bluuebunny/crossref_metadata_2025 huggingface dataset:
Structural and Dynamical Properties of an LiCl · 3H2O Solution
Authors: Tamura Y. , Tanaka K. , Spohr E. , Heinzinger K.
Published: February 2015

An MD simulation of an 18.5 molal LiCl aqueous solution was performed with the flexible Bopp-Jancso-Heinzinger model for water, ion-water pair potentials derived from ab initio calcula­tions and the ion-ion interactions described by a potential of Born-Mayer-Huggins (BMH) type. The comparison with a simulation of the same system, where the ion-ion interactions were described by a (12-6) Lennard-Jones + Coulomb potential, demonstrates that such a change affects not only the ion-ion but also the ion-water radial distribution functions significantly, and that the results with the BMH potential conform better to X-ray results. The self-diffusion coefficients for water and the ions are found to be lower by almost one order of magnitude compared with dilute solutions, in good agreement with experimental results. The spectral densities of the hindered translational motions as well as those of the librations and the internal vibrations of the water molecules have been calculated from the simulations through the corresponding velocity autocorrelation functions.
Parametrically Driven One-Dimensional Sine-Gordon Equation and Chaos
Authors: Herbst B. M. , Steeb W.-H.
Published: February 2015

The chaotic behaviour of the parametrically driven one-dimensional sine-Gordon equation with periodic boundary conditions is studied. The initial condition is u(x, 0) = ƒ(x), ut (x, 0) = 0 where ƒ is the breather solution of the one-dimensional sine-Gordon equation at t = 0. We vary the amplitude of the driving force, the frequency of the driving force and the damping constant. For appropriate values of the driving force, frequency and damping constant chaotic behaviour with respect to the time-evolution of w(x = fixed, t) can be found. The space structure u(t = fixed, x) changes with increasing driving force from a zero mode structure to a breather-like structure consisting of a few modes.
A Comparative Study of Variational Techniques for Schrödinger Equations. Pointwise Quality Criteria
Authors: Yurtsever E.
Published: February 2015

Different variational schemes for solving the Schrodinger equation are tested for the model potential of Kratzer-Fues. Wavefunctions are analyzed in terms of their global (expectation values) and local properties which are expressed as functions of coordinates. The Rayleigh-Ritz variation almost uniformly produces the most accurate expectation values. However the point properties show qualitatively different behaviour for different regions of the coordinate space. To define the local quality, a set of criteria is proposed.
The Stability and Decomposition of Gaseous [Mn(CO)5]2(μ-SiH2)
Authors: Stauf G.T. , La Graffe D. , Dowben P. A. , Emrich K. , Barfuss S. , Hirschwald W. , Boag N. M.
Published: February 2015

The ionic decomposition of gaseous bridge-bonded dimanganese silyl carbonyl [Mn(CO)5]2(μ-SiH2) has been investigated via photon and electron induced ionization mass spectroscopy, as well as gas-phase photoabsorption measurements. The thermodynamic cycle incorporating ionic fragments has been constructed from these results. The thermodynamic cycle illuminates the decomposition process of this organometallic compound. This has potential application in the production of silicide Mn2Si coatings by both pyrolysis and by patterned photolysis using an UV laser.
Plasma Parameters and Weakly Non-Ideal Behaviour of a High Density, Super-Atmospheric 2kA Cascade Arc in Argon
Authors: Timmermans C. J. , Kroesen G. M. W. , Vallinga P. M. , Schram D. C.
Published: February 2015

Experimental results are reported for simultaneous pressure and current pulses up to 14 bar and 2200 A superimposed on an atmospheric pressure 60 A dc cascade arc. A current density over 108 A/m2, previously 107 A/m2 (power density 1012W m3, previously 1010W/m3) has been ob­tained. The electron temperature of the thermal plasma was deduced from the end-on measured radiance of argon lines, and the electron density from the absolute continuum emission. The values found for the quantities mentioned during the quasi-stationary phase of the current pulse, lasting ~ 1 ms, were 27000 K and 3 · 1023 m-3, respectively, at a pressure of ~ 1.5 bar (ionization degree 100%), and 18000 K and > 1024 m-3, respectively, for a pressure of 14 bar (ionization degree 60%). These values satisfy the LTE relation. Deviations from the Spitzer conductivity have been observed in this weakly non-ideal plasma.

In general, the high ionized thermal plasma studied with its composition of neutral, singly ionized and doubly ionized argon atoms can serve as a useful medium for spectroscopic studies of highly ionized systems and as a valuable source of radiation in the visible a well as in the near and far ultraviolet parts of the spectrum.
Analysis of Dispersion and Damping of Ion Waves in Plasma
Authors: Turky A.-A.
Published: February 2015

Experimental results are presented on the dispersion and damping of ion waves having a frequency range extending up to the ion plasma frequency. It was found that the Landau damping rate increases exponentially when the frequency of the ion wave approaches the ion plasma frequency ; while its phase velocity decreases slightly. The experimental results agree reasonably with previous theoretical predictions. The study indicates significant changes in Landau damping even with small variations in the wave velocity.
Resolution of the Ehrenfest Paradox in the Dynamic Interpretation of Lorentz Invariance
Authors: Winterberg F.
Published: February 2015

