bluuebunny/crossref_metadata_2025 huggingface dataset:
Das Laser-Seitenbandverfahren: IR-Spektroskopie mit Mikrowellengenauigkeit
Authors: Kreiner W. A. , Prinz H. , Magerl G.
Published: February 2015

Infrared spectroscopy with laser sidebands at microwave modulation frequencies Infrared spectroscopy with laser sidebands at microwave modulation frequencies (12-18 GHz) is described. After the basics of this technique several examples of saturation spectroscopy on gaseous molecules are given. As a result it is shown that, in the infrared between 900 and 1100 cm-1 this broadband tunable laser source achieves resolution (3 parts in 109) as well as absolute accuracy in frequency measurement (± 3 x 10-6 cm-1) which are comparable to microwave spectroscopy.
A Theoretical Considerationon Uranium Isotope Effects Observed in Chemical Uranium-235 Enrichment Processes
Authors: Oi Takao , Kakihana Hidetake
Published: February 2015

Theoretical consideration on the uranium isotope effects in chemical chromatographic uranium isotope enrichment processes are presented, making use of up-to-date spectroscopic, solution chemical and separation factor data. It is shown that hydration of the uranyl (UO2+
2) and uranous (U4+) ions has a profound effect on the reduced partition function ratios (RPFR’s) of these ions and that, in accordance with experiment, the RPFR of the uranous ion is larger than that of the uranyl ion. Future prospects concerning the separation factors in chemical processes are mentioned.
Deuterium Isotope Effects on the Silver Ion-Promoted Hydrolyses of S,S-Diethvlacetals of p-Substituted Benzaldehydes
Authors: Satchell Derek P. N. , Satchell Rosemary S.
Published: February 2015

Solvent deuterium isotope effects support the view that the p-N02 and p-Me derivatives of benzaldehyde S,S-diethylacetal undergo silver ion-promoted hydrolysis in water by different mechanisms.
Calculation of the Melting Curves of some Alkali-halides with CsCl Structure and their Thermodynamic Properties along these Curves
Authors: Soulayman S. Sh. , Harfoush A.
Published: February 2015

The paper presents a study of three semi-empirical laws of melting. The study utilises the Improved Unsymmetrized Self-Consistent Field Method (IUSCFM) for strongly anharmonic crystals with complex lattice and the energy criterion in calculating the melting curves of some alkali-halides. The energy criterion was proven correct along the melting curves particularly in the case of CsCl type of structure. The calculations of the melting curves for crystals of nine alkali-halides (KCl, KBr, KI, RbCl, RbBr, Rbl, CsCl, CsBr, Csl) are presented. The thermodynamic properties of these salts along the curves are also determined. A comparison of the calculated results and the experimental data is included.
Triplet Exciton and Trap States in the Charge - Transfer Crystal Anthracene / Tetrachlorophthalic Anhydride (A/TCPA)
Authors: Mühle W. , Krzystek J. , von Schütz J. U. , Wolf H. C.
Published: February 2015

Mobile triplet excitons in A/TCPA have been detected from 1.2 to 300 K via ESR and zero-field ODMR. Their features such as linewidth and zero-field-splitting (zfs) parameters are discussed in terms of the temperature-dependent crystal structure. Between 1.2 and 4.2 K the excitons are caged by barriers. When raising the temperature a thermally activated hopping takes place between two triplet bands separated by 40 cm−1, having different zfs parameters | DA | = 2126.5, |EA| = 241.0, | DB | = 2112.5, | EB | = 238.0 MHz and different zfs tensor orientations. Above 100 K an increase of the librations of the anthracene molecules broadens the homogeneous excitonic lines. The homogeneous linewidth is measured by the free induction decay. The CT character of the triplet state is estimated as c2
CT <̳4%.
Characteristic Relaxation Times of Low-temperature Semiconductor Breakdown Kinetics
Authors: Peinke J. , Parisi J. , Rau U. , Clauß W. , Weise M.
Published: February 2015

The nonlinear transport behavior during low-temperature avalanche breakdown of extrinsic germanium is associated with the self-generated formation of spatio-temporal current structures. Very close to the critical phase transition between different conducting states, the underlying physical relaxation processes develop on relatively slow macroscopic time scales in the ms range. We have evaluated the slowing down of the characteristic time constants from independent measurements of the system response behavior to external pulsed excitations.
Infrared Spectra of 14C2H2 and 12C14CH2 : The ν1
5 Band
Authors: Dobos S. , Kling F. , Winnewisser G. , Keresztury G.
Published: February 2015

The infrared absorption lines of a mixture of 14C2H2 and 12C14CH2 around 725 cm−1 have been recorded with a high resolution (0.04 cm−1) FTIR spectrometer. Rotational structures of P, R and Q branches of the ν1
5 bands were analyzed and molecular constants ν0, B′, B″, D′ and D″ calculated.
Simplification of Rotational Spectra and Spectral Hole Burning by Selective Excitation Techniques in Microwave Fourier Transform Spectroscopy
Authors: Vogelsanger B. , Bauder A.
Published: February 2015

Selective excitation techniques have been applied to pulsed microwave Fourier transform spectroscopy. The frequency selectivity in excitation has been reached either by a long, weak pulse, or by a DANTE multi-pulse sequence. The corresponding excitation spectra calculated from a density matrix theory are in good agreement with the experimental results. The selective excitation techniques have been combined with double resonance sequences in order to simplify the recorded one-or two-dimensional spectra. Furthermore, selective excitation techniques have been applied to burn ‘holes’ into rotational transition lines broadened by an inhomogeneous Stark field.
Deuterium Quadrupole Coupling Constants in Deuterochloroacetylene
Authors: Heineking N. , Andolfatto M. , Keussen U. , Mues A. , Dreizler H.
Published: February 2015

The deuterium and chlorine nuclear quadrupole coupling constants have been determined for both of the chlorine isotopomers of deuterochloroacetylene (DCCC1), along with the rotational, centrifugal distortion, and chlorine spin-rotation coupling constants. The values are B = 5186.97631 (22) MHz, DJ= 1.13(2) kHz, eQq(Cl)= -79.7358(19) MHz, cI(Cl) = 1.10(31)kHz, and eQq(D) = 207.0(28)kHz for DCCCl-35, and B = 5084.17839(30) MHz, DJ = 0.99(2) kHz, eQq(Cl)= -62.8451(27) MHz, cI(CI) = 0.76(43) kHz, and eQq(D) = 205.8(39)kHz for DCCCl-37.
O 1s Core-Level Positions of Bi2Sr2CaCu2O8-x by OKα-Ray Emission
Authors: Burgäzy F. , Politis C. , Lamparter P. , Steeb S.
Published: February 2015

The measured O Kα X-ray emission spectrum of the high-Tc superconductor Bi2Sr2CaCu2O8-x is compared with a spectrum based on local density band structure calculations. By taking also into account the shape of the measured O 1s X-ray photoelectron spectrum an energy level diagram for the O 1s core-level binding energies of the three different oxygen sites is constructed. The O 1s binding energy in the Bi2O2-layers is found to be about the same as that one in the SrO-layers, whereas the binding energy in the CuO2-layers is lower by about 0.5 eV.
Dipole-Dipole Transport of Excitation in Liquid Solutions: Influence of Multi-Stage Energy Transfer on Donor Photoluminescence Yield
Authors: Kuśba J.
Published: February 2015

On the basis of expressions obtained earlier, numerical calculations of relative donor quantum yields in the presence of multi-stage dipole-dipole energy transfer and material diffusion are carried out. Transfer rates of the second order obtained from the numerical solution of the diffusion equation with reflecting boundary conditions are used in the calculations. The results reflect the influence of donor and acceptor concentration, magnitude of diffusion coefficients and molecular size effects.
Nitrogen and Deuterium Hyperfine Structure in the Rotational Spectrum of Morpholine
Authors: Grabow J.-U. , Ehrlichmann H. , Dreizler H.
Published: February 2015

We reinvestigated the rotational spectra of morpholine and N-deutero morpholine with the higher precision of microwave Fourier transform spectroscopy. The rotational, centrifugal, and nitrogen quadrupole coupling constants were improved and the deuterium quadrupole coupling constants determined.
Dust in the Solar System
Authors: Fechtig H.
Published: February 2015

Properties of cometary dust particles are better known since the space missions to Comet Halley. Their properties (densities, atomic composition) are compared with relevant observations from lunar microcraters and in-situ experiments. At 1 AU in the eliptic, 2/3 of the dust grains are normal density particles, presumably of asteroidal origin and irregularly shaped, while the remaining 1/3 are low density particles, presumably of cometary origin, but due to solar irradiation in a processed state (corresponding to “Brownlee”-particles). Beyond the asteroidal belt only black cometary dust grains are observed which have recently been released from comet nuclei orbiting on highly eccentric trajectories.
Xenon in Chondritic Metal
Authors: Marti K. , Kim J. S. , Lavielle B. , Pellas P. , Perron C.
Published: February 2015

We report xenon isotopic abundances observed in the stepwise release of noble gases in a highpurity metal separate of the Forest Vale (H4) chondrite. We identify a 244Pu-derived fission component, due to recoils into the metal, a cosmic-ray-produced spallation component and a new trapped component (FVM; 132Xe: 134Xe: 136Xe = 3.16:1.235:1.000) which is isotopically distinct from known solar system reservoirs. We discuss several processes which might account for observed isotopic shifts and conclude that the signature of FVM xenon may provide clues regarding the origin of chondritic metal.
The Trace Element Chemistry of the Metal in IAB Iron Meteorites
Authors: Larimer John W. , Rambaldi Ermanno R.
Published: February 2015

Metal grains from a silicate inclusion in Landes, a group IAB iron-meteorite, were separated and analyzed via IN A A for 14 siderophile elements. The same 14 elements were determined in matrix metal from Landes, 5 other IAB meteorites and three anomalous iron meteorites. Compared to the other samples and to chondritic metal, the inclusion metal is enriched in siderophile elements. In chondritic metal, the siderophile element contents are higher when Fe0 is oxidized to FeO. Silicates in IAB inclusions contain little FeO, yet the metal is as rich in siderophile elements as the most oxidized chondrites.

Evidently the IAB body contained its full cosmic complement of S resulting in an FeS content ~5 x that of ordinary chondrites. This explains the composition of the metal since sulfurization, like oxidation, reduces the available Fe0. IAB meteorites contain their full cosmic complement of other moderately volatile elements, which implies an equally high S content. A high S content significantly affects the melting and freezing of FeNi-metal. About 85% of the metal melts at the Fe-FeS eutectic (~960 °C), and all of the metal is molten at ~1050°C. During cooling, ~85% of the metal crystallizes with a Ni content of 6±1% between 1050°c and 960°C. Besides a small depletion in elements with low melting points or chalcophile tendencies this metal is little fractionated. Bellow 960 °C, the Ni content of the metal increases until the melt is exhausted. This Ni-rich metal also becomes progressively depleted in refractory elements and enriched in volatile elements. The crystallization process thus yields products that mimic the abundance and composition of group IAB meteorites.
Axisymmetric Dynamo Solutions
Authors: Lortz D.
Published: February 2015

It is shown that a small anisotropy of the magnetic diffusivity tensor admits stationary axisymmetric solutions of the kinetic dynamo problem. For the case of a large aspect ratio the solutions can be expressed explicitly in terms of elementary functions
QED Based on Self-Fields: A Relativistic Calculation of g-2
Authors: Barut A. O. , Dowling Jonathan P.
Published: February 2015

A recently advanced theory of quantum electrodynamics which is not second quantized, but rather based on self-fields is adopted to a relativistic calculation of (g-2). In analogy to classical electrodynamics, radiative corrections are seen as arising from the back reaction of the self-field upon the source. Vacuum field fluctuations, assumed to be the physical cause of radiative correction in standard QED. are absent in the present self-field approach, which recently has been applied to calculate spontaneous emission, Lamb shift, vacuum polarization, and to a non-relativistic calculation of (g-2), all in free space as well as in cavities. We conclude that the self-field of the electron can be consistently considered to be the physical origin of all radiative processes, as an alternative picture to hypothetical vacuum fluctuations
Algebraic Studies of Kekulé Structures. A Semilattice Based on the Sextet Rotation Concept
Authors: Gutman I. , Teodorović A. V. , Kolaković N.
Published: February 2015

A semilattice defined by Ohkami et al. on the set of the Kukulé structures of a benzenoid hydrocarbon is examined and some of its properties are pointed out
Structural Phase Transitions in [(C2H5)4N]3Sb2Br9 and [(C2H5)4N]3Bi2Br9
Authors: Zaleski J. , Jakubas R. , Galewski Z. , Sobczyk L.
Published: February 2015

Dielectric, DSC and preliminary X-ray diffraction studies on [(C2H5)4N]3Sb2Br9 (TEABA) and [(C2H5)4N]3Bi2Br9 (TEABB) are reported. The compounds are isomorphous, space group P6322. The static electric permittivity measurements on single crystals in the temperature range 220 - 290 K revealed that both compounds show two distinct dielectric anomalies; TEABA at Tc1 = 258 K and Tc2 = 252 K, while TEABB at Tc1= 265 K and Tc2 = 248 K. The DSC studies show only one anomaly of first order at Tc1 =258 K for TEABA, and Tc1 =266 K for TEABB. These transitions are presumably related to a freezing of the reorientational motion of the tetraethylammonium cations
Dynamical Instabilities in a Diffusion Layer
Authors: Baier Gerold , Urban Peter , Wegmann Klaus
Published: February 2015

We investigate the dynamics of a reaction-diffusion-convection enzyme system as a function of relevant parameters and observe reproducible types of periodic and aperiodic oscillations. These oscillations arise within a narrow diffusion layer only. Some implications for more complex reaction networks are considered
Large-N Expansion for a Nucleon-Nucleon Potential
Authors: Büyükkilic Fevzi , Demirhan Dogan
Published: February 2015

