bluuebunny/crossref_metadata_2025 huggingface dataset:
Darstellung und Kristallstrukturen einiger Übergangsmetall-Komplexverbindungen mit Liganden mit dem 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-on-Gerüst / Synthesis and X-Ray Crystal Structures of Some Transition-Metal Complexes Involving Ligands with the 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-one Framework
Authors: Fischer Axel , Neda Ion , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

4,5-Benzo-2-diethylamino-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 and 4,5-benzo-2-[bis- (2-chlorethyl)amino]-3-methyl-1,3,2-oxazaphosphorinan-6-one 3 reacted with dichloro- (cycloocta-1,5-diene)platinum(II) [(COD)PtCl2] to give the ds-dichloro-platinum(II) com­plexes 2 and 4, respectively. The reaction of 1 with tricarbonyl(cycloheptatriene)molybdenum(0) led to a mixture of isomers including fac-tris-(4,5-benzo-2-diethylamino-3-methyl- 1,3,2-oxazaphosphorinan-6-one)tricarbonylmolybdenum(0) 5. The reaction of 4,5-benzo- 2-acetylamino-3-methyl-1,3,2-oxazaphosphorinan-6-one 6 with dichloro(cycloocta-1,5-diene)- platinum(II) furnished the cis-complex 7. 4,5-Benzo-2-fluoro-3-methyl-1,3,2-oxazaphosphorinan-6-one 8 reacted with both tetracarbonyl(norbornadiene)molybdenum(0) and dichloro- (cycloocta-1,5-diene)platinum(II) to form the cis-complexes 9 and 10. 31P-31P coupling con­stants from the 31P NMR spectra for the complexes 2, 4 and 9 are reported. The structures of 5, 7, 9 and 10 were established by single crystal X-ray analysis. All ligands coordinate via phosphorus only. The structure of 5 shows strongly distorted octahedral coordination geome­try associated with the presence of three bulky ligands. The Mo-P bond lengths in 5 are, for the same reason, significantly longer than in 9. The heterocycles of the ligands in 5 do not show the expected envelope conformation but are almost planar. The platinum(II) complex 7 shows crystallographic C2-symmetry, the coordination geometry at platinum being almost ideally square-planar. The same coordination geometry is observed for 10, the ligands of which possess the expected envelope conformation with phosphorus out of the plane.
Die Kristallstruktur des Tetraphenylphosphonium-Monoiodohexahydroc/ oso-Hexaborats [P(C6H5)4][B6H6I] / The Crystal Structure of Tetraphenylphosphonium Monoiodohexahydro-closo-hexaborate [P(C6H5)4][B6H6I]
Authors: Preetz W. , Sonnak D.
Published: February 2015

The crystal structure of [P(C6H5)4][B6H6I] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1 with a = 7.5137(9), b = 12.623(2), c = 13.6363(13) Å, α = 87.787(13)°, β = 83.836(13)°, γ = 88.156(10)°. The additional H atom could be refined with B-H distances of 1.13 to 1.31 A above one of the facettes of the B6 octahedron opposite to the I substituent.
Radical-Initiated Hydrosilylation-Cyclization Reactions of Bis(vinyldimethylsilyl) Compounds, CH2=CH(CH3)2SiXSi(CH3)2CH=CH2 (X = O, CH2, NH, NCH3, NSi(CH3)3
Authors: Seyferth Dietmar , Friedrich Holger , Krska Shane W.
Published: February 2015

The di-tert-butyl peroxide-initiated reactions of triethyl- and tri-n-propylsilane with bis-(vinyldim ethylsilyl) compounds, CH2=CH(CH3)2SiXSi(CH3)2CH=CH2(X-O,CH2, NH,NCH3 and NSiMe3) resulted in hydrosilylation-cyclization to give mixtures of trialkylsilylm ethyl-substituted disilacyclohexanes and trialkylsilylm ethyl-substituted disilacyclopentanes. The ratio of six-membered to five-membered ring products obtained is dependent on the linking group X and decreased in the order X=O>CH2>NH>NCH3. For X = NSiMe3 only a mixture of the cis and trans isomers of the five-membered ring product was obtained.
The Crystal Structure and Chemical Properties of U2Al3C4 and Structure Refinement of Al4C3
Authors: Gesing Thorsten M. , Jeitschko Wolfgang
Published: February 2015

A well crystallized sample of U2Al3C4 was obtained by melting the elemental components in a carbon crucible in a high frequency furnace. The crystal structure of this compound was determined from single-crystal diffractometer data of a twinned crystal: P63mc, a = 342.2(1) pm. c = 2323.0(3) pm. Z = 2 , R = 0.030 for 537 structure factors and 18 variable parameters. The structure can also be described in the higher symmetry space group P63/mmc with one split aluminum position. It consists of close packed layers of uranium and aluminum atoms with carbon atoms at interstitial sites. The structure is closely related to that of Al4C3, which was refined from single-crystal X-ray data to a residual of R = 0.033 for 135 F-values and 11 variables. The hydrolysis of U2Al3C4 with diluted hydrochloric acid resulted in about 74 (wt-)% methane, 8% ethane and ethylene, and 18% saturated and unsaturated higher hydrocarbons.
Synthesis and Characterization of Copper(II) and Nickel(II) Complexes Derived from α-Substituted Malondialdehydes
Authors: Reyes V. Salas , Aguilera C.
Published: February 2015

The synthesis and characterization of two series of novel bis(4′-alkyloxyphenyl)malondialdehydes of copper(II) and nickel(II), (R=CnH2n+1, n = 9, 10, 11, 12) from 2-(4′-hydroxyphenyl)- 3-dimethylamino acrolein is described.
Kristallisation und Strukturuntersuchung von Alkali-Parawolframaten / Crystallization and Structure Determination of Alkaline Metal-Paratungstates
Authors: Chrissafidou A. , Fuchs J. , Hartl H. , Palm R.
Published: February 2015

The syntheses and crystal structures of the following paratungstates-Z with different alkaline cations are reported and discussed:

Na10[H2W12O42] · 20H2O (I), Na10[H2W12O42] · 27H2O (II), Na10[H2W12O47] · 28H2O (III), K10[H2W12O42] · 10H2O (IV), K6Na4[H2W12O42] · 13H2O (V), Cs6Na4[H2W12O42] · 16H2O (VI), Cs8Na2[H2W12O42] · 10H2O (VII), Cs8Na2[H2W12O42] · 12H2O (VIII), K3Na7[H2W12O42] · 24H2O (IX) and K5Na2[H2W12O42] · 12H2O (X). Priority has been set on the description of the coordination of the cations with the oxygen ligands H2W12O42
10- and H2O.
Ein Beitrag zur Kristallchemie der Alkali-Erdalkalimetall-Oxovanadate: Synthese und Struktur von K3CaV5O15/A Contribution to the Crystal Chemistry of Alkaline-Alkaline-Earth Oxovanadates: Synthesis and Structure of K3CaV5O15
Authors: Martin F.-D. , Miiller-Buschbaum Hk.
Published: February 2015