In the dynamic Lorentz-Poincare interpretation of Lorentz invariance, clocks in absolute motion through a preferred reference system (resp. aether) suffer a true contraction and clocks, as a result of this contraction, go slower by the same amount. With the one-way velocity of light unobservable, there is no way this older pre-Einstein interpretation of special relativity can be tested, except in cases involving rotational motion, where in the Lorentz-Poincare interpretation the interaction symmetry with the aether is broken. In this communication it is shown that Ehrenfest’s paradox, the Lorentz contraction of a rotating disk, has a simple resolution in the dynamic Lorentz-Poincare interpretation of Lorentz invariance and can perhaps be tested against the prediction of special relativity.
Coion-Interactions in Molten Salt Systems (M1 ,M2 )X3
Authors: Klemm Alfred , Schäfer Lutz
Published: February 2015

The association-model of binary molten salt systems (M1,M2)X3 is critizised and the friction coefficients r1,3, and r23 of the system (6Li, 7Li)Cl are calculated from ancient mobility mea-surements, showing that the coion-interactions, represented by r12, are about as strong as the ion-counterion-interactions, represented by r13 and r23.
1H and 19 F NMR Studies on Molecular Motions in Two Solid Phases of t-Butylammonium Tetrafluoroborate
Authors: Ishida Hiroyuki
Published: February 2015

Differential thermal analysis (DTA), differential scanning calorimetry (DSC), and the temperature dependence of the spin-lattice relaxation time (T1) and the second moment (M2) of 1H and 19F NMR were studied in (CH3)3CNH3BF4 and (CH3)3CND3BF4 . DTA and DSC revealed a solid-solid phase transition at 219 K for (CH3)3CNH3BF4 and at 221 K for (CH3)3CND3BF4 . The motions of cations and anions in the two solid phases were studied by T1 and M2 experiments. The motional modes of the ions and their motional parameters were determined.
Particular Solutions for a (3+1)-dimensional Generalized Shallow Water Wave Equation
Authors: Gao Yi-Tian , Tian Bo , Hong Woopyo
Published: February 2015

The shallow water wave equations (SWWEs) are of current interest in nonlinear sciences. In this paper we obtain a new family of soliton-like solutions for a (3-1)-dimensional generalized SWWE. Samples are given.
The Stannide Zr5CuSn3
Authors: Pöttgen Rainer
Published: February 2015

Zr5CuSn3 was prepared from the elements in an arc-melting furnace and investigated by X-ray diffraction of powders as well as of single crystals. The crystal structure was refined from four-circle diffractometer data: P63/mcm, a = 860.04(7) pm, c = 586.80(5) pm, V = 0.3759(1) nm3, Z = 2, wR2 = 0.0402 for 371 F2 values and 15 variables. A refinement of the occupancy parameters re­vealed that the copper position is occupied to only 95.3(8)% in the crystal used for the X-ray investigation. Zr5CuSn3 crystallizes in the Hf5CuSn3 type structure, a filled variant of the Mn5Si3 type. The main features of the Zr5CuSn3 structure are condensed Zr6 octahedra that are centered by copper atoms
„BaNb3O6“ ist ein Perowskit BaNbO3, eine Korrektur und ein Beitrag zu BaxNbO3/“BaNb3O6“ is a Perovskite BaNbO3, a Correction and a Contribution to BaxNbO3
Authors: Grin Y. , Müller-Buschbaum Hk. , Schnering H. G. von
Published: February 2015

It is shown that the trigonal compound “BaNb3O6” described earlier actually is the cubic perovskite BaNbO3 with an unusually small lattice constant of 4.039 A. Furthermore, the refinement of the single crystal data prepared by CO2-LASER techniques did not reveal defects at the Ba position, but defects at the positions of niobium and oxygen, corresponding to the composition Ba(NbO3)0.9 or Ba1.08NbO3.
AgSr[B7O12]: Das erste wasserfreie quaternäre Silber(I)-Borat mit vierfach koordiniertem Silberion und einem neuartigen Boratanion/ AgSr[B7O12]: The First Anhydrous Quaternary Silver(I)-Borate with Fourfold Coordinated Silver Ion and a New
Authors: Wiesch A. , Bluhm K.
Published: February 2015

Single crystals of AgSr[B7O12] were obtained by using a B20 3 flux-technique and Ag2CO3 and SrCO3 as starting materials in a silver ampoule at 800 °C. X-ray investigations on single crystals led to the space group C 2/c with a = 664.2(5); b = 1153.6(3); c = 2198.0(6) pm; β = 92,52(3)°; Z = 8. Ag+ is fourfold coordinated by oxygen atoms and forms distorted AgO4 tetrahedra while Sr2+ has nine nearest neighbours. The compound contains a hitherto unknown two dimensional borate anion [B7O12]3-which contains four trigonal planar BO3 groups and three BO4 tetrahedra per unit.
The Molecular Structures and Conformational Preferences of Bis(dimethylstibyl)- Oxane, -Sulfane and -Selane, E(SbMe2)2, E = O, S or Se, Me = CH3, by Density Functional Theory Calculations and Gas Electron Diffraction
Authors: Haaland Arne , Ivanovitch Sokolov Vasili , Vidar Volden Hans , Breunig Hans Joachim , Denker Michael , Rösler Roland
Published: February 2015