The Schrödinger equation has been solved by \/N expan­ sion for a two nucleon system which interacts by an attrac­ tive Yukawa potential. For the ground and first excited states, energy eigenvalues have been obtained.
Magnetic Field Distribution Measurement by the Modified FLASH Method
Authors: Weis Ján , Frollo Ivan , Budinský Luboš
Published: February 2015

Magnetic field inhomogeneities cause blurring and distortion of images gained by nuclear magnetic resonance. In order to adjust the magnetic coils finely, a precise and rapid method for measuring the magnetic field is needed. We describe a gradient echo technique of the FLASH version for mapping static magnetic fields.
Eine Auswertmethode für DSC-Kurven binärer Gemische sowie die Phasendiagramme einige rMethylchlorsilane mit Lutidin / A New Evaluation of DSC-curves of Binary Mixtures and the Phase Diagrams of Some Methylchlorosilanes with Lutidine
Authors: Hensen Karl , Dräbing Michael
Published: February 2015

A new evaluation of DSC-curves of binary mixtures is given. By analyzing the phase diagrams of methyltrichlorosilane and dimethyldichlorosilane with some lutidines the existence of the incongruently melting addition compounds MeSiCl3 · (2.3-Lutidine)-,, MeSiCl3 · 2.3-Lutidine, (MeSiCl3)2 · 3.4-Lutidine, Me,SiCl2 · (2.3-Lutidine)2, Me2SiCl2 · (2.5-Lutidine),, Me2SiCl2 · 2.5-Lutidine, Me2SiCl2 · (2.6-Lutidine)2, Me2SiCl2 · 2.6-Lutidine, Me2SiCl2 · (3.4-Lutidine)2, Me,SiCl2 · 3.4-Lutidine, (Me2SiCl2)2 · 3.4-Lutidine, Me2SiCl2 · (3.5-Lutidine)2, Me2SiCl2 · 3.5-Lutidine, and the congruently melting compound MeSiCl3 ·(3.4-Lutidine)2 was proven.
Ion Dip Spectrum of the Fluorobenzene-Argon van der Waals Complex in a Supersonic Jet
Authors: Bader H. , Krätzschmar O. , Selzle H. L. , Schlag E. W.
Published: February 2015

The ion dip spectrum of the fluorobenzene-Argon van der Waals complex has been measured and the complex shift in the ground state is determined. The observed dips then could be assigned by comparison with the ion dip spectra and hotband spectra of the fluorobenzene molecule.
Relativistic Ground and Excited State Energies of a/1-Particle in Hypernuclei Using Woods-Saxon Potentials
Authors: Koutroulos C. G.
Published: February 2015

The relativistic Dirac equation with a scalar potential and the fourth component of a vector potential of the Woods-Saxon shape is solved numerically for potential parameters obtained by a last squares fitting procedure of the ground state binding energies of the Λ in a number of hypernuclei and its binding energies in the ground and excited states (as well as the relevant spacings) for various hypcrnuclei are determined. The results are in very good agreement with the preliminary experimental ones given by Chrien on the basis of the (π+, K+) reaction on nuclei.
Die isoelektronischen Molekülkomplexe TiCl3(NPPh3) und TiCl3(OSiPh3) / The Isoelectronic Molecular Complexes TiCl3(NPPh3) and TiCl3(OSiPh3)
Authors: Rübenstahl Thilo , Wolff von Gudenberg Dorothea , Weller Frank , Dehnicke Kurt , Goesmann Helmut
Published: February 2015

TiCl3(NPPh3) and TiCl3(OSiPh3) have been prepared from titanium tetrachloride and Me3SiNPPh3 and HOSiPh3, respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations.

TiCl3(NPPh3): Space group R3̄̅, Z = 6, structure analysis with 959 observed unique reflections, R = 0.039. Lattice dimensions at -68°C: a = b = 1370.5(7), c = 1845.9(9) pm.

TiCl3(OSiPh3): Space group P21/c, Z = 8, structure analysis with 4549 observed unique reflections, R = 0.049. Lattice dimensions at 19°C: a = 2127.7(2), b = 947.2(1), c = 2136.8(1) pm, β = 105.081(5)°.

Both complexes form monomeric molecules in which the titanium atom is tetrahedrally coordinated by three chlorine atoms, the nitrogen atom of the phosphorone iminato ligand and the oxygen atom of the silyloxy group, respectively. The bond lengths TiN of 171.9(4) pm and TiO of 171.0(3) (in average) correspond to double bonds.
Darstellung, Eigenschaften und elektronische Raman-Spektren von Di(bromo)phthalocyaninatometallaten(III) der Eisengruppe / Synthesis, Properties and Electronic Raman Spectra of Di(bromo)phthalocyaninatometalates(III) of the Iron Group Elements
Authors: Sievertsen Svend , Schlehahn Hendrik , Homborg Heiner
Published: February 2015

Low spin di(bromo)phthalocyaninatometalates of tervalent iron, ruthenium and osmium ([MBr2Pc2-]-) are formed by the reaction of [FeBrPc2-] or H[MBr2Pc2-] (M = Ru, Os) with excess bromide in DMF or THF and isolated as (nBu4N)+ salts. The electronic spectra show the typical π- π*- transitions (B, Q, N region) of the Pc2- ligand together with a number of extra bands due to trip-multiplett and (Pc, Br → M)CT transitions. νs(MBr) is observed in the resonance Raman (RR) spectrum (RR enhanced for M = Fe, Ru) at 161 cm-1 (Fe), 183 cm-1 (Ru) and 192 cm-1 (Os), νas(MBr) at 251 cm-1 (Fe), 234 cm-1 (Ru) and 218 cm-1 (Os) in the FIR spectra. The RR spectra obtained by excitation at low absorbance between the B and Q region are dominated by the intraconfigurational " Γ7 →Γ 8" transition due to spin orbit splitting of the 2T2g ground state for Fe at 583 cm-1, Ru at 1026/1050 cm-1 and Os at 3131 cm-1 . In the MIR resp. NIR spectra vibronically induced transitions are observed for the Ru or Os complex.
Ligandenmangelkomplexe des Cadmiums. Synthese und spektroskopische Charakterisierung molekularer (Pentafluorphenyl)cadmium-Thiolate und die Struktur des Cubankomplexes [{Cd(C6F5)(SBut)}4] / Ligand-Deficient Complexes of Cadmium. Synthesis and Spectroscopic Characterization of Molecular Pentafluorophenyl Cadmium Thiolates and the Structure of the Cubane Complex [{Cd(C6F5)(SBut)}4]
Authors: Duhme Anne-Kathrin , Strasdeit Henry
Published: February 2015

In toluene, bis(pentafluorophenyl)cadmium(II) and thiols RSH (R = But, 2,4,6-Pri
3C6H2, 2,4,6-But
3C6H2) react to give soluble pentafluorophenyl cadmium thiolates [(Cd(C6F5)(SR)}n] The compounds [{Cd(C6F5)(SBut)}4] (1) ∙ 0.5 C6H5CH3, [ {Cd(C6F5)(SC6H2Pri
3-2,4,6)}n ] (2) ∙ ca. 0.25n C6H5CH3, and [{Cd(C6F5)(SC6H2But
3-2,4,6)} n] (3) ∙ ca. 0.25 n C6H5CH3 have been prepared in 65, 59 and 78% yield, respectively. 1 ∙ 0.5 C6H5CH3 crystallizes in the triclinic space group P1̄ with a = 11,635(1)Å, b = 11.583(1)Å, c = 21.480(2)Å, α = 82.12(1)°, β = 76.26(1)°, γ = 89.35(1)°, and Z = 2. 1 is a cubane-type complex with a {Cd4(μ3-SBut)4}4+ core. Each Cd atom is coordinated by three bridging thiolato ligands and one terminal C6F5 group (Cd - S 2.62 Å, Cd - C 2.15 Å (mean values)).

