bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesen mit Nitrilen, LIV Reduktion von Oximinomalonitril zu Aminomalonitril mittels Raney-Katalysatoren / Syntheses with Nitriles, LIV Reduction of Oximinomalonitrile to Aminomalonitrile Using Raney-Catalysts
Authors: Junek Hans , Mittelbach Martin
Published: February 2015

An improvement of the synthesis of aminomalononitrile (2) can be achieved by using Raney-catalysts for the reduction of oximinimalonitrile at a H2-pressure of 4 atm and 20 °C. Due to the reactivity of oximinomalonitrile some new derivatives of oximinocyanoacetamide are obtained by O-and N-acylation. Condensation of 2 with benzilmonoxime leads to 2-amino-5,6-diphenyl-pyrazine-carbonitrile, with N-phenyl-formamidate 2-amino-2,2-dicyano-1-(N-phenylimino)-acetaldehyde (10) is yielded.

Oximinomalonitrile, Aminomalononitrile, Oximinocyanoacetamide
Organophosphorus Compounds of Expected Biological Activity, Part II Preparation of Thiourea Derivatives and N-Aryl-phosphorothiomonoamidates
Authors: Abdel-Hay F. I. , Omara M. A. , El-Barbary A. A. , El - Badawi M.
Published: February 2015

The examples of cyclodiphosphazanes so far studied do not contain any nuclei of biological interest [1]. In the present investigation we aimed to introduce ethyl p-amino-benzoate, 2-aminopyridine residues in the phosphazane molecule. For this purpose phosphorus pentachloride was treated with ethyl p-aminobenzoate, p-anisidine, 2-amino-pyridine and 5-aminoquinoline to give 1,3-di-p-ethoxycarbonylphenyl-, 1,3-di-p-methoxy-phenyl-, 1,3-di-2-pyridyl-and 1,3-di-5-quinolinyl-2,2,2,4,4,4-hexachlorocyclo-diphos-phazane (1 a-d), respectively. The compounds 1 a-d were treated with potassium thio-cyanate in acetone. The oily products formed were then treated with p-anisidine, ethyl-p-aminobenzoate and 2-aminopyridine whereupon solid products (2 a-h) were obtained. The reaction probably takes place according to the following mechanism [2].
Quenching of Singlet Oxygen by Sodium Azide in Reversed Micellar Systems
Authors: Miyoshi Norio , Tomita Giiti
Published: February 2015

The oxidation reaction of singlet oxygen with 1,3-diphenylisobenzofuran was investigated in cyclohexanic reversed micellar solutions of dodecylammonium propionate, using pyrene as photosensitizer. The furan oxidation was effectively inhibited by azide ion-bound reversed micelles. Empty reversed micelles also inhibited the furan oxidation to some extent. The inhibition of the furan oxidation was due to the quenching of singlet oxygen by azide ion-bound and empty reversed micelles. Such singlet oxygen quenching was dependent on the concentration of water added.

Results obtained were discussed in connection with the polarity in the interior of reversed micelles, micellar size, the state of water solubilized in reversed micelles and the lifetime of singlet oxygen. The heavy atom effect on the quenching of singlet oxygen was also studied using heavy water.
Notizen: AB2X2-Verbindungen des Berylliums mit 2 A - und 5 B-Elementen / AB2X2 Compounds of Beryllium with 2 A - and 5 B - Elements
Authors: Tiburtius Christoph , Schuster Hans-Uwe
Published: February 2015

The new compounds MgBe2P2, MgBe2As2, CaBe2P2 and CaBe2As2 have been prepared. They are supposed to crystallize trigonally in a CaAl2Si2-type structure.
Tetrazen aus Diazen / Tetrazene from Diazene
Authors: Wiberg Nils , Häring Heinz-Wolfgang , Vasisht Sham Kumar
Published: February 2015

The acid-catalyzed decomposition of diazene, formed as an intermediate by the reaction of bis(trimethylsilyl)diazene with acids, leads by dimerisation via tetrazene to ammonium azide.
Zur Kristallstruktur von SrLaNiO4 / On the Crystal Structure of SrLaNiO4
Authors: Pausch H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of SrLaNiO4 were prepared with a new high temperature and high oxygen pressure method (CO2-Laser radiation). The X-ray investigation shows, that this compound belongs to the K2NiF4-type (a - 381.3; c = 1268.7 pm; space group D17
4h-I4/mmm), with a stretched octahedral oxygen coordination around Ni3+. The octahedral distortion can only be explained by a geometrical effect.
Darstellung und Kristallstruktur von NH4SbS2 / On the Preparation and Crystal Structure of NH4SbS2
Authors: Volk Klaus , Bickert Peter , Kolmer Raimund , Schäfer Herbert
Published: February 2015

NH4SbS2 has been prepared and its crystal structure determined. The new compound crystallizes triclinic, space group P1̄, with the following cell-constants: a = 1213 pm, b = 641.9 pm, c = 634.0 pm, a = 102.9°, β = 98.9°, γ = 101.2°. In the structure there are ψ-SbS4-trigonal bipyramids connected to chains by common edges.
Darstellung und Kristallstruktur von K2Sb4S7 · H2O / Preparation and Crystal Structure of K2Sb4S7 · H2O
Authors: Eisenmann Brigitte , Schäfer Herbert
Published: February 2015

K2Sb4S7 · H2O crystallizes in the triclinic system with a = 1171.4(5) pm, b = 952.0(5) pm, c = 715.6(5) pm and α = 99.36(5)°, β = 86.80(5)°, γ= 103.48(5)°. One half of the Sb atoms has three sulfur neighbours forming with the free electron pair a ψ-ShS3 tetrahedron, while the other half is coordinated by four S atoms to build a ψ-trigonal SbS4 bipyramid. These polyhedra are connected by common edges and corners to a three-dimensional network with two types of channels, in which either K+ ions only or K+ ions and water molecules are located.
15N-NMR-Spektroskopie bei Kohlenstoffaziden / 15N NMR Spectroscopy of Carbon Azides
Authors: Müller Joachim
Published: February 2015

The following triply 15N labelled azides CH3N3, C6H5N3, O2NC6H4N3, (O2N)3C6H2N3, NCN3, and (NCN3)3 were investigated by 15N NMR and partially by vibrational and 13C NMR specrtoscopy. The signals of the β- and γ-N atom show an overcrossing. 1J(15N -13C) is zero for the arylazides.
Ringöffnung CO+- und COOCH3
+·-substituierter Cyclopropane und CO-Eliminierung aus isomeren C3H5CO+-Ionen / Ring Opening of CO+ and COOCH3
+· Substituted Cyclopropanes and CO Loss from Isomeric C3H5CO+ Ions
Authors: Schwarz Helmut , Wesdemiotis Chrysostomos
Published: February 2015