Density Functional Theory calculations on E(SbMe2)2, E = O, S or Se, Me = CH3, indicate that the equilibrium structures are syn-syn or near syn-syn conformers with over-all C2 symmetry. The barriers restricting rotation about E-Sb bonds are very low, the equilibrium values for the dihedral angles ϕ(Sb-E-Sb-lp) where lp denotes the direction of the electron lone pair on one of the Sb atoms are probably less than 45°. The calculations further indicate the existence of syn-anti conformers some 4 kJ mol-1 above the more stable syn-syn. Gas electron diffraction data show that both conformers are present in gaseous O(SbMe2)2, while the presence of the syn-anti conformer in gaseous Se(SbMe2)2 is uncertain; least-squares refinements yielded the mole fraction χ = 0.27(18). The Sb-O and Sb-Se bond distances are 197.6(14) and 255.1(5) pm respectively, the valence angles of the syn-syn conformers are <SbOSb = 122.3(16)° and <SbSeSb = 96.3(11)°. It is suggested that the wide <SbOSb angle is due to across-angle repulsion between the Sb atoms.
Rb[B2P2O8(OH)] und Cs[B2P2O8(OH )]: Die ersten Borophosphate mit dreidimensional vernetzter Anionenteilstruktur /Rb[B2P2O8(OH)] and Cs[B2P2O8(OH )]: The First Borophosphates with a Threedimensional Anionic Tetrahedral Structure
Authors: Häuf Cornelia , Kniep Rüdiger
Published: February 2015

The isotypic borophosphates Rb[B2P2O8(OH)] and Cs[B2P2O8(OH)] were grown under hydrothermal conditions. The crystal structures were solved by single crystal methods (Rb[B2P2O8(OH)]/ Cs[B2P2O8(OH)]: monoclinic, P21/c, a = 676.2(3)/682.7(3), b = 1217.3(5)/ 1236.8(5), c = 885.0(4)/900.6(5) pm, β = 97.3(1)/ 98.1(1)°. Z = 4). The structures contain a complex framework of three-, four-, six-, nine- and twelvemembered rings of tetrahedra. Along [100] the twelve-membered rings are stacked to give wide channels which contain the Rb+/Cs+-ions in an icosahedral coordination.
Aluminiumphosphate mit nichtzentrosymmetrischen Schicht-und Raumnetzstrukturen aus topologisch verwandten Motiven: 1. KAl2(PO4)2(OH)·4H2O/Aluminum Phosphates with Non-Centrosym metric Layer-and Framework-Structures of Topologically Related Motifs 1. KAl2(PO4)2(OH)·4H2O
Authors: Dick Stefan , Großmann Gisbert , Ohms Gisela , Zeiske Thomas
Published: February 2015

KAl2(PO4)2(OH)·4H2O could be obtained by the reaction of gibbsite with a potassium-phosphate solution of pH = 5.5 at 333 K. A single crystal X-ray structure analysis showed that KAl2(PO4)2(OH)·4H2O is isotypic with the mineral minyulite. Crystal data: orthorhombic space group Pba2, a = 934.7(1), b = 982, 1 (1), c = 551,0(1) pm, Z = 2. It possesses dimeric units of Al-octahedra which are bridged by an OH-and two bidentate phosphate groups. The dimers are linked by phosphate to plane polar layers. Cavities in the layers are occupied by K ions. One corner of each phosphate tetrahedron is not connected to Al but accepts four hydrogen bonds from water molecules bound to Al of the adjacent layer. A powder neutron scattering experiment with KAl2(PO4)2(OD)·4D2O showed that four D atoms and P coordinate the hydrogen bond accepting O in KAl2(PO4)2(OD)·4D2O like a square pyramid. Analogous dimeric building units are found in the Al phosphate minerals minyulite and morinite; similar dimers of Fe octahedra occur in the mineral copiapite, a number of Fe containing enzymes and numerous synthetic iron complexes.

High-resolution 31P solid-state NMR spectra show only one isotropic line at δiso = -9.6 ppm and confirm the presence of one symmetry independent phosphorus site in the unit cell. In the 1H-MAS-NMR spectra the water molecules and the bridging OH groups show signals at 5.4 and 1.4 ppm, respectively
Aluminiumphosphate mit nichtzentrosymmetrischen Schicht- und Raumnetzstrukturen aus topologisch verwandten Motiven: 2. KAl2(PO4)2(OH)·2H2O/Aluminum Phosphates with Non-Centrosymmetric Layer- and Framework-Structures of Topologically Related Motifs: 2. KAl2(PO4)2(OH)·2H2O
Authors: Dick Stefan , Großmann Gisbert , Ohms Gisela , Müller Manfred
Published: February 2015

KAl2(PO4)2(OH)·2H2O was obtained by the reaction of gibbsite with a potassium-phosphate solution of pH = 5.5 at 373 K. A single crystal X-ray structure analysis showed that it is an ordered, F-free K-analog of the microporous compound AIPO4-CI2 . Crystal data: orthorhombic space group P212121, a = 920.5(1), b = 970.7(2), c = 982.8(2) pm, Z = 4. The structure consists of dimeric units of AIO6 octahedra and AIO5 trigonal bipyramids, bridged by an OH and two bidentate phosphate groups. The dimers are linked by phosphate to form corrugated layers which are topologically related to the layers in KAl2(PO4)2(OH)·4H2O and minyulite. The layers are connected by Al-O-P and hydrogen bonds to a three dimensional framework structure with K ions in channel-like cavities. A neutron powder scattering experiment with KAl2(PO4)2(OD)·2D2O showed that the bridging OD group and only one D of each water molecule are involved in hydrogen bonding.

