N,N-Dimethylglycinatokomplexe von Platin(IV)

N,N -Dimethylglycinato Complexes of Platinum(IV) The aquapentachloroplatinic acid (H₃O)-[PtCl₅(H₂O)] · 2(18-cr-6) · 6 H₂O ( 1 ) reacts with N,N-dimethylglycine (Me₂glyH) to give cis-[PtCl₂(N,O-Me₂gly)₂] · (18-cr-6) ( 6 ) and (Me₂glyH₂)[PtCl₄(N,O-Me₂gly)] ( 7 ). Complexes 6 and 7 are characterized by microanalysis, ¹H-NMR and IR spectroscopy as well as by X-ray structure analysis. In both complexes the N,N-dimethylglycinato ligands are N,O-coordinated. In 6 , the amino groups are mutually trans and the carboxylato groups are cis (configuration index: OC-6–22). In the crystal, there are only weak C–H…O interactions between the N-methyl groups of the [PtCl₂(N,O-Me₂gly)₂] complex and the oxygen atoms of the crown ether (shortest C…O contacts: 3.10(2) Å and 3.21(2) Å). In the solid state, 7 exhibits strong cation-anion interactions: The carboxyl group of the cation (Me₂glyH₂)⁺ forms a strong O–H…O bridge to the exocyclic oxygen atom of the carboxylate group of the glycinato ligand (O…O 2.61(1) Å).     

An Expected Calcium Carbido Borate Chloride: Ca9Cl8(BC2)2

Ca₉Cl₈(BC₂)₂ was obtained by solid state reaction of a mixture of CaCl₂, Ca, B and C. The structure was solved by single crystal X-ray structure determination. Ca₉Cl₈(BC₂)₂ crystallizes in the orthorhombic space group Cmcm (No. 63, a = 1162.91(8) pm, b = 1341.59(10) pm and c = 1208.62(9) pm, Z = 4). The most striking element of the title compound is the bent BC₂^5– unit that is surrounded by a bicapped trigonal prismatic arrangement of calcium ions.     

Synthese und Molekülstruktur von [Li(THF)4][{(CO)4Mo}2(μ-PPh2)(μ-PPh2PPh2)]: Die erste Verbindung mit einem 1,3-Dimetalla-cyclopentaphosphan-Gerüst

Synthesis and Molecular Structure of [Li(THF)₄][{(CO)₄Mo}₂(μ-PPh₂)(μ-PPh₂PPh₂)]: The First Compound with an 1,3-Dimetalla-cyclopentaphosphane Ring [Mo(CO)₄(NBD)] (NBD = norbornadiene) reacts with LiPPh₂ and PPh₂PPh₂ in THF at –80 °C to give [Li(THF)₄][{(CO)₄Mo}₂(μ-PPh₂)(μ-PPh₂PPh₂)] ( 1 ). 1 exhibits an A₂X coupling pattern in the ³¹P NMR spectrum. A crystal structure determination showed the presence of bridging phosphanido (PPh₂) and diphosphane ligands (PPh₂PPh₂). The central Mo₂P₃ five-membered ring adopts a half-chair conformation and thus resembles an inorganic cyclopentane.     

Über die Koexistenz von tetragonalem und monoklinem CaC2: Strukturelle und spektroskopische Untersuchungen an Erdalkalimetallacetyliden,MC2 (M = Ca,Sr, Ba)

On the Coexistence of Tetragonal and Monoclinic CaC₂: Structural and Spectroscopic Studies on Alkaline Earth Metal Acetylides, MC₂ (M = Ca, Sr, Ba) The alkaline earth acetylides CaC₂, SrC₂ and BaC₂ can be considered to occur in three polymorphic structures each. The monoclinic low-temperature form, the tetragonal form, and the cubic high-temperature form. No deviation from axial symmetry is obtained for the C₂^2– ions in the tetragonal structure determinations, as confirmed by X-ray single-crystal structures and ¹³C MAS NMR studies. The CaC₂ samples prepared by us were always a mixture of monoclinic and tetragonal phase. Their Raman spectra exhibited two distinct C₂ streching vibrations. Problems arising from the coexistence of these two phases for the interpretation of ¹³C MAS NMR spectra are discussed.     