The non-decomposing molecular ions of methyl cyclopropanecarboxylate (14) are found to rearrange to ionised methyl but-3-enoate (15). For ions with sufficient internal energy to decompose, this isomerization is in competition with · OCH3 loss, via direct cleavage of the ester group. Collisional activation spectroscopy may be used to distinguish between the C3H5CO+ ions formed by · OCH3 loss from the molecular ions of 14, 15 and other isomeric precursors. Four distinct C3H5CO+ species (18-21) can be identified in this way; these C3H5CO+ ions may themselves decompose, via CO elimination. Consideration of the metastable peak shape for CO loss, in conjunction with collisional activation spectroscopy on the resulting C3H5
+ -ions, leads to two main conclusions, (i) Two C3H5
+ ions (22 and 27) exist in potential energy wells. The very narrow metastable peaks for CO loss from 19 and 21 (leading to 22 and 27, respectively) show that these processes are continuously endothermic. In contrast, CO loss from either 18 or 20 gives rise to much broader metastable peaks. This suggests that rate-determining rearrangement of the incipient C3H5
+ cations, to a more stable isomer, occurs prior to decomposition, (ii) Elimination of CO from the [M- · OCH3]+ fragment of 14 gives rise to a composite metastable peak, thus indicating the occurrence of two competing channels for dissociation. These channels are assigned to CO loss from 18 (larger kinetic energy release) and CO loss from 19 (smaller kinetic energy release).
13C-NMR-Spektren einiger Acridon-Derivate [1] / 13C NMR Spectra of Some Acridone Derivatives [1]
Authors: Mester I. , Bergenthal D. , Rózsa Zs. , Reisch J.
Published: February 2015

The 13C NMR spectra of acridone derivatives 3-5, 8-12, melicopicine (14), melicopidine (15) and melicopine (16) are presented. The substituent parameters for OH and OCH3 groups in acridone derivatives have also been given.
Die Kristallstruktur der orientierungsfehlgeordneten kubischen Hochtemperaturphase des Natriumperchlorats NaClO4 / The Crystal Structure of the Orientationally Disordered, Cubic High-temperature Phase of Sodium Perchlorate NaClO4
Authors: Berthold Hans Joachim , Kruska Brigitte Gabriele , Wartchow Rudolf
Published: February 2015

The crystal structure of the orientationally disordered, cubic high-temperature phase of NaC104 has been investigated using single crystal X-ray diffraction data. Space group Fm3m-O5
h, Z = 4, sodium and chlorine as in NaCl, oxygen in position 96 j (occupation factor 1/6).
Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen, VIIIa Elektronenmikroskopischer Nachweis neuer, eng begrenzter Defekte bei Blockstrukturen und Berechnung ihrer O/Me-Werte / Contributions to the Study of Inorganic Non-Stoichiometric Compounds, VIIIa Electronmicroscopical Proof of New, Small Area Defects of Block Structures and Calculation of Their O/Me Values
Authors: Heurung Günter , Gruehn Reginald , Brunner Herbert
Published: February 2015

Compounds of the systems Fe2O3-Nb2O5 (O/Me < 2.5) and Nb2O5-WO3 (O/Me > 2.5) were prepared by chemical transport. The block structures of the obtained phases were investigated by high resolution transmission electron microscopy.

The unusual defects observed were nearly identical in both systems. A recently developed method to calculate the O/Me value of block structures [1] was extended and used for these defects.
Derivate des Benzo[1.3]dioxols, 44 [1]Darstellung von p-chinoiden Brenzkatechinmethylenethern / Derivatives of 1,3-Benzodioxoles, 44Preparation of 1,4-Benzoquinones Fused to Cyclic Diethers
Authors: Dallacker Franz , Reichrath Germanus , Schnackers Gerard
Published: February 2015

The preparation of 5,6-dimethyl- (1g), 5-methoxy-6-methyl-1,3-benzodioxole-4,7- quinone(1k), 6,7-dimethyl-1,4-benzodioxan-5,8-quinone (3e), 7,8-dimethyl-3,4-dihydro- 2H-1,5-benzodioxepin-6,9-quinone (4e), 8,9-dimethyl-2,3,4,5-tetrahydro-1,6-benzodioxo- cin-7,10-quinone (5f) and of 9,10-dimethyl-3,4,5,6-tetrahydro-2H-1,7-benzodioxonin-8,11-quinone (6e) by potassiumnitrosodisulfonate-oxidation of the phenols 1f, 1j, 3d, 4d, 5e, and 6d is described. To obtain the phenols by Baeyer-Villigeroxidation of the aldehydes 1e, 1i, 3c, 4c, 5d, 6c, the cyclic ethers are subjected to bromination, bromine-lithium-exchange, and formylation of the lithium-compounds.
Eine neue Synthese von Bis(1.5 -cyclooctadien)platin / A New Synthesis of Bis( 1,5-cyclooctadiene)platinum
Authors: Herberich Gerhard E. , Heßner Bernd
Published: February 2015

Bis(1,5-cyclooctadiene)platinum has been pre­pared in 74-82% yield by reduction of dichloro-(1,5-cyclooctadiene)platinum with bis(cyclopentadienyl)cobalt in the presence of excess 1,5-cyclooctadiene.
Inhaltsstoffe aus Clausena anisata (Willd.)Oliv. (Rutaceae), III [1,2]13C-NMR-Spektren des Mupamins, des Carbazols und einiger Carbazol-Derivate / Constituents of Clausena anisata (Willd.) Oliv . (Rutaceae) , III [1,2] 13C NMR Spectra of Mupamine , Carbazole and Some Carbazole Derivatives
Authors: Mester I . , Bergenthal D. , Reisch J.
Published: February 2015

The fully interpreted 13C NMR spectra of mupamine, carbazole, and of some carbazole derivatives are reported.
Neue bicyclische λ3 -Phosphazane / New Bicyclic λ3 - Phosphazanes
Authors: Zeiss Werner , Endrass Werner
Published: February 2015

Symmetrically 1,5 bridged cyclotetra(λ3 -phosphazanes) 2a, b are formed from cyclotri-(λ3 -phosphazanes) 1a, b and heptamethyldisilazane. Substitution of halogens at P3 and P7 in 2a, b by alkoxy or phenoxy substituents is achieved with alcohols in the presence of triethylamin to give 2c, d. NMR spectroscopy shows 2a, b to exist as isomers A or B, whereas for 2c, d additional asymmetric isomers like C or D are assumed.
Darstellung, Eigenschaften und Kristallstruktur von Tl6Au2I10 / Preparation, Properties, and Crystal Structure of Tl6Au2I10
Authors: Stoeger W. , Rabenau A.
Published: February 2015

Tl6Au2I10 forms black crystals with a golden luster. In a closed system the temperature of decomposition is 276 °C. In vacuum or under inert gas Tl6Au2I10 decomposes above 65 °C forming 1 mol I2. Above 180 °C a second mol I2 is formed giving TlI and gold. The space group is P6̅2c with the lattice constants a = 10.569 and c = 13.431 Å and Z = 2. Tl6Au2I10 is built up by a framework of Tl6I6 with channels parallel to the c-axis. These channels contain Au+ mainly with a trigonal planar coordination or linear I-
3-polyiodide ions and I- ions, resp.
The Reaction of (h5-Cyclopentadienyl)carbonyl(triphenylphosphine)iridium and Bis(pentafluorophenyl)acetylene
Authors: Rausch M. D. , Gastinger R. G.
Published: February 2015

The reaction between (h5-cyclopentadienyl)carbonyl(triphenylphosphine)iridium and bis(pentafluorophenyl)acetylene has been investigated in detail. As in earlier studies involving the analogous cobalt and rhodium complexes, the metallocyclic product 1-(h5-cyclopentadienyl)-1-triphenylphosphine-2,3,4,5-tetrakis-pentafluorophenyl)iridole (3) has been obtained, although in very low yield. A variety of highly fluorinated organic products have also been isolated and identified, including hexakis(pentafluorophenyl)-benzene (5), Zraws-1,2-bis(pentafluorophenyl)ethene (6) and 1,2,3,4-tetrakis(pentafluoro-phenyl)naphthalene (4). The latter product has been synthesized by an independent method. Reaction mechanisms to account for the formation of 4 under these conditions are discussed.
Notizen: Kinetics of the Alkaline Decarboxylation of Trichloroacetate Ion in Water - Ethanol Solutions
Authors: Diefallah El-Hussieny M.
Published: February 2015

The calculation of the radius of the transition state in the alkaline decarboxylation of trichloroacetate ion in water-ethanol solutions has been discussed. In applying a simple electro- static theory to solvent mixtures with water mole fractions less than about 0.7, it is shown that the radius of the transition state complex is about 5.5 Å and that the volume of the activated molecule is about four times that of the reactant ion. This result is in agreement with the postulated reaction mechanism and the experimentally calculated activation parameters. In the water rich solutions, the simple electrostatic theory is not applicable.
Notizen: Azide und Nitrile cyclischer λ5-Phosphazene / Azides and Nitriles of Cyclic λ5-Phosphazenes
Authors: Roesky Herbert W. , Banek Manfred
Published: February 2015

The kinetically stable triazatriphosphorinyl and tetraazatetra-phosphorocinyl azides 3 and 4 are prepared from the corresponding chlorides 1, 2 with sodium azide. 3 and 4 react with phosphanes to yield the λ5 -diphosphazenes 5a-d. By the reaction of 1 or 2 with KCN the nitriles 6 and 7 are formed. -The new compounds are characterized on the basis of IR and mass spectra.
K5CuSb2 – eine Verbindung mit gestreckten Sb–Cu–Sb-Einheiten / K5CuSb2 – a Compound with Linear Sb-Cu-Sb-Units
Authors: Savelsberg Gerhard , Schäfer Herbert
Published: February 2015

The new compound K5CuSb2 crystallizes in the space group R3̄m with the constants a = 591(2) pm, c = 2814(4) pm, c/a = 4.76. There are linear (Sb-Cu-Sb)5- groups in the structure which are isoelectronic to the HgCl2 molecule.
Na6Pt8Ge8, eine ternäre intermetallische Phase mit tetraedrischen Platinclustern / Na6Pt8Ge8, a Ternary Intermetallie Phase with Tetrahedral Platinum Clusters
Authors: Thronberens Werner , Schuster Hans-Uwe
Published: February 2015

Na6Pt8Ge8 was prepared from the elements; it crystallizes in a cubic structure, space group I4̄3m, a= 761.4 pm. The phase contains two structural elements:

The Pt-atoms form tetrahedra, which are covered by bigger Ge-tetrahedra. The Na-atoms build a 3-D-network consisting of chains crossed under right angels.
NMR Studies on Halogeno-cis-bis(phosphine)-nido-pentaboranyl Derivatives of Nickel, Palladium, and Platinum
Authors: Kennedy John D. , Staves John
Published: February 2015

An examination of the 1H-{11B}, 11B, 11B-{1H}, and 31P-{1H} NMR behaviour of the compounds [M(B5H8)(X)(dppe)] has been made [M = Ni, Pd and Pt; X = halogen; dppe = bis(diphenylphosphino)ethane]. Some relaxation phenomena are rationalised, and it is concluded that all the compounds examined have a static metallo -nido-penta -borane structure in which the metal atom occupies a bridging position between two basal boron atoms. Some temperature and solvent effects are also presented and briefly discussed.
Konformationsstudien an Partialsequenzen von ACTH und Analogen. Theoretische Vorhersagen und CD-Untersuchungen an Polyethylenglykol-gebundenen Oligopeptiden / Conformational Studies on Partial Sequences of ACTH and Analogues. Theoretical Predictions and CD Investigations of Polyethylene glycol)-bound Oligopeptides
Authors: Mutter Hildegard , Mutter Manfred , Bayer Ernst
Published: February 2015

Conformational studies on synthetic segments)* of ACTH using circular dichroism (CD) are described. The segments [Val4]-ACTH (1-10) = I, [Pro1, Ala2, Ala3, Val4]-ACTH (1-10) = II and ACTH (11-23) = III have been synthesized according to the Liquid-Phase-Method with polyethylene glycol (PEG) as solubilizing C-terminal protecting group. The peptide PEG esters were studied in water and 2,2,2-trifluoroethanol (TFE) and the dependence of chain length, side chain protection and solvent upon the conformation has been evaluated. From these measurements, I shows partially helical structure in TFE and β-conformation in H2O. The modified 10-peptide II with strong helix formers at the N-terminus shows substantial amounts of helical structure in TFE and in water. A significant increase in helical structure is observed by adding the Pro residue to the N-terminus. The CD spectra of the 13-peptide III ist also typical for partially helical structure, however other types of ordered conformations cannot be excluded. The experimental data are compared with the results from calculations of the secondary structure deduced from the empirical prediction scheme of Chou and Fasman and the more elaborated statistical mechanical treatment of peptide conformations proposed by Tanaka and Scheraga. The agreement between experimental data and theoretical prediction is reason-able for I and II, whereas III is expected to adopt extended conformations beside unordered forms. The experimentally found unique behaviour of Prolin was rationalized by the asymmetric helix nucleation feature of this residue. A model for the most probable conformation of ACTH is proposed and a critical evaluation of the predictive schemes is given.
Das JerJ-Butyl-Kation in Lösungen von Aluminiumbromid in Mono-, Di- und Tribrommethan / The terf-Butyl-Cation in Solutions of Aluminium Bromide in Mono-, Di- and Tribromomethane
Authors: Brüggeller Peter , Mayer Erwin
Published: February 2015

The tert-butyl cation is formed from tert-BuBr in concentrated solutions of AlBr3 in CH3Br, CH2Br2 and CHBr3 and was characterized by 1H NMR spectroscopy. Stabilization of the cation depends strongly on the AlBr3 concentration: in CH3Br saturated with AlBr3, C(CH3)3+ is formed in 80% yield; in dilute solutions of AlBr3 in CH3Br the usual de-composition occurs. In saturated solutions of AlBr3 in CH2Br2 and CHBr3 the C(CH3)3+ yield is 60 and 40%, resp. The concentration of the cation decreases in all three solvents by 20 to 30% within 10 days at room temp. In concentrated solutions of AlBr3 in CH3Br the formation of the methyl-tert-butylbromonium ion as a rapidly equilibrating species is suggested. The 1H NMR chemical shift of C(CHs)3+ in the presence of AlBr3 (δ = 5.19 in CHsBr, δ = 5.23 in CH2Br2, δ = 5.35 in CHBr3) indicates strong deshielding in comparison with shifts in SbF5 and SbF5/SO2
Darstellung und Eigenschaften trimerer Chlorotellurate(IV). Kristallstruktur von (C6H5)CTe3Cl13/ Preparation and Properties of Trimeric Chlorotellurates(IV). Crystal Structure of (C6H5)3CTe3Cl13
Authors: Krebs Bernt , Paulat Volker
Published: February 2015

The trimeric chlorotellurate(IV) ion Te3Cl13- is obtained in benzene solution as a degradation product of cubane-like tetrameric tellurium(IV) chloride Te4Cl6 and can be isolated by crystallization in the form of salts with large cations. The crystal structure of the triphenyl-methyl salt (C6H5)3CTe3Cl13 (P21/c, a = 1109.5, b = 1644.4, c = 2043.9 pm, β = 114.50°) shows the Te3Cl13- ion to have approximate C3V symmetry; as a fragment of the Te4Cl16 cube it consists of three edge-sharing octahedra with a central triply bridging Cl. Bond distances Te-Cl (tripl.br.) 292.4-298.4, Te-Cl (doubl.br.) 270.6-286.3, Te-Cl (term.) 232.0-238.8 pm. The vibrational spectrum of Te3C13- is discussed.
Phosphoraustausch im Cyclophosphazenring bei der Reaktion Hydridocyclotri(phosphazen)/Perthiophosphonsäureanhydrid [1] / Exchange of Phosphorus in the Cyclophosphazene Ring in the Reaction Hydridocyclotri (phosphazene )/Perthiophosphonic Anhydride [1]
Authors: Högel Johann , Schmidpeter Alfred
Published: February 2015

The 2-hydrido-2-methyl-cyclotri(phosphazene) (1) reacts with perthiophosphonic anhydrides (2) to give cyclotri(phosphazene)diene-2-thiones (3). When 2 contains R ≠ CH3, mixtures of CH3-3 and R-3 are obtained. This must be due to a competition of sulfur transfer from 2 to 1 and the insertion of a RPS unit from 2 into 1 involving the opening and reclosure of the N3P3 ring. The unusual lability of the cyclotri (phosphazene) ring probably arises from the prototropy in 1
Darstellung und Kristallstruktur von BaMn2Sb2, BaZn2Sb2 und BaCd2Sb2 / Preparation and Crystal Structure of BaMn2Sb2 , BaZn2Sb2 and BaCd2Sb2
Authors: Brechtel Erwin , Cordier Gerhard , Schäfer Herbert
Published: February 2015

The new compounds BaMn2Sb2, BaZn2Sb2 and BaCd2Sb2 have been prepared and structurally characterized. The crystallographic data are: BaMn2Sb2: I4/mmm, a = 441.8 ± 0.6 pm, c = 1440 ± 2 pm, ThCr2Si2 structure, BaZn2Sb2 : Pnma, a = 1053.9 ± 0.8 pm, b = 450.2 ± 0.2 pm, c = 1163.9 ± 0.8 pm, BaCu2S2 structure, BaCd2Sb2: P3̅m 1 , a = 477 ± 1 pm, c = 808 ± 2 pm, Ce2O2S structure
Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, XXIV [1] Synthese von Sulfonamidoboranen und Sulfonamidosilanen / Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules, XXIV [1] Synthesis of Sulfonamidoboranes and Sulfonamidosilanes
Authors: Maringgele Walter , Meiler Anton
Published: February 2015

The reaction of trimethylsilylsulfonamides with halodiorganylboranes leads to the corresponding sulfonamidoboranes and halotrimethylsilane. Trimethylsilylsulfonamides are prepared by reaction of the corresponding sulfonyl chlorides with primary amines, followed by the addition of chlorotrimethylsilane in the presence of excess triethylamine. 1H, 11B NMR spectra and mass spectra are reported
Zur Thioketalisierung mit Tris(ethylthio)boran, II / Synthesis of Thioketals with Tris(ethylthio)borane, II
Authors: Klein Helmut A.
Published: February 2015

Tris(ethylthio)borane (1) is a convenient donor for ethanthiol, esp. for the ketalization of carbonyl compounds. With amides, amide thioacetals are obtained
Substituenteneinfiüsse auf die Geschwindigkeit der Photobilin-Bildung / Substituent Effects upon the Rate of Photobilin Formation
Authors: Jürgens Uwe , Brockmann Hans
Published: February 2015

The structural requirements for the regioselective photochemical ring-opening of chlorin derivatives and the corresponding rate of formation of the pertinent photobilins are reported. The structure of one of the photobilins is verified by X-ray analysis.
Donor-Akzeptorkomplexe des ReO3Cl mit Metallchloriden / Donor Acceptor Complexes of ReO3Cl with Metal Chlorides
Authors: Lössberg Rainer , Dehnicke Kurt
Published: February 2015

ReO3Cl with AICI3 and NbCls, respectively, forms the donor acceptor complexes

AlCl3 · ReO3Cl and NbCl5 • ReO3Cl. According to their IR spectra the complexes contain Re = O-Metal bridges. GaCl3 also forms a weak donor acceptor complex with ReO3Cl, which catalyzes the reaction of ReO3Cl with CCl4 forming COCl2
Abhängigkeit der Calcium-Isotopenseparation bei der Ionenaustauschchromatographie von der HNO3-Elutionsmittelkonzentration / Calcium Isotope Separation by Ion Exchange Chromatography in Dependence on the HNO3 Eluant Concentration
Authors: Heumann Klaus G. , Klöppel Helmut
Published: February 2015

Using a strongly acidic cation exchanger resin, the dependence of the calcium isotope separation on the HNO3 eluant concentration is investigated on column experiments. The elementary separation effect of the isotope ratios 44Ca/40Ca and 48Ca/40Ca is determined. Up to HNO3 concentrations of about 1.5 M the lighter calcium isotopes are enriched in the resin phase, whereas, using more concentrated HNO3 solutions, the heavier isotopes are enriched in the ion exchanger. A comparison of these results with those using hydrochloric acid and perchloric acid show, that there is a strong dependence of the isotope separation on the concentration and the counter ion of the eluant solution
Molecular Rearrangements, XV Photolysis and Thermolysis of N-a- and ß-Phenethyl Toluidines
Authors: Badr M. Z. A. , Aly M. M. , E l - N a g g a r G. M. , Fahmy A. M.
Published: February 2015

Direct irradiation of each of N-a- and /3-phenethyl toluidine in carbon tetrachloride solution leads t o homolysis of the phenethyl-nitrogen bond forming phenethyl and arylamino free radicals. The fates of such radicals are discussed in terms of the identified products.