31P MAS NMR spectra show two isotropic lines at δiso = -6.9 and -18,7 ppm of the intensity ratio 1:1 and confirm the presence of two crystallographically independent P atoms in the unit cell. In the 1H MAS NMR spectra the water molecules and the bridging OH group show signals at 5.9 and 1.1 ppm, respectively.
Darstellung und Kristallstruktur der oligomeren Iodo-d10-metallate(II) [M(I)(CH3CN)4]4[Cd6I16] · 1,5 CH3CN mit M(I) = Cu, Li/Synthesis and Crystal Structure of the Oligomeric Iodo-d10-metallate(II) [M(I)(CH3CN)4]4[Cd6I16] · 1,5 CH3CN with M(I) = Cu, Li
Authors: Bach Ansgar , Hoyer Michael , Hartl Hans
Published: February 2015

The reaction of CuI or Lil with Cdl2 in the polar solvent acetonitrile results in the formation of the iodocadmates [Cu(CH3CN)4]4[Cd6I16] · 1.5CH3CN (1) and [Li(CH3CN)4]4[Cd6I16] · 1.5CH3CN (2) with the oligomeric anion [Cd6I16]4-. This new type of halometallate anion, which is found in both isotypic structures, is built up by six alternating corner and edge sharing Cdl4 tetrahedra. 1: Space group P1̄ (No 2), a = 838.5(4), b = 1465.9(9), c = 1929.8(6) pm, α = 93.01(3), β = 99.13(3), γ = 105.11(3)°; 1: Space group P1̄(No 2), a = 841.7(8), b = 1470(9), c = 1945.5(9) pm, α = 93.27(5), β = 99.13(5), γ = 104.83(5)°.
peri-Interactions in Naphthalenes, 3 [1]. On Hypercoordination in 8-Dimethylamino-naphth-1-yl-phosphonium salts and -phosphines
Authors: Schiemenz Günter Paulus , Bukowski Ralph , Eckholtz Lars , Vamskühler Bernhard
Published: February 2015

In (alkyl)di(aryl)(8-dimethylamino-naphth-1-yl)phosphonium salts and in the parent phos­phines, there is no experimental evidence of dative N→P interactions. Conclusions to the contrary are based on the choice of improper standards of comparison
Phenylmercury Chloride: Its Single-Crystal X-Ray Structure and Some Aspects of its Biological Chemistry
Authors: Wilhelm Michaela , Saak Wolfgang , Strasdeit Henry
Published: February 2015

A single crystal of phenylmercury chloride (PhHgCl) was obtained by serendipity from a solution of diphenylmercury (HgPh2) and dihydrolipoic acid in tetrahydrofuran / carbon tetrachloride. The crystal structure of PhHgCl is pseudotetragonal. It is best described in the orthorhombic space group Cmma with a = 6.856(1), b = 6.882(1), c = 14.309(2) Å (at 193 K), and Z = 4. The Cl-Hg-C moiety of the PhHgCl molecule is exactly linear. The bond lengths at the Hg atom are Hg-Cl 2.345(2) and Hg-C 2.044(9) Å. In the crystal, the molecules are arranged in double layers parallel to the a,b plane. In a model medium for the gastric juice (0.1 M DCl in D2O / [D8]dioxan, 37 °C), HgPh2 reacts to form PhHgCl. HgCl2, which would result from complete dearylation, cannot be isolated from the reaction mixture. However, it appears that a small equilibrium concentration of HgCl2 may be present, because on addition of 1,4,7-trithiacyclononane (ttcn) and diethyl ether, the dichloride can be trapped as solid [Hg(ttcn)2][HgCl4]. We estimate that after oral uptake of HgPh2 20 -90% are transformed into PhHgCl in the stomach after 30 min
Synthese, Struktur und Reaktivität von Aminomethylpyridin- zinkdihalogeniden / Synthesis, Structure and Reactivity of Aminomethylpyridine Zinc Dihalides
Authors: Westerhausen Matthias , Bollwein Tobias , Polborn Kurt
Published: February 2015

Zinc dichloride reacts with aminomethylpyridine (AMP) to the corresponding 1:1 adduct 1, whereas ZnBr2 forms an ionic 1:2 complex of the type [(AMP)2ZnBr]+ Br- 2, which loses one neutral coligand upon heating in Me-C (O)OEt to yield nearly insoluble (AM P)ZnBr2 3. The condensation reaction of these compounds with acetone yields propylideneaminomethylpyridine zinc dichloride (4) and dibromide (5), respectively. The reaction of ZnI2 with AMP and acetone gives propylideneaminomethylpyridine zinc dichloride (6) in quantitative yield. The structures of 3, 4, and 6 confirm the linear relationship between the Zn-N distance and the X-Zn-X angle in compounds of the type (L2)ZnX2 with L2 being a bidentate amino base, whereas short Zn-N bonds enforce small X-Zn-X angles. Compound 2 consists of separated ions in the solid state with a five coordinate zinc atom in a distorted trigonal bipyramidal coordination sphere
Reaktionsbeteiligung elektrophiler Funktionen bei der Dehydrierung 4-substituierter Piperidine / Participation of Electrophilic Groups with the Dehydrogenation of 4-Substituted Piperidines
Authors: Möhrle H. , Jeandrée M.
Published: February 2015

Dehydrogenation of 2-(1-piperidinyl)-benzaldehydes 1-3 using mercury(II)-EDTA gen­ erated the lactams 4-6, indicating a reversible reaction of a carbinolamine intermediate with the formyl group. The yields and oxidation rates decreased by 4-substitution in the piperidine moiety.

The 2-(1-piperidinyl)-acetophenones 11, 16-19 showed a similar behavior with mercury(II)-EDTA but gave rise to a product pattern. The trans-benzoquinolizidones 12, 20, 23, 26, 29 resulted from the cyclic iminium compounds reacting with the acetyl group as nucleophile. By another oxidation these species were partially transformed to the quinolinones 13, 21, 24, 27, 30. An intermediate electrophilic neighboring of the carbonyl group with the cyclic hemiaminals led finally to the lactams 14, 22, 25, 28, 31. Mechanisms for the reactions are proposed
Chemical Constituents of Ajuga parviflora
Authors: Nawaz Hafiz Rub , Malik Abdul , Muhammad Pir , Ahmed Saeed , Riaz Muhammad
Published: February 2015

Two new antifungal withanolides, (1) and (2) have been isolated from the defatted methanolic extract of Ajuga parviflora. Their structures were established as 3β,17β,20-trihydroxy-1-oxo-(20R, 22R)-witha-5,14,24-trienolide (1), 28-hydroxy-14,20-epoxy-1-oxo-(22R)-witha-2,5,24-trienolide (2) on the basis of spectroscopic data including two dimensional NMR tech­niques. The pyrrolizidine alkaloids senecionine (3) and integerrimine (4) are also reported for the first time from A. parviflora
Di-tert-alkyl Nitroxyl Radicals. Synthesis, Physical Properties and Applications as Inhibitors of Vinyl Polmerization at Elevated Temperatures
Authors: Sosnovsky George , Jawdosiuk Mikolaj , Clumpner J. Michael
Published: February 2015

Stable di-tert-alkylnitroxyl radicals, tert-butyl-tert-pentylnitroxyl (4a), di-tert-pentylnitroxyl (4b) and tert-octyl-tert-pentylnitroxyl (4c), the homologs of di-tert-butylnitroxyl (1), were synthesized from tert-alkyl amines 7a-c via the 3-tert-alkylamino-3-methyl-1-butynes 8a-c. Oxidation of 8a,b with hydrogen peroxide lead to relatively unstable N-tert -alkyl-N -(1,1-dimethylprop-2-ynyl)nitroxyl radicals 15a,b. The thermal stability, vapor pressure data, ultraviolet, visible and electron paramagnetic resonance spectra of 4a-c were recorded. The radicals were explored as potential inhibitors of unwanted alkene polymerization reactions at elevated temperatures, in comparison with the aliphatic di-tert-butyl nitroxyl (1), the alicyclic nitroxyl radicals 2,2,6,6-tetramethylpiperidin-1-oxyl (2) and 4-hydroxy-2,2,6,6-tetramethyl-piperidin- 1-oxyl (3), some commercial polymerization inhibitors, such as diethyl-hydroxylamine (Pennstop, 16), ammonium salt of N-hydroxy-N-nitrosobenzenamine (Cupferron, 17 ), bis(2,2,6,6- tetramethyl-4-piperidyl) sebacate (Tinuvin 770, 18), and the well-known spin traps 2-methyl- 2-nitrosopropane (19) and tert-butylhydroxylamine (20)
Intermetallic Cerium Compounds with Ordered U3Si2 Type Structure
Authors: Pöttgen Rainer , Fugmann Artur , Hoffmann Rolf-Dieter , Rodewald Ute Ch. , Niepmann Dirk
Published: February 2015

New intermetallic cerium compounds Ce2T2Mg (T = Ni, Cu, Pd), C2T2Cd (T=Pd, Pt, Au), and C2T2Pb (T = Pt, Au) were prepared by reaction of the elements in sealed tantalum tubes in a high-frequency furnace. Most C2T2X (X = Mg, Cd, Pb) compounds are stable after annealing at about 1000 K, while Ce2Pd2Mg is obtained as single phase only after melting and quenching. A thermal treatment at about 1000 K leads to decomposition in CePdMg and CePd. The eight compounds were investigated by X-ray diffraction both as powders and single crystals, and most structures were refined from single crystal data. They adopt an ordered U3Si2 type structure with space group P4/mbm: a = 759.6(1), c = 376.71 (9) pm, wR2 = 0.0562, 294 F2 values, 12 parameters for Ce2Ni2Mg, a = 787.41(9), c = 387.23(7) pm, wR2 = 0.0438, 222 F2 values, 12 parameters for Ce2Cu2Mg, a = 777.14(8), c = 400.03(7) pm, wR2 = 0.0276, 221 F2 values, 13 parameters for Ce2Pd2.03Mg0.97, a = 777.90(6), c = 393.28(6) pm, wR2 = 0.0360,317 F2 values, 12 parameters for Ce2Pd2Cd, and a = 779.90(7), c = 389.97(7) pm, wR2 = 0.0453, 315 F2 values, 12 parameters for Ce2Pt2Cd. Refinement of the occupancy parameters revealed full occupancy for most sites. A mixed palladium/magnesium (97 % Mg / 3 % Pd) occupancy was observed only for the 2a site of Ce2Pd2.03Mg0.97, indicating a small homogeneity range for this compound. Ce2Au2Cd (a = 804.93(7), c =393.36(6) pm) and the plumbides Ce2Pt2Pb (a = 794.63(7), c = 381.50(6) pm) and Ce2Au2Pb (a = 810.70(7), c = 394.85(7) pm) were characterized through their Guinier powder data. The structures of the Ce2T2X compounds can be interpreted as an intergrowth of distorted AIB2 and CsCl related slabs of compositions CeT2 and CeX. The course of the lattice parameters and chemical bonding within the series of Ce2T2X compounds are briefly discussed.
Synthese und Kristallstruktur des Bromdifluormethyl-triphenyl- phosphoniumbromids, [(C6H5)3PCF2Br]+ Br- / Synthesis and Crystal Structure of Bromodifluoromethyl-triphenylphosphonium Bromide, [(C6H5)3PCF2Br]+ Br-
Authors: Bender C. , Wulff-Molder D. , Vogt H. , Ritschl F. , Meisel M.
Published: February 2015

Difluorobromomethyl-triphenylphosphonium bromide [(C6H5)3PCF2Br]+ Br- (1) has been prepared by the reaction of triphenylphosphine with dibromodifluoro-methane in acetonitrile or methylene chloride. The colorless crystals are monoclinic, space group P 21/n, Z=4, a = 1067.1(2), b = 1488,5(2), c = 1178,2(2) pm, β = 95,67(3)°. The lattice contains Br- anions and [(C6H5)3PCF2Br]+ cations with a Br-Br distance of 322,33(11) pm.. For the title compound the results of AM 1, PM 3 ,and MNDO calculations are in good agreement with corresponding values determined by the X-ray analysis only in the case of PM 3.

The yellow-red [(C6H5)3PCF2Br]+ Br3
- (2) has been obtained by treating 1 with equimolar quantities of elemental bromine in methylene chloride solution.
Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-(n-Bu4N)2[ReBr4(NCS)2 ], cis-(n-Bu4N)2[ReBr4(NCSe)2] und cis-(n-Bu4N)2[ReBr4(NCS)(NCSe)] / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of cis-(n-Bu4N)2[ReBr4(NCS)2], cis-(n-Bu4N)2[ReBr4(NCSe)2,] and cis -(n -Bu4N)2[ReBr4(NCS)(NCSe)]
Authors: Homolya L. , Preetz W.
Published: February 2015

The crystal structures of cis-(n-Bu4N)2[ReBr4(NCS)2] (1) (triclinic, space group P1̄, a = 11.475(6), b = 20.096(16), c = 22.144(11) Å, α = 110.56(6), β = 92.97(5), γ = 99.77(7)°, Z = 4), cis-(n-Bu4N)2[ReBr4(NCS)2] (2) (triclinic, space group P1̄, a = 11.527(3), b = 20.237(7), c = 22.07(2) Å, α = 110.05(4), β = 93.86(6), γ = 99.49(4)°, Z = 4) and cis-{n- Bu4N)2[ReBr4(NCS)(NCSe)] (3) (triclinic, space group P1̄, a = 11.488(2), b = 20.164(6), c = 22.158(5) Å, α = 110.44(2), β = 93.34(2), γ = 99.626(18)°. Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on these molecular parameters the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.70 (1), 1.70 (2) and 1.72 (3), fd(ReBr) = 1.36 (1), 1.30 (2) and 1.36 mdyn/Å (3).
Substituent Influences on the Keto-Enol Tautomerism in 1-(2-Hydroxyphenyl)-3-α-and -β-naphthylpropane-1,3-diones Monitored by 1H and 13C NMR Spectroscopy
Authors: Jios Jorge L. , Duddeck Helmut
Published: February 2015

Synthesis of 18 1-(2-hydroxyphenyl)-3-α- and -β-naphthylpropan-1,3-diones is described. Their 1H and 13C NMR spectra were completely and unambiguously assigned using a combination of both homo- and heteronuclear (gs-COSY ), 1H -detected heteronuclear one-bond (gs-HMQC ) and long-range (gs-HMBC) correlation experiments. Substituent and conformation effects on the tautomeric equilibria were identified and interpreted in terms of steric and electronic contributions.
Endogenous Alkaloids in Man, Part 33. Dimethyl (2S,4S)-and (2R,4S)-5,5-Dimethyl-1,3-thiazolidine-2,4-dicarboxylates, Two Diastereomeric Glyoxylate-Derived Heterocycles
Authors: Bringmann Gerhard , Feineis Doris , Saeb Wael , Hesselmann Christiana , Peters Eva-Maria , Peters Karl
Published: February 2015

Both title compounds were obtained in stereochemically pure form by refluxing 5,5-dim ethyl-1 ,3-thiazolidine-2,4-dicarboxylic acid (3) with methanolic HCl, followed by a separation of the two diastereomers 4a and 4b on silica gel. The X-ray structure analyses of these stereoisomers confirm the relative configuration to be cis for 4a and trans for 4b with respect to the two carboxymethyl substituents at C(2) and C(4). For both molecules, an envelopetype conformation of the thiazolidine ring was found with C(5)-S(1)-C(2)-N(3) being located in a plane showing a small ring torsion angle of -11.2° and -3.1° for the cis- and the rrafts-epimer, respectively. The trans-configured compound 4b adopts a nearly ideal envelope conformation with C(4) being the flap atom, while the cis-isomer 4a. apparently because of steric interactions of the C(2) and C(4) substituents, shows a twisted envelope conformation.
Alternative Method for the Preparation of 4,5-Ethylenedithio-1,3-dithiole-2- thione and Related Compounds
Authors: Papavassiliou G. C. , Mousdis G. A. , Papadima A.
Published: February 2015

The compounds 4,5-ethylenedithio-1,3-dithiole- 2-thione, 4,5-(methyl) ethylenedithio-1,3-dithiole- 2-thione and 4,5 (dimethyl) ethylenedithio-1,3- dithiole-2-thione were prepared by reaction of 1,3-dithiole-2,4,5-trithione with ethylene, propylene and trans-2-butene, respectively. The preparative and spectroscopic data are identical with those obtained from the corresponding authentic samples.
New Diazasilaphosphetidines and their Precursors
Authors: Eichhorn Bettina , Nöth Heinrich
Published: February 2015

A series of aminosilanes (R′HN)2SiR2: have been prepared. In case of bulky substituents R′ the aminolysis of Ph2SiCl2 stops at the (R′HN)ClSiPh2 stage. Replacement of the Cl atom is achieved with LiNHR′ which allows the synthesis of mixed bisaminosilanes (R′HN)(R″HN)SiPh2. The X-ray structures of three of these compounds have been determined. There are no intermolecular N-H···N hydrogen bonds in these compounds in the solid state. Several 1,3,2,4-diazaphosphetidines have been synthesized using bis(N-lithioamino)silanes and bis(N-lithioamino)phosphanes . Amongst these the heterocycle 18 possesses an almost planar four membered N2SiP ring system.
The Solid State Conformation of Diaryl Ditellurides and Diselenides: The Crystal and Molecular Structures of (C4H3E2)2E'2 (E = O, S; E' = Te, Se)
Authors: Oilunkaniemi Raija , Laitinen Risto S. , Ahlgrén Markku
Published: February 2015

The crystal and molecular structures of dithienyl ditelluride (C4H3S)2Te2 (1), difuryl ditelluride (C4H3O)2Te2 (2), dithienyl diselenide (C4H3S)2Se2 (3), and difuryl diselenide (C4H3O)2Se2 (4) are reported in this paper and compared to those of other simple diaryl ditellurides and diselenides. The chalcogen-chajcogen bonds exhibit approximately single bond lengths [Te-Te = 2.7337(8) and 2.7240(4) Å in 1 and 2, respectively; Se-Se = 2.357(1) and 2.368(2) Å in 3 and 4, respectively], as do the chalcogen-carbon bond lengths [Te-C = 2.095(9) - 2.104(6) in 1 and 2.091(6) - 2.105(9) Å in 2; Se-C = 1.87(1) - 1.90(1) Å in 3 and 1.887(8) - 1.897(10) Å in 4]. The aromatic rings are disordered. The dihedral angles C-E-E-C range from 79(2) to 96(1)° are consistent with the concept of minimized p lone-pair repulsion of adjacent chalcogen atoms. The dependence of molecular parameters on the angle between the aromatic rings and the chalcogen-chalcogen bonds follow trends established previously for aromatic disulfides. Though the bond parameters and conformations of 1 - 4 are similar, the packing of the molecules is different. The two ditellurides 1 and 2 show short Te···Te contacts (3.900 - 4.002 Å in 1 and 4.060 - 4.172 Å in 2). The two diselenides 3 and 4 do not exhibit close chalcogen-chalcogen interactions. The NMR spectroscopic properties of 1 - 4 are discussed.
Kristallstruktur und schwingungsspektroskopische Daten von Silbercyanamid / Crystal Structure and Spectroscopic Data of Silver Cyanamide
Authors: Becker Michael , Nuss Jürgen , Jansen Martin
Published: February 2015

Ag2CN2 precipitates on mixing aqueous solutions of H2CN2 and silver nitrate as a yellow crystalline solid. The title compound was characterised by single crystal X-ray diffraction and IR-spectroscopy (monoclinic, P21/c (No. 14), a = 7.315(1), b = 6.010(1), c = 6.684(1) Å; β = 102.29( 1)°; Z = 4). The anion is slightly bent (177.1 (5)°) and exhibits two significantly different bond lengths (C-N(l): 1.194(6), C-N(2): 1.266(5) Å).
Luminescence Detection and Photodimerization of 1,3-Dimethyluracil Coordinated to Copper(I)
Authors: Kunkely Horst , Vogler Amd
Published: February 2015

1,3-Dimethyluracil (DMU) forms a complex with copper(I) iodide which shows a green luminescence at λmax = 505 nm. With PF6
- counter ions a photoactive Cu(I)DMU complex is generated which shows a long-wavelength absorption at λmax = 335 nm. Light absorption by this band leads to a dimerization of DMU to its cyclobutane dimer.
Supersilylsilane R*SiX3: Darstellung, Charakterisierung und Strukturen; sterische und van-der-Waals Effekte der Substituenten X [1] / Supersilylsilanes R*SiX3: Syntheses, Characterization and Structures; Steric and van-der-Waals Effects of Substituents X [1]
Authors: Wiberg Nils , Niedermayer Wolfgang , Nöth Heinrich , Knizek Jörg , Ponikwar Werner , Polbom Kurt
Published: February 2015

Supersilylsilanes R*SiX3 (R* = supersilyl = SitBu3; X = H, Me, tBu, Ph, SiMe3, F, Cl, Br, I, OMe, OSO2CF3) are prepared (i) by reactions of supersilylhalosilanes with supersilyl sodium NaR* (Hal/R* exchange), (ii) by reactions of supersilylhalosilanes with hydride H- (Hal/H exchange), (iii) by reactions of supersilylsilanes with halogens Hal2 (H/Hal exchange, R*/Hal exchange), (iv) by reactions of supersilylhalosilanes with nucleophiles like F- , MeO- (Hal/F or Hal/OMe exchange) and (v) by reactions of supersilylsilanes with strong acids (H/OSO2CF3 exchange). NMR chemical shifts δ (29Si) of the SiX3 groups of R*SiX3 strongly depends on the nature of X. The supersilylsilanes R*SiX3 are in part moisture sensitive (especially compounds with SiX3≡SiHHal2 and SiH2Hal), in part sensitive against oxygen (compounds with SiX≡SiBr or SiI), and some of them react with supersilyl sodium by supersilanidation (for example R*SiF3, R*SiH2Cl, R*SiMeHCl) or by reduction (for example R*SiCl3, R*SiMeBr2, R*SiPhBrCl). X-ray structure analyses of disilanes tBu3Si-SiX3 with SiX3≡SitBu3, SiPh3, Sil3, SiPhCl2 show a staggered conformation. Due to steric repulsion of the tBu3Si and SiX3 groups as well as van-der-Waals attraction of the substituents tBu and X in tBu3Si-SiX3 the SiSi bonds are longer than 2.34 Å (the normal SiSi single bond length) and the torsion angles are smaller/larger than 60° (the ideal staggered conformation). From the extent of SiSi bond elongation and CSiSiX angle compression it is concluded that the bulkiness of X increases in direction Cl < I < Ph < SiMe3 < CMe3 (tBu3Si-SitBu3 has to date the longest SiSi bond of all disilanes) and the van-der-Waals forces between tBu/X increase in direction tBu/I < tBu/tBu < tBu/Ph.
Synthese und Kristallstrukturen der Bis(oxalato)metallate trans-K3[RhCl2(C2O4)2]· 4 H2O und cis -K3[IrCl2(C2O4)2]· H2O / Synthesis and Crystal Structures of the Bis(oxalato)metallate trans-K3[RhCl2(C2O4)2]· 4 H2O und cis -K3[IrCl2(C2O4)2]· H2O
Authors: Rohde J.-U. , Preetz W.
Published: February 2015

By treatment of RhCl3 or IrCl3 with K2C2O4 the bis(oxalato)metallates trans-K3[RhCl2(C2O4)2] and cis-K3[IrCl2(C2O4)2] are formed. From the aqueous solutions single crystals were grown by slow diffusion of ethanol and X-ray structure determinations of trans-K3[RhCl2(C2O4)2] · 4 H2O (monoclinic, space group I2/m, a = 6.218(1), b = 11.837(2), c - 10.357(2) Å, β = 95.55(3)°, Z = 2) and cis-K3[IrCl2(C2O4)2] · H2O (monoclinic, space group /2/a, a = 14.060(3), b = 7.586(2), c = 23.488(5) Å, β = 90.44(3)°, Z = 8) have been performed. The oxalato and chloro ligands of the complex anions are connected via hydrogen bonds and electrostatic interactions to water molecules and potassium ions. The potassium ions are eightfold and in one case ninefold coordinated.
Carbacylamidophosphates: Synthethis and Structure of N,N'-Tetramethyl-NM-benzoylphosphoryltriamide and Dimorpholido-N-benzoylphosphorylamide
Authors: Gubina Katerina E. , Ovchynnikov Vladimir A. , Amirkhanov Vladimir M. , Skopenkoa Viktor V. , Shishkinb Oleg V.
Published: February 2015

N,N′-Tetramethyl-N"-benzoylphosphoryltriamide (I) and dimorpholido-N-benzoylphosphorylamide (II), and their sodium salts Nal, Nall were synthesized and characterized by means of IR and 1H, 31P NMR spectroscopy. The structures of I, II were determined by X-ray diffraction: I monoclinic, space group P2i/c with a = 10.162(3), b= 11.469(4), c = 12.286(4) Å , β = 94.04°, V = 1428.4(8) A 3, Z = 4, p(calcd) = 1.187 g/cm3; II monoclinic, space group C2/c with a = 15.503(4), b = 10.991(3), c = 22.000(6) Å, β = 106.39°, V = 3596.3(17) Å3, Z = 8, p(calcd.) = 1.253 g/cm3. The refinement of the structures converged at R = 0.0425 for I, and R = 0.068 for II. In both structures the molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.
Crystal Structure of Bis(triethylammonium)closo-decahydrodecaborate, [(C2H5)3NH]2[B10H10]
Authors: Hofmann Kathrin , Albert Barbara
Published: February 2015

The crystal structure of bis(triethylammonium)closo-decahydrodecaborate [bis(triethylammonium) decaboranate(10)], [(C2H5)3NH]2[B10H10], was determined and refined (space group Pