bluuebunny/crossref_metadata_2025 huggingface dataset:
Optisch aktive Übergangsmetall-Komplexe, LVII [1] (+)- und (-)-C5H5M(CO)(P∅2R*)X mit M = Fe, 57Fe und X = I, COCH3, CH3 / Optically Active Transition Metal Complexes, L VII [1] (+)- and (-)-C5H5M(CO)(P∅2R*)X with M = Fe, 57Fe, and X = I, COCH3, CH3
Authors: Brunner Henri , Muschiol Manfred , Nowak Wilfried
Published: February 2015

In the reaction of C5H5Fe(CO)2l and C5H5Fe(CO)2CH3, respectively, with S-(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5) (abbreviated P∅2R*) the complexes C5H5Fe(CO)(P∅2R*)I (1), C5H5Fe(CO)(P∅2R*)COCH3 (2), and C5H5Fe(CO)(P∅2R*)CH3 (3) are formed as pairs of diastereoisomers the components of which differ only in the configu­ration at the iron atom. CsH5Fe(CO)(P∅2R*)CH3 (3) can be obtained in higher yield by photochemical decarbonylation of C5H5Fe(CO)(P∅2R*)COCH3 (2). The (+)365- and (-)365-diastereoisomers of each pair exhibit different chemical shifts in the 1H NMR spectra. Diastereoisomer separation can be achieved by fractional crystallization.

Starting with 57Fe metal (-)365-C5H5
57Fe(CO)(P∅2R*)I was prepared via 57Fel2, 57Fe(CO)4l2, C5H557Fe(CO)2l, and C5H557Fe(CO)(P∅2R*)I in order to demonstrate optical activity of a 57Fe compound in the y region by Mössbauer polarimetry in later experiments to be reported elsewhere.
Organische Schwefelverbindungen, XXIX [1] Thiocarbonyl-Derivate von 2-Thioxo-Malonsäureestern / Organic Sulfur Compounds, XXIX [1] Thiocarbonyl Derivatives of 2-Thioxomalonic Acid Esters
Authors: Beelitz Klaus , Höhne Gerhard , Praefcke Klaus
Published: February 2015

The first derivatives of the hitherto unknown 2-thioxo malonic acid ester could be achieved. In dependence of conditions and presence of an enophile (3) substituted dihydro thiopyrans (5) as 4 + 2 addition products of hypothetic 2-thioxo malonic acid esters with 3 or α-oxo-methylene bisxanthates 7 resp. are formed in reactions of dibromo malonic acid esters 1 with potassium O-ethylxanthate (2).
Zur ionischen Leitfähigkeit gemischter Lithiumiodid-Verbindungen / The Ionic Conductivity of Mixed Lithium Iodide Samples
Authors: Eichinger Günter
Published: February 2015

The ionic conductivity of some polycrystalline samples of the general formula Lil · yXI(y = 1/4 or 1/10) X = Rb+, NH4+, N(CH3)4
+, NEt4
+) is measured. These mixtures generally exhibit higher activation energies for ionic movement than pure lithium iodide. At temperatures above 50 °C, the overall conductivity is higher them that of pure lithium iodide.
Über Tetraphenylphosphonium-Isopolymolybdate / Tetraphenylphosphonium-Isopolymolybdates
Authors: Grase Roger , Fuchs Joachim
Published: February 2015

From acidified sodium molybdate solutions mixtures of two polymolybdates are precipitated by addition of tetraphenylphosphonium ions. The pure compounds obtainable by separation with selective organic solvents were identified analytically and by their vibrational spectra as octamolybdate, [P(C6H5)4]4Mo8O26, with "Lindqvist structure" and as hexamolybdate, [P(C6H5)4MO6019. They are characterized by their UV-VIS spectra and X-ray powder patterns. The precipitation of the hexamolybdate from strong acidic solution can be used analytically for the determination of molybdenum.
Schichtverbindungen der Polyanionenbildenden Nebengruppenelemente mit Kationenaustauschvermögen / Layer Compounds of Polyanion-Forming Transition Elements with Cation Exchange Capacity
Authors: Beneke Klaus , Lagaly Gerhard
Published: February 2015

Most of the polyacid salts AxMyOz of the transition elements M = Ti, V, Nb, Mo, W, U with layer structure can exchange the alkali or earth alkali ions A for other suitable cations. Especially suited are large organic ions such as alkylammonium ions whose large layer separation makes the interlayer cations accessible for the exchange reaction.
Die Kristallstruktur von Tetramethylstiboniumtetrachlorogallat [(CH3)4Sb]+[GaCl4]- / The Crystal Structure of Tetramethylstibonium Tetrachlorogallate [(CH3)4Sb]+[GaCl4]-
Authors: Hausen Hans-Dieter , Binder Herbert , Schwarz Wolfgang
Published: February 2015

Tetramethylstiboniumtetrachlorogallate crystallizes in the hexagonal space group P63mc with two formula units per cell. The lattice constants are a=b = 768.8 pm and c= 1251.2 pm. The structure shows isolated cationic and anionic tetrahedra, which are only slightly distorted. The averaged bond lengths are: Sb-C 212.6 pm and Ga-Cl 217.2 pm.

In good agreement with the short Ga-Cl distance (the shortest of all compounds ((CH3)nGaCl4-n)-; n = 1-3) are the measured ionization energies of Ga-3d-electrons and the calculated Pauling Qp-values.
Über Derivate des Hydrazins, VIII [1] Bis(trimethylsilyl)amino-isocyanat und -isothiocyanat / On Derivatives of Hydrazine, VIII [1] Bis(trimethylsilyl)amino-isocyanate and -isothiocyanate
Authors: Wiberg Nils , Hübler Gerhard
Published: February 2015

Bis(trimethylsilyl)aminoisocyanate (1) is formed by reaction of the hydrazides LiN2(SiMe3)3 or Li2N2(SiMe3)2 with phosgene. Bis(trimethylsilyl)aminoisothiocyanate (2) is obtained by thermolysis of the hydrazide (Me3Si)3N2CSSLi, which is readily prepared from LiN2(SiMe3)3 and carbon disulfide. (It is generally found that LiN2(SiMe3)3 and Li2N2(SiMe3)2 add to heterocumulenes X = C = Y (X = TosN, O, S; Y = O, S), and that reaction of the addition products with Me3SiCl yields (Me3Si)3N2CXYSiMe3. While 1 is obtained solely as a thermostable dimer, 2 is a thermolabile monomer). Thermolysis of 2 at ambient temperature yields (Me3Si)4NiC2S and (Me3Si)4NiC2S3. Thermolysis of 2 in ether solution at elevated temperatures mainly yields bis(trimethylsilyl)carbodiimide and sulfur
Darstellung und Kristallstruktur von K3Cu3P2 / On the Preparation and Crystal Structure of K3CU3P
Authors: Savelsberg Gerhard , Schäfer Herbert
Published: February 2015