Thermolysis of the title compounds either alone or in presence of aromatic solvents such as isoquinoline or ß-naphthol leads, in addition to the products obtained from photolysis, to partial attack of the so formed radicals on the solvent nuclei forming simple substitution products or polynuclear compounds of the indole, acridine and carbazole series
Carbonfunctional Organosilicon Compounds: Synthesis of Some Silylcoumarins
Authors: Ghose B. N.
Published: February 2015

The syntheses of some silylcoumarins of the formulae 7-HOC9H4O2-4-(CH2)nSiMe2(F) [n = 3 and 4], and 7-HOC9H4O2-4-C6H4(CH2)nSiMe2(F)-4' [n= 1, 2 and 3] are reported
Heterocyclische Siebenring-Verbindungen, XXIII [1] Synthese und Thermolyseverhalten von 2-Methyl-4-phenyl-l-benzothiepinen / Heterocyclic Seven-Membered Ring Compounds, XXIII [1] Synthesisand Thermolytic Behaviourof 2-Methyl-4-phenyl-1-benzothiepins
Authors: Hofmann Hans , Heidrich Rainer
Published: February 2015

The anions derived from the seven-membered 2-methyl-diketone (3) and the enolether (4) were alkylated resp. acylated to the 2-methyl-4-phenyl-l-benzothiepins (6), (7) resp. (8). Compound 4 could also be obtained by C-methylation of the enolether (2). The thermal decomposition of the 2-methyl-4-phenyl-l-benzothiepins yielded exclusively sulphur and the corresponding I-methyl-3-phenyl-naphthalenes (9), (10) resp. (11).
Funktionelle Trimethylphosphinderivate, XI Trisphosphinomethane (R2P)3CH und isomere Phosphorylide R2P-PR2 =CH-PR2 /Functional Derivatives of Trimethylphosphine, XI Trisphosphinomethanes (R2p)3CH and Isomeric Phosphorus Ylids R2P-PR2=CH-PR2
Authors: Karsch Hans H.
Published: February 2015

The metallated diphosphinomethanes Li[R2PCHPR2′] (R,R′ = CH3, C6H5) react with R2 ″PCl (R ″ = CH3, C6H5) to give trisphosphinomethanes, [(R2P)(R2′P)(R2″P)]CH. The reaction is shown to proceed via electrophilic attack at the phosphorus of Li[R2PCHPR2′]by formation of the phosphorus ylids R2 ″P-PR2=CH-PR2′under certain conditions, mainly controlled by steric effects.These ylids slowly rearrange to the trisphosphino- methanes in solution,but with R ″=tC4H9,the ylids are stable.

The compounds are characterized by 1H 31P and 13C NMR spectra.
Übergangsmetall-Carbin-Komplexe, L Darstellung und nukleophile Substitution von Tetracarbonyl(organylcarbin)tetrafluoroborato-metall-Komplexen /Transition Metal Carbyne Complexes, L Preparation and Nucleophilic Substitution of Tetracarbonyl(organylcarbyne)tetrafluoroborato Metal Complexes
Authors: Fischer Ernst Otto , Gammel Franz J.
Published: February 2015

Pentacarbonyl[methoxy(organyl)carbene]chromium complexes react in boron trifluoride dimethyletherate in the presence of BF3 to form tetracarbonyl(organylcarbyne)-tetrafluoroborato complexes of chromium. In the analogous tungsten complex BF4(CO)4WCC6H5 the BF4
--ligand is displaced by nucleophilic reagents. With As(C6H5)3 and t-C4H9NC the cationic derivatives [As(C6H5)3(CO)4WCC6H5][BF4]as well as [t-C4H9NC(CO)4WCC6H5][BF4]are obtained.
Präparative, spektroskopische und kristallographische Untersuchungen an Phosphinato-Komplexen des Rheniums mit verschiedenen einzähnigen Liganden /Preparative, Spectroscopic and Crystallographic Investigations on Phosphinato Complexes of Rhenium with Various Unidentate Ligands
Authors: Lindner Ekkehard , Trad Sadek , Hoehne Sigurd , Oetjen Hans-Henning
Published: February 2015

The stable phosphinato complexes [μ-R2PO2Re(CO)3L]n (1, 2b-f) [L = THF (a), py (b), NH3 (c), P(C6H5)3 (d), As(C6H5)3 (e), P(C6H11)3 (f), O(C2H5)2 (g)] are obtained by addition of the ligands L to the compounds [μ-R2PO2Re(CO)3]n (1, 2) [R = CH3 (1), C6H5 (2)] at 20-40 °C (1, 2c: -35 °C). 1, 2b, d, e are also formed when THF in 1, 2a is substituted by the ligands b, d, and e. The unstable ether adducts 1, 2 g which result photochemically from Re2(CO)10 and the acids R2PO2H, are transformed to 1, 2 by elimination of ether. At 20 °C 1, 2 a react with liquid ammonia to give the ionic complexes [(OC)3Re(NH3)3][O2PR2] (1, 2h). On the basis of their mass and vibrational spectra, and a crystallographic in­vestigation, the methyl [1a-f] and phenyl compounds [2a-f] are dimeric and oligomeric, respectively. The rhenium atoms are bridged via R2PO2
- ligands (phosphinato-O,O′). 1a crystallizes monoclinic in the space group C2/m with Z = 2.
Neue ternäre Boride der Erdalkalimetalle mit Rhodium und Iridium /New Ternary Borides of the Alkaline Earth Metals with Rhodium and Iridium
Authors: Jung Walter
Published: February 2015

The ternary borides SrRh2B2, SrIr2B2, BaRh2B2, BaIr2B2 and Ba7lr12Bi12 were prepared and structurally characterized.

The crystallographic data are (pm):

SrRh2B2 : Fddd, a = 1067.2, b= 939.9, c =598.9, Z = 8.

SrIr2B2 : Fddd, a = 1072.3, b = 940.4, c =602.7, Z = 8.

BaRh2B2 : I4/mmm, a = 391.5, c = 1125.0, c/a = 2.874, Z = 2.

BaIr2B2 : I4/mmm, a = 393.5, c = 1140.7, c/a = 2.899, Z = 2.

Ba7Ir12Bi12 : R3̄m, a = 1522.2, c = 835.8, c/a = 1.821, Z = 3.

SrIr2B2 and SrRh2B2 are isostructural with CaIr2B2 and CaRh2B2, while BaRh2B2 and BaIr2B2 crystallize in the ThCr2Si2-type. Ba7lr12Bi2 has a new structure which contains structural elements of the compound SrIr2B2.
Li3Ce5Ge4, ein neuer Typ eines ternären Germanids des Lithiums mit Selten-Erd-Metallen Li3Ce5Ge4, a New Type of Ternary Compound of Lithium with Rare Earth Metal and Germanium
Authors: Czybulka Axel , Schuster Hans-Uwe
Published: February 2015

The ternary compound Li3Ce5Ge4 has been prepared and structurally characterized. It crystallizes orthorhombically (a = 1885 pm, b = 694.7 pm, c = 447.6 pm, space group B 2 mm). The structure shows germanium chains in a three-dimensional network of metal atoms.
Darstellung und Molekiilstruktur von 1.3.5.7-Tetraaza-2.4.6.8-tetrasila-bicyclo [3.3.0] octan/ Preparation and Molecular Structure of 1,3,5,7-Tetraaza-2,4,6,8-tetrasila-bicyclo[3,3,0]octane
Authors: Clegg William , Hluchy Hans , Klingebiel Uwe , Sheldrick George M.
Published: February 2015