Single crystals of K3CaV5O15 have been prepared by crystallization from melts. The com pound shows a new structure type with orthorhombic symmetry, space group D2h
21-Cmma, a = 25.953(5), b = 15.688(3), c = 7.804(4) Å, Z = 8. Typical features of K3CaV5O15 are isolated cyclic V4O12 and V6O18 groups of corner sharing VO4 tetrahedra.
Über das Oxomolybdat AgKCu3Mo4O16 mit Silber in siebenfacher Koordination / About the Oxomolybdate AgKCu3Mo4O16 with Silver in Seven-Fold Coordination
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of AgKCu3Mo4O16 have been prepared by crystallization from melts and investigated by X-ray diffractometer techniques. This compound crystallizes with monoclinic symmetry, space group C2h
5 - P21/c, a = 5.056(1), b = 14.546(4), c = 19.858(9) Å, β = 86.64(5)°, Z = 4. The crystal structure of AgKCu3Mo4O16 is closely related to K2Cu3Mo4O16 showing ribbons of edge-sharing CuO6 and AgO7 polyhedra. The ribbons are linked by tetrahedrally coordinated molybdenum and K2O10 groups. Another kind of MoO4 tetrahedra occupies the cavities inside the ribbons. The crystal structure and the coordination of silver, copper, potassium and molybdenum by oxygen are discussed with respect to K2Cu3Mo4O16.
Trifluormethyl-substituierte Germanium-Heterocyclen durch [4+1]-Cycloaddition / Trifluoromethyl Substituted Germanium Heterocycles via [4+1] Cycloaddition Reactions
Authors: Karsch Hans H. , Bienlein Fritz , Heckei Maximilian , Steigeimann Oliver , Burger Klaus , Cyrener Jörg
Published: February 2015

Formation of partially fluorinated imidazoles 6 from 4,4-bis(trifluoromethyl)-1,3-diazabuta-1,3-dienes 1 in the presence of low-valent metal compounds is shown to proceed via a [4+1] cycloadduct in the case of germanium(II)-chloride. The resulting germole 3 has been characterized by X-ray analysis. The five-membered ring is planar and the germanium atom adopts tetrahedral configuration.
Synthesis of Coumarins and Quinolones by Intramolecular Aldol Condensation Reactions of Titanium Enediolates
Authors: Fürstner Alois , Jumbam Denis N. , Shi Nongyuan
Published: February 2015

Low-valent titanium prepared by the reduction of TiCl3 with zinc dust oxidatively adds to α-ketoamides or α-ketoesters with the formation of the corresponding titanium enediolates. These 1,2-difunctional nucleophiles, which have hardly been used in organic synthesis so far, undergo regioselective intramolecular aldol condensation reactions with various electrophiles such as aldehydes, ketones, nitriles, esters and amides. This methodology allows the synthesis of differently substituted coumarin and 2-quinolone derivatives.
Pentamethylcyclopentadienylbis(ethen)eisen - ein 17e-Halbsandwichkomplex mit leicht verdrängbaren Ethenliganden / Pentamethylcyclopentadienylbis(ethene)iron - a 17e Halfsandwich Complex with Easily Displaceable Ethene Ligands
Authors: Jonas Klaus , Klusmann Peter , Goddard Richard
Published: February 2015

The new room temperature stable halfsandw ich complex Cp*Fe(tmeda)Cl (2) has been synthesized by the 1:1 reaction of FeCl2(thf)1.5 with LiCp* in a mixture of THF and TMEDA at - 30 °C. 2 is an ideal starting material for the synthesis of a wide range of new iron complexes. Treatment of 2 with lithium sand in THF in the presence of COD or ethene followed by the addition of TMEDA yields the ferrates [Li(tmeda)][Cp*Fe(cod)] (3) or [Li(tmeda)][Cp*Fe(C2H4)2] (4). By delithiation with dichloroethane, 3 and 4 can be transformed into the novel 17 e iron complexes Cp*Fe(cod) (5) and Cp*Fe(C2H4)2 (6). 6 is extremely labile. Since the ethene ligands can be easily displaced, the title compound is a synthetically valuable source of the Cp*Fe fragment. Whereas the photochemically generated 17e dicarbonyl species CpFe(CO)2 rapidly recombines to give the dimer [CpFe(CO)2]2, the isoelectronic 6 is stable in ethene saturated pentane for several days at 0 °C. Without the stabilizing effect of ethene (in pure pentane or under vacuum ), 6 loses ethene to give the dinuclear complex (Cp*Fe)2(C2H4)2 (8) irreversibly. The structure of 8 has been characterized by X -ray analysis.
Amphiphilic Carbohydrate-Based Mesogens, 10. Synthesis of Mesogenic 2-O-n-Alkyl-L-threitols
Authors: Dahlhoff Wilhelm V. , Radkowski Karin , Zugenmaier Peter , Dierking Ingo
Published: February 2015

Dimethyl-L-tartrate 1 is converted into 2,3-O-n-heptylidene-decylidene dimethyl-L-tartrates 2 which are reduced with ethyldiboranes alone and then in the presence of 9-methylsulfonyloxy- 9-borabicyclo[3.3.1]nonane (MSBBN ) to yield 2-O -alkyl-L -threitols 4, after deprotection. The amphiphilic compounds 4 are thermotropic mesogens which display the smectic A liquid crystalline phase on melting.
Thermodynamics of Complexation of Sodium Ion with 12-Crown-4 and 18-Crown-6 in Pyridine
Authors: Ohtsu Kumiko , Ozutsumi Kazuhiko , Kurihara Makoto , Kawashima Takuji
Published: February 2015

The complexation of sodium ion with 1,4,7,10-tetraoxacyclododecane (12-crown-4) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) has been studied by titration calorimetry in pyridine (PY) containing 0.1 mol dm-3 (C2H5)4NClO4 as a constant ionic medium at 25 °C. The calorimetric titration data were well explained in terms of the formation of the [Na(12-crown-4)]+, [Na(12-crown-4)2]+, and [Na(18-crown-6)]+ complexes, and their formation constants, reaction enthalpies, and entropies were determined. The formation of [Na(18-crown-6)]+ is much pronounced in PY over N,N-dimethylformamide (DMF) and water, and the stability order is PY > DMF > water. The enthalpy values for the formation of [Na(18-crown-6)]+ are all negative in PY, DMF, and water, and increase in the order PY < DMF < water. The complexation is the least exothermic in water, though sodium ion is the most weakly solvated in water. This is because 18-crown-6 is much stabilized in water by forming hydrogen bonds with water molecules. Despite the stronger electron pair-donating ability of PY than DMF, the complexation is more exothermic in PY than in DMF. This is ascribed to the different solvation number of the sodium ion in P Y and DMF, i.e., the sodium ion is coordinated with a smaller number of solvent molecules in the former solvent than in the latter.
Thermochromism of Metal Exchange Reaction between Zinc(II) and Mercury(II) Porphyrins
Authors: Tabata Masaaki , Ide Masahiro , Kaneko Kentaro
Published: February 2015

