unattacked, but one or two moles of SO2 can be inserted into Sn—C6H5 bonds depending on experimental conditions.
Umsetzung von Hydroxymethylferrocen mit Aminoarsinen / Reaction of Hydroxymethylferrocene with Aminoarsines
Authors: Kober Friedhelm
Published: March 2015

The syntheses of O-(alkylarsino)-hydroxymethylferrocenes are reported. 1H-NMR and IR-spectra are discussed.
13C—NMR-Spektren und Bindungsverhältnisse von Ketenen / 13C—NMR-Spectra and Bonding Situation of Ketenes
Authors: Firl Joachim , Runge Wolfgang
Published: March 2015

18C-NMR spectra of alkyl- and arylsubstituted ketenes are reported1e. The terminal carbon atom resonances are found at extreme highfield positions ranging from 2.5 ppm to about 50 ppm. They are the most shielded sp2-carbon-atoms observed until now. The central carbon atom resonances appear from about 190 ppm to 206 ppm. From comparisons of the chemical shifts of the ketene carbon atoms with that of analogously substituted alienes and olefines conclusions concerning the bonding situation in ketenes are drawn.
Die Molekülstruktur eines neuen [3 + 1]-Cycloadditionsproduktes · Röntgenstrukturanalyse von 3-Cyclohexylimino-2-(p-fluorphenyl)-4.4-bis(trifluormethyl)-1-azetin / Molecular Structure of a New [3 + 1]-Cycloaddition Product. X-Ray Structure Analysis of 3-Cyclohexylimino-2-(p-fluorophenyl)-4,4-bis-(trifluoromethyl)-1-azetine
Authors: Gieren Alfred , Burger Klaus , Thenn Willy
Published: March 2015

The structure of a [3 + 1]-cycloaddition product of a nitrile ylide - obtained from a 4,5-dihydro-1,3,5-oxazaphosph(V)ole - and cyclohexylisonitrile was determined by X-ray structure analysis. The constitution of this molecule, which was proposed by way of spectroscopic datas, could be verified and the configuration at the exocyclic double bond was elucidated. Details of the conformation are discussed. Bond distances and angles are compared with other molecules, which contain very similar bonding systems, but in different structural relationships. The four-membered azetine ring is strained. The bond lengths of the endoand exocyclic C = N double bond of the 1.4-diaza-1.3t-butadiene system are significantly different.
Paramagnetic Intermediates in Oxidative Coupling Reactions of Tertiary Aromatic Amines in Liquid Sulphur Dioxide
Authors: Donbavand M. , Möckel H.
Published: March 2015

Results are presented which complement earlier studies on oxidative coupling processes in aromatic amines and demonstrate strikingly the ease with which such reactions take place in liquid sulphur dioxide. Further, yields and stability of the intermediate cation radicals in this solvent compared with others of similar dielectric constant implies the participation of ionising forces not directly connected with dielectric properties. It is suggested that liquid SO2 may prove a very useful solvent in which to study radical intermediates of many oxidation reactions.
Synthesis and Spectroscopic Studies of N-(Aryl)-N'-(2-thiazolo)-thioureas
Authors: Dhar Durga Nath , Munjal Ramesh C.
Published: March 2015

In a study of the contribution of different functional groups towards the spectral characteristics of heterocycles, the synthesis and spectroscopic study of the title compounds have been carried out and are reported in this communication.
Synthesen und Reaktionen von 5H-Dibenz[c.e]azepin-N-oxiden / Syntheses and Reactions of 5H-Dibenz[c.e]azepine-N-oxides
Authors: Kreher Richard , Pawelczyk Hubert
Published: March 2015

5H-Dibenz[c,e]azepine-N-oxides were prepared by oxidation of the corresponding N-hydroxy-6,7-dihydro-5H-dibenz[c.e]azepines. Reactions of the isolated cyclic nitrones towards nucleophiles, dienophiles and dipolarophiles have been examined.
Synthesen D-markierter Carotinoide / Syntheses of Specifically Deuterated Carotinoids
Authors: Brzezinka H. , Johannes B. , Budzikiewicz H.
Published: March 2015

The syntheses of a series of specifically deuterated carotenoids are described.
Notizen: cis-Bis(trifluorophosphazodifluorophosphine) tetracarbonyl Molybdenum
Authors: Röschenthaler Gerd-Volker , Schmutzler Reinhard , Niecke Edgar
Published: March 2015

A new synthesis method for F3P=N=-PF2, involving Si-N cleavage in (Me3Si)2NPF2 with PF5, is described; F3P=N-PF2 is separated from the accompanying Me3SiF coordination to the tetracarbonyl molybdenum group.
Die Kristallstrukturen der Verbindungen Ca5Si3 und Ca5Ge3 / The Crystal Structures of Ca5Si3 and Ca5Ge3
Authors: Eisenmann B. , Schäfer H.
Published: March 2015

The new compounds Ca5Si3 and Ca5Ge3 were prepared and their structure determined.

They crystallize in the Cr5B3-structure type.
Über ein Tetramethylammonium(1:8)-molybdat / Tetramethylammonium(1: 8)-molybdate
Authors: Fuchs Joachim , Knöpnadel Imme , Brüdgam Irene
Published: March 2015

The tetramethylammoniummolybdate [N(CH3)4]2Mo8O25 · 5 H2O, obtained from an aqueous solution, belongs to an as yet unknown polymolybdate structure type. The manner of the water attachment was explored by thermal dehydration, wide line NMR spectroscopic methods as well as by the comparison of its IR spectrum with the deuterated analogs. The vibration spectra are discussed. Cell constants were determined by X-ray techniques.
29Si-Kernresonanzuntersuchungen an wäßrigen Silicatlösungen / 29Si NMR Studies on Silicate Solutions in Water
Authors: Marsmann H. C.
Published: March 2015

29Si NMR measurements show that in waterglass solutions the silicon exists mainly in the form of tetrafunctional branching groups (-107.2 ppm), trifunctional branching groups (—94.6 ppm), middle groups (—86.6 ppm) and end groups at —77.4 ppm. The ortho-silicate anion resonance was found between — 68.7 and —72.3 ppm. The variation is probably due to different degrees of ionization.
Notizen: Umlagerungen metallierter, organosubstituierter Harnstoffe, II / Rearrangements of Metallated Organosubstituted Ureas, II
Authors: Dannecker Walter , Fariborz Manoutchehr
Published: March 2015