The structure of the title compound 1 has been determined from X-ray diffractometer data. 1 is formed by reaction of dilithiated hydrazine with N,N-bis(fluorodimethylsilyl)- 2,4,6-trimethylaniline. 1 has approximate D2 symmetry with planar nitrogen atoms. A >N-N<-unit is shared by the two five-membered rings.
Notizen: Die Struktur des K3PS4·H2O/ Crystal Structure of K3PS4·H2O
Authors: Volk Klaus , Schäfer Herbert
Published: February 2015

K3PS4 · H2O crystallizes in the orthorhombic system, space group P21212 with a = 1205 ± 1 pm, b = 1251 ± 1 pm, c = 667.8 ± 5 pm. There are isolated PS4
3- -tetrahedra in the structure with P-S-bond lengths between 202.9 and 206.1 pm.
Übergangsmetallphosphidokomplexe, III [1] Neuartige Nickel-Phosphor-Drei-und Vierringkomplexe / Transition Metal Phosphido Complexes, III [1] Novel Nickel Phosphorus Three-, and Four-Membered Ring Complexes
Authors: Schäfer Hans
Published: February 2015

(R3P)2NiCl2 and LiP(SiMe3)2 react in a complex reaction sequence finally yielding (R3P)2Ni(PSiMe3)2 (5), containing a three-membered PNiP ring system, and [R3PNiP(SiMe3)2]2 (6), containing a (PNi)2 four-membered ring system with a nickel-nickel bond, respectively. NMR data are reported.
Hydrido -carbonyl -, Deuterido -carbonyl - und Carbamoyl-carbonyl-cobalt(I)-Komplexe des Tetrakis(diphenylphosphinomethyl)metlians [1] / Hydrido-carbonyl, Deuterido-carbonyl and Carbamoyl-carbonyl-cobalt(I) Complexes of Tetrakis(diphenylphosphinomethyl)methane [1]
Authors: Bauernschmitt Dieter , Behrens Helmut , Ellermann Jochen
Published: February 2015

[CO(CO)2(R2PCH2)3CCH2PR2][CO(CO)4] (R = C6H5) was synthesized in a simple manner from Co2(CO)8 and the tetratertiary phosphine C[CH2P(C6H5)2]4, which acts only as a tridentate ligand. [Co(CO)2(R2PCH2)3CCH2PR2][Co(CO)4] reacts with NH4PF6, NaBH4, NaBD4 or liquid ammonia at 20 °C to [Co(CO)2(R2PCH2)3CCH2PR2]PF6, CoH(CO)2(R2PCH2)2C(CH2PR2 · BH3)2, CoD(CO)2(R2PCH2)2C(CH2PR2 · BD3)2 or Co(CO)(CONH2)(R2PCH2)3CCH2PR2. In liquid ammonia [Co(CO)2(R2PCH2)3CCH2PR2][Co(CO)4] at 60 °C yields the hydride CoH(CO)(R2PCH2)3CCH2PR2. The new compounds were characterized, as much as possible, by their IR, Raman and 1H NMR data.
Diazen und andere Distickstoffhydride: Bildungswärmen, Dissoziationsenergien, Auftrittspotentiale, Protonenaffinitäten [1] / Diazene and other Dinitrogen Hydrides: Heats of Formation, Dissoziation Energies, Appearance Potentials, Proton Affinities [1]
Authors: Wiberg Nils , Fischer Gerd , Bachhuber Heinz
Published: February 2015

Ionisation and appearance potentials were obtained for diazene HN = NH (prepared by thermolysis of TOSN2H2M, M = Li, Na, K), isodiazene H2N = N (prepared by thermolysis of TOSN2H2CS and N2H4 microwave radiolysis, respectively), and other hydrides N2Hn (cf. Table I). The following energy data (kcal/mole) have been determined for diazene: heat of formation (32), enthalpy of isomerisation to isodiazene (13), NN-dissoziation energy (122), NH-dissoziation energy (81), hydrogen atom affinity (45), proton affinity (176).
Optisch aktive Übergangsmetall-Komplexe, LXIII [1] Asymmetrische Induktion in C5H5Mo(CO)2LX-Diastereomeren-Gleichgewichten / Optically Active Transition Metal Complexes, LXIII [1] Asymmetrie Induction in C5H5Mo(CO)2LX Diastereoisomer Equilibria
Authors: Brunner Henri , Bauer Isabella , Lukas Rainer
Published: February 2015

The thioamidato complexes C5H5(CO)2MoSC(R)NCH(CH3) (Ar), derived from acetic acid R = CH3 and benzoic acid R = C6H5, were prepared and characterized. The diastereo-isomers, differing in their 1H NMR spectra, were partly separated by fractional crystallization. After equilibration with respect to the labile Mo configuration the diastereoisomer ratio, a measure for the asymmetric induction from the chiral ligand on the formation of the two Mo configurations at equilibrium, was determined by 1H NMR integration. The asymmetric induction is very high for Ar = o-tolyl [76% (R = C6H3) and 84% (R = C6H5)] compared to Ar = phenyl [48% (R = CH3) and 56% (R = C6H5)] and Ar = m-and p-tolyl [52 and 44% (R = CH3)]. The (CO)3Cr complexed phenyl substituent with only 10% asymmetric induction does not show the β-phenyl effect, a weak attraction between aryl groups in β-position to the metal atom and the MC5H5 moiety.
An Unusual N-Dealkylation-Neighbouring Group Participations of Oximino Function [1]
Authors: Dubey S. K. , Sharma Satyavan , Iyer R. N.
Published: February 2015

Reaction of N,N-dialkyl-β-aminoketones (5 and 7) with hydroxylamine hydrochloride in pyridine results in the dealkylated oximine (6). The mechanism of this N-dealkylation may be explained as due to the neighbouring group participation of the oximine formed during the reaction.
Fluorhaltige Nitrile als Komplexliganden / Fluorine Containing Nitriles as Complex Ligands
Authors: Froböse Rolf , Mews Rüdiger , Glemser Oskar
Published: February 2015

N-Cyano-sulfurdifluoride-imide NC-NSF2 and N-cyano-sulfuroxide-difluoride-imide NC-NSOF2 will react with AsFs to give the N-bonded nitrile adducts F5As · NC-NSF2 (F5As · NC-NSOF2). With [M(CO)5SO2]+AsF6- (M=Mn,Re) the expected complexes [(CO)5MNC-NSF2]+AsF6-

[(CO)5MNC-NSF2]+AsF6-are formed in quantitative yield.
Direct Evidence for the Polymeric Structure of Some Platinum-blue Complexes in Aqueous Solution
Authors: Zaplatynski Peter , Neubacher Harald , Lohmann Wolfgang
Published: February 2015

The anticancer active compound, cis-dichloro-diammine platinum (II), and the biomolecules cytosine and thymine form paramagnetic complexes in aqueous solution. The electron spin resonance spectra which can be attributed to paramagnetic platinum, exhibit large anisotropy in frozen solution as well as in liquid solution. This fact can be explained by assuming poly-meric structures also in liquid solution.
Darstellung und Charakterisierung von „Nitrenkomplexen“ des Molybdän und Wolfram der Zusammensetzung [(η5-C5H5)OM]2(μ-NCOOC2H5)2 (M = Mo, W ) und [(η5-C5H5)OMo]2(μ-NCO2C2H5)(μ-O) / Synthesis and Characterization of "Nitrene Complexes" of Molybdenum and Tungsten of Composition [(η5-C5H5)OM]2(μ-NCOOC2H5)2 (M = Mo, W ) and [(η5-C5H5)OMo]2(μ-NCO2C2H5)(μ-O)
Authors: Korswagen Richard , Weidenhammer Klaus , Ziegler Manfred L.
Published: February 2015

The photolytical reactions of η5-C5H5Mo(CO)3CH3 (1) or η5-C5H5W(CO)3CH3 (2) with N3CO2C2H3 (3) in CH2Cl2 yield the “nitrene” complexes [(η5-C5H5JMoO)(μ-NCO2C2H5)2 (4), [(η5-C5H5)WO]2(μ-NCO2C2H5)2 (5) and [(η-C5H5JMoO]2(μ-NCO2H5)(μ-O) (6) together with some η5-C5H5Mo(CO)3Cl (7) and η5-C5H5W(CO)3Cl (8), proving that the solvent takes part in the reaction. Compounds 4, 5 and 6 contain bridging imido groups, arising from the capture of probably free nitrenes NCO2C2H5 by organometallic species. Evidence for the presence of free nitrenes in the reaction medium is provided by the isolation of urethane (9), tetrachlorethene (10), 7 and 8 as secondary products.
Über neue Carbamoyl-carbonyl-Komplexe des Eisens, Rutheniums und Osmiums [1] / About New Carbamoyl Carbonyl Complexes of Iron, Ruthenium and Osmium [1]
Authors: Jungbauer Anton , Behrens Helmut
Published: February 2015

The covalent carbamoyl compounds M(CO)2(PR3)2(Hal)(CONH2) (M = Fe, Ru, Os; Hal = Cl, Br; R = Ph, Cyclohexyl) and Os(CO)(NO)(PPh3)2(CONH2) are formed by the reactions of the cationic complexes [M(CO)3(PR3)2(Hal)]+ and [Os(CO)2(NO)(PPh3)2]+ with liquid NH3 between -75 and -40 °C.
Perfluormethyl-EIement-Liganden, XXII [1]. Darstellung und spektroskopische Untersuchung von Cr(CO)5L-Komplexen (L=R2EER′2, R2EE′R; R, R′ =CH3, CF3; E = P, As; E′ =S, Se, Te) / Perfluoromethyl Element Ligands, XXII [1]. Preparation and Spectroscopic Investigation of Cr(CO)5L Complexes (L = R2EER′2, R2EE′R; R, R′ = CH3, CF3; E = P, As; E′ = S, Se, Te)
Authors: Grobe Joseph , Van Duc le
Published: February 2015

Cr(CO)5L complexes (L = R2EER′2, R2EE′R; E, R′ = CH3 and/or CF3; E = P, As; E′ = S, Se, Te) have been prepared by reaction of Cr(CO)5THF with L at room tem­perature. Thew new compounds were characterized by analytical and spectroscopic (IR, NMR, MS) methods.
Solvatisierte HalogenochaLkogen(IV)säuren, I Darstellung und Struktur des Hexabromoselen(IV)säure-Hydrats (H5O2)2SeBr6 · 4H2O / Solvated Halogeno-Chalcogen(IV) Acids, I Preparation and Structure of the Hexabromoselenium(IV) Acid Hydrate (H5O2)2SeBr6 · 4H2O
Authors: Krebs Bernt , Hein Michael
Published: February 2015

Hexabromoselenium(IV) acid with the stoichiometric composition H2SeBr6 · 8 H2O is prepared from solutions of SeBr4 in concentrated aqueous HBr. If separated from the solution, the crystalline compound is stable only at low temperatures.

A single crystal X-ray structure analysis at -100 °C (monoclinic, C2/m, a = 1039.4(5), b = 1028.8(4), c = 836.6(3) pm, β = 104.11(4)°) shows the acid to contain, besides regular octahedral SeBr6
2- ions (Se-Br: 255.3(2)-257.9(2) pm), H5O2
+ hydronium ions (O···O: 255(2) pm). The remaining H2O molecules are involved in a hydrogen bond system with O···O: 264(2)-275(2) pm and O···Br: 342(1), 351(1) pm. The formula has to be written as (H5O2)2SeBr6 · 4 H2O.
Zum Problem der Farbträger des Ultramarin-Grün und des Ultramarin-Rot / On the Problem of the Colored Species in Ultramarine Green and Ultramarine Red
Authors: Seel Fritz , Güttler Hans-Joachim , Więckowski Andrzej B. , Wolf Bernhard
Published: February 2015

ESR and UV/VIS spectra indicate that the color of ultramarine green is due to two radical ions S2
- (yellow) and S3
- (blue) whereas ultramarine red contains the neutral sulfur molecule S4 (red) predominantly. On heating in chlorine gas, ultramarine violet was converted to a red powder which exhibited the ESR signal of SO3
- with g = 2.0036 and in its reflection spectrum the characteristic band of S3 near 24,400 cm-1.
NaCdAs und TlCdSb, ternäre Verbindungen mit modifizierter anti-PbCl2-Struktur / Ternary Compounds in a Modified anti-PbCl2-Structure
Authors: Krenkel Burkhard , Tiburtius Christoph , Schuster Haas-Uwe
Published: February 2015

The compounds NaCdAs and TlCdSb were prepared from the elements, they crystallize in a modified anti-PbCl2-type lattice, space group Pnma-D2h
16. The lattice constants are NaCdAs: a = 757.6(4) pm; b = 447.1(4) pm; c = 804.4(4) pm; TICdSb: a = 817.7(5) pm; b = 488.5(5) pm; c = 851.4(5) pm.
Beiträge zur Chemie des Phosphors, 91 [1]. Li3P7, ein Polyphosphid mit fluktuierenden Bindungen: Synthese aus P2H, und Überführung in P7H3 / Contributions to the Chemistry of Phosphorus, 91 [1] Li3P7, a Polyphosphide with Fluctuating Bonds: Synthesis from P2H4 and Conversion to P7H3
Authors: Bäudler Marianne , Ternberger Hans , Faber Wolfgang , Hahn Josef
Published: February 2015

Trilithiumheptaphosphide, Li3P7 · 3 solvents (monoglyme, THF) (1), was obtained as the final product in the reaction of diphosphane-4 with n-C4H9Li or LiPH2. 1 was charac­terized by elemental analysis, IR, Raman and NMR spectroscopy as well as by the formation of the derivatives (Me3Si)3P7 and P7MO3 (3). Studying the temperature depend­ence of the 31P NMR spectrum, all P atoms in the cage structure of 1 were found to become equivalent at + 80 °C. Thus trilithiumheptaphosphide is the first known poly­phosphide with fluctuating bonds. Silylation of 1 with Me3SiCl and subsequent solvolysis with MeOH leads to the corresponding hydride, P7H3 (2), which can be remetalated to the lithium salt 1. 2 was also characterized by its IR, Raman and mass spectra.
Kalium-und Tetrachloroantimon(V)-phosphate / Potassium and Tetrachloroantimony(V) Phosphates
Authors: Bräuninger Monika , Schwarz Wolfgang , Schmidt Armin
Published: February 2015

The potassium dimethoxi-, -dimethylaminomethoxi- and -bis(dimethylamino)phosphates (1), (2) and (3) were prepared by reaction of KOH and the corresponding phos­phoric esterchlorides. 2 reacts with antimony(V) chloride to yield the dimeric tetrachloro- antimony(V) dimethylaminomethoxiphosphate (4). The crystal and molecular structures of 4 and the dimeric tetrachloroantimony(V) dimethoxiphosphate (5) were determined by X-ray analysis. The vibrational and NMR spectra of 1-4 are reported and briefly discussed.
Ternäre Alkalimetallverbindungen vom Mg32(Zn,Al)49-Typ mit Elementen der 4. Hauptgruppe / Ternary Compounds of the Mg32(Zn, Al)49-Type Structure with Alkali Metals and IV B-Elements
Authors: Döring Wolfgang , Seelentag Werner , Buchholz Werner , Schuster Hans-Uwe
Published: February 2015

In the ternary systems Li-Cu-Si, Li-Ni-Si and Na-Au-Si (Ge, Sn) five phases could be prepared and characterized by single crystal investigations, which crystallize in a cubic body-centered lattice and are related to the Mg32(Zn, Al)49-type structure (T-phases).
1.3-Dioxolohetarene, 3 [1]. Darstellung und Reaktionen von Pyrido[2.3-d]- und Pyrido[3.4-d] [1.3]dioxolen / 1,3-Dioxolohetarenes, 3 [1]. Preparation and Reactions of Pyrido[2,3-d]-and Pyrido[3,4-d][1,3]dioxoles
Authors: Daliacker Franz , Fechter Peter , Mues Volker
Published: February 2015

The methylester of 3,4-dihydroxy-pyridine-6-carboxylic acid (1) reacts with bromochloromethane/potassjumcarbonate leading to the methylester of pyrido[3,4-d][1,3]-dioxole-6-onrhoxylic apid (2a). 2,3-Dihydroxy-pyridine (3a), 6-methyl- (3b), 5-chloro- (3c), and 5-bromo-2,3-dihydroxy-pyridine (3d) lead under the same conditions to the pyrido-[2,3-d][1,3]dioxole derivatives 4a, 4b, 4c, and 4d. The ester of 2,3-dihydroxy-pyridine-5-carboxylic acid (3e) and 4,6-dibromo-2,3-dihydroxy-pyridine (3f) also can be subjected to methylenation yielding the pyrido[2,3-d][1,3]dioxole compounds 4e and 4f.

Treatment of 6-bromo-pyrido[2,3-d][1,3]dioxole (4d) with n-butyllithium gives 6- lithium-pyrido[2,3-d][1,3]dioxole (5a) allowing reaction with carbondioxide, N,N-di- methylformamide, N,N-dimethylacetamide, and sulphur/iodine to obtain the carboxylic acid 5b, the aldehyde of, the ketone 5g, and the disulfide 5n.

The structures of compound 5b, 5f, and 5g were proofed by synthesis of derivatives.
Der Einfluß der Kettenlänge auf die massenspektrometrigche Fragmentierung höherer 1.ω-Diphenylalkane / The Influence of the Chain Length on the Mass Spectrometric Fragmentation of Higher 1, ω-Diphenylalkanes
Authors: Kuck Dietmar , Grützmacher Hans-Friedrich
Published: February 2015

The mass spectrometric fragmentation of 1,ω-diphenylalkanes (2 ≤ ω ≤ 22) has been studied in order to elucidate the effect of the chain length on the reactions of unstable and metastable molecular ions with respect to the occurrence of internally solvated ions in the gas phase. The unstable molecular ions of all 1,ω-diphenylalkanes react predominantly by formation of C7H7
+ and C7H8
+ ions, the latter ones are also formed by metastable molecular ions. Neither the variation of the relative abundances of these fragment ions with the chain length nor the fragmentation of specifically deuterated molecular ions indicate any internal solvation in the reacting ions. Inspite of the localized activated C-H bonds at the benzylic positions, these “activated” H atoms are not involved in intra­molecular hydrogen exchange reactions or the formation of C7H8
+ ions (with the exception of ω = 3). Especially the higher homologues (co ≿ 12) react very similarly to the molecular ions of 1-phenylalkanes, while the fragmentation of the lower homologues (co ≲ 6) is determined by specific (“vinculoselective”) competitive reactions, e.g. loss of C7H7 and C8H8.
Oxotitanate mit gemischter Valenz, II Zur Kenntnis von Sr2Ti6O13 / Oxotitanates with Mixed Valence, II About Sr2Ti6O13
Authors: Schmachtel J. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Sr2Ti6O13 were prepared by heating a mixture of SrO·Ti2O3·2TiO2 in a vacuum furnace to 1800 °C for 6 hours. X-ray investigations show monoclinic symmetry (a = 1525,0, b = 376,9, c = 916,4 pm; β = 99,15°, space group C3
2h-C2/m). Sr2Ti6O13 is isotypic with Ba2Ti6O13.
Darstellung und Kristallstruktur von Barium-Quecksilber-Thiostannat(IV), BaHgSnS4 / Preparation and Crystal Structure of Barium-Mercury-Thiostannate(IV), BaHgSnS4
Authors: Teske Chr. L.
Published: February 2015

BaHgSnS4 was prepared for the first time and the crystal structure determined by using single crystal X-ray methods, a = 1080,4, b = 1084,o, c = 661,3 pm. Space group: C10
2V-Pnn2 (No. 34) orthorhombic. There are pairs of edge-sharing tetrahedra linked together to form two-dimensional net works. The crystal structure is similar to that of BaCdSnS4 [1].
Di-μ-iodo-bis [dicarbonyl(di-tert-butylphosphin)ruthenium(I)] (Ru-Ru) und Bis(tri-tert-butylphosphonium)-di-μ-iodo-bis[carbonyl-diiodo- (di-tert-butylphosphin)ruthenium(II)] / Di-μ-iodo-bis[dicarbonyl(di-tert–butylphosphine)ruthenium(I)](Ru-Ru) and Bis(tri-tert–butylphosphonium)di-μ-iodo-bis[carbonyl-diiodo- (di–tert-butylphosphine)ruthenium(II)]
Authors: Schumann Herbert , Opitz Joachim
Published: February 2015

[(t-C4H9)3PH]2[{Ru(μI)I2(CO)[P(t-C4H9)2H]}2] is prepared by the reaction of RUC13 · (H2O)x with CO, NaI, and P(t-C4H9)3 in 2-methoxyethanol. Its IR, Raman, and NMR spectra are reported and discussed. [Ru(μ-I)(CO)2P(t-C4H9)2H)2 is obtained by the reaction of [Ru(μ-I)I(CO)3]2 with P(t-C4H9)3 in 2-methoxyethanol. The X18MAA′M′X′18 spin system of its 1H NMR spectrum is analysed.