The central C atoms of the ButS− ligands of 1 show a remarkable low-field shift o f their 13C NMR resonance (12.3 ppm relative to the value of the free thiol). A characteristic spectral feature of (Cd(C6F5) }+ complexes is the large value of the coupling constant 2J (19F ,13C) of the ipso-C atom (1, 2: 68 Hz; 3: 67 Hz). The complexes [Cd(C6F5)(SR) + H]+, [Cd(SR)2 + H]+, and [Cd2(SR)3]+ were identified in the Cl mass spectra (iso-butane) of 2 and 3.
8-(Phenylamino)-l-naphthalinsilbersulfonat (8,1 ANS-Ag) / 8-(Phenylamino)-l-naphthalene-silversulfonate (8,1 ANS -Ag)
Authors: Hüttenhain Stefan H. , Balzer Wolfgang
Published: February 2015

8-(Phenylamino)-l-naphthalene-silver sulfonate 2 was prepared from the corresponding ammonium salt 1 and silver nitrate under ambient conditions in ethanol. From 2 salts with several other monovalent cations were obtained. All of them show similar fluorescence properties. Attempts to esterify the sulfonate group by means of alkylhalides were unsuccessful. Only after prolonged reaction times several decomposion products were detected in the TLC.
Thiazyltrifluorid-Komplexe von Mg und Zn / Thiazyltrifluoride Complexes of Mg and Zn
Authors: Behrens Ulrich , Hoppenheit Reinhard , Isenberg Wilhelm , Lork Enno , Petersen Jan , Mews Rüdiger
Published: February 2015

The preparations of [Mg(NSF3)4](AsF6)2 (2a) and [Zn(NSF3)4](AsF6)2 (2b) are reported. The structure of 2b was determined by X-ray diffraction. The ligand properties of NSF3 are discussed.
Zinc Complexes of Dimethyl(phthalimidomethyl)phosphine Oxide
Authors: Varbanov Sabi , Russeva Elena , Ganchev Andrei
Published: February 2015

A series o f zinc complexes of dimethyl(phthalimidomethyl)phosphine oxide (DPPO, L) have been synthesized: ZnX2L2, where X = Cl, Br, I or NO3. The complexes are characterized by elemental analysis, infrared and 1H NMR spectra and X-ray powder analysis. Infrared spectral data show that L is coordinated to zinc via the phosphoryl oxygen atom. The zinc halide complexes are found to be isostructural, while the pattern o f Zn(NO3)2L2 differs considerably from those o f halide complexes.
Das THF-9-Natriumoxy-9-borabicyclo[3.3.1]nonan-Tetramer [1] / The THF-9-Sodiooxy-9-borabicyclo[3.3.1]nonane Tetramer [1]
Authors: Köster Roland , Seidel G. , Bläser Dieter , Boese Roland
Published: February 2015

The thermolysis of Na[C8H14B(Et)OH] (2), prepared from 9-Et-9-BBN (1) and NaOH, leads at about 100 °C in the presence of NaHBEt3 as catalyst to ethane and the solid NaOBC8H14 (3), which crystallizes with one mole THF as the tetrameric heterocubane 4 in the triclinic space group P1̄. The lattice constants of 4 (at 120 K) are: a = 1127.7(2), b = 1179.5(2), c = 2055.9(4) pm; α = 87.06(2), β = 87.83(2), γ = 75.37(2)°. 4 contains a slightly distorted central Na4O4 cube with C8H14B and THF substituents at the oxygen and the sodium atoms respectively. 3 can also be prepared by heating an equimolar mixture of Na[H2BC8H14] (5) and Na[(HO)2BC8H14] (6), or from (9H-9-BBN)2 and NaOH and from 9-HO-9-BBN and NaH in THF.
Dimere 9-Hydrochalkogeno-9-BBN-Verbindungen - Bildung und Kristallstruktur [1] / Dimeric Hydrochalcogeno-9-BBN Compounds - Formation and Crystal Structure [1]
Authors: Köster Roland , Seidel Günter , Bläser Dieter , Boese Roland
Published: February 2015

The trans-dimer of (9-HS-9-BBN)2 (1)2, obtained from H2S with (9H-9-BBN)2 or with (9-BBN)2S, crystallizes in the monoclinic space group C2/m [lattice constants (at 120 K): a = 15.279(2), b = 15.909(3), c = 6.822(4) Å; β = 91.05(4)°] with a planar B2S2ring. The cis-dimer of (9-HSe-9-BBN)2 (2)2, obtained from (9-BBN)2Se with aniline, crystallizes in the monoclinic space group P21/n [lattice constants (at 225 K): a = 6.892(1), b= 20.623(3), c = 12.226(2) Å; β = 97.28°] with an folded B2Se2ring.
Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XLIII [1]: Photoreaktionen von Hexacarbonyl-μ-η5:5-fulvalen-dimolybdän und -diwolfram mit konjugierten Cyclodienen / Hindered Ligand Movements in Transition Metal Complexes, XLIII [1]: Photoreactions of Hexacarbonyl-μ-η5:5-fulvalene-dimolybdenum and -ditungsten with Conjugated Cyclodienes
Authors: Kreiter Cornelius G. , Conrad Wolfgang
Published: February 2015

Hexacarbonyl-μ-η5:5-fulvalene-dimolybdenum (1) reacts photochemically with 1,3-cyclopentadiene (a), and 1,3-cyclohexadiene (b) to yield the corresponding tetracarbonyl-η4-1,3-cyclodiene-μ-η5:5-fulvalene-dimolybdenum complexes 4a, 4b. With a also mixed valent tricarbonyl-η5-cyclopentadienyl-μ-η5:5-fulvalene-hydrido-dimolybdenum (3) is formed. Hexacarbonyl-μ-η5:5-fulvalene-ditungsten (2) yields with a only tricarbonyl-η5-cyclopentadienyl-μ-η5:5-fulvalene-hydrido-ditungsten (5). The η4-1,3-cyclodiene ligands in 4a, 4b are u-oriented towards fulvalene. The complexes 4a, 4b show hindered inversions with energy barriers of ΔG#
273 = 59.9 ± 2 kJ/mol (4a) and ΔG#
293, = 62.7 ± 2 kJ/mol (4b).
Synthese und Kristallstraktur von [{Cp(CO)2Fe}2Sn(F)FBF3] / Synthesis and Crystal Structure of [{Cp(CO)2Fe}2Sn(F)FBF3]
Authors: Merzweiler Kurt , Weisse Laurent , Kraus Harald
Published: February 2015

[{Cp(CO)2Fe}2SnCl2] reacts with AgBF4 to form [{Cp(CO)2Fe}2Sn(F)FBF3] 1.1 crystallizes in two monoclinic modifications with a = 1018.2(4), b = 1321.1(5), c = 1364.8(5) pm, β = 104.96(4)° (1a), and a = 983.1(2), b = 1760.2(6), c = 1060.4(3) pm, β = 104.28(2)° (1b). 1a and 1b contain a nearly tetrahedrally coordinated tin atom which is bonded to two {Cp(CO)2Fe} fragments, a F atom and a BF4 group.
Synthesis of Ethylene Bridged Biscyclopentadiene Ligand Precursor Compounds and Some of their ansa-Zirconocene Derivatives via Chiral Epoxides: A Synthetic Strategy of High Variability
Authors: Rieger Bernhard , Jany Gerhard , Steimann Manfred , Fawzi Riad
Published: February 2015

The chiral ligand precursor systems [1-Cp1-R1-2-R2-2-Cp2]ethane 5a-d bearing two different cyclopentadienyl fragments (Cp1, Cp2 = Cp, Ind, Flu) and a variable bridge substitution pattern (R1, R2=H, Ph, cyclopentyl, cyclohexyl) were prepared starting from the corresponding epoxides. The solid state structures of six organic intermediates are reported in order to prove the stereochemistry of the ligand forming reactions. Treatment of the dilithio salts of 5a-d with ZrCl4 in CH2Cl2 afforded chiral ansa-zirconocene dichlorides (6a-d).
Homoleptische 1,4-Diazadienverbindungen elektronenarmer Übergangsmetalle. Synthese, Eigenschaften und Strukturen von (DAD)2Ti und (DAD)3Ti [1] / Homoleptic 1,4-Diazadiene Compounds of Early Transition Metals. Syntheses, Properties and Structures of (DAD)2Ti and (DAD)3Ti [1]
Authors: Goddard Richard , Krüger Carl , Hadi Ghassan Abdul , Thiele Karl-Heinz , Scholz Joachim
Published: February 2015

Syntheses and structures of homoleptic 1,4-diaza-1,3-diene (DAD) complexes of titanium are described. The spiranoid DAD complexes of formula (DAD)2Ti 3a-c are formed by reaction of TiCl4·2THF with the disodium salts Na2DAD 2a-c or by reduction of TiCl4·2TH F with magnesium in presence of two equivalents of DAD 1a-c . The endiaide complexes 3a-c are thermally stable, very sensitive to oxygen and water, and soluble in all com monorganic solvents. An X-ray crystal structure determination of 3 c reveals the titanium atom to be in a strongly distorted tetrahedral environment. The two five-membered metallacyclic

rings are folded along the N,N′ axis. Temperature-dependent 1H NMR spectra of 3a-c indicate a rapid intramolecular inversion of this non-planar ring system in solution even at room temperature.

Reduction of TiCl4·2THF with magnesium in presence of excess DAD 1d-f leads to the formation of the blue-violet complexes (DAD)3Ti 4d-f. At low temperatures three sterically crowded DAD ligands cause a rigid conformation as demonstrated by their unique lowtemperature 1H NMR spectra.
μ2-Halogenokomplexe von N-Iodsuccinimid. Die Kristallstrukturen von PPh4[X(N-Iodsuccinimid)2] · CH3CN mit X = Cl, Br, / μ2-Halogeno Complexes of N-Iodosuccinimide. The Crystal Structures of PPh4[X(N-Iodosuccinimide)2] · CH3CN with X = Cl, Br, I
Authors: Ghassemzadeh Mitra , Dehnicke Kurt , Goesmann Helmut , Fenske Dieter
Published: February 2015

The μ2-halogeno complexes PPh4[X(N-Iodosuccinimide)2] · CH3CN with X = CL Br, I have been prepared by reactions of N-Iodosuccinimide with the corresponding tetraphenylphos- phonium halides PPh4X in acetonitrile solutions. The compounds form pale yellow crystal needles, which were characterized by IR spectroscopy and by crystal structure determinations.

PPh4[Cl(N-Iodosuccinimide)2] · CH3CN (1): Space group Pna21, Z = 4, 4461 observed unique reflections. R = 0.027. Lattice dimensions at -60 °C: a = 1840.5(9), b = 2589(1), c = 728.2(4) pm.

PPh4[Br(N-Iodosuccinimide)2] · CH3CN (2): Space group Pna21 Z = 4, 4284 observed unique reflections, R = 0.034. Lattice dimensions at -70 °C: a = 724.8(4), b = 1838.6(9), c = 2601(1) pm.

PPh4[I(N-Iodosuccinimide)2] · CH3CN (3): Space group Pna21, Z = 4, 5775 observed unique reflections. R = 0.031. Lattice dimensions at -60 °C: a = 1849.2(9). b = 2644(1), c = 730.3(4) pm.

1-3 are isotypical. There structures consist of PPh4
+ ions, including acetonitrile molecules without bonding interactions, and anions [X(iodosuccinimide)2]-, in which the halide ions X- are coordinated bv the iodine atoms of the N-iodosuccinimide molecules. The bond angles I··· X···I range from 90.13(4)° (X = Cl) and 88.84(3)° (X = Br) to 87.83(3)° (X = I). The bond angles N- I ··· X are nearly linear.
Benzyliden-und Methylen-bis-silyltriflate als neue Synthesebausteine für Organosiliciumpolymere/ Benzylidene-and Methylene-bis-silyltriflates as New Synthetic Materials for Organosilicon Polymers
Authors: Uhlig W.
Published: February 2015

The title compounds have been prepared by reaction of phenyl-, allyl- or amino-substituted disilylmethanes and disilylphenylmethanes with trifluoromethanesulfonic acid. New organo- silicon oligomers and polymers are obtained in good yields and high purities from these silyltriflates and lithium acetylides, triphenylgermyllithium or diphenylsilanediol/triethylamine. In these compounds the carbosilane units are connected by alkyne or siloxane bridges. The structures have been confirmed by NMR spectroscopy (29Si, 13C, 1H) and elemental analysis.
Neue metallorganisch substituierte Zinn-Tellur-Verbindungen. Synthese und Kristallstrukturen von [{Cp(CO)2Fe}4Sn2Te2], [{Cp(CO)3Mo}4Sn2Te2] und [{Cp(CO)3Mo}4Sn4Te6] / New Organometallic Tin-Tellurium Compounds. Syntheses and Crystal Structures of [{Cp(CO)2Fe}4Sn2Te2], [{Cp(CO)3Mo}4Sn2Te2] and [{Cp(CO)3Mo}4Sn4Te6]
Authors: Merzweiler Kurt , Kraus Harald
Published: February 2015

Organometallic tin halides R2SnCl2 (R = {Cp(CO)2Fe}, {Cp(CO)3Mo}) react with Te(SiMe3)2 to form the compounds [{Cp(CO)2Fe}4Sn2Te2] 1, [{Cp(CO)3Mo}4Sn2Te2] 2 and [{Cp(CO)3Mo)4Sn4Te6] 3. According to crystal structure determinations, 1 and 2 contain planar Sn2Te2 rings. 3 consists of an adamantane-like Sn4Te6 framework.
A Pentamethylcyclopentadienyl Ligand Functionalized with a Pendant Pyridyl Group; Crystal Structure of its Ferrocene-Type Iron Complex
Authors: Siemeling Ulrich , Neumann Beate , Stammler Hans-Georg
Published: February 2015

The novel cyclopentadiene HMe4C5CH2CMe2py [py = 2-(4-tert-butyl)pyridyl] 2H has been prepared from tetramethylfulvene and lithiated 2-isopropyl-4-tert-butylpyridine. Lithiation of 2H with BunLi and subsequent reaction with FeCl2 yields the ferrocene (2)2Fe, which crys­tallizes in the triclinic space group P1̅ with a = 8.368(1), b = 8.468(1), c = 14.313(1) Å, α = 80.64(1), β = 86.67(1), γ = 80.12(1)° and V = 985.4(2) Å3.
Beiträge zur Chemie des Phosphors, 228 [1] Funktionalisierte Diphosphane als Synthesebausteine: LiH(t-BuP)2, Li2(t-BuP)2, K2(i-PrP)2, (i-PrP)2Cl2 / Contributions to the Chemistry of Phosphorus, 228 [1] Functionalized Diphosphanes as Synthetic Building Blocks: LiH(t-BuP)2, Li2(t-BuP)2, K2(i-PrP)2, (i-PrP)2Cl2
Authors: Baudler Marianne , Tschäbunin Helmut , Suchomel Horst , Hasenbach Jürgen
Published: February 2015

1-Lithiurn-2-hydrogen-1,2-di-tert-butyldiphosphide (1) and 1,2-dilithium-1,2-di-tert-butyldiphosphide (2) have been synthesized by the metalation of 1,2-di-tert-butyldiphosphane with H-butyllithium. 1,2-Dipotassium-1,2-diisopropyldiphosphide (3) and 1,2-dichloro-1,2-diisopropyldiphosphane (4) were obtained by the degradation of a mixture of isopropylcyclophosphanes (i-PrP)3,4 by potassium and phosphorus(V) chloride, respectively. The compounds 1-4 are easily accessible starting materials for the synthesis of open-chain and cyclic terf-butylor isopropylphosphanes. The 31P NMR parameters of 1 -4 as well as of the triphosphide K2(i-PrP)3 and the tetraphosphide K2(i-PrP)4 are reported
Ubergangsmetallkomplexe mit schwefel-liganden, cv* ni(ii)- und ni(iii)-komplexe mit dem funfzahnigen thioether- thiolat-amin-liganden 'nmes4'2-('nmes4'2- = dianion von 2,2'-bis(2-mercaptophenylthio)diethylmethylamin) / Transition metal complexes with sulfur ligands, cv* ni(ii) and ni(iii) complexes with the pentadentate thioether- thiolate-amine-ligand 'nmes4'2- ('nmes4'2- = dianion of 2.2'-bis(2-mercaptophenylthio)diethylmethylamine)
Authors: Sellmann Dieter , Hofmann Thomas , Knoch Falk
Published: February 2015

Paramagnetic [Ni('NMeS4')]2 1 ('NMeS4'2- = 2.2'-Bis(2-mercaptophenylthio)diethylmethylamine(2-)) was synthesized from Ni(ac)2 and Na2-'N MeS4' and characterized by X-ray structure analysis. In solid state, 1 contains two pseudo-octahedral [Ni('NMeS4')] fragments bridged via thiolate donors. In contrast to the parent complex [Ni('NHS4')]2, the thiolate and thioether donors coordinate cis to the Ni center forming meso [Ni('N MeS4')] fragments of CS symmetry. 1 readily dissociates in solution to give mononuclear [Ni('NMeS4')]. Reaction of [Ni('NMeS4')]2 1 with PMe3 yielded [Ni(PMe3)('NMeS4')] 2, oxidation by iodine gave the Ni(III) complex [Ni(I)('NMeS4')] 3
Ein gemischtvalentes Oxometallat mit Cr3+ anstelle von Ti3+: Ba2Ti4
4+Cr2O13 / A Mixed Valent Oxometallate with Cr3+ Instead of Ti3+ Ba2Ti4
4+ Cr2O13
Authors: Möhr S. , Müller-Buschbaum
Published: February 2015

Single crystals of Ba2Ti3+Cr2Oi3 were prepared by C02-LASER high temperature reactions and investigated by X-ray work. The compound crystallizes with monocli­nic symmetry, a = 15.0185, b = 3.9419, c = 9.0764 Å. β = 98.137°, Z = 2. Ba2Ti4Cr2O13 is isotypic to Na2Ti6O13. The crystal structure is discussed with respect to ordered or disordered distributions of Ti4+ and Cr3+ using calculations of Coulomb terms of lattice energy. It is shown, that the stability of this structure type will be decre­ased by replacement of Na+ by ions with higher oxidation states.
Zur Kenntnis von SrCo2V2O8 und SrCo2(AsO4)2 / On SrCo2V2O8 and SrCo2(AsO4)2
Authors: Osterloh D. , Müller-Buschbaum Hk.
Published: February 2015

SrCo2V2O8 (I) and SrCo2(As04)2 (II) were prepared by crystallization from melts and investigated by X-ray single crystal technique. (I) is isotypic to the SrNi2V2O8-type and crys­tallizes with tetragonal symmetry, space group C12
4v-I41cd, a = 12.267: c = 8.424 Å: Z = 8. (II) is isotypic to the lately found SrNi2(PO4)2, space group C1
i-P1̅, a = 5.713; b = 6.903; c = 9.417 Å: a = 110.48; β = 101.43; γ = 99.13°, Z = 2.
Metallkomplexe von Farbstoffen, V [1] Ein Triplatin(II)-Komplex mit dem Trianion von Trichinolobenzol als Tris(chelat)-Ligand / Metal Complexes of Dyes, V [1] A Trisplatinum(II) Complex with the Trianion of Triquinolobenzene as Tri(chelate) Ligand
Authors: Lenz Andreas , Polborn Kurt , Beck Wolfgang
Published: February 2015

The complex [(n7Bu3P)(Cl)Pt]3(triquinolobenzene-3H+) is obtained from the trisodium salt of triquinolobenzene and (nBu3P)(Cl)Pt(μ-Cl)2Pt(Cl)nBu3) and has been characterized by X-ray diffraction. The three platinum atoms are syn positioned outside of the not ideal plane of the triquinolobenzene frame.
Synthesis and Spectroscopic Studies of Pentacarbonylfumaronitrile-chromium(0), -molybdenum(0), and -tungsten(0)
Authors: Mour İzzet A. , Ozkar Saim , Kreiter Cornelius G.
Published: February 2015

Photolysis of hexacarbonyl-chromium(0), -molybdenum(0), and -tungsten(0) in presence of fumaronitrile yields at room temperature pentacarbonyl-fumaronitrile-chromium(0) (1), - molybdenum(0) (2), and -tungsten(0) (3). The complexes were purified by crystallization and characterized by IR and 13C-NMR spectroscopy. The fumaronitrile ligand is bonded to the M(CO)5 moiety by one nitrile nitrogen atom rather than by the carbon-carbon double bond. In toluene 2 dissociates into fumaronitrile and pentacarbonyl-molybdenum(0), which is stabi­lized by the solvent. Fumaronitrile and solvated pentacarbonyl-molybdenum(0) exist in solu­tion together with 2 in an equilibrium which lies in favour of the former species.
Eine zweite polymorphe Form von Te4(WCl6)2 / A Second Polymorphie Form of Te4(WCl6)2
Authors: Beck Johannes
Published: February 2015

The reaction of tellurium with WCl6 in the presence of bromine in a sealed evacuated ampoule in the temperature range from 220 to 150 °C yields dark blue monoclinic crystals of β-Te4(WCl6)2, space group P21/c, lattice constants a = 664,3(2), b = 1273,2(3), c = 1233,6(3) pm, ß - 94,13(3)°. The structure is built of square planar Te4
2+ cations and slightly distorted octahedral WCl6
- anions and shows a close relationship to the previously reported triclinic α-form, which was obtained in the absence of bromine. The difference between the two structures lies in a different packing of the ions
Phasenuntersuchungen im System 2 Ha–TaS2–2Hc–MoS2 / Investigations on Phases in the System 2 Ha-TaS2-2Hc-MoS2
Authors: Remmert Peter , Fischer Edmund , Hummel Hans-Ulrich
Published: February 2015

Ternary phases in the system TaS2-MoS2 have been obtained by thermal reactions at 1050 °C of binary layered disulfides and NH4Cl as promotor.

Ternary phases Ta1-xMoxS2 exist in the range 0.5 ≤ x ≤ 0.9. In the range of 0.25 ≤ x ≤ 0.55 the reactions are quantitative and the phase-compositions are determined by the amounts of the starting materials. For x < 0 .2 1 T-TaS2 and for x > 0.60 2 Hc-MoS2 are contaminating the resulting ternary phases.

Ternary phases have been characterized by X-ray powder diffraction and are indexed rhombohedrally on the basis of a 3 R-structure with metals in trigonal-prismatic coordination. The phases Ta1-xMoxS2 with 0.25 ≤ x ≤ 0.55 show a reversible transition of higher order associated with a change in the electrical conductivity mechanism. Below 420 K the phases show semiconductivity while above 460 K metallic conductivity is observed
The Crystal Structure of [Bis(tri-tbutyl-phosphine)gold(I)] Chloride
Authors: Zeller Edgar , Schier Annette , Schmidbaur Hubert
Published: February 2015

The title compound is available from the reaction of labile gold(I) chloride complexes and an excess of the ligand (tBu3P), or from the NaBH4 reduction of (tBu3P)AuCl. It forms dark red cubic crystals, [a = 14.297(1) Å at -56 °C, space group P213, Z = 4], with isolated chloride anions and [(tBu3P)2Au]+ cations of C3 symmetry, with linear two-coordinate gold centers
Asymmetrische Katalysen, 88 [1] kinetik der rh-katalysierten hydrierung von (z)-(α)-n-acetylaminozimtsäure mit optisch aktiven schalenphosphinen als liganden / Asymmetrie catalysis, 88 [1] kinetics of the rh catalysed hydrogenation of (z)-(α)-n-acetam idocinnamic acid with optically active layer-phosphines as ligands
Authors: Brunner Henri , Fürst Josef , Nagel Ulrich , Fischer Andreas
Published: February 2015

The kinetics of the hydrogenation of (Z)-(a)-N-acetamidocinnamic acid catalysed by Rh complexes of the optically active layer-phosphines 2-7 was examined. The turnover was calculated from the consumption of hydrogen during the reaction. The catalytic activities of the layer-phosphines 2-7, which depend on the position of the borneoxy substituents on the phenyl rings, were compared with the catalytic activity of the parent ligand dppe 1
Die Einlagerung von Pyridin in ternäre Übergangsmetalldisulfide Ta1-xMoxS2 / Intercalation of Pyridine into Ternary Transition Metal Disulfides Ta1-xMoxS2
Authors: Remmert Peter , Hummel Hans-Ulrich
Published: February 2015

Ternary phases Ta1-xMoxS2 with 0.25 ≤ x ≤ 0.55 have been investigated regarding their intercalation potential using pyridine as guest molecule. Intercalation yields hexagonal phases Ta1-xMoxS2·(pyridine)n. The different phases have been characterized by elemental analysis as well as TGA and powder diffraction patterns, which have been indexed using the space group P3m1. For the compound Ta0.65Mo0.35S2·(pyridine)0.38 a structural model was developed, based on powder diffraction data: P3m1, a = 3.275(2), c = 12.008(7)Å and Z = 1. During intercalation the stacking sequence of the host lattice is changed from BaB/AcA/CbC to BaB(pyr)/BaB(pyr). Intercalation of pyridine into Ta1-xMoxS2 proceeds via a two-step mechanism. In the first step orthorhombic phases are formed with reduced pyridine content as compared to the final intercalation product; e.g. Ta0.55Mo0.45S2·(pyridine)0.38. The first step intercalation compounds can be obtained by interruption of the intercalation reaction after 7 days.
Diinkomplexe von Wolfram(VI). Die Kristallstruktur von [(Et2S)WCl4(Me3Si-C≡C-(CH2)4-C≡C-SiMe3)WCl4(SEt2)] / Diyne Complexes of Tungsten(VI). The Crystal Structure of [(Et2S)WCl4(Me3Si-C≡ C-(CH2)4-C≡C-SiMe3)WCl4(SEt2)]
Authors: Dierkes Peter , Fenske Dieter
Published: February 2015

The diyne complexes [(Et2S)WCl4(R-C≡C-(CH2)n-C≡C-R)WCl4(SEt2)] (R = SiMe3, n = 3, 4, 8; R = C6H5, n = 4, 8) have been prepared by the reaction of trans-[WCl4(SEt2)2] with the corresponding diyne in toluene solutions. The complexes form green or orange, diamagnetic, moisture sensitive crystal powders, which were characterized by their IR and 13C NMR spectra. The crystal structure of the complex with R = SiMe3 and n = 4 has been determined.

[(Et2S)WCl4(Me3Si-C≡C-(CH2)4-C≡C-SiMe3)WCl4(SEt2)]: Space group P21/c, Z = 2, 3620 observed unique reflections with I > 2σ(I), R = 0.027. Lattice dimensions at -70 °C: a = 1431.8(11), b = 839.6(8), c = 1731.3(11) pm, β = 112.74(2)°. The structure consists of molecules in which both tungsten atoms are surrounded by four chlorine atoms in equatorial positions, both alkyne groups are bonded side on (η2) to the tungsten atoms, whereas the sulfur atoms of the diethylsulfide molecules are located trans to the alkyne groups.
Synthese und Struktur diastereomerer, zweikerniger Kupferkomplexe [1] / Synthesis and Structure of Diastereomerie Dinuclear Copper Complexes [1]
Authors: Saalfrank Rolf W. , Struck Oliver , Peters Karl , Schnering Hans Georg von
Published: February 2015

Depolymerisation of a copper(II)/pyrrolidine-based 2D -polymer 2 by 4,4′-bipyridyl [molar ratio: 2 (CuL2) : 1 (Bipy)] and recrystallisation of the reaction product leads to two visually distinguishable crystal charges, composed of dark green octahedra meso-4 and light green rod-shaped crystals racem-5. Separation of the conglomerate of the morphologically different crystals is accomplished by pick out. The structure of the dinuelear complex racem-5 has been established unambigously by X-ray structure analysis. EPR and susceptibility measurements of mixtures of complex meso-4 and racem-5 indicate that there is no interaction be­tween the two copper(II) centres.
Ein neuer Zugang zu ionischen Thionylimiden. Einkristallstruktur von N(CH3)4NSO / A New Access to Ionic Thionylimides. Single Crystal Structure of N(CH3)4NSO
Authors: Mann S. , Jansen M.
Published: February 2015

Single crystals of N(CH3)4NSO have been prepared via ion exchange from RbNSO or CsNSO and tetraalkylammonium halides in liquid ammonia and investigated by X-ray single crystal techniques (I4̅, a = 1137.6(1), c = 1134.9(2) pm, Z = 8, T = -100 °C). The crystal structure of N(CH3)4NSO is related to the CsCl-type of structure. Using the same preparative route NMe3BzNSO has been obtained. Its lattice powder data (orthorhombic primitive; a = 896.3(2), b = 1235.4(3), c = 1070.7(4) pm).
Eightfold Functionalization of the Octasilsesquioxane Core
Authors: Jutzi P. , Batz C. , Mutluay A.
Published: February 2015

Eightfold functionalized octasilsesquioxanes (R8Si8O12) are synthesized using the hydrosilylation method. Different types of groups R, consisting of an (-O-SiMe2(CH2)2) spacer unit and various terminal units (-CH2(C2Me)B10H10, - C5H3MeMn(CO)3, -SiMe2C5H4FeC5H5, -SiMe2Cl, -SiMeCl2, -Si(OEt)3) have been introduced. The hydrosilylation products have been characterized by 1H, 13C, 29Si NMR and infrared spectroscopy and elemental analysis. The redox properties of the ferrocenyl substituted compound have been studied by cyclovoltammetry.
1.2.3.4.5-Penta(4-alkylphen-1-yl)-1,3-cyclopentadiene und deren Natrium-, Indium(I)- und Thallium(I)-Komplexe / 1.2.3.4.5-Penta(4-alkylphen-1-yl)-1,3-cyclopentadienes and their Sodium-, Indium(I)- and Thallium(I) Complexes
Authors: Schumann Herbert , Lentz Alexander
Published: February 2015

(Cyclopentadiene pentayl)pentakis[(1,4-phenylene)alkanones] C5H(C6H4C(0)R-4)5 (R=CH3 (1a), C3H7 (1b), C5H7 (1c), C7H15 (1d)) react with N2H4(H2O)/KOH or Et3SiH/ CF3COOH to yield the oxygen free ligands C5H(C6H4CH2R-4)5 (2a, 2b, 2c and 2d), which after reaction with NaNH2 give the corresponding sodium salts Na[C5(C6H4CH2R-4)5] (3a, 3b, 3c and 3d). The sodium salts Na[C5(C6H4C(O)R-4)5] (R=CH3 (4a), C5H11 (4c) and 3a react with InCl to give In[C5(C6H4C(O)R-4)5] (5a, 5c) and In[C5(C6H4CH2R-4)5] (6a). 2a, 2b, 2c and 2d react with TlOC2H5 yielding Tl[C5(C6H4CH2R-4)5] (7a, 7b, 7c and 7d). The 1H and 13C NMR spectra of the new compounds are reported and discussed.
Beiträge zur Chemie des Phosphors, 232 [1]. Partiell organylsubstituierte Polycyclophosphane / Contributions to the Chemistry of Phosphorus, 232 [1]. Partially Organyl Substituted Polycyclophosphanes
Authors: Bäudler Marianne , Jachow Harald
Published: February 2015

The new partially organylsubstituted polycyclophosphanes P7Pri
4H, iso-P7Pri
4H, P8Pri
5H, P9Pri
4H, and P10Pri
5H have been obtained by reaction of PriPCl2 with PCl3 and magnesium and subsequent chromatographic work-up of the crude reaction product containing isopro-pylphosphorus magnesium compounds. According to 31P NMR spectroscopic investigations, P7Pri
4H is 7-hydrogen-2,3,5,6-tetraisopropylbicyclo[2.2.1]heptaphosphane, iso-P7Pri
4H is hydrogen tetraisopropylbicyclo[2.2.1]heptaphosphane, P8Pri
5H is hydrogen pentaisopropylbicyclo[3.3.0]octaphosphane (two constitutional isomers), P9Pri
4H is hydrogen tetraisopropyltricyclo[3.3.1.03,7]nonaphosphane (two configurational isomers), and P10Pri
5H is 10-hydrogen-3,4,5,8,9-pentaisopropyltricyclo[5.2.1.02,6]decaphosphane (two configurational isomers).
Direct Synthesis of Zinc and Nickel(II) Complexes with 1,4-Diazabicyclo[2.2.2]octane
Authors: Petrusenko Svitlana R. , Sieler Joachim , Kokozay Vladimir N.
Published: February 2015

The peculiarities of the formation of zinc and nickel(II) complexes by interaction of metal powder or metal oxide with ammonium salts (halides, nitrate, thiocyanate) were investigated in non-aqueous solutions (methanol, acetonitrile, N,N-dimethylformamide=DMF, dimethylsulfoxide=DMSO) in presence of 1,4-diazabicyclo[2.2.2]octane. The stoichiometry of the com ­ plexes was found to depend on the initial reagent ratio Ni/ZnO:NH4X and Ni/ZnO:Ten. The compounds of compositions Zn(HTen)(H2O)(NO3)3 and Ni(HTen)(Ten)Cl3 were character­ized by X-ray crystallography. Both complexes contain five-coordinate metal atoms. The zinc compound possesses monomeric molecular structure whilst the nickel complex is polymeric.