By the reaction of two equivalents of butyllithium with N-benzyl-N,N′-diorganylureas, no dimetallated ureas were recovered; rather intensive-coloured solutions were formed, with subsequent identification of N, α-diorganylbenzylamnines and lithiumcyanate.
Zur Struktur der Verbindung TlTe / On the Structure of TlTe
Authors: Weis J. , Schäfer H. , Eisenmann B. , Schön G.
Published: March 2015

The crystal structure of TlTe was redetermined and by this way the Te-sublattice corrected. There are short Te-Te atomic distances which are comparable with covalent Te-Te bond distances.
Neubestimmung der Kristallstruktur von Tribromborsulfol / Redetermination of the Crystal Structure of Tribromoborthiin
Authors: Schwarz Wolfgang , Hausen Hans-Dieter , Hess Heinz
Published: March 2015

The crystal structure of (BrBS)3 was redetermined. Significant differences between this structure determination and an older one arise both in the molecular and crystal structure. Mean values of the bond distances and ring angles are: B-S 1.807 Å, B-Br 1.895 Å, B-S-B 109.2°, S-B-S 130.7°.
Ein polymeres Ammoniumdimolybdat aus wäßriger Lösung / A Polymeric Ammonium Dimolybdate from Aqueous Solution
Authors: Hunnius Wolf-Dietrich
Published: March 2015

The preparation of ammonium dimolybdate from aqueous solution is described, and the Raman and infrared spectrum are reported. A structure is proposed on the basis of its vibrational spectra. The ammonium salt does not contain discrete Mo2
7
2— ions, but is evidently built up by infinite chains, formed by two MoO6 octahedra with a dioxo-bridge and tetrahedra sharing corners.
Kernresonanzspektroskopische Untersuchungen an 1.4-Difluor-2-thiophenol / Nuclear Magnetic Resonance Spectroscopic Investigations on 1,4-Difluoro-2-thiophenol
Authors: Hägele Gerhard , Richter Jens , Peach Michael
Published: March 2015

Reaction of 1,2,5-trifluorbenzene with sodiummethylmercaptide yields difluorothioanisol. 60 and 220 MHz proton- and 56 MHz fluorine-resonance-spectroscopy established the structure of 2,5-difluorothioanisol. Methods and results of ABCXY-spectralanalysis are discussed together with the NMR parameters obtained.
Redox-Untersuchungen an Jodboranen, XV / Redox-Studies on Iodoboranes, XV
Authors: Siebert Walter , Schaper Klaus-Juergen , Asgarouladi Bagher
Published: March 2015

Of the three diiodobenzenes the 1,3- and 1,4-isomer react with BI3 to give the corresponding bis(diiodoboryl)benzenes. Due to the electronic acceptor properties of the BI2-group the formation of the 1,3-isomer is favored over the 1,4-product. Attempts to prepare the 1,2-bis(diiodoboryl)benzene resulted in the formation of a dibenzo-1,4-diborine derivative.
Ternary Complexes in Solution, XX
Authors: Fischer Beda E. , Sigel Helmut
Published: March 2015

The stability constants of the ternary Cu2+ complexes containing 1,2-diaminobenzene and oxalate or salicylate have been calculated from potentiometric titration curves published by G. K. CHATURVEDI and J. P. TANDON (Z. Naturforsch. 23b, 303 [1968]; 25b, 26 [1970]). A comparison of the results with data of the literature reveals that the qualities of 1,2-diaminobenzene in ternary complexes correspond to those of ethylenediamine, while the qualities of both amines differ considerably from those of 2,2′-bipyridyl, which has a stability-enhancing effect.
Mößbauer-Spektren von Eisencarbonylkomplexen mit carbenoiden Liganden / Mössbauer Spectra of Ironcarbonyl Complexes with Carbenoid Ligands
Authors: Pebler Jürgen , Petz Wolfgang
Published: March 2015

From Mössbauer spectra of the addition products of [Al(NMe2)3]2 and Ti(NMe2)4 to Fe(CO)5 it can be deduced, that the formal oxidation number of the central atom remains unchanged. The resulting carbenoid ligands occupy axial positions. Reaction of both products with LiOC2H5 yields (CO)4FeC(NMe2)OLi · 2 THF. In this product the basic structure of the starting materials is retained.
Notizen: 1,2-Benzthiazolinone: Reaction with Sulphite, Cyanide, and Cyanate
Authors: Farrar W. V.
Published: March 2015

Reactions of title compound with sulphite, cyanide, and cyanate are described.
Verbindungen mit Tellur in niedrigen Oxidationsstufen, I / Compounds of Tellurium in Low Oxidation States, I
Authors: Schulz Petra , Klar Günter
Published: March 2015

The synthesis and properties of aryltellurenyl bromides and iodides are described using equivalent amounts of halogen and diaryl ditellurides in non polar solvents.
Verbindungen mit Tellur in niedrigen Oxidationsstufen, II./ Compounds of Tellurium in Low Oxidation States, II.
Authors: Schulz Petra , Klar Günter
Published: March 2015

The reactions of bis(2-biphenylyl) ditelluride with halogens which give 2-biphenylyltellurenyl bromide and 2-biphenylyltellurenyl iodide, bis(2-biphenylyl) ditellurium tetraiodide or 2-biphenylyltellurium triiodide are reported and the properties of these hitherto unknown compounds are described.
Bestimmung des nucleophilen Charakters der Zinn-Kohlenstoff-Bindung, II / Determination of the Nucleophilicity of Tin-Carbon Bond, II
Authors: Kunze Udo , Koola Johnson D.
Published: March 2015

The SO2-insertion into tin-carbon bonds of mixed tetraorganostannanes, R3SnR′ (R=C6H5, CH3; R'=CH3, C6H5, CH2=CH), is determined by the nucleophilicity of the organic residue attached to metal and shows a decreasing rate in the order aryl > alkenyl > alkyl. A correlation to Taft’s constant is given. The behaviour of triphenylvinyltin toward sulfur dioxide is in good agreement with this rule, as the insertion of one or two moles of SO2 takes place only into Sn—C6H5 bond.
Zur Stereochemie der Phosphinoxydspaltung von R-(+)-Methyl-phenyl-α -naphthyl-allyl-phosphoniumbromid / The Stereochemistry of the Phosphine Oxide Cleavage of R-(+)-Methyl-phenyl-α-naphthyl-allyl-phosphonium Bromide
Authors: Luckenbach Reiner
Published: March 2015