Thermochromism was observed for an aqueous solution containing zinc(II) and mercury( II) cations and N-p-nitrobenzyl-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (NO2Bz(Htpps)4-) in the temperature range 10 to 70 °C. The equilibrium constants and the thermodynamic parameters of Zn(NO2Bztpps)3- and Hg(NO2Bztpps)3- have been determined spectrophotometrically to elucidate the thermochromism at 10, 15, 20, 25 and 30 °C in 0.1 mol dm-3 NaNO3. The protonation and metalation constants of NO2Bz(Htpps)4- are defined as K2 = [H2P][H+]-1[HP]-1, K3 = [H3P][H+]-1[H2P]-1 and KMP = [M P][H+][M2+]-1[HP]-1, where HP and MP denote the free base form of the prophyrin and the metalloporphyrins of zinc(II) and mercury(II), respectively. Charges of the prophyrin and metalloporphyrins are omitted for simplicity. The following values were found: logK2 = 7.75 ±0.02 (25 °C), ΔH°/kJmol-1 = -21.2±0.5 and ΔS°/Jmol-1K-1 = 77±1, logK3 = 2.55±0.02 (25 °C), ΔH°/kJmol-1 = -25±0.8 and ΔS°/Jmol-1K-1 = -35±3 and log KZnP = 0.63±0.03 (25 °C), ΔH°/kJmol-1 = 31.0±0.8 and ΔS°/Jmol-1K-1 = 116±3, logKHgP = 6.22±0.03 (25 °C), ΔH°/kJmol-1 = 4.5±0.7 and ΔS°/Jmol-1K-1 = 134±2. The distribution curve calculated from the thermodynamic parameters sufficiently agrees with the observed metal exchange reaction between the metalloporphyrins.
Spectroelectrochemical Study of some μ3-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes
Authors: Takahashi Kenta , Umakoshi Keisuke , Kikuchi Akihiro , Sasaki Yoichi , Tominaga Masato , Taniguchi Isao
Published: February 2015

New trinuclear rhodium(III) complexes, [Rh3(μ3-O)(μ-CH3COO)6(L)3]+ (L = imidazole (Him), 1-methylimidazole (Meim), and 4-methylpyridine (Mepy)) have been prepared. The Him, Meim, and Mepy complexes show reversible one-electron oxidation waves at E1/2 = +1.12, +1.12, and +1.28 V vs Ag/AgCl, respectively, in acetonitrile. Electronic absorption spectra of the one electron oxidized species of these complexes and [Rh3(μ3-O)(μ-CH3COO)6(py)3]+ (py = pyridine) (E1/2 = +1.32 V ) were obtained by spectroelectrochemical techniques. While the Rh3(III,III,III) states show no strong visible absorption, the Rh3(III,III,IV ) species give a band at ca. 700 nm (ε = 3390-5540 mol dm-3 cm-1). [Ir3(μ3-O)(μ-CH3COO)6(py)3]+ with no strong absorption in the visible region, shows two reversible one-electron oxidation waves at +0.68 and +1.86 V in acetonitrile. The electronic absorption spectrum of the one-electron oxidized species (Ir3(III,III,IV )) also shows some absorption bands (688 nm (ε, 5119), 1093 (2325) and 1400 (ca. 1800)). It is suggested that the oxidation removes an electron from the fully occupied anti-bonding orbital based on metal-dπ-μ3-O-pπ interactions, the absorption bands of the (III,III,IV ) species being assigned to transitions to the anti-bonding orbital.
The First Liquid-Chromatographic Separation of the (R)- and (S)-Enantiomers of a Chiral Silanol, Silane and Germane
Authors: Tacke Reinhold , Reichel Dirk , Günther Kurt , Merget Stefan
Published: February 2015

The racemic mixtures of the muscarinic antagonists cyclohexyl(phenyl)(2-pyrrolidinoethyl)silanol (sila-procyclidine, rac-1), cyclohexyl(hydroxymethyl)phenyl(2-piperidinoethyl)-silane (rac-2) and cyclohexyl(hydroxymethyl)phenyl(2-piperidinoethyl)germane (rac-3) were resolved by analytical liquid chromatography (HPLC) using chemically modified cellulose (1) or amylose (2, 3) as the chiral stationary phase. This chromatographic method was used for the quantitative determination of enantiomeric purity of the (R)- and (S)-enantiomers of 1 - 3 , which were obtained by preparative resolution with chiral auxiliary agents. Furthermore, the enantiomeric purity of these samples was established by 13C NMR studies using chiral shift reagents. According to these studies, the resolved antipodes of 1 - 3 (obtained by preparative resolution) were almost enantiomerically pure [HPLC: ≥ 98.2% ee ((R )-3) to 99.4% ee ((R)-1, (S)-1); NMR: ≥ 97% ee].
Synthese und Kristallstruktur von [TeCl2(NPMe3)2]2/ Synthesis and Crystal Structure of [TeCl2(NPMe3)2]2
Authors: Folkerts Hella , Dehnicke Kurt , Magull Jörg
Published: February 2015

[TeCl2(NPMe3)2]2 has been prepared by the reaction of TeCl4 with Me3SiNPMe3 in acetonitrile solution. Tlie compound forms white moisture sensitive crystals which have been characterized by IR spectroscopy and by a crystal structure determination. Space group P21/c, Z = 2, structure solution with 3510 independent reflections, R = 0.029. Lattice dimensions at - 70 °C; a = 1206.0(9); b = 1054.7(7); c = 1156.0(6) pm; β = 99.27(5)°. [TeCl2(NPMe3)2]2 forms centrosymmetric molecules via TeCl2Te bridges with bond lengths Te-Cl of 267.2 and 366.9 pm, the longer one being in trans-position to one of the terminally bounded (NPMe3
-) groups. The TeN bond lengths of 190.1 and 192.6 pm are unusually short.
Trimethylaminoxidaddukte an Tetrakis[bis(trimethylsilyl)methyl]dialuminoxan: R2Al – O – AlR2 · ONMe3 und R2Al – O – AlR2 · 2ONMe3 mit gewinkelten Al – O – Al-Gruppen / Adducts of Trimethylaminoxide with Tetrakis[bis(trimethylsilyl)methyl]dialuminoxane: R2Al – O – AlR2 · ONMe3 and R2Al – O – AlR2 · 2ONMe3 with Bent Al – O – A l Groups
Authors: Uhl Werner , Koch Matthias , Pohl Siegfried , Saak Wolfgang , Hiller Wolfgang , Heckel Maximilian
Published: February 2015