K3CU3P2 was obtained by melting potassium, copper and red phosphorus in an sealed copper vessel. The compound crystallizes trigonally with a = 572 ± 2 pm, c = 1993 ± 3 pm, R3m, Z = 3. The structure analysis revealed nets of puckered 12-membered rings in which the Cu-atoms are linearly coordinated while the P-atoms are located on the apices of trigonal pyramids
Li5NaSn4 - eine Phase mit gewellten Sn-Sechsecknetzen / Li5NaSn4 - a Phase with Puckered Nets of Six-Membered Sn-Rings
Authors: Volk Klaus , Müller Wiking
Published: February 2015

The new compound LisNaSiu has been prepared and its crystal structure determined. It crystallizes trigonal, a = 471.0 ± 0.6 pm, c = 3172 ± 5 pm, space group R3m-C5
3V. Half of the Sn atoms build up a puckered net of connected six-membered rings, the other half is bound to the net atoms, forming a tetrahedral Sn-Sn coordination for these. The structural relations of this Sn sublattice to the diamond lattice are discussed
Mechanism of Hg(II) Oxidation of D-Galactose in Alkaline Medium
Authors: Singh M. P. , Singh A. K. , Kumar Mandhir
Published: February 2015

The present paper deals with the kinetics of oxidation of D-galactose by Nessler's reagent in alkaline medium. The reaction is zero order with respect to Hg(II) and first order with respect to reducing sugar. The direct proportionality of the reaction rate at low hydroxide ion concentrations shows retarding trend at higher concentrations. The reaction rate is inversely proportional to iodide ion concentration. A mechanism has been proposed taking HgI3- as the reacting species
Kurzzeitpyrolyse, VIII [1] Reaktionen bei der CO-Eliminierung aus ehinoiden Verbindungen / Short Time Pyrolysis, VIII [1] Reactions after CO-Elimination from Quinoid Compounds
Authors: Schaden Gerhard
Published: February 2015

Fuchsone (4-diphenylmethylene-2,5-cyclohexadien-l-one) (1) eliminates CO upon gasphase pyrolysis. The resulting biradical (2) either formes by double ring closure and dehydrogenation benzo[c]phenanthrene (6) or recombines to 6,6-diphenylfulvene (3) which gives after dehydrogenative ring closure and rearrangement 1-phenylacenaphthylene (11)
Reaction of Br3
·2- with 2-Deoxy-D-ribose. A Preferred Attack at C-1
Authors: Parsons Barry J. , Schulte-Frohlinde Dietrich , Sonntag Clemens von
Published: February 2015

In the photolysis of 5-bromouracil containing DNA Br atoms are expected inter mediates. In order to evaluate the possible site of attack of the Br atom at the sugar moiety of DNA the reaction of 2-deoxy-D-ribose with the Br atom (complexed with two bromide ions) was investigated. Hydroxyl radicals generated by the radiolysis of N2O saturated aqueous solutions were converted into Br3
·2- radicals by 1 M bromide ions. Br3
·2- reacts with 2-deoxy-D-ribose (k = 3.7 · 104M-1s-1, pulse radiolysis). The major product is 2-deoxy-D-erythro-pentonic acid (G = 2.4, γ-radiolysis). It is formed by hydrogen abstraction from C-l and oxidation of this radical by other radicals. An alternative route via the radical at C-2 is neglible. It follows that Br3
·2- reacts preferentially at C-1 of 2-deoxy-D-ribose
Zur Besetzung von Oktaederund Tetraederpositionen in Bi2Ca2Fe2O9 / About Occupation of Octahedral- and Tetrahedral Positions of Bi2Ga2Fe2O9
Authors: Müller-Buschbaum Hk. , Chales de Beaulieu D.
Published: February 2015

Single crystals of Bi2Ga4O9 and Bi2Ga2Fe2O9 were prepared by CO2-Laser technique and analysed by X-ray single crystal methods. Bi2Ga4O9 is one of the rare examples containing Ga3+ in octahedral as well as tetrahedral surrounding of oxygen. In Bi2Ga2Fe2O9 the coordination of oxygen atoms around Ga3+ is exclusively tetrahedral. Thus this compound represents positive evidence of the preferential occupation of tetrahedral holes by gallium
Die Kristallstruktur von Na3AsS4 • 8 H2O / The Crystal Structure of Na3AsS4 • 8 H2O
Authors: Dittmar Günter , Schäfer Herbert
Published: February 2015

Na3AsS4 • 8 H2O crystallizes in the space group P21/c with the cell parameters a = 865,1(3), b = 1299,5(4), c = 1359,6(5) pm, β = 102,77(7)°. The cell contains 4 formula units. The structure found consists of tetrahedral AsS4-groups and Na-Ions, octahedrally coordinated by water molecules and/or sulfur atoms
The X-ray Structure of N4P4Cl7(NPPh3) - a Novel Conformation of the NPPh3 Group
Authors: Sudhakara Babu Y. , Manohar H. , Stanley Cameron T. , Shaw Robert A.
Published: February 2015

The X-ray crystal structure of heptachloro- (triphenylphosphazenyl)cyclotetraphosphazatetraene N4P4Cl7(NPPh3) reveals a novel conformation (tending to Type III) of the triphenylphosphazenyl group with respect to the adjacent ring segment. This observation is contrasted with the structure of N3P3Cl5(NPPh3) where a Type I conformation is observed
A NMR Study of the Exchange Kinetics of the Nonamethylimidodiphosphoramide with its Complexes of Diamagnetic Cations
Authors: Rubini P. R. , Rodehüser L. , Delpuech J.-J.
Published: February 2015

The ligand exchange on nonamethylimidodiphosphoramide (NIPA) complexes is found to be very slow comparatively to analogous monodentate ligands; the rates determined by 1H or 31P NMR spectroscopy are: k(25°C)=4.3 × 10-2 s-1; 31.6 s-1 • M-1; 3.7 × 104 S-1 • M-1 and 1.35 × 104 s-1 · M-1 for Mg2+, Ca2+, Sr2+ and Li+ cations respectively. For the Al3+, Ga3+, In3+ and Be2+ ions no exchange could be detected by 1H NMR spectroscopy up to 120 °C, indicating rates lower than about 10-3 s-1
Beiträge zur Chemie des Phosphors, 84 [1]. 1.2.3-Trimethyl-1.2.3-triphosphol, (PMe)3C2H2, und 2.3.4.6.7.8-Hexamethyl- 2.3.4.6.7.8-hexaphosphabicyclo [3.3.0] octan, (PMe)6C2H2 / Contributions to the Chemistry of Phosphorus, 84 [1]. 1,2,3-Trimethyl-1,2,3-triphosphole, (PMe)3C2H2, and 2,3,4,6,7,8-Hexamethyl- 2,3,4,6,7,8-hexaphosphabicyclo[3,3,0]octane, (PMe)6C2H2
Authors: Baudler Marianne , Tolls Elmar
Published: February 2015

The reaction of K2(PMe)4 · 2 THF with cis-1,2-dichloroethylene yields the hitherto unknown cyclocarbaphosphanes 1,2,3-trimethyl-1,2,3-triphosphole, (PMe)3C2H2 (1), and 2,3,4,6,7,8-hexamethyl-2,3,4,6,7,8-hexaphosphabicyclo[3,3,0]octane, (PMe)6C2H2 (2). Be­sides, (PMe)5, (PMe)4CH2, (PMe)3C2H4, and the new six-membered heterocycle (PMe)2(C2H2)2 are formed. The cyclocarbaphosphanes 1 and 2 were characterized by elemental analysis, mass, IR, Raman, and MR spectra. For the bicyclic compound 2 two diastereomers were obtained and separated. They differ in the position of the methine hydrogens and of the methyl substituents (cis-2 and trans-2). Compound 2 is also produced in the reaction of K2(PMe)4 * 2 THF with trans- 1,2-dichloroethylene whereas with 1,1,2,2- tetrachloroethane mainly (PMe)s is formed. In 1 and in each of the five-membered rings of cis-2 and trans-2 the methyl substituents at adjacent phosphorus atoms are situated on opposite sides of the ring.
Langlebige Radikalkationen und anodische Substitution einfacher Aromaten / Long-lived Radical Cations and Anodic Substitution of Simple Arenes
Authors: Fritz Heinz P. , Gebauer Helmut
Published: February 2015

In media of low nucleophilicity solutions of coloured radical cations of simple arenes can be obtained by anodic oxidation. A straightforward mechanism for the nucleophilic substitution of these species is suggested by the experimental results.
Cation-Ordering in Synthetic Mg2-xFexSiO4-Olivines
Authors: Riekel Ch. , Weiss Armin
Published: February 2015

In annealed, synthetic samples of Mg2-xFexSiO4 the Mg2+ and Fe2+ ions are not randomly distributed. With 0.1 ≦ x ≦ 0.6 the larger Fe2+ ions replace preferentially Mg2+ in octahedral sites of symmetry m and the lattice dimensions do not change in this range. Quenching tends to yield samples with more randomly distributed cations and the lattice dimensions approach those of natural olivines.
The Stereochemistry of P-N Bond Cleavage in the Staudinger -Wittig-type Reaction of 2-Anilido-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine-2-thiones
Authors: Lesiak Krystyna , Stec Wojciech J.
Published: February 2015

Both isomers of 2-anilido-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine-2-thiones (2 a and 2 b) derived from (-)ephedrine were obtained and converted to corresponding 2-thiomethyl derivatives (3 a and 3 b). The Staudinger-Wittig-type reaction of P-N bond cleavage was found to proceed with full retention of configuration at P-atom involved into five-membered ring system.
Untersuchung yon Dipeptiden durch Elektronenstoß-und Felddesorptions-Massenspektrometrie / Investigation of Dipeptides by Electron Impact and Field Desorption Mass Spectrometry
Authors: Lüderwald I. , Przybylski M. , Ringsdorf H. , Silberhorn D.
Published: February 2015

The combined application of field desorption and electron impact ionization techniques in the mass spectrometry of free dipeptides can be used to obtaine informations about primary structure and molecular weight. Characteristic fragmentation pathways of dipeptides are discribed and the mechanism of diketopiperazine formation is discussed.
Deblocking of 2-Bromoethyl Esters via Thiazolium Salts
Authors: Ho Tse-Lok
Published: February 2015

Carboxylic acids are recovered from 2-bromo-ethyl esters by successive treatment with 4-methyl-5-thiazoleethanol, sodium bicarbonate followed by pyrolysis and quenching with dilute acid.
Darstellung und Struktur des Bicyclo-[4.4.0]-1.4.6.9-tetraazadecans C6H14N4 Preparation and Structure of Bicyclo-[4,4,0]-l,4,6,9-tetraazadecane C6H14N4
Authors: May Wolfgang , von Schnering Hans Georg
Published: February 2015

By the weak acid interaction of polymeric phosphanes the condensation of ethylendi-amine yields in a small amount bicyclo-[4,4,0]-1,4,6,9-tetraazadecane C6H14N4. The compound crystallizes triclinic in the space group P1̅ with a = 841.6 pm, b - 463.6 pm, c = 529.2 pm, a= 109.05°, β= 108.35°, γ = 84.13° and Z= 1 formula unit per unit cell. The two condensed six-membered rings have chair conformations. The mean N-C bond lengths are 146.0 pm, the bridging C-C bond is 150.3 pm, whereas the other C-C bonds are 155.1 pm. Structure and condensation reaction are discussed.
Umsetzungen von Metall-und Metalloidverbindungen mit mehrfunktionellen Molekülen, XVIII [1] Synthese von Amidinoborazinen / Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules, XVIII [1] Synthesis of Amidinoborazines
Authors: Meiler Anton , Maringgele Walter , Kablau Klaus-Dieter
Published: February 2015

The reaction of trimethylsilylamidines with 2-chloro-1,3,4,5,6-pentamethylborazine leads to the corresponding amidinoborazines and chlorotrimethylsilane. 1H, 11B, 11F NMR spectra, mass spectra and characteristic IR group frequencies are reported.
Beiträge zur Chemie der Pyrrolpigmente, XXIII [1] Die Struktur eines Bilatrien-abc-Derivates im gelösten Zustande / On the Chemistry of Pyrrole Pigments, XXIII [1] The Structure of a Bilatriene-abc Derivative in the State of Solution
Authors: Falk Heinz , Grubmayr Karl , Thirring Klaus
Published: February 2015

The (Z,Z,Z)-configuration of the mono-lactim-ether of an alkyl substituted bilatriene-abc, Etiobiliverdin-IV-γ, was established for chloroform solutions. Moreover the conformation of this molecule is a helical one (syn-syn-syn) with a twist along the single bonds at the methine groups of approximately 20°. The two tautomeric lactam-forms with a proton on one or the other nitrogen atom of the pyrromethene subsystem are indistin-guishable by the methods used in this investigation: 1H NMR pattern, Lanthanide induced shift technique and Nuclear Overhauser Effect measurements.
Photolysis (λ 185 nm) of Liquid Tetrahydropyran
Authors: Schuchmann Heinz-Peter , Naderwitz Peter , Sonntag Clemens von , Schuchmann Heinz-Peter , Naderwitz Peter , Sonntag Clemens von
Published: February 2015

The main products of the 185 nm photolysis of neat liquid tetrahydropyran are pent-4-en-l-ol (7) (∅ = 0.40), 2-(5′-hydroxypentyl)tetrahydropyran (10) (0.21), valeraldehyde (6) (0.13), and pentan-1-ol (8) (0.08). These products are thought to be formed via the biradical ·O(CH2)4ĊH2 and/or through intramolecular (6, 7, 8) and intermolecular (10) photoreactions. In the case of 10, the probability of a specific intermolecular photoreaction involving two tetrahydropyran molecules is suggested by the fact that in the photolysis of solutions of tetrahydropyran in cyclohexane and formaldehyde dimethyl acetal products analogous to 10 made up of a tetrahydropyran and a solvent molecule moiety, are not formed.
Darstellung und Charakterisierung von Tetraalkylammonium-lithiumphthaloeyaninen / Preparation and Characterisation of Tetraalkylammonium-lithium-phthalocyanines
Authors: Homborg H. , Kalz W.
Published: February 2015

The preparation of some tetraalkylammonium-lithium-phthalocyanines is described. In contrast to the known dilithium-phthalocyanine these quarternary “onium”-salts are, dependent on the size of the alkyl groups, soluble in non-polar, aprotic solvents. The electronic spectra are investigated as a film on a quartz disk at 10 K. Under these conditions a large number of narrow bands is observed instead of the normally diffuse ones.

Solid state resonance Raman spectra were studied at 85 K by a method involving spinning KBr disks. It is shown that nearly all the lines are as a rule very sensitive to excitation conditions. The vibrational spectra are compared with the structural features of the compounds.
ABX-Verbindungen mit Ni2In-Struktur Darstellung und Struktur der Verbindungen CaCuP(As), SrCuP(As), SrAgP(As) und EuCuAs / ABX Compounds with the Structure Ni2In Preparation and Crystal Structure of CaCuP(As), SrCuP(As), SrAgP(As), and EuCuAs
Authors: Mewis Albrecht
Published: February 2015

The compounds CaCuP(As), SrCuP(As), SrAgP(As) and EuCuAs were prepared and investigated by X-ray methods. They are isotypic and crystallize in a modified Ni2In structure (space group P 63/mmc-D6h
1) with the lattice constants:

CaCuP a = 405.5(1) pm, c = 780.3(3) pm,

CaCuAs a = 418.4(1) pm, c = 786.8(2) pm,

SrCuP a = 414.6(1) pm, c = 837.6(3) pm,

SrCuAs a = 427.3(2) pm, c = 845.2(3) pm,

EuCuAs a = 425.4(2) pm, c = 827.4(3) pm,

SrAgP a = 440.9(1) pm, c = 823.0(3) pm,

SrAgAs a = 452.9(1) pm, c = 829.1(2) pm.
15N—NMR-Spektroskopie bei Stickstoffwasserstoffsäure und Chlorazid / 15N NMR Spectroscopy at Hydrazoic Acid and Chlorine Azide
Authors: Müller Joachim
Published: February 2015

The 15N NMR spectra of HN3 and CIN3 solutions were recorded under triply labelled conditions. The chemical shifts and coupling constants are discussed with respect to the structure and in relation to other isoelectronic compounds.
Über die Chemie der Oberfläche des Titandioxids, V Die Oberflächenacidität von Titandioxid und von mit Phosphationen belegtem Titandioxid /On the Chemistry of the Surface of Titaniumoxide, V Surface Acidity of Titanium Dioxide and of Titanium Dioxide Covered with Adsorbed Phosphate Ions
Authors: Cornejo J. , Steinle J. , Boehm H. P.
Published: February 2015

The acidity of surface OH groups on TiO2 (anatase and rutile) was determined using the Benesi titration technique. The most acidic groups have acidity constants (Ho) between 3 and 5. On treatment with solutions of phosphoric acid or phosphates, H2PO4 -ions are adsorbed by ion exchange for basic OH -ions of the surface. The chemisorbed H2PO4 -ions react strongly acidic with an acidity constant Ho between -5.6 and -3.3. Possible reasons for this extreme increase in acidity are briefly discussed.
(CO)5CrFe2(CO)6PPh, ein tetraedrischer Cluster mit achtfach koordiniertem Chrom(O)/ (CO)5CrFe2(CO)6PPh, a Tetrahedral Cluster Containing an Eightfold Coordinated Chromium(O)
Authors: Huttner G. , Mohr G. , Friedrich P.
Published: February 2015

The title compound may be prepared by irradiation of (CO)5CrFe2(CO)8PPh, which itself is accessible from Fe2(CO)9 and (CO)5CrPPhCl2. It forms a tetrahedral cluster in which a pentacarbonylchromium fragment acts as the apex of a tetrahedron the base of which ist formed by an Fe2P-triangle. X-ray analysis reveals that the chromium atom interacts strongly with all three atoms of the tetrahedral base, thus substantiating a coordination number of eight for Cr(O).
Eine Bleidioxid-Bezugselektrode /A Lead Dioxide Reference Electrode
Authors: Wabner Dietrich , Hindelang Fritz , Huss Rainer
Published: February 2015

For research work in nitric acid and during the deposition of lead dioxide from nitric baths a reference electrode has proven its value, which consists of a lead dioxide layer on a titanium carrier. Its potential against n.h.e. lies at 1.455 + 0.002 V in 1 N Pb(NO3)2 + 0.1 N HNO3 at 295 K. This space-saving electrode can be used in the same electrolyte. It is stable against temperature variations and electronic control currents.
Metallorganische Polychalkogenid-Chelate, X [1]. Disulfidobis(η5 -cyclopentadienyl)molybdän(IV), ein pseudotetraedrisches Disulfid-Chelat / Organometallic Polychalcogenide Chelates, X [1]. Disulfidobis(η5 -cyclopentadienyl)molybdenum(IV), a Pseudotetrahedral Disulfide Chelate
Authors: Köpf Hartmut , Hazari Saroj K. S. , Leitner Manfred
Published: February 2015

On reaction of (C5H5)MoCl2 (1) with equivalent amounts of Na2S2 in ethanol, (C5H5)2MoS2 (2) is formed together with (C5H5)2MoS4 (3) and separated from 3 by vacuum sublimation. The more stable tetrasulfide 3 is obtained as the main product from 1 or 2 with excess Na2S2 and also from 2 or (C5H5)2Mo(SH)2 (4) with S8 in chloroform. A threemembered ring chelate structure involving side-on bonded S2
2- ligands and pseudotetrahedrally coordinated Mo+4 central atoms is postulated for 2.
Übergangsmetall-substituierte Phosphine, Arsine und Stibine, XVIII [1]. Nachweis einer konformativen Isomeric an Dicarbonyl(cyclopentadienyl)eisen-substituierten Arsinen / Transition Metal Substituted Phosphines, Arsines and Stibines, XVIII [1]. Evidence for a Conformational Isomerism of Dicarbonyl(cyclopentadienyl)iron Substituted Arsines
Authors: Malisch Wolfgang , Panster Peter
Published: February 2015

Cp(CO)2Fe-4,4,5,5-tetramethyl-1,3,2-dioxarsolane (1) is prepared from 2-chloro-dioxarsolane and Na[Fe(CO)2Cp]. 1 reacts with THF · Cr(CO)5 to yield the hetero dinuclear compound

(2) and is easily converted into Cp(CO)2Fe-AsCl2 (3) by reaction with CH3C(O)Cl. 1 and 3 exhibit four υCO absorption bands instead of the two predicted. υCO doubling is attributed to the first examples of conformational isomerism about the arsenic-iron bond. Assignment of the CO stretching frequencies to the separate conformers is achieved by use of the 13CO satellite bands.
Untersuchungen an Stickstoff-Iod-Verbindungen, XVII [1]. Weitere tertiäre N-Basen als Stabilisatoren des Iodonium-Kations und der Iodhalogenide / Studies on Nitrogen-Iodine Compounds, XVII [1]. Further Tertiary N-Bases as Stabilizers of the Iodonium Cation and Iodine Halides
Authors: Jander Jochen , Maurer Alexander
Published: February 2015

The preparation and properties of the new compounds [I(2,4 lutidine)2]NO3, -ClO4, [I(2,6 lutidine)2]NO3, -ClO4, [I(2,4,6 collidine)2]NO3, -ClO4, [I(TEDA)2]NO3, [I(quinu-clidine)2]SbCl6, quinuclidine · IBr, quinuclidine · ICl, quinuclidine · IClSbCl5, TEDA · I2, I2 · TEDA · I2, and ClI · TEDA · ICl are reported. The molecular vibrations and force constants are compared to those of similar compounds previously prepared.
Heavy Atom Kinetic Isotope Effects in HCN Elimination from Some Tricyanides in Methanol [1]
Authors: Fouad Fouad M. , Farrell Patrick G.
Published: February 2015

Rates of HCN elimination from polycyanides N,N-dimethyl-4-(1,2,2-tricyanoethyl)-aniline (1), 9-cyano-9-dicyanomethyl fluorene (2), 1,1-diphenyl-1,2,2-tricyanoethane (3), and 2-phenyl-1,1,2-tricyanopropane (4) have been studied in methanol. Elimination from 1 occurs via (E 1 c B)R, mechanism. On the other hand olefin formation from 2-4 has been shown to occur via (E 1)anion pathway. Heavy atom kinetic isotope effects indicated that product stability is not the sole factor controlling the transition state geometries. Values of k12/k14 were found to be in the order 2 > 3 > 4 > 1 which implied transition states with more carbanion-like structure in the opposite direction. Solvent isotope effects and enthalpies of activation were also determined and discussed in terms of transition states geometries.
CaAgP und CaAgAs -Zwei Verbindungen mit Fe2P-Struktur/CaAgP and CaAgAs -Two Compounds with the Fe2P-Structure
Authors: Mewis Albrecht
Published: February 2015

The compounds CaAgP and CaAgAs have been prepared and their structures have been determined. They are isotypic and crystallize in a modified Fe2P-structure (space group P6̄2m-D3
3h) with the lattice constants:

CaAgP a = 704,5(1) pm, c = 417,4(1) pm,

CaAgAs a = 720,4(1) pm, c = 427,0(1) pm.
Derivatives of cis-NPCl2(NSOCl)2 and (NPCl2)2NSOCl, Part XI /Preparation of Amino-phenyl Derivatives of NPCl2(NSOCl)2
Authors: Berg J. B. van den , Grampel J. C. van de
Published: February 2015

Reaction of NPClNH-n-Bu(NSOCl)2 with benzene in the presence of AlCl3 (molar ratio ring compound: AlCl3=1:2) yields NPClNH-n-Bu(NSOPh)2 in three isomeric forms. Using an excess of AlCl3, two isomers with formula NPNH2Ph(NSOPh)2 are formed. These NH2 derivatives can also be isolated from the reaction mixture of NPClPyr(NSOPh)2 (Pyr = pyrrolidino), benzene and an excess of AlCl3.
Photoinduzierte Dechlorierungsreaktion an Dichlorbenzolen, Anilinen und Phenolen in Gegenwart von Protonendonatoren/ Photoinduced Dechlorination Reaction of Dichlorobenzenes, Chloroanilins and Chlorophenols in the Presence of Protondonors
Authors: Parlar H. , Steven P. G. W. , Baumann R. , Korte F.
Published: February 2015

Photokinetic experiments show that the dechlorination reaction of dichlorobenzenes, chloroanilins, and chlorophenols is dependent on nature of solvent, but undependent on oxygen. Quantum yields determined in n-hexane indicate that there is a strong deviation within the ortho, meta, and para products.
Strukturwandel eines Benzocyclobutadiens bei seiner Komplettierung/Structural Change of a Benzocyclobutadiene by Complexation
Authors: Straub Henner , Döring Gerd , Winter Werner
Published: February 2015

η4 (1,2-Di-tert-butyl-3,4,5,6-tetramethylbenzo-cyclobutadiene)tricarbonyliron (2) is prepared by reaction of the respective free benzocyclo-butadiene (1) and nonacarbonyl-diiron at room temperature. X-ray data of the free and complexed ligand are compared.
Regioselektive Ringspaltung von Bacteriochlorophyll-Derivaten durch Photooxidation/Regioselective Ring Cleavage of Bacteriochlorophyll Derivatives by Photooxidation
Authors: Brockmann Hans , Belter Clemens
Published: February 2015

In the presence of oxygen and light magnesium free derivatives of bacteriochlorophyll c form linear tetrapyrroles by oxidative ring cleavage. The structure of these photobilines has been determined by spectroscopic methods.
5aH.10aH.15aH-Tribenzo [b.f.j] [1.4.7] trioxa [9 b] azaphenalene - vermeintliche Benzoxete / 5aH, 10aH, 15aH-Tribenzo[b,f,j][l,4,7]trioxa[9 b]azaphenalenes - Supposed Benzoxetes
Authors: Meier Herbert , Issa Ahmed , Merkle Ursula
Published: February 2015

A supposed benzoxete is determined as a complex polycyclic system: cis,cis,cis-5 aH,10 aH,15 aH-tribenzo[b,f,j][1,4,7]trioxa[9 b]azaplienalene. The structure elucidation is performed by spectroscopycal methods (IR, 1H NMR, 13 C NMR and mass spectroscopy) and by degradation reactions in an acidic or an alkaline medium.
Synthese Pyridin-analoger Tetrahydrocannabinol / Synthesis of Pyridine-analogous Tetrahydrocannabinols
Authors: Lötz Friedhelm , Kraatz Udo , Körte Friedhelm
Published: February 2015

Starting from 4-methylpyridine a 3-aza-Δ8 -tetrahydrocannabinol-analogous (2d) was prepared. The reaction sequence also includes the first synthesis of a 6 H-benzo(4,5)-pyrano(2,3-c)-pyridin-6-on, a novel ring-system. The proposed structures were supported by spectroscopic data (1 H NMR, IR, MS).
Kristallstruktur von SrGe2 bei hohen Drücken / Crystal Structure of SrGe2 at High Pressures
Authors: Evers Jürgen , Oehlinger Gilbert , Weiss Armin
Published: February 2015

After a high pressure -high temperature treatment of orthorhombic SrGe2 (BaSi2 type of structure) a trigonal polymorph (EuGe2 type of structure) is obtained: space group P3̄m 1; a - 410.4 pm, c - 516.5 pm; Z - 1; zGe = 0.406.
Zur Synthese von 2.5-und 2.6-verbrückten Tetrahydromethanoindanen / Synthesis of 2,5-and 2,6-Crosslinked Tetrahydromethanoindanes
Authors: Hustert K. , Schmitzer J. , Parlar H. , Körte F.
Published: February 2015

A direct synthetic method for some 2,5-and 2.6-crosslinked chlorinated tetrahydromethano-indanes, which are the most important conversion products of cyclodiene insecticides under abiotic conditions, is described. The structures of the resulting compounds are confirmed with the aid of MS and 1H NMR.
dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] Ein durch Carbonsäuren stabilisiertes dimeres Antimonoxitrichlorid / dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloro-antimony(V)]A Dimeric Trichloro Antimony(V) Oxide Stabilized by Carboxilic Acids
Authors: Koller Franz-J. , Schwarz Wolfgang , Schmidt Armin
Published: February 2015

Tetrachloroantimony(V) carboxilates and tetrachloroantimony(V) alkoxides, resp., react with carboxilic acids and alkohols or water, resp., to yield d,h-μ-carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] (1, R = H, CH3), a new type of cyclic antimony(V) compounds. The crystal and molecular structure of 1 (R = CH3) is determined by X-ray analysis. Units of 1 (R - CH3) are associated by strong hydrogen bonds. The vibrational spectra of 1 (R = H, CH3) are discussed.
Über die Natur der Siliciumdioxidmodifikation Silica-X / On the Nature of the Silica Modification "silica-X"
Authors: Beneke Klaus , Lagaly Gerhard
Published: February 2015

Silica-X described in 1964 as a new SiO2 modification is the dehydrated form of the crystalline silicic acid H2Si8O17 · xH2O which is obtained by cation exchange from the potassium silicate K2Si8O17 · xH2O.
Neue Modifikationen des Siliciumdioxids / New Modifications of Silica
Authors: Lagaly Gerhard , Beneke Klaus , Kammermeier Haymo
Published: February 2015

A new family of modifications of silica is obtained by thermal dehydration of crystalline silicic acids with layer structures. Examples are SiO2 · 0.11 H2O, SiO2 · 0.04 H2O, SiO2 prepared by dehydration of H2Si14O29 · 5.4 H2O, H2Si8O17 · xH2O and H2Si4O9. The “water content” can amount up to 3 weight percent and results from uncondensed inter-layer silanol groups or from water molecules which are trapped between the layers. In some cases dehydration in the presence of organic interlayer molecules leads to different forms of silica.
Zur Kristallstruktur der Thiocuprate K3Cu8S6 und Rb3Cu8S6 / On the Crystal Structure of the Thiocuprates K3Cu8S6 and Rb3Cu8S6
Authors: Burschka Christian
Published: February 2015

The title compounds can be synthesized by fusion reaction of the alkali carbonates with copper and sulfur at 790 °C. The structure was solved from X-ray diffractometer data of single crystals and refined to an R-value of 0.06. The compounds crystallize with the same layer-type structure which is closely related to that of KCU3S2. Crystal data for K3Cu8S6 (Rb3Cu8S6): space group C2/m,z = 2, ϱcalc = 4.27(4.76) g/cm 3 , a = 17.332(4) (17.840(6)) Å, b = 3.830(2) (3.865(1)) Å, c = 9.889(4) (10.011(3)) Å, β = 104.12(2)° (104.91(2)°).
Die Kristallstruktur des Antimonfluoridchlorids SbCl4
+[Sb2F10,5Cl0,5]— / The Crystal Structure of the Antimony Fluoride Chloride SbCl4
+[Sb2F10,5Cl0,5]-
Authors: Müller Ulrich
Published: February 2015

Compounds with the composition SbCl4
+[Sb2F11-sCls]- with 0 ≤ s ≤ 2 can be obtained from SbF5/SbCl5 mixtures. The title compound is one of them. Its crystal structure was determined with X-ray diffraction data and was refined to a residual index of R = 0.052. It is isotypic to the compounds with s = 0 and s = 2, crystallizing in the space group P21/n with a = 1103, b = 1055, c = 1290 and β = 95,9°. In the anion [F4(F1-uClu)Sb-F-Sb(F1-vClv)F4]- two ligand positions that are cis to the bridging F atom are statistically occupied by fluorine and chlorine, with u = 0,1 and v = 0,4. The tetrahedral SbCl4
+ ion is coordinated to the anion so that on top of each of the tetrahedron faces there is one F atom at a distance of 298 to 335 pm.
Preparation and Properties of Two Tris o-Semiquinone Complexes
Authors: Brown Dennis G. , Johnson W. Leo
Published: February 2015

Tris o-benzosemiquinone complexes of iron and chromium are reported. These complexes contain three 3,5-di-t-butyl-o-semiquinato ligands and a trivalent metal ion. The iron complex can be obtained from either the more highly oxidized o-quinone or reduced catechol dianion precursor. The coordinated o-semiquinone ligand is surprisingly stable. A simple infrared criterion is suggested for detecting the presence of a coordinated o-semiquinone.
Notizen: Darstellung und Schwingungsspektrum von ReO3(O2PCl2) · POCl3 / Preparation and Vibrational Spectrum of ReO3(O2PCl2) · POCl3
Authors: Essawi Mervat El , Dehnicke Kurt
Published: February 2015

ReO3 (O2PCl2 ) · POCl3 is prepared by the reaction of ReCl5 with Cl2O in the presence of POCl3. According to the vibrational spectrum the structure consists of dimeric units with bridging O2PCl2 groups.
Notizen: Über Schwefelapatite: Darstellung und Struktur von Ba5S(AsO4)2SO4, Sr5S(AsO4)2SO4 und Sr5S(PO4)2SO4 / On Sulfurapatites: Preparation and Crystal Structure of Ba5S(AsO4)2SO4, Sr5S(AsO4)2SO4 and Sr5S(PO4)2SO4
Authors: Schiff-Frangois Alain , Savelsberg Gerhard , Schäfer Herbert
Published: February 2015

Three sulfurapatites have been prepared. They crystallize in the hexagonal system (P63/m) with the following lattice constants:
Über Oxidpnictide: Zur Kenntnis von A2Mn3B2O2 mit A = Sr, Ba und B = As, Sb, Bi / On Oxidpnictides: Preparation and Crystal Structure of A2Mn3B2O2 with A = Sr, Ba and B = As, Sb, Bi
Authors: Brechtel Erwin , Cordier Gerhard , Schäfer Herbert
Published: February 2015

Five new oxidpnictides have been prepared and structurally characterized. They crystallize in the tetragonal system, I4/mmm, with the following constants:

Sr2Mn3As2O2: a = 416 ± 1 pm, c = 1884 ± 4 pm, c/a = 4.529,

Ba2Mn3As2O2 : a = 424.8 ± 0 5 pm, c = 1977 ± 3 pm, c/a = 4.654,

Sr2Mn3Sb2O2 : a = 426.2 ± 0.4 pm, c = 2011 ± 2 pm, c/a = 4.718,

Ba2Mn3Sb2O2 : a = 436.7 ± 0.5 pm, c = 2078 ± 2 pm, c/a = 4.758,

Sr2Mn3Bi2O2 : a = 428 ± 1 pm, c = 2055 ± 5 pm, c/a = 4.801.

Mn- and As(Sb,Bi) atoms form tetragonal pyramids, connected by common edges in the basis to two-dimensional sheets. These sheets are separated by double layers of Sr atoms, in which Mn and O atoms are located forming MnO4 square plane nets.
Das Perowskitsystem CH3NH3 [Pb,Sn1-nX3] (X = Cl, Br, I) / The Perovskite System CH3NH3[PbnSn1-nX3] ( X = C1, Br, I)
Authors: Weber Dieter
Published: February 2015

The mixed Sn(II)/Pb(II) compounds of the type CH3NH3[PbwSn1-nX3] (X=Cl, Br, I) have the cubic perovskite structure which is established by X-ray powder data and 119Sn Mössbauer spectroscopy. With exception of the chloro system the coloured compounds show electrical conductivity which increases with increasing Sn(II) content. Their physical properties can be interpreted by means of a "p-resonance bonding". Replacement of Sn(II) by Pb(II) and I by Br and Cl decreases this bonding effect, which is produced by the interaction of filled X p-orbitals with empty p-orbitals of Sn(II) or Pb(II). The synthesis is described
Ein Beitrag zur Photochemie aromatischer Nitroverbindungen, III / A Contribution to the Photochemistry of Aromatic Nitro Compounds
Authors: Keim Jürgen
Published: February 2015

During UV irradiation of nitrobenzene and some derivatives in benzene solution biphenyls are formed as in the case of the corresponding iodobenzenes. Using fluorobenzene as a solvent, isomeric fluorobiphenyls (o, m, p) will be found as reaction products having a definite distribution (o >m > p), which is characteristic for substitution by radicals. Therefore, we conclude that the CN-bond is split homolytically. Besides the biphenyls, other important reaction products of the aromatic nitro compounds - phenols and nitrophenols - are identified
Synthese und Reaktionen von Eisen-Schwefel-Komplexen mit CO- und P(CH3)3-Liganden [1] / Synthesis and Reactions of Iron Sulfur Complexes with CO and P(CH3)3 Ligands
Authors: Seilmann D. , Unger E.
Published: February 2015

Cis-dicarbonyl complexes of Fe(II) with o-benzenedithiolate and o-methylthiobenzenethiolate ligands react with PMe3 yielding [Fe(CO)2(PMe3)2(C6H4S2)] and [Fe(CO)(PMe3)(CH3S-C6H4-S)2], respectively. The reaction of [Fe(CH3S-C6H4-S)2], accessible only in solution, with PMe3 affords the labile [Fe(PMe3)2(CH3S-C6H4-S)2], which with CO rapidly yields the monocarbonyl complex [Fe(CO)(PMe3)(CH3S-C6H4-S2)]. The anion [Fe(CO)2(C6H4S2)2]2-, hitherto accessible in solution only, could be precipitated in the presence of NaBH4 as (NMe4)2[Fe(CO)2(C6H4S2)2]
Darstellung und Struktur von K2PdAs2 / Preparation and Structure of K2PdAs2
Authors: Schuster Hans-Uwe , Rozsa Sandor
Published: February 2015

K2PdAs2 was prepared from the elements. It crystallizes orthorhombically , space group Cmcm,

a = 653.6 pm, b =1412.1 pm, c = 602.5 pm, forming infinite Pd-As2-zig-zag-ribbons and conforming to a filament
(—)D-und (+)D-4-Methoxyphenylmethyl- thiophosphinsäure, Überprüfung der Racematspaltung mittels 31P{ 1H}-NMR-Spektroskopie/(—)D-and (+ )D-4-Methoxyphenylmethyl- thiophosphinic Acid, Control of the Resolution by 31P{1H} NMR Spectroscopy
Authors: Kuchen Wilhelm , Kutter Jurgen
Published: February 2015

(-)D-and (+)D-4-methoxyphenylmethyl-thiophosphinic acid, quinine salts of (-)D-and (+)D-4-methoxyphenylmethylthiophosphinic acid, checking of resolution by 31P{ 1H} NMR-spectroscopy

(-)D-and(+)D-4-CH3OC6H4(CH3)P(S)OH acid were obtained from fractional crystallization of the quinine salt of the racemic acid. 31P{1H} NMR spectroscopy proved to be very useful in checking the separation process as well as the optical purity of the diastereomers and enan­tiomers.
Notizen: Molybdän(V)-nitridobromid, MoNBr2 /Molybdenum(V)-nitridobromide, MoNBr2
Authors: Krüger Norbert , Dehnicke Kurt
Published: February 2015

MoNBr2 is prepared by thermolysis of MoNBr3 in vacuo at 260 °C. It forms a dark brown hygroscopic powder; the IR spectrum indicates a MoN-multiple bond. The magnetic moment (μeff = 0.65 B.M.) is smaller than in undisturbed d1-systems, which is due to spin-spin-interaction. The monohydrate, MoNBr2 · H2O, can be identified by the mass spectrum.
Copper(II) Complexes Containing 3-n-Nonylcatechol: Preparation and Ligand Oxidation
Authors: Brown Dennis G. , Hughes William J.
Published: February 2015

Ternary copper(II) complexes containing the dianion of 3-n-nonylcatechol and a number of bidentate nitrogen containing counter ligands have been prepared and characterized. It has been demonstrated that, in the presence of oxygen, the catecholato ligand undergoes intradiol ring cleavage in a fashion similar to that carried out by intradiol aromatic dioxygenases. The 3-n-nonylcatecholato ligand was chosen as an analog for the naturally occuring 3-pentadecylcatechols or "urushiols" which are the active allergens in plants such as poison ivy.
Beiträge zur Chemie der Pyrrolpigmente, XXXIII [1] Darstellung, Struktur und Eigenschaften von isomeren N-Methyl-Bilatrienen-abc (N-Methyl-etiobiliverdine-IV-γ) / On the Chemistry of Pyrrole Pigments, XXXIII [1] Synthesis, Structure and Properties of Isomeric N-Methyl-bilatrienes-abc (N-Methyl-etiobiliverdines-IV-γ)
Authors: Falk Heinz , Thirring Klaus
Published: February 2015

Methylation of etiobiliverdin-IV-γ yields a ring-A N-methylated product the structure of which was proven by comparison with the corresponding monolactimether and the ring-B methylated product which was synthesized on an independent route. The configura-tion (Z,Z,Z) was deduced by 1H-NMR experiments and a more or less helical conformation which is most twisted at the ring-A methine fragment was found. Photoisomerization exclusively takes place at this position giving the (E,Z,Z) diastereomer, a reaction which is discussed in terms of the correlation of light absorption, methine single bond twist and photochemical selectivity.
Darstellung eines Zinnhomologen der "Methylidyn-Cluster" / Preparation of a Tin Homologue of the "Methylidyne Clusters"
Authors: Schwarzhans Karl E.
Published: February 2015

A new tin-cobaltcarbonyl-cluster, a homo-logue of the methylidyne clusters, has been prepared and identified by IR and masspectro-metric measurements.
Über den Chemismus der Wiesner-Reaktion auf Lignin / On the Chemistry of the Wiesner Reaction on Lignin
Authors: Geiger Hans , Fuggerera Helga
Published: February 2015

It is demonstrated that the Wiesner reaction (detection of lignin with phloroglucinol/HCl) is due not only to cinnamic aldehyde but also to cinnamic alcohol units of the lignin. The limits of detection of some compounds related to lignin with phloroglucinol/HCl, naphthoresor-cinol/HCl and orcinol/HCl are determined. The chemistry of the reactions is discussed.
ESR Evidence of Peroxy Radical Formation during Radiolysis of Frozen Carbohydrate Solutions
Authors: Plonka Andrzej , Bednarek Janusz , Żegota Henryk
Published: February 2015

During thermal annealing of the frozen polycrystalline samples of aqueous carbohydrate (dextran, melibiose, maltose, glucose, and xylose) solutions y-irradiated at 77 K the formation of peroxy radicals by addition of oxygen to the primary carbon-based radicals was observed at 190-220 K by the ESR method.
Baldwin Rules for Ring Closure - a Re-examination of the Concept
Authors: Kansal V. K. , Bhaduri A. P.
Published: February 2015

The reaction of 5,5-diphenyl-γ-butyrolactone (3) with primary amines and ethyl γ-γ-diphenyl vinyl acetate with Aqu HBr in acetic acid served as examples for the exception to Baldwin rules for 5-exo-tet and 5-exo-trig ring closures. The structure of the reaction product of 3 with primary amines have been assigned on the basis of spectral data and conversion to γ-γ-diphenyl vinyl substituted acetamides, the authentic samples of which were prepared by an unambigous route of synthesis.
Electrochemical Syntheses, XVII [1]. Ozone Synthesis by Electrolysis of Water
Authors: Fritz Heinz P. , Thanos Jordanis C. G. , Wabner Dietrich W.
Published: February 2015

Dimensionally stable lead dioxide anodes on a titanium substrate [2, 3] were tested for application in ozone electrosynthesis in a variety of aqueous electrolytes. At room tem­perature an ozone concentration of up to 13% by weight in the anodic gas composed of O3 and O2 is attained by using an aqueous phosphate electrolyte.
Cs2Sb8S13, ein neuer Formel-und Strukturtyp bei Thioantimoniten / Cs2Sb8S13 -A New Formula and Structure Type in the Group of Thioantimonites
Authors: Volk Klaus , Schäfer Herbert
Published: February 2015

Cs2Sb8S13 has been prepared and its structure determined. It crystallizes in the triclinic system P1̄ with

a = 1543.7(5) pm, b = 1148.8(4) pm, c = 829.9(4) pm;

α = 71.89(5)°, β = 102.45(5)°, γ = 95.16(5)°.

SbS3-ψ-tetrahedra and SbS4-ψ-trigonal bipyramids are connected together to sheets, separated by Cs ions.
Über einen Chrom-Mangan-Spinell mit Kationenmangelstruktur, CrMn1,5O4 / About a Chromium Manganese Spinel with Cation Deficient Structure: CrMn1,5O4
Authors: Priebe Reinhold , Sabrowsky Horst
Published: February 2015

Thermal decomposition of the black precipitate Cr2Mn3O9 · aq at 1300 K leads to the dark brown spinel CrMn1,5O4 (a = 847.9 pm; Z = 8; Fd3m). By magnetic measurements and model calculations from powder data of the spinel we propose the ionic distribution CrIV[MnIIMnIV
0,5]O4 with x = 0.35.
Neue elektrovalente ternäre Verbindungen des Kaliums mit Magnesium und Elementen der 5. Hauptgruppe / New Ternary Compounds of Potassium with Magnesium and Elements of the 5. Main Group
Authors: Vogel Rainer , Schuster Hans-Uwe
Published: February 2015

Ternary Potassium Compounds, Crystal Data The compounds KMgP, KMgAs, KMgSb and KMgBi were prepared and their structures determined by powder and single crystal data. The compounds crystallize in a modified Cu2Sb type structure, space group P4/nmm-D4h
7. The cell parameters are:

KMgP: a = 444,6pm, c = 754,4pm, c/a = 1,69,

KMgAs: a = 454,6pm, c = 771,6pm, c/a = 1,69,

KMgSb: a = 481,2 pm, c = 820,2 pm, c/a = 1,70,

KMgBi: a = 488,1 pm, c = 838,2 pm, c/a = 1,72.
Notizen: Über neue ternäre Fluoride vom Typ Ag3MF3, und AgMF4 / On New Ternary Fluorides of the Type Ag3MF6 and AgMF4
Authors: Lösch Roland , Hebecker Christoph
Published: February 2015

Unit cell dimensions of new Ag3MF6 com­pounds have been determined by Guinier-photographs: Ag3AlF6 and Ag3GaF6 crystallize tetragonally (isostructurally to Rb3TlFe); Ag3ScF6, Ag3lnFe and Ag3TlF6 are monoclinic (Na3AlF6- type). AgGaF4 crystallizes tetragonally (iso­structurally to KFeF4), AgScF4 monoclinic in a new, unknown structure type.
Notizen: Synthese und Eigenschaften des Oktafluorodirhenat(III) -anions, [Re2F8]2- / Synthesis and Properties of the Octafluorodirhenate(III) Anion, [Re2F8]2-
Authors: Peters G. , Preetz W.
Published: February 2015

The reaction of [Re2Cl8]2- and F-, both dis­solved as ion pairs with [(n-C4H9]+ in nearly anhydrous CH2Cl2 gives elder-coloured [(n-C4H9)4N]2[Re2F8] · 4H2O. On Laser irradia­tion of the solid complex at 80 K resonance Raman spectra are observed, exhibiting up to five overtones of v1 = 320 cm-1 (Re-Re, A1g) and combination tones with V2 = 625 cm-1 (Re-F, A1g). The spectroscopic constants are ω1 = 319,6 ± 0.6 cm-1, and x11 = -0,45 ± 0,05 cm-1. The Re-Re bond energy is estimated to be 162 ± 20 kcal/mol.
Darstellung und Eigenschaften von trans-Dihalogeno-tetrakis(pyridin)osmium(II)-Komplexen / Preparation and Properties of trans-Dihalo-tetrakis(pyridine)osmium(II) Complexes
Authors: Behrensdorf J. , Preetz W.
Published: February 2015

The reaction of fac-K2[OsX3l3] (X = Cl, Br) with pyridine and glycerin gives dark red crystals of trans-[OsClI(py)4] or trans-[OsBrI(py)4], soluble in organic solvents, and sublimable in vacuum at 300 or 320 °C. The structure is established by vibrational and mass spectra. With HX adducts of type trans-[OsXI(py)4]·2 HX are formed, soluble in water with violet colour.
Reactions with the Arylhydrazones of some α-Cyanoketones
Authors: Kandeel Ezzat Mohemed , Sadek Kamal Usef , Elnagdi Mohamed Hilmy
Published: February 2015

The N-methylarylhydrazones of mesoxalodinitrile (3) and of ethyl cyanoglyoxalate (7) could be prepared via methylation of the corresponding phenylhydrazones 4 and 6 respectively. The hydrazones 3 and 8 reacted with hydrazine hydrate to yield the amidra-zone 1 and the hydrazide 2 b. The behavior of compounds 1 and 2 a, b towards a variety of reagents is reported. A variety of new α-arylhydrazononitriles were synthesised.