The stereochemical course of the ‘phosphine oxide cleavage’ of chiral R-(+)-methylphenyl-α-naphthyl-allyl-phosphonium bromide is reported. While the α-naphthyl group is cleaved by alkali with predominant retention of configuration at the central phosphorus atom, the allyl group is split off with predominant inversion.
Notizen: Das Infrarotspektrum von LaGaO3 / Infrared Spectrum of LaGO3
Authors: Baran Enrique J.
Published: March 2015

The IR spectrum of LaGaO3 is reported and discussed in comparison with those of related compounds. The valence force constant for the Ga–O bonds is also estimated.
Thermolyse von N-Alkyl-6.7-dihydro-5H-dibenz[c.e]azepin-N-oxiden / Thermolysis of N-Alkyl-6,7-dihydro-5H-dibenz[c,e]azepine-N-oxides
Authors: Kreher Richard , Pawelczyk Hubert , Gerhardt Werner
Published: March 2015

The thermolysis of N-Alkyl-6,7-dihydro-5H-dibenz[c,e]azepine-N-oxides has been examined with regard to preparative and mechanistic aspects; the dependence of the competing reactions from the substituents at the nitrogen has been qualitatively evaluated.
Zur Reaktivität von C =N-Doppelbindungssystemen, VI Reaktionen mit Sulfonamiden und Sulfamiden / The Reactivity of the C=N-Double Bond System, VI Reactions with Sulfonamides and Sulfamides
Authors: Ziegler Erich , Ruf Walter
Published: March 2015

Benzenesulfonic amide reacts with N-methylene-tert-butylamine and acetic anhydride in boiling benzene to give 5-tert-butyl-1,3-benzenesulfonyl-perhydro-1,3,5-triazine. Sulfamide, and benzylidene aniline, and acetic anhydride (1:1:1) yield N-benzylidene sulfamide, or (1:2:2) N,N′-bis-benzylidene sulfamide.
In vivo Inhibition von Friend-Leukämie-Viren durch [X2W18O62] Ionen (X = P(V), As(V)) / In vivo Inhibition of Friend-Leukemia-Viruses by [X2W18O62] Ions (X = P(V), As(V))
Authors: Schönfeld B. , Steinheider G. , Glemser O.
Published: March 2015

It is known, that the makroheteropolyanion [Sb8W20O80]16- protects mice against Friend Leukemia. We found the similar effect of two other great heterpolytungstates and the in vivo inactivity of some smaler related compounds. Some aspects of the mode of action of these substances are discussed.
Notizen: Charge-Transfer Spectra of Some Heterocyclic Cations
Authors: Párkányi Cyril , Leu Ginger J.
Published: March 2015

Energies of the first charge-transfer bands of complexes of heterocyclic pyridinium-like cations with various electron donors (the iodide ion, benzenoid hydrocarbons) yield linear correlations with the HMO energies of the lowest unoccupied π-molecular orbitals (LUMO) of the heterocyclic acceptors. The experimental chargetransfer band maxima were taken from the literature. Charge-transfer band maxima for the complexes of the 2,4,6-trimethylpyrylium cation with several electrons donors (diethylamine, N,N-dimethylaniline, pyridine N–oxide, anthracene) have been determined and compared with the analogous data for the tropylium cation.
Die Kristallstruktur von MnIn2Te4, eine neue Ordnungsvariante für Defektzinkblendephasen / The Crystal Structure of MnIn2Te4, a New Type of Ordered Defect Zincblende Phases
Authors: Range Klaus-Jürgen , Hübner Heinz-Joachim
Published: March 2015

MnIn2Te4 was prepared by direct synthesis from the elements at 800°C. The crystals are tetragonal, space group I 4̅ 2 m, with a = 6.191 Å, c = 12.382 Å, and Z = 2. The structure can be derived from the zincblende structure. It is related to the CdGa2S4 and β-Cu2HgJ4 type structures with the same ordered arrangement of vacancies. In MnIn2Te4, however, the different cations are distributed randomly over the occupied tetrahedral sites.
Kristall- und Molekülstruktur des Chlorodinitrosyltriphenylphosphineisens(-I) / Crystal and Molecular Structure of Chlorodinitrosyltriphenylphosphineiron(-I)
Authors: Kopf Jürgen , Schmidt Jörn
Published: March 2015

Crystals of [Fe(NO)2PØ3Cl] are monoclinic with a = 1.6265(7) [nm], b = 1.4495(7) [nm], c = 1.5609(6) [nm] and β= 96.86(2) deg.; the space group is C 2/c. The structure was determined by three dimensional Patterson and Fourier methods on the basis of 2266 independent intensities. The unit cell consists of 8 isolated molecules. Within the coordination polyhedron, a distorted trigonal pyramid, the Cl, Fe, P plane approximately represents a mirror plane of the molecule. The nitrosyl ligands are bent towards each other with an N-Fe-N angle of 115.6(3) and Fe-N-O angles of 166.4(5) and 165.5(5) deg. The geometry of the molecule is discussed with regard to other dinitrosyl complexes and to electronic structure.
Kristallstruktur von α-Bromo(2-dibutylaminoäthanolato)kupfer(II) / The Crystal Structure of a-Bromo(2-dibutylaminoethanolato)copper(II)
Authors: Mergehenn R. , Haase W.
Published: March 2015

The crystal structure of α-Bromo(2-dibutylaminoethanolato)copper(II) has been determined by single-crystal X-ray diffractometer methods using 1488 independent reflexions and MoKα radiation. The compound crystallized in the orthorhombic space group P212121 with four dimers in a unit cell of dimensions a = 21.235(13), b = 15.220(8) and c = 8.390(5) Å. The structure was refined by least-squares methods giving a final residue of R = 0.087. The dimer molecules with Cu-Cu-separations of 3.019(4) Å consist of nonplanar Cu2O2-rings with Cu-O-distances of 1.92(2) Å (mean value). The coordination around each copper atom is distorted square planar. The averaged Cu-N-distance is 2.06(2) Å and Cu-Br-separations are 2.333(4) A. In good agreement with the calculated density of 1.55 g cm-3 is the experimental value of 1.53(3) g cm-3.
Spekktroskopische Untersuchungen in der Festkörperchemie, IX / Spectroscopic Investigations in the Solid-State Chemistry, IX
Authors: Burkert Paul K. , Hutter Frank , Koth Detlev
Published: March 2015

The four 185Re, 187Re—NQR-transitions of RbReO4 were measured. From the NQR-coupling constants, asymmetry-parameter and normal temperature-coefficient in the range of 77-300°K one can conclude, that the anomalons temperature dependence of the NQR-frequencies of NH4ReO4 is not caused by the absolute values of certain lattice parameters.