Mass bounds on a very light neutralino

Within the Minimal Supersymmetric Standard Model (MSSM) we systematically investigate the bounds on the mass of the lightest neutralino. We allow for non-universal gaugino masses and thus even consider massless neutralinos, while assuming in general that R-parity is conserved. Our main focus is on laboratory constraints. We consider collider data, precision observables, and also rare meson decays to very light neutralinos. We then discuss the astrophysical and cosmological implications. We find that a massless neutralino is allowed by all existing experimental data and astrophysical and cosmological observations.     

Noncommutative baby Skyrmions

We subject the baby Skyrme model to a Moyal deformation, for unitary or Grassmannian target spaces and without a potential term. In the Abelian case, the radial BPS configurations of the ordinary noncommutative sigma model also solve the baby Skyrme equation of motion. This gives a class of exact analytic noncommutative baby Skyrmions, which have a singular commutative limit but are stable against scaling due to the noncommutativity. We compute their energies, investigate their stability and determine the asymptotic two-Skyrmion interaction.     

Correlation between optical constants and crystal chemical parameters of ZrW2O8

The refractive indices of ZrW₂O₈, measured at wavelengths of 435.8-643.8 nm, were used to calculate n_D at λ=589.3 nm and n_∞ at λ=∞ from a one-term Sellmeier equation. Refractive indices, n_D and dispersion values, A, are, respectively, 1.8794 and 114×10⁻¹⁶ m². The high dispersion, relative to other molybdates, tungstates and Zr-containing compounds, is attributed to the low value of E_o=7.7 eV and mean cation coordination number. Total electronic polarizabilities, α_total, were calculated from n_∞ and the Lorenz-Lorentz equation. The unusually large difference between the observed polarizability of 20.087 Å³ and the calculated total polarizability α_T of 17.59 Å³ (Δ=+12.4%) is attributed to (1) a large M-O-W angle, (2) a high degree of W 5d-O_(terminal) 2p and Zr nd-O 2p hybridization, and (3) unusually high oxygen displacement factors, B(O), normalized to B(W).     

Hysteresis Behaviour of 51CrV4 and Viscoplastic Modeling Aspects

In this work we investigate the material behaviour of steel 51CrV4 in classical uniaxial strain controlled tension tests of different strain rates interposed by relaxation steps, in which the equilibrium stress observed is significantly smaller than the stresses seen in slowest strain rate test. Also, some cyclic experiments with different strain rates and amplitudes were done to analyze the hysteresis behaviour of the material. Against this background of experimental data the modeling possibilties of two models are explored: the Lion model and the Chaboche model with kinematic hardening ansatz. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical Simulation of Free Surface-Structure-Interaction with Multi-Regional Mesh Deformation

The Fluid-Structure-Interactions (FSI) for technological constructions on sea are becoming nowadays very important in view of growing consumption of renewable energy sources. Exceptionally the offshore wind farms are exposed to extreme weather conditions due to breaking and non-breaking wave loads. This work presents numerical Finite-Volume-Method (FVM) analysis of fluid and structure interactions with water waves impact on elastic solid structures. We develop a Free Surface-Structure-Interaction (FSSI) solver in OpenFAOM [1] with multi-regional mesh deformation. A two dimensional numerical water impact model on a damping element prototype of an offshore wind turbin tower is investigated. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Valence Tautomerism in Octahedral and Square‐Planar Phenoxyl–Nickel(II) Complexes: Are Imino Nitrogen Atoms Good Friends?

The two tetradentate ligands H(2)L and H(2)L(Me) afford the slightly distorted square-planar low-spin Ni(II) complexes 1 and 2, which comprise two coordinated phenolate groups. Complex 1 has been electrochemically oxidized into 1(+), which contains a coordinated phenoxyl radical, with a contribution from the nickel orbital. In the presence of pyridine, 1(+) is converted into 1(Py) (+), an octahedral phenolate nickel(III) complex with two pyridines axially coordinated: An intramolecular electron transfer (valence tautomerism) is promoted by the geometrical changes, from square planar to octahedral, around the metal center. The tetradentate ligand H(2)L(Me), in the presence of pyridine, and the hexadentate ligand H(2)L(Py) in CH(2)Cl(2) afford, respectively, the octahedral high-spin Ni(II) complexes 2(Py) and 3, which involve two equatorial phenolates and two axially coordinated pyridines. At 100 K, the one-electron-oxidized product 2(Py) (+) comprises a phenoxyl radical ferromagnetically coupled to the high-spin Ni(II) ion, with large zero-field splitting parameters, while 3(+) involves a phenoxyl radical antiferromagnetically coupled to the high-spin Ni(II) ion.