The sterically highly shielded and monomeric tetrakis[bis(trimethylsilyl)methyl]dialuminoxane R2Al - O - AlR2 (R = CH(SiMe3)2) 1 forms 1:1 and 1:2 adducts on treatment with trimethylamine oxide. Both products have been characterized by crystal structure determination. Contrary to the linear educt 1, the complexes show bent Al - O - Al groups with bond angles of 162.3 and 161.4°. The mono adduct 2 has three- and four-coordinated Al atoms with a very short Al - O bond between the bridging oxygen and the coordinatively unsaturated Al atom (168.7 pm), possibly indicating a π-interaction. The second bond of the dialuminoxane fragment is lengthened to 175.3 pm and represents a “normal” Al - O distance. The Al - O bond to the amine oxide ligand (184.6 pm) lies within the range o f dative Al - O bonds. As shown by NMR spectroscopy the unsymmetrical structure is preserved in toluene solution up to 90 °C. In the bis(amine-oxide) adduct 3 both A l atoms are four-coordinated with very similar inner Al - O bond lengths o f 173.6 pm.
Block Synthesis of Oligosaccharides under Mild Conditions
Authors: Wang Yali , Zhang Hong , Voelter Wolfgang
Published: February 2015

Details on a synthesis of the trisaccharide α-D-Glc(1→6)-β-D-Glc(1→6)-D -Glc are reported. The O-glycosidic linkages were constructed using the sulfoxide glycosylation reaction. This approach proves to be a rapid glycosylation method leading to high yield and good selectivity.
Zur Kenntnis des Oxocuprats (Cu,Co)3,75Mo3O12 / On the Oxocuprate (C u,Co)3,75Mo3O12
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (Cu,Co)3,75Mo3O12 have been prepared by recrystallization from melts and investigated by X-ray diffractometer techniques. The compound crystallizes with orthorhombic symmetry, space group D16
2h-Pnma, a = 5.092(1), b = 10.624(3), c = 17.804(4) Å, Z = 4 and is isotypic to NaCo2.31Mo3O12. The crystal structure is discussed and it is shown, that the trigonal prismatically coordinated copper positions are occupied in a different manner. One of the alternate sites is beside the centre of the prisms, and the other one is shifted towards one of the faces of the rectangular prism. This detail may be interpreted by assigning the valance states CuI and CuII. The MO6 octahedra are occupied statistically by copper and cobalt.
Zur Darstellung und Kristallstruktur eines neuen Kupfer-Antimon-Oxomolybdats: CuSbMo2O8 / On the Synthesis and Crystal Structure of a New Copper Antimony Oxomolybdate: CuSbMo2O8
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of the hitherto unknown compound CuSbMo2O8 were prepared by recrystallization from melts in closed copper tubes and investigated by X-ray diffractometer technique. CuSbMo2O8 crystallizes in a new structure type with monoclinic symmetry, space group C6
2h - I12/a1, a = 5.554(2), b = 4.916(1), c = 21.519(4) Å, β = 93.42(3)°, Z = 4. The crystal structure shows SbIII in a one-sided coordination by four oxygen. Molybdenum shows the rare octahedral coordination by oxygen. MoO6 and CuO6 octahedra form triple layers stacked and connected by Sb ions along [001].
Ga1.93V0.97S4, eine neue gemischtvalente Verbindung mit α-FeGa2S4-Struktur / Ga1.93V0.97S4, a New Mixed Valent Compound with α-FeGa2S4 Structure
Authors: Cordes W. , Reil S. , Haeuseler H.
Published: February 2015

The mixed valence compound Ga1.93V0.97S4 has been prepared and characterized by X-ray powder methods. The compound crystallizes in an α-FeGa2S4 structure. The lattice parameters of the hexagonal cell are a = 363.6 and c = 1207.1 pm. The structure has been refined by Rietveld methods.
Synthesis of a New Optically Active Triphosphine with a Neopentane Backbone
Authors: Heidel Horst , Huttner Gottfried , Zsolnai Laszlo
Published: February 2015

The resolution of the racemate (BzlOCH2)(Me)C (COOH)(COOEt) (±)1 is the entry point for the enantioselective synthesis of the key compound 7 (MeC(CH2Cl)(CH2Br)(CH2OTfl)). Successive phosphination of 7 furnishes the triphosphine 10 (MeC(CH2PPh2)(CH2DBP)(CH2P(3,5-Me2C6H3)2) in both enantiomeric forms (DBP = dibenzophospholyl). The structures of the precursors (+)8S(MeC(CH2PPh2)(CH2DBP)(CH2Cl)) and (±)9 (MeC(CH2Br)(CH2Cl)(CH2DBP)) have been confirmed by X-ray analysis.
CuTb2[B8O16]: Das erste „Metaborat“ mit einem 1
∞[B8O16]8--Anion / CuTb2[B8O16]: The First “Metaborate” with a 1
∞[B8O16]8- Anion
Authors: Schaefer Jan , Bluhm Karsten
Published: February 2015

Pale bluish-green single crystals of the new compound CuTb2[B8O16] have been obtained by a B2O3 flux technique. They crystallize in an unknown structure type. X-ray investigations on single crystals led to the space group C5
2h-P21/c (Nr. 14) with lattice parameters a = 1024.6(1); b = 834.93(6); c = 622.87(6) pm , β = 90.45(2)°; Z = 2. The structure contains 1
∞[B8O16]8- chains isolated from each other, which include tri- and tetracoordinated boron. The chains consist of alternating twelve- and eight-membered rings of boron and oxygen connected by BO4 units. Tb3+ is octacoordinated and Cu2+ is hexacoordinated in elongated octahedra by oxygen. The relation to the crystal structures of Tb[B3O6] and CuTb[B5O10] is pointed out.
Der erste stabile Metallkomplex mit Hydrid- und Carbonyl-Brücke ohne weitere Brücken- und π - Akzeptorliganden [(TMEDA)Ni(μ-H,μ-CO)Ni(TMEDA]X (TMEDA: N,N,N′,N′ -Tetramethylethylendiamin, X = Monoanion der cis-Cyclohex-4-en oder Cyclohexandicarbonsäure) / The First Stable Metal Complex with Hydrid- and Carbonyl Bridges without Supporting Bridging and π-Acceptor Ligands [(TMEDA)Ni(μ-H,μ-CO)Ni(TMEDA)]X (TMEDA: N,N,N′,N′-Tetramethylethylenediamine, X = Mono-anions of cis-Cyclohex-4-ene or Cyclohexanedicarboxylic Acid)
Authors: Storch Christine , Fischer Reinald , Walther Dirk , Kempe Rhett
Published: February 2015

The complex [(TMEDA)Ni(μ-H,μ-CO)Ni (TMEDA)]X 1a (TMEDA: N,N,N',N'-Tetramethylethylenediamine, X: Monoanions of cis-cyclohex-4-ene- or cyclohexane-dicarboxylic acid) could be isolated as the product of a stepwise reaction in THF solution of Ni(COD)2, TMEDA and cis-cyclohex-4-ene-dicarboxylic-anhydride in the presence of a small amount of water. Similar results are obtained with cyclohexane-dicarboxylic-anhydride. NMR- and IR-spectroscopic measurements and the single crystal X-Ray diffraction analysis of 1a have established the structure: Both a hydride- and a carbonyl bridge are linking two (TMEDA)Ni fragments in the cationic part. The Ni(I) centers are connected by a Ni-Ni-bond . The compounds are the first (TMEDA)Ni(I) complexes and the first binuclear hydrido-carbonylcomplexes which are stable without further bridging and π-acceptor ligands. They contain hydrido and protic hydrogen in the same compound.
Kristallstrukturen der „supramolekularen“ 1,4-Diazabicyclo[2.2.2]octan- Quecksilber(II)-Komplexe [Hg(dabco)I2] und [Hg(dabco)(SCN)2] / Crystal Structures of the “Supram olecular” 1,4-Diazabicyclo[2.2.2]octane Mercury(II) Complexes [Hg(dabco)I2] and [Hg(dabco)(SCN)2]
Authors: Pickardt Joachim , Shen Jing , Gong Gill-Taik
Published: February 2015

Reactions of 1,4-diazabicyclo[2.2.2]octane (“dabco”) with K2[HgI4] or Hg(SCN)2 yield crystals of [Hg(dabco)I2] (1) and [Hg(dabco)(SCN)2] (2). 1 crystallizes monoclinically, space group P21/a. Z = 4, a = 1211.6(5), b = 682.3(6), c = 1430.4(3) pm, β = 98.90(5)°; 2 is orthorhombic, space group Pmmn, Z = 2, a - 740.5(3), b = 609.1(4), c = 1220.0(8) pm. In 1 HgI2 groups are connected by bridging dabco molecules to give a chain structure. The Hg atoms are tetrahedrally coordinated. In 2 the Hg atoms are bridged by two SCN ligands and the chains thus formed are again interconnected by bridging dabco molecules, whereby layers are formed. The coordination polyhedron for the Hg atoms is a distorted octahedron.
Über das erste Oxopalladat-Arsenat: KMg3Pd(AsO4)3 / On the First Oxopalladat-Arsenate: KMg3Pd(AsO4)3
Authors: Frerichs D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of KMg3Pd (AsO4)3 have been p repared by solid state reactions below the melting point of the reaction mixture. This compound crystallizes isotypic to the mineral Johilleriteo with monoclinic symmetry, space group C 2h
6 -C 2/c , a = 12.098(3) Å, b = 12.853(5) Å , c = 6.688(3) Å, β = 112.92(3)°, Z = 4. The crystal structure is characterized by AsO4 tetrahedra, isolated planar but twisted PdO4 polygons, MgO6 octahedra and a 2+4+2- coordination of potassium . From the point of view of crystal chemistry KMg3Pd (AsO4)3 both belongs to the arsenates and oxopalladates(II).
Ternary Antimonides LnTSb3 with Ln = La-Nd, Sm and T = V, Cr
Authors: Brylak Markus , Jeitschko Wolfgang
Published: February 2015

The title compounds were prepared by reaction of the elemental components. They crystallize in a new structure type, which was determined from single-crystal X -ray data of CeCrSb3: Pbcm, a = 1310.8(3), b = 618.4(1), c = 607.9(1) pm, Z = 4, R = 0.029 for 648 structure factors and 32 variable parameters. The structure of the antimonide CeVSb3 is isotypic: a = 1319.0(2), b = 623.92(8), c = 603.03(8) pm , R = 0.041 for 477 structure factors and 32 variables. The transition metal site and one of the three antimony sites were found to have partial occupancies resulting in the exact compositions CeV0,91(1)Sb2,916(4) and CeCr0,901(9)Sb2,909(4). The structures contain fractional Sb -Sb bonds with distances varying between 301,5 and 316.4 pm. The transition metal atoms have octahedral antimony coordination. These TSb6 octahedra share faces resulting in linear infinite strings with V - V and Cr - Cr bond distances of 301.5 and 304.0 pm, respectively. The structure of these com pounds contains building elements, which are also found in antimonides with ThCr2Si2, CaBe2Ge2, and HfCuSi2 type structures.
Photochemical Generation of Tribromostannate(II) by Redox and Substitution Reactions
Authors: Pawlowski V. , Kunkely H. , Vogler A.
Published: February 2015

Hexabromostannate(IV) in acetonitrile undergoes a photochemical reductive elimination according to the equation [SnBr6]2- →[SnBr3]- + Br3
- with ϕ= 0.06 at λirr = 313 nm. The formation of [SnBr3] - takes place also by irradiation of [Ru(SnBr3)5 Br]4- in acetonitrile with visible light. This photosubstitution occures with ϕ > 0.09 at λirr = 436 nm.
Synthese und Charakterisierung von 1,3,5-Hexahydrotriazin-Komplexen des Moo und MoVI / Synthesis and Characterization of 1,3,5-Hexahydrotriazine Complexes of Mo0 and M oVI
Authors: Schumann Hans
Published: February 2015

Organo-substituted 1,3,5-hexahydrotriazine complexes of the type (RNCH2)3Mo(CO)3 (R = CH3, i - C3H7 and CH2C6H5) are obtained by ligand displacement from η6-C7H8Mo(CO)3 in high yields. These products have been characterized by 1H, 13C, 95Mo NMR, IR as well as mass spectroscopy and contain an electron-rich Mo(C O)3 center bonded to the 1,3,5-hexahydrotriazine 6e donor via three Mo -N bonds. Oxidation of the Mo0 complex 1,3,5-(CH3NCH2)3Mo(CO)3 with H2O2 under carefully controlled conditions allows isolation of 1,3,5-(CH3NCH2)3MoO3 containing a MoVI center. Chemical and spectroscopic properties of these complexes are compared with those of related Mo complexes with neutral macrocyclic ligands containing N3 donor sets.
Der kürzeste Weg zu C1-symmetrischen, chiralen tripod-Liganden mit Neopentan-Grundgerüst / The Shortest Way to C1-Symmetrical, Chiral Tripod Ligands with Neopentane Backbone
Authors: Seitz Thomas , Muth Andreas , Huttner Gottfried
Published: February 2015

Chiral tripod-ligands of the type 5 are easily accessible in four steps starting from the dibromide 1. The cleavage of the oxetane 4 b by LiPPh2 yielding the tripod-ligand 5 can be modified enantioselectively by the addition of (-)-sparteine.
Die Kristallstrukturen der silylierten Phosphanimine Me3SiNPPh3 und Me3SiNPPh2 - C2H4 - PPh2NSiMe3 / Crystal Structures of the Silylated Phosphanimines Me3SiNPPh3 und Me3SiNPPh2 - C2H4 - PPh2NSiMe3
Authors: Weller Frank , Kang Hak-Chul , Massa Werner , Rübenstahl Thilo , Kunkel Frank , Dehnicke Kurt
Published: February 2015

The crystal structures of two silylated phosphanimines have been determined. Me3SiNPPh3: Space group P 1̃, Z = 2, structure refinement with 2907 observed unique reflections with Fo > 5 σ(Fo), R = 0.052. Lattice dimensions at 19 °C: a = 876.6(1), b = 1125.8(1), c = 1151.2(1) pm, α = 61.71(1)°, β = 88.08(1)°, γ = 87.18(1)°. The compound forms monomeric molecules with a SiNP bond angle of 140.2° and bond lengths PN of 154.2 pm and SiN of 168.6 pm which correspond with PN double and SiN single bonds. Me3SiNPPh2 - C2H4 -PPh2N SiMe3: Space group P31, Z = 3, structure refinement with 4251 independent reflections, R = 0.061 for 3587 reflections with I > 2σ(I). Lattice dimensions at - 80 °C: a = b = 1591.4(1), c = 1165.8(1) pm. The compound forms monomeric molecules with a c/s-conformation of the PNSiMe3 groups. Bond angles and bond lengths (average) are SiNP = 140.8°, PN = 153.8 pm, SiN = 165.6 pm.
Synthesis of (Aminoalkyloxymethyl)dimethylphosphine Oxides
Authors: Vassileva Vesselina , Varbanov Sabi , Tashev Emil
Published: February 2015

Several (aminoalkyloxymethyl)dimethylphosphine oxides with the formula (CH3)2P(O)CH2ORNH2 have been synthesized via the Williamson reaction from (chloromethyl) dimethylphosphine oxide and sodium alcoholates of amino alcohols. The new compounds were characterized by analytical methods, IR, 1H NMR, 31P NMR spectroscopy and by mass spectrometry.
NMR Investigation and Conformational Analysis of a Synthetic Hexasaccharide
Authors: Hiegemann Monika , Duddeck Helmut , Schmidt Richard R. , Toepfer Alexander
Published: February 2015

The structure of the hexasaccharide 1 has been examined by a spectroscopic investigation using one- and two-dimensional NMR spectroscopy All 1H and 13C signals of the saccharide part were assigned. NOESY and ROESY experiments allowed to discuss the flexibility of the molecule.
Improved Conditions for Solid Phase Synthesis of Oligonucleotides on PS-PEG Copolymers
Authors: Bayer Ernst , Bleicher Konrad , Maier Martin
Published: February 2015

Polystyrene-polyethylene glycol (PS-PEG) tentacle polymers with loadings of up to 60/<μmol/g were used for standard oligonucleotide synthesis. As these resins are easy to handle and stable under reaction and cleavage conditions they may be used alternatively to controlled pore glass (CPG) as the most commonly used solid support for oligonucleotide synthesis. However, structural and chemical properties of the PS-PEG resins require modified conditions to guarantee syntheses with high coupling efficiencies. Oligonucleotides (ODN ) of various sequences and lengths have successfully been synthesized using HPLC and capillary electrophoresis (CE) for purity control. Additionally, electrospray mass spectrometry (ES-MS) was used for product identification.
Notizen: Ungewöhnliche Struktureinheiten in gemischten Metall-Alkoxid-Chloriden / Unusual Structural Units in Mixed Metal Alkoxide Chlorides
Authors: Veith Michael , Wolfanger Holger , Huch Volker
Published: February 2015

As found by X-ray structure analysis (tBuO)4AlSnCl (1) is monomeric in the crystal and has a central AlO2Sn four-membered ring (Sn -O 2,153(5) Å , Al-O 1,807(7)Å). The corresponding iso-propyl derivative 2 reacts with SnCl2 to yield a coordination polymer (iPrO)4AlSn2Cl3 3 incorporating a new trigonal bipyramidal Sn2Cl3
+ cation [angles at tin from 67,18(5) - 83,90(5)°]. 3 reacts with moisture to give the compound [(iPrO)5Cl2Al2]2O2Sn4Cl2 (4) which has a central O2Sn4Cl2-cluster of approximately D2h symmetry with four-coordinate η4-bridging chlorine atoms.
Synthese und Kristallstruktur von CuLn2[B2O5]2 (Ln = Er3+, Lu3+): zwei Kupferlanthanoidborate mit 2
∞[B2O5]4--Anionen / Synthesis and Crystal Structure of CuLn2[B2O5]2 (Ln =Er3+, Lu3+): Two Copper Lanthanoid Borates with 2
∞[B2O5]4--Anions
Authors: Schaefer J. , Bluhm K.
Published: February 2015

Single crystals of the new compounds CuLn2[B2O5]2 (Ln = Er3+(I), Lu3+(II)) were obtained by a B2O3 flux-technique. They crystallize in the space group C52h -P21/c with I: a = 453.14(6); b = 721.94(5); c = 929.5(4) pm; β = 90.01(3)°; Z = 2 und II: a = 451.4(4); b = 718.3(1); c = 928.1(3) pm; β = 90.00(6)°; Z = 2. The compounds are isotypic to CuTm2[B2O5]2 as well as to the mineral Gadolinite (FeY2 [BeSiO5]2) and exhibit layer like 2
∞[B2O5]4--anions consisting of edge sharing BO4 -tetrahedra, which form four- and eight-membered rings. The borate anions are separated by layers of elongated CuO6-octahedra and slightly distorted tetragonal LnO8-antiprisms.
Synthese und Kristallstruktur des koordinativ ungesättigten Komplexes [FeRu(CO)5(μ-PBut
2)2] / Synthesis and Crystal Structure of the Coordinatively Unsaturated Complex [FeRu(CO)5(μ-PBut
2)2]
Authors: Böttcher Hans-Christian , Hartung Helmut , Krug André
Published: February 2015

[{Ru(CO)3Cl2}2] reacts with the in situ prepared reagent Li2[Fe(CO)3(PBut
2)2] to give the new heterobinuclear complex [FeRu(CO)5(μ-PBut
2)2] (1). Crystals of 1 are isomorphous to those of the known compound [Fe2(CO)5(μ-PBut
2)2] (2) and crystallize in the triclinic space group P1̄ with a = 867,5(1), b = 1181,0(2), c = 1373,1(2) pm; α = 76,64(1), β = 79,72(1) and γ = 76,48(1)°. A double bond between the two metal atoms concluded for 2 from the results of EHMO calculations is also proposed for 1 (Fe=Ru: 259,8(1) pm).
Die Kristallstrukturen von (η5-C5Me5)MoMe4 und (η5-C5Me5)WMe4 / The Crystal Structures of (η5-C5Me5)MoMe4 and (η5-C5Me5)WMe4
Authors: Köhler Katrin , Steiner Alexander , Roesky Herbert W.
Published: February 2015

The crystal structures of (η5-C5Me5)MoMe4 1 and (η5-C5Me5)WMe4 2 are reported. 1 and 2 crystallize in the orthorhombic space group Pbcm with the lattice parameters a = 681.4(2) pm, b = 1538.6(6) pm, c = 1402.4(6) pm with 4 units per cell (1), and a = 684.99(6) pm, b = 1547.3(2) pm, c = 1405.5(2) pm with 4 units per cell (2). Both compounds are monomeric and have a square-pyramidal geometry.
Axial Coordination of Phosphine or Phosphite to Iron(III) Chlorophyll a
Authors: Inoue Hidenari , Akahori Hiromi , Ohno Yuri , Nakazawa Katsuo , Nonomura Yoshimune , Yoshioka Naoki , Heckmann Gernot , Fluck Ekkehard
Published: February 2015

The adduct formation of iron(III) chlorophyll a with phosphines or phosphites has been studied by spectroscopic methods. The red-shift in the Soret and Q bands caused by the axial coordination of phosphine or phosphite to iron(III) chlorophyll a is an evidence for the autoreduction of the central iron(III) ion. The 31P{1H} NMR spectrum of bis-adducts measured in the presence of excess phosphine or phosphite ligands gave a single peak in the down field range compared to that of the corresponding free ligand. The ESR and X-ray photoelectron spectra have revealed that the central iron atom of the bis-adduct of iron chlorophyll a with phosphines or phosphites is divalent and in the low-spin state. The axial coordination of phosphine or phosphite influences the electronic configuration of the central iron atom and the macrocyclic chlorine ligand to induce the autoreduction of the central iron(III) ion.
Hexacarbonyldieisen-stabilisierte Sulfimid-Derivate, Fe2(CO)6(μ-SNR) / Hexacarbonyl Diiron Stabilized Sulfimide Derivatives, Fe2(CO)6(μ-SNR)
Authors: Herberhold Max , Bertholdt Uwe , Milius Wolfgang
Published: February 2015

Hexacarbonyl diiron complexes of N-substituted sulfimides (SNR) have been obtained from the parent tetrahedrane, Fe2(CO)6(μ-SNH) (1), by deprotonation to give the anion Fe2(CO)6(μ-SN-) (2) and subsequent reaction with either trialkyloxonium or carbenium tetrafluoroborates. The new aza-diferra-thia-tetrahedranes, Fe2(CO)6(μ-SNR) (R = CH3 (3a), C2H5 (3b), CPh3 (3c), cyclo-C3Ph3 (3d), cyclo-C7H7 (3e), and cyclo-(C7H7)M (CO)3 with M = Cr (3f), Mo (3g), W (3h)) were characterized by their 1H and 13C NMR as well as their IR and MS spectra. The molecular structure of Fe2(CO)6[SN-cyclo-C7H7Mo(CO)3] (3g) has been determined by X-ray diffraction.
Difurocoumarins, Psoralen Analogs: Synthesis and DNA Photobinding
Authors: Caffieri Sergio , Moor Anne C. E. , van Henegouwen Gerard M. J. Beijersbergen , Dall'Acqua Francesco , Guiotto Adriano , Chilin Adriana , Rodighiero Paolo
Published: February 2015

A new tetracyclic derivative, difurocoumarin, was synthesized and studied in order to ascertain its possible use as a photochemotherapeutic agent alternative to psoralens. The compound proved able to photobind monofunctionally to DNA on irradiation with UV-A. A photocycloadduct with thymine was isolated and characterized spectroscopically.
Liquid Crystalline Compounds in the Thiophene Series, Part 11+ Liquid Crystalline Thiophene Carboxylic Esters
Authors: Koßmehl Gerhard , Hirsch Barbara
Published: February 2015

The new series of ten 4,4'-bis(5-alkyl-2-thienylcarbonyloxy)azobenzenes (2a -2j) and ten 2,5-bis(5-alkyl-2-thienylcarbonyloxy)toluenes (3a -3j) were prepared. These, as yet unknown esters were characterized in relation to their structures by elemental analyses, IR, UV, 1H NMR spectra and MS.

The azobenzene-esters 2a -2j which form liquid crystalline phases were studied by microscopy under polarized light and DSC (differential scanning calorimetry). Through the observation of the optical textures nematic phases were monitored. Only 2j has an additional smectic phase; 2h and 2i form monotropic smectic phases during cooling. The toluene-esters 3a -3j do not form liquid crystalline phases.
NOTIZEN: Mg6Ni16As7 - eine neue G-Phase / Mg6Ni16As7 - a New G Phase
Authors: Keimes Viktor , Mewis Albrecht
Published: February 2015

Mg6Ni16As7 (F m 3m ; a = 11.479(1) Å; Z = 4) was prepared by heating a mixture of the elements and investigated by means of single crystal X-ray methods. The arsenide crystallizes in a modified Th6Mn23 type structure, similar to many ternary compounds of the composition A6M16X7, called G phases.
Über die Reaktion von CF3OCI mit Lewis-Säuren und Br2 und I2 / Reaction of CF3OCI with Lewis Acids and with Br2 and I2
Authors: Minkwitz Rolf , Konikowski Detlef
Published: February 2015

The reactions of CF3OCl with SbX5 (X = F, Cl) and AsF5 at 195 K yield the adducts CF3OCl · SbX5 and CF3OCl · AsF5 respectively. At 213 K CF3OCI · SbCl5 forms SbCl4F, Cl2 and OCF2, while compounds CF3OCl · MF5 (M = As, Sb) slowly decompose giving ClF, OCF2 and mixed M(V) halides.

The formation of IF5, OCF2 and Cl2 in the oxidative fluorination of I2 with CF3OCl at 293 K is described. Br2 reacts with CF3OCl to give BrF3 under similar conditions.
New Dimeric Tetrapeptide Enkephalin Analogues with Fiveor Six-Carbon Hydrophilic Spacers
Authors: Zajączkowski I. , Stępiński J. , Temeriusz A. , Tam S. W.
Published: February 2015

To investigate the role of distance between two opioid peptide pharmacophores on binding activities to delta, mu and kappa receptor in vitro, a number of new dimeric enkephalin analogues were synthesized in which two identical tetrapeptides: Tyr-D-Ala-Gly-Phe were connected together at their C-termini by α,ω-diamino-α,ω-dideoxyalditols. The length of the hydrophilic spacer (3 -6 carbons) did not affect the affinities for delta receptors, whereas the affinities for mu and kappa receptors were dependent on the length as well as the configuration of the spacer. The analogues had high affinities, and some of them possessed moderate delta selectivity.
Aminolyse von Cp2ZrCl{P(SiMe3)2} - Synthese und Molekülstruktur von Cp2ZrCl(NHPh) / Aminolysis of Cp2ZrCl{P(SiMe3)2} - Synthesis and Molecular Structure of Cp2ZrCl(NHPh)
Authors: Lindenberg Frank , Hey-Hawkins Evamarie , Baum Gerhard
Published: February 2015

The reaction of Cp2ZrCl{P(SiMe3)2} with aniline yields the terminal zirconocene phenylamido complex Cp2ZrCl(NHPh) (1) and HP(SiMe3)2. 1 was characterized spectroscopically (n.m.r., i.r.) and by X-ray structure determination (monoclinic space group P2 {ln, a - 6.589(2), b = 19.978(3), c = 13.512(2) Å , β = 101.09(2)° (at 200 K)). The NHPh group is planar with Zr -N 2116(10) Å.
Darstellung, 11B-NMR- und Schwingungsspektren von cis-Monocyanomononitrotetrahydro-closo-hexaborat(2-) , as-[B6H4(CN)(NO2)]2- und cis-μ-Nitroso-bis(monocyanotetrahydro-closo-hexaborat)(3-), cis-[(CN)B6H4(NO)B6H4(CN)]3– sowie Kristallstruktur von [As(C6H5)4]2-cis-[B6H4(CN)(NO2)] / Preparation, n=11B-NMR and Vibrational Spectra of cis-Monocyanomononitrotetrahydro-closo-hexaborate(2-) , cis-[B6H4(CN)(NO2)]2-,cis -μ-Nitroso-bis(monocyanotetrahydro-hexaborate)(3-), cis-[(CN)B6H4(NO)B6H4(CN)]3– and the Crystal Structure of [As(C6H5)4]2-cis-[B6H4(CN)(NO2)]
Authors: Franken A. , Preetz W.
Published: February 2015

By electrochemical oxidation of [B6H5(CN)]2- in the presence of nitrite ions and of the base DBU in dichloromethane solution cis-[B6H4(CN)(NO2)]2- and cis- [(CN)B6H4(NO)B6H4(CN)]3- are formed and can be isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of the tetraphenylarsonium salt has been determined by single crystal X-ray diffraction analysis.

[As(C6H5)4]2-cis-[B6H4(CN)(NO2)] is monoclinic, space group P21/a with a = 20.343(5), b = 10.896(2), c = 21.572(5) A and β = 107.30(2)°. The 11B NMR spectra are consistent with disubstituted octahedral B6 cages with local C2v symmetry. The IR and Raman spectra exhibit characteristic NO2, NO, CN, BH, and B6 vibrations.
Methanolothermale Synthese und Kristallstruktur von Diselenido- und Ditelluridogermanaten(IV) der Alkalimetalle K – Cs / M ethanolothermal Synthesis and Crystal Structure of Diselenido- and Ditelluridogerm anates(IV) of the Alkali Metals K – Cs
Authors: Sheldrick W. S. , Schaaf B.
Published: February 2015

Methanolothermal reaction of M2CO3 (M = K, Rb) with Ge and Se yields respectively the diselenidogermanates(IV) K2GeSe4 and Rb2GeSe4, both of which contain chain anions 1
∞[GeSe4
2-] in which GeSe4 tetrahedra are linked via Se-Se bonds. A similar structural principle is found in the ditelluridogermanates(IV) Rb2GeTe4 and Cs2GeTe4, prepared by reaction of M2CO3 (M = Rb, Cs) with Ge and Te in methanol at temperatures of respectively 200 and 160 °C. The effect of cation size on the chain conformation is discussed. Rb4Ge4Se10 · CH3OH, which is formed together with Rb2GeSe4, exhibits isolated anions [Ge4Se10]4- with an adamantane-like structure.
Synthese und Strukturen von 9,10-Dihydro-9,10-diboraanthracen-Derivaten / Synthesis and Structures of 9,10-Dihydro-9,10-diboraanthracene Derivatives
Authors: Müller P. , Huck S. , Köppel H. , Pritzkow H. , Siebert W.
Published: February 2015

A series of alkyl and amino derivatives of the tricyclic organoborane system 9,10-dihydro- 9.10-diboraanthracene was synthesized and examined. The reactions of 9,10-dichlor-9,10-dihydro- 9,10-diboraanthracene ( la ) with suitable reagents yield the corresponding alkyl, aryl or amino derivatives 1c-h , respectively. The compounds have been characterized by 1H, 13C and 11B NMR spectroscopy. X-ray structure analyses have shown that the amino derivatives have bent structures, while the H2N compound 1h is planar. Calculations were carried out to study the reasons for the deformation of some of the amino-substituted derivatives. These calculations indicate that steric reasons are responsible for the deformation. Electrochemical investigations show reversible reductions of the dimethyl derivative 1c leading to the radical anion and the dianion. Both anions have been structurally characterized by X-ray diffraction studies.
Enantioselektive Katalyse, 96 [1]. Naphthalin-Aufbauglieder in der Synthese von optisch aktiven Zweischalenphosphinen / Naphthalene Units in the Synthesis of Optically Active Two-Layer-Phosphines
Authors: Brunner Henri , Berghofer Josef
Published: February 2015

Two-layer phosphines were synthesized by reacting optically active bromonaphthyl derivatives with 1,2-bis(dichlorophosphino)ethane. The optically active bromonaphthyl ethers and amines were obtained from l-bromo-2,6-bis(bromomethyl)naphthalene and the optically active alcohol (-) borneol and the optically active amine (+)-N-methyl-3-aminomethylpinane.
Zur Kristallstruktur von Ce2(WO4)3 / On the Crystal Structure of Ce2(WO4)3
Authors: Gressling T. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ce2(WO4)3 have been prepared by crystallisation from molten mixtures of WO3 and CeO2. The compound shows monoclinic symmetry, a = 7.813(4), b = 11.720(2), c = 11.586(3), β = 109.36(3)°, Z = 4, and is isotypic to Eu2(WO4)3, but shows large differences of the atomic coordinates especially of oxygen. The crystal structure of Ce2(WO4)3 is characterized by W(1)O4 tetrahedra, square W(2)O5 pyramids and a distorted capped trigonal prism of oxygen around cerium. The decrease of the oxidation states of Ce4+ or W6+ was proved by thermogravimetric and magnetic measurements as well as by calculations of the Coulomb terms of lattice energy.
Lineare Oligophosphaalkane, XXVIII [1] Redox-Cyclisierung funktioneller Methylenbisphosphane XRP-CH2-PRX (X = H, C) mit Cyclopolyphosphanen / Linear Oligophosphaalkanes, XXVIII [1] Redox Cyclization of Functional Methylenebisphosphanes XRP-CH2-PRX (X = H, Cl) with Cyclopolyphosphanes
Authors: Bitterer Frank , Langhans Klaus Peter , Stelzer Othmar
Published: February 2015

Reaction of P-H or P-Cl functional methylenebisphosphanes X (R )P - CH2-P(R)X (X = H, Cl; R = Ph, tBu) with cyclopolyphosphanes (R′P)„ (R′ = Ph, tBu, Me; n = 4, 5) affords cyclocarbatetraphosphanes CH2(RP)2(R′P)2 (2-6 ). The cyclopolyphosphanes (R′P)„ em ployed may be synthesized in situ by reaction of chlorophosphanes R′PCl2 with primary phosphanes R′PH2, LiH or magnesium, respectively, providing a single stage synthesis for unsymmetrically substituted cyclocarbatetraphosphanes.