An experimental correlation of the Re—NQR-coupling constants of scheelite-structured perrhenates with the length of the elementar cell was found and discussed.
Visible and Near IR Spectra of Some Divalent Transition Metal Cupferron Complexes
Authors: El Ela A. H. Abou , Abdelkerim F. M. , Aly H. F. , Afifi H. H.
Published: March 2015

The visible and near IR spectra of the ammonium salt of cupferron and manganese, cobalt, nickel and copper divalent cupferrate complexes are investigated. New absorption bands observed are given and assigned using the Tanabe-Sugano diagrams. In the absorption spectra of the divalent transition metal cupferrates a characteristic shift in the maxima and minima appears. Solvent effects on this shift were investigated.
Neue Methoden zur spektrophotometrischen pK-W ertbestimmung, II / New Methods for Spectrophotometric Determination of pK-Values, II
Authors: Blume Rüdiger , Lachmann Heinrich , Polster Jürgen
Published: March 2015

The number of linear independent dissociation equilibria of spectrophotometric titration may be determined experimentally by means of absorbance diagrams and absorbance-difference-quotient diagrams. The different types of spectrophotometric titration curves in two-step titrations are classified. By simulation of systematic error functions the limits of pK determination using turning points of two-step titration curves are demonstrated. By means of certain absorbance diagrams it is possible to determine the absorbance of pure ampholyte and to construct the absorbance triangle of all three pure components. From this triangle all concentration- vs pH-curves and the pK-values of a bivalent protolyte may be established. To avoid electrometric pH-measurements new methods are devised to calculate the difference of pK-values of bivalent protolytes. These new methods are demonstrated using as examples o-phthalic acid, 3-hydroxy-4-nitrobenzoic acid and sozoiodolic acid.
Notizen: Internal Vibrations of the Antimonate Octahedron in Ordered Perovskites
Authors: Blasse G. , Heuvel G. P. M. van den
Published: March 2015

The infrared and Raman spectra of the perovskites SrLaMgSbO6 and Ba4LiSb3O12 are reported and discussed in terms of antimonate internal modes.
Notizen: Über die 35Cl NQR Spektren von Amid Trichlorboranen / 35Cl NQR Spectra of Amid-trichloroboranes
Authors: Lucken E. A. C. , Meller A. , Gerger W.
Published: March 2015

The 35Cl NQR spectrum od dimethylcarbamoylchloride-trichloroborane shows an extraordinarily high shift of the C—Cl resonance compared to the uncomplexed dimethyl-carbamoylchloride. The reasons are discussed.
Notizen: Hochdruckreaktionen, IX.
Authors: Roemer-Mähler J. , Bieniek D. , Korte F.
Published: March 2015

Cyclooctatetraene dimerises at high pressure (12 Kbar, 20°C) to the isomers 2 and 3. At 120°C compound 2 isomerises quantitatively to compound 3. The conversion rate of Hexamethyldewarbenzene to Hexamethylbenzene at high pressures depends on kind of solvent, whereas the influence of temperature is small in the range between 20° and 80°C.
Die Kristallstruktur von KTlF4 / Crystal Structure of KTlF4
Authors: Hebecker Ch.
Published: March 2015

The results of X-ray structure determinations on single crystals of KTlF4 are reported.

The unit cell is trigonal with α = 8.025, c = 10.16 A, Z = 6; space group: P 31 - C2
3. KTlF4 is a new superstructure variant of the CaF2-type. Each Tl is coordinated by 7, K by 8 resp. 9 F. Other A+B3+F4-type compounds (A+ = Na, Ag, K; B3+ = In, Tl, Ln) are isostructural with KTlF4.
The UV Photolysis (λ = 185 nm) of Liquid Methyl n-Propyl Ether
Authors: Schuchmann Heinz-Peter , von Sonntag Clemens
Published: March 2015

The main products of the 185 nm photolysis of liquid methyl n-propyl ether (quantum yields in parentheses) are n-propanol (0.70), methane (0.29), sec-butyl methyl ether (0.20), methanol (0.16), propionaldehyde (0.13), 3,4-dimethoxyhexane (0.09), ethane (0.08), and ethyl n-propyl ether (0.08). The quantum yields of further 24 minor products have been measured. The quantum yield of the sum of primary photochemical processes, the main ones of which are the homolytic scissions of the C–O bonds (reactions i and ii), is close to unity.

Reaction (i) is favoured over reaction (ii) by nearly a factor of five. The elimination of molecular methane (iii) is the only other process of importance. C–H and C–C bond splitting is marginal.
Cyclopropenschemie, VI.
Cyclopropenone Chemistry, VI.
Authors: Dehmlow Sigrid S. , Dehmlow Eckehard V.
Published: March 2015

The synthesis of methyl-phenylcyclopropenone (1 a) is decribed. Bromination of this and of diphenylcyclopropenone yields saltlike complexes 2 which are in equilibrium with their components. Di-n-propylcyclopropenone and bromine give the ring opened product 3d. la and N-bromosuccinimid give 4 and 5, phenyl brominated derivatives, in sulfuric acid. With cupric bromide substituted β-bromoacrylic acids are formed along with cyclopropenone dimers (7).
Axial Preference of Methylthio Substituent in Dioxaphosphorinanyl Ring System
Authors: Okruszek A. , Stec W. J.
Published: March 2015

The spatial disposition of a 2-methylthio group in the 4-methyl-1,3,2-dioxaphosphorinanyl ring system was studied by stereochemical correlation, 1H, 13C and 81P NM-R. It has been established that a CH3S-group prefers an axial orientation much more strongly than does a methoxy group.
Conductometric Studies on the Interaction of Some of the Lanthanon Nitrates with Monofunctional Bidentate Schiff Bases
Authors: Agarwal S. K. , Tandon J. P.
Published: March 2015

Conductometric titrations of some of the lanthanon nitrates with monofunctional bidentate Schiff bases in the ethanolic medium reveal the formation of Ln(NO3)3· 3 SBH and Ln′(NO3)3 · 2 SBH (where, Ln = La(III), Pr(III) or Sm(III); Ln’ = Yb(III) and SBH = 2,4-pentanedionebenzylimine or o-hydroxyacetophenoneanil) type of derivatives. Preparative studies also support these results.
Kristallisierte Koordinationsverbindungen von 1.2-Benzochinondioximen mit den Metall-Ionen Ni(II), Pd(II) und Cu(II): Festkörper mit Metall-Metall-Wechselwirkungen / Crystallized Coordination Compounds of 1,2-Benzoquinonedioximes with the Metal Ions Ni(II), Pd(II) and Pt(II): Solids with Metal-Metal Interactions
Authors: Endres H. , Keller H. J. , Megnamisi-Bélombé M. , Nöthe D.
Published: March 2015

Metal complexes obtained by reacting various 1,2-benzoquinonedioximes with metal salts of Ni(II), Pd(II), Pt(II) and Cu(II) show evidence of considerable metal-metal interactions. In the diamagnetic Pd(II) and Pt(II) derivatives the intermolecular interactions are accomplished by direct metal-metal contacts, which are heavily influenced by different substituents on the 1,2-benzoquinonedioxime (BCDH) moiety as evidenced by their optical behaviour. The unpaired electrons of the paramagnetic copper(II) species interact via ligand atoms in dinuclear clusters or linear chain polymers. The former solids crystallize with stoichiometry [Cu(BCD)2], while the latter compounds have the composition CuCl · BCDH.
On the Molecular Motion in the Orthorhombic Solid Acetylene-d2
Authors: Koski Harri K.
Published: March 2015

The mean square thermal displacements of the carbon and deuterium atoms in crystalline orthorhombic acetylene-d2, C2D2, derived from earlier thermal neutron powder diffraction studies were interpreted as rigid-body translational and librational motions of the C2D2 molecule. An attempt to assign the derived amplitudes of the angular vibrations to the Raman-active rotational lattice modes was not unambiguous. Finally, a calculation was made to correct the apparent shortening in the bond lengths and the molecular dimension.
Die Komplexbildung der Zitronensäure, II.
Authors: Veith Josef A. , Wiese Günther
Published: March 2015

Mixtures of citric acid (H3Ci) and Fe(NO3)3 with variable molar ratios (H3Ci/Fe(NO3)3 from 0 to 2.55) were titrated with NaOH. The change in pH and the occurring inflection points were registered with a potentiograph (Fig. 1). For each inflection point (I.P.) the existing H3Ci/Fe(NO3)3 molar ratio was plotted against the NaOH/Fe(NO3)3 molar ratio which existed at the corresponding inflection point (at most three I.P. for each titration curve). The coefficients ej, fj and gj for each dehydrated

Fe-Ci-complex [Fefj(OH)gj-3ejCicj](gj-3fj)⁻ with j = 1, 2, . . . ,

could be calculated from the points of intersection (Pj) in the x-y-diagram (Fig. 2). Thus, the following three Fe-Ci-complexes were calculated:

From the 1st I.P. [Fe10(OH)18Ci5]3- with its maximum at pH ≃ 4.3.

From the 2nd I.P. [Fe5(OH)9Ci4]6- with its maximum at pH ≃ 8.0.

From the 3rd I.P. [Fe4(OH)11Ci]2- with its maximum at pH ≃ 10.1.

The range of their existence as functions of H3Ci/Fe(NO3)3 ratios (Fig. 3 and 4) and pH (Fig. 4) is discussed.
Dielectric Polarisation of Pyridine
Authors: Joshi V. K.
Published: March 2015

This paper deals with the study of dielectric polarisation of pyridine at 35°C in four non polar solvents namely benzene, carbon tetrachloride, dioxan and cyclohexane. The results have been discussed to understand the merits of PALIT equation. It is observed that the moment value μs obtained by this is fairly comparable with that calculated by the method of HALVERSTADT and KUMLER2. The order of apparent dipole moment has been discussed in terms of influence of solvent and solute-solvent interaction as well.
Untersuchung der Konformation bicyclischer Imidderivate mit Hilfe der 270 MHz NMR-Spektroskopie / Study of the Conformation of Bicyclic Imide Derivatives with 270 MHz NMR Spectroscopy
Authors: Van Binst G. , Steger Y. , Flitsch W.
Published: March 2015

The stable conformation of 1-azabicyclo[3,3,0]octane-2,8-dione (1), 2,8-biscyanomethylen-l-azabicyclo[3,3,0]octane (2) and 2-oxo-8-ethoxycarbonylmethylen-1-azabicyclo[3,3,0]octane (3) was obtained by analysis of the 270 MHz PMR spectra. The results are correlated with force field calculations.
Notizen: Über die Darstellung eines 1-Bora-4-phospha-cyclohexadien(2.5)-Derivats / Synthesis of a 1-Bora-4-phosphacyclohexadiene(2,5) Derivative
Authors: Berger Hans-Otto , Nöth Heinrich
Published: March 2015

Radical initiated hydrophosphination of diethylaminodipropinylborane with phenylphosphine leads to the new heterocyclic system 1-bora-4-phospha-cyclohexadiene. Some properties and NMR data of the 3,5-dimethyl-1-diethylamino-4-phenyl derivative are reported.
Notizen: Radiation Chemistry of DNA-Model Compounds, VII. On the Formation of 5-Deoxy-D-erythro-pentos-4-ulose and the Identification of Twelve Further Products from γ-Irradiated Aqueous Solutions of Ribose-5-phosphate
Authors: Stelter Lothar , von Sonntag Clemens , Schulte-Frohlinde Dietrich
Published: March 2015

Different mechanisms are considered to explain the formation of 5-deoxy-D-erythropentos-4-ulose in the γ-radiolysis of ribose-5-phosphate in aqueous solution. On the basis of deuterium labelling experiments one mechanism involving an enol as an intermediate could be excluded.

The identification of twelve further radiolysis products from ribose-5-phosphate is reported.
Über die Koordinationspolymeren M(II)[Pt(CN)6], II Schwingungsspektren und Kraftkonstanten / Coordination Polymers M(II)[Pt(CN)6], II Vibrational Spectra and Force Constants
Authors: Siebert Hans , Weise Manfred
Published: March 2015

The IR spectra (33-4000 cm-1) and the RAMAN spectra (0-2500 cm-1) of the complexes M(II)[Pt(CN)6] (M = Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd) have been recorded. In the region 33-300 cm-1, the IR spectra of the isotopic compounds with 64Zn and 68Zn68Zn and with 58Ni and 62Ni have been obtained. The observed frequencies are assigned to the normal modes of the lattices.

A normal coordinate analysis has been carried out for the above coordination polymers. The force constants of the Pt(CN)6 moiety are with one exception identical with those obtained for the isolated ion. The CN valency force constant is slightly shifted to higher values. The valency force constants of the coordinative bonds M(II)-N are in the range 0,1-1 mdyn/Å. This variability is considered to stem primarly from ligand field effects.
Darstellung und Röntgenstrukturanalyse von (CH3)3C-C7H7Mo(CO)3 (1-6- η-7-tert-Butyl-cycloheptatrien)(tricarbonyl)molybdän(0) / Synthesis and Crystal Structure of (CH3)3C-C7H7Mo(CO)3 (1-6-η-7-tert-Butyl-cycloheptatriene)(tricarbonyl)molybdenum(0)
Authors: Tremmel Peter O. , Weidenhammer Klaus , Wienand Henning , Ziegler Manfred L.
Published: March 2015

The title compound has been synthesized by three different methods and its structure determined from three dimensional X-ray data by Patterson and Fourier methods. The crystals are triclinic with unit cell dimensions a = 1022.60 ± 0.07 pm, b = 638.69 ± 0.27 pm, c = 1478.00 ± 0.19 pm, α = 78.48 ±0.02°, β = 131.049 ± 0.008°, γ = 87.16 ± 0.03 °, space group Ci
1—PT and Z = 2. Least squares refinement by use of 2160 independent reflections measured on a diffractometer has reached R = 5.4%.

There are discrete (CH3)3C—C7H7Mo(CO)3 molecules, the central molybdenum atom is octahedrally coordinated.
Reactions of tert-Butylperoxy Esters, XIII
Authors: Sosnovsky G. , Zaret E. H. , Gasiecki A.
Published: March 2015

The interaction of dialkyl tert-butylperoxy phosphates, (RO)2P(O)OOCMe3 (1) with primary and secondary cycloalkylamines, R′R″NH, R′ = cyclo-C6H11, R″= H; R′= R″= cyclo-C6H11 (2) in the presence and absence of water, produces the corresponding dialkyl cycloalkyl ammonium phosphates, (RO)2P(O)O-N+H2R″R′ (3), and tert-butanol. In carbon tetrachloride the reaction produces in addition to 3 the corresponding cyclohexylammonium chloride. Possible mechanisms of the reaction are discussed.
Reactions of tert-Butyl Peroxy Esters, XIV. Further Observations on the Preparation of Dialkyl tert-Butylperoxy Phosphates
Authors: Sosnovsky G. , Zaret E. H.
Published: March 2015

The preparation of dialkyl tert-butylperoxy phosphates (2, R = alkyl) has been achieved by the reaction of the corresponding dialkyl phosphorochloridates (1, R = alkyl) with tert-butyl hydroperoxide either in the presence of pyridine or in the presence of aqueous potassium hydroxide solution. Neither of these routes is suitable for the preparation of dialkyl tert-butylperoxy phosphates in quantity since they yield peroxyphosphates which are contaminated either with the corresponding tetraalkyl pyrophosphates or dialkyl phosphates; the contaminants cannot easily be removed by conventional means from the peroxyphosphates. The method of choice for the preparation in high yield of large quantities of pure dialkyl tert-butylperoxy phosphates involves the interaction of the corresponding dialkyl phosphorochloridate with sodium tert-butyl peroxide which has been prepared in situ from the reaction of tert-butyl hydroperoxide with sodium hydride.
Chemistry of Lanthanons, XLII Preparation and Characterization of Isonicotine and Picoline Hydrazide Complexes of Lanthanons
Authors: Dutt N. K. , Sen Gupta A. K.
Published: March 2015

Isonicotine hydrazide (INH) and picoline hydrazide (PH) complexes of lanthanides are described. Solid compounds of the compositions Ln(NO3)3, 3 INH where Ln-La, Nd, Gd, Er, Y; Ln(ClO4)3, 5 INH where Ln-La, Pr, Nd and Ln(ClO4)3, 3 INH. H2O when Ln-Gd, Dr and Y and Ln Cl3 · 3 PH when Ln-La and Nd have been synthesized. The complexes have been characterized by visible (Pr, Nd) and IR spectra, conductance measurements and thermal studies. Some of the nitrate and perchlorate ions have been inferred to lie within the coordination sphere raising the coordination number beyond six.
Pyrimidine Derivatives and Related Compounds, I Synthesis of Some 2,3-Disubstituted-4,5,6,7-Tetrahydropyrazolo[1,5-a]-Pyrimidine Derivatives
Authors: Elnagdi Mohamed Hilmy , Fahmy Sherief Mahmoud , Elmoghayab Mohamed Riffaat Hamza , Ilias Mohamed Ajmal Mohamed
Published: March 2015

The 5-aminopyrazole derivatives (1 a-c) react with acrylonitrile to yield the corresponding 1-β-cyanoethyl-5-aminopyrazole derivatives (2 a-c) which could be readily cyclised into the corresponding pyrazolo[1,5-a]pyrimidines (3 a-c). Under similar conditions 1 a-c has failed to react with methylacrylonitrile or methyl methactylate. However, when the reaction of 1 a-d with these reagents was conducted in ethanolic sodium ethoxide, the pyrazolo[1,5-a]pyrimidine derivatives (3d-f) were formed. Structures of resulting products was established by their synthesis via interaction of β-cyanoethylhydrazine (4) and β-cyanopropylhydrazine (10) with the appropriate β-bifunctionalnitrile. Compounds 1 a, b also reacted with methyl phenylpropiolate to yield the pyrazolo[1,5-a]pyrimidine derivatives (18).
Notizen: Neue ternäre Silizide des Lithiums mit 1B-Elementen / New Ternary Silicides of Lithium with 1B Group Elements
Authors: Schuster Hans-Uwe , Seelentag Werner
Published: March 2015

Three new ternary silicon-phases with the formulas LiCuSi, Li8Ag3Si5 and Li8Au3Si5 have been prepared and their crystal datas have been determined by single-crystal resp. powder methods.
Notizen: 2.2.4.4.6-Pentachlor-2.4-diphospha-1.3.5-striazin / 2,2,4,4,6-Pentachloro-2,4-diphospha-1,3,5-s-triazine
Authors: Fluck E. , Schmid E. , Haubold W.
Published: March 2015

Preparation, properties and mass spectrum of [PNCl2]2[CNCl] are described.
Notizen: Dehnung einer Metall-Metall-Bindung durch sterische Hinderung Die Kristallstruktur von FeMn(CO)8P(C6H5)2 / Lengthening of a Metal-Metal-Bond by Steric Hindrance The Crystal Structure of FeMn(CO)8P(C6H5)2
1
Authors: Vahrenkamp Heinrich
Published: March 2015

The crystal structure of the title complex 1 shows that its metal-metal bond length is not determined by the radii of the metal or phosphorus atoms but by steric hindrance between vicinal carbonyl groups.
Zur Kenntnis von Ca11Sb10 und Ca11Bi10
Authors: Deller Klaus , Eisenmann Brigitte
Published: March 2015

The new intermetallic compounds Ca11Sb10 and Ca11Bi10 crystallize tetragonal in the Yb11Sb10-structure type. There are 4-membered Sb(Bi)-rings, Sb2(Bi2)-dumb-bells and isolated Sb(Bi)atoms in the structure
Präparative und spektroskopische Untersuchungen zur Dimorphie von CsNiF3.
Authors: Haegele R. , Babel D. , Reinen D.
Published: March 2015

While the stable modification of CsNiF3 is of green colour, a yellow phase is obtained by fluorination of CsNiCl3 and decomposition of the product “CsNiF4”, which contains Ni4+ and Ni3+ besides Ni2+. The two modifications have the 2L- and 9L-perovskite-structure, respectively, and are characterized by their X-ray patterns and low-temperature ligand field spectra. The differences in colours and spectral band positions are discussed with respect to the Ni-F-Ni bond angles
Darstellung und Charakterisierung von Sulfinatokomplexen π-C7H7Μο(CO)2SO2R (R=-C6H5, -C6H4CH3) sowie von ein- und zweikernigen Thioarylverbindungen der Zusammensetzung π-C7H7Mo(CO)2SR′ bzw. [π-C7Η7Μο(CO)SR′]2 (R′ =-S-C6H5, -S-C6H4CH3, -S-C6F5, -S-C6H4NO2).
Authors: Mohr Dieter , Wienand Henning , Ziegler Manfred L.
Published: March 2015

The aryl-sulfinato complexes π-C7H7Mo(CO)2SO2R have been synthesized by reaction of π-C7H7Mo(CO)2J with the Ag-SO2-R compounds. The sulfinate group is S-bonded. Mononuclear and dinuclear thioaryl complexes were isolated by reaction of π-C7H7Mo(CO)2Br with aryl mercaptanes R′-S-H in the presence of (C2H5)3N which functioned as a proton acceptor. IR data indicate the dependence of the π-acceptor abilities of the sulfur atom from R′
Organometallphosphin-substituierte Übergangsmetallkomplexe, ΧΧΠ Darstellung und komplexchemisches Verhalten von Dimethylstannandiylbis(di-t ert-butylphoshin).
Authors: Schumann Herbert , Μοnt Wolf-Walther Du
Published: March 2015

Dimethylstannandiylbis(di-tert-butylphosphine) reacts with tetracarbonyl nickel under formation of tricarbonyl-dimethylstannandiylbis(di-tert-butylphosphine)nickel and polymeric dicarbonyl-dimethylstannanediylbis(di-tent-butylphosphine)nickel and with hexacarbonylchromium under UV-irradiation as well as with tetracarbonyl-norbornadienechromium yielding tetracarbonyl-dimethylstannandiylbis(di-tent-butylphosphine)-chromium. IR and NMR spectra of the new compounds are discussed
Angular Heterocycles. The Reaction of N-(3-Chloro-1,4-dihydro-1,4-dioxo-2-naphthyl)acetamide with Isoelectric Bifunctional Aromatic Amines
Authors: Agarwal N. L. , Mital R. L.
Published: March 2015

N-(3-chloro-1,4-dihydro-1,4-dioxo-2-naphthyl)acetamide (1) reacts with aromatic amines to give the 2-acylamino-3-arylamino-1,4-naphthoquinones. Whereas with the substituted o-phenylenediamines, o-aminophenols, o-aminobenzenethiols and 2-amino-3-hydroxy pyridine it gives angular heterocyclic compounds. A common reaction path is suggested
Reactions with 2-Thiohydantoin, Synthesis of Imidazothiazolone Derivatives and Mannich Bases of 5-Arylidene-2-thiohydantoin
Authors: Shalaby A. F. A. , Daboun H. A. , Aziz M. A. Abdel
Published: March 2015

Treatment of 5-arylidene-2-thiohydantoin (1a-d) with alkyl bromoacetate and chloroacetic acid gave the esters 2a-f and the acids 2g-j, respectively. 2a was refluxed with concentrated hydrochloric acid to give 5-benzylidene hydantoin. 2 was cyclized with acetic anhydride to give the bicyclic product 3. 5-Arylidene-2-thiohydantoin derivatives (1a, b) and (8a) condense with formaldehyde and primary or secondary amines to give the corresponding Mannich bases 6a-f and 8c-e, respectively. The assigned structure 6 and 8 finds support from the chemical evidences
Notizen: Über Einkristalle von Goldoxid Au2O3. / On Single Crystals of Gold Oxide Au2O3
Authors: Schwarzmann Einhard , Mohn Jürgen , Rumpel Horst
Published: March 2015

Amorphous Au2O3, aq can be transformed in perchloric acid solution (1,6-1,9 n: quartz tube, filling grade 30%: 275→235°C) to single crystals of ruby orthorhombic Au2O3. Space group Fdd 2
Notizen: 1.3-Di(tert-butyl)-2.4-dichlor-diazaphosphaarsetidin / 1,3-Di(tert-butyl)-2,4-dichlorodiazaphosphaarsetidine
Authors: Scherer Otto J. , Schnabl Günter
Published: March 2015

Kleine, ausschließlich Heteroatome enthaltende Element-Stickstoff-Ringe werden vielfach bevorzugt dann gebildet, wenn an das N-Atom eine tert-Butyl- oder Trimethylsilyl-Gruppe gebunden ist1.

Ausgehend vom zweifach tert-Butyl-substituierten Phosphatriazen (1)2 erhält man durch 1.2-Addition von AsCl3 die offenkettige Zwischenverbindung3 2, die ihrerseits durch cyclisierende Si-N-Spaltung 1.3-Di(tert-butyl)-2.4-dichlor-diazaphosphaarsetidin (3) bildet6
13C-Kernresonanzspektroskopische Untersuchungen an Carbonyl-, Phosphonyl- und Sulfonyl-Verbindungen mit Methylen-Brücken / 13C NMR Spectroscopic Investigations of Methylene-bridged Carbonyl, Phosphonyl and Sulfonyl Compounds
Authors: Althoff Wolfgang , Fild Manfred , Rieck Hans-Peter
Published: March 2015

Compounds of the type R1-CH2-R2, where R1 and R2 represent phosphonyl, carbonyl and sulfonyl groups have been investigated by 13C NMR. Chemical shifts and coupling constants of carbon to phosphorus or fluorine are discussed.
Photoelektronenspektren von Verbindungen der V. Hauptgruppe, ΙII Methylhalogenverbindungen MeEHaI2 und Me2EHal / Photoelectron Spectra of Group V Compounds, III Methylhalogen Compounds MeEHal2 and Me2EHal
Authors: Elbel Susanne , Dieck Heindirk Tom
Published: March 2015

The He I photoelectron spectra of certain MeEHal2 and Me2EHal compounds (E = (N), P, As, Sb; Hal = (F), Cl, Br, J; Me = CH3) are interpreted in terms of a “composite molecule” approach derived for C3vCs systems. Although an “internal standard” is missing here, substituent group-orbitals (nHal, C—H) may be classified with respect to their orientations in space (R, V, T). Ionisation energies are assigned according to this assumption.

PE data of the isoelectronic EMe3/EHal3 compounds and of related molecules (Me2EH, MePH2, CF3PBr2) as well as EHMO calculations with partial inclusion of spin orbit coupling are used to confirm the assignments given for Me2EHal/MeEHal2 series.

Correlations between PE ionisation energies (e.g. nE (IE)) and molecular or atomic properties are critically revised and discussed.
Notizen: Umsetzung von Tris-[dimethylaminino]-arsin mit Arsinigsäurediolestern, eine ungewöhnliche Arsolansynthese / Reaction of Tris-[dimethylamino]-arsine with Arsinous Acid Diolesters, an Unusual Synthesis of Arsolanes
Authors: Rühl Werner J. , Kober Friedhelm
Published: March 2015

The reaction of tris-[dimethylamino]-arsine As(NMe2)3 with arsinous acid diolesters HO—RO—AsMe2 leads to the formation of the arsolanes RO2AsY (Y = NMe2, OROAsMe2) and the arsines Me2AsX (X = NMe2, OROAsMe2). The reaction mechanism is discussed; IR and 1H NMR spectral data are presented.
Übergangsmetallkomplexe mit Aminosäuren und Dipeptiden / Transition Metal Complexes of Amino Acids and Dipeptides
Authors: Guntner Hans , Schwarzhans Karl E.
Published: March 2015

A series of transition metal complexes with the ligands L-Tyr, Gly-L-Tyr and Gly-L-Phe has been prepared. The magnetic moments, the IR and EPR spectra of the isolated compounds have been collected.
Radiation Chemistry of DNA Model Compounds, IX. Carbohydrate Products in the γ-Radiolysis of Thymidine in Aqueous Solution. The Radical-Induced Scission of the N-Glycosidic Bond
Authors: Dizdaroglu Miral , Neuwald Klaus , Sonntag Clemens Von
Published: March 2015

In the γ-radiolysis of deoxygenated N2O-saturated aqueous solutions of thymidine (10-3 M, room temperature, dose rate 4· 1018 eV/g.h., dose 6.7 1017-3.3 • 1018 eV/g) the following products (G-values in parentheses) have been identified : 2,5-dideoxy-pentos-4-ulose (1) (0.01), 2,4-dideoxy-pentodialdose (2) (0.02), 2,4-dideoxy-pentos-3-ulose (3) (0.03), 2,3-dideoxy-pentos-4-ulose (4) (0.01), 2-deoxy-pentos-4-ulose (5) (0.1), 2-deoxyribonic acid (6) (0.02) and thymine (8) ( ≤ 0.2). In the presence of oxygen (N2O/O2 80/20 v/v saturated) products 1-4 are absent, G (5) = 0.2, G (6) = 0.07 and G (8) ≤ 0.4. Furthermore, 2-deoxy-tetrodialdose (7) which is absent in deoxygenated solution is formed with a G-value of 0.03. Mechanisms are proposed to account for the scission of the N-glycosidic linkage. Product 6 is thought to be due to a primary OH radical attack at C-1′ of the sugar moiety, 8 arises from an attack at C-3′, 1, 4 and 5 from an attack at C-4′, and 2 and 7 from an attack at C-5′.
Umsetzung von 2-Dimethylamino-3-methyl- [1.3.2] oxazarsolan mit Protonensäuren / Reaction of 2-Dimethylamino-3-methyl-[1,3,2]oxazarsolan with Acid Molecules
Authors: Adler Oswald , Kober Friedhelm
Published: March 2015

The reactions of 2-dimethylamino-3-methyl-[1,3,2]oxazarsolane with acid molecules HXR, H2X, HNR2 and H2NR (X = O, S; R = alkyl-group) are examined. IR, NMR and mass spectral data of the obtained arsolanes are discussed. The molecular weight determinations and the mass spectra with chemical ionization show an assoziation by As–N–Asor As–X–As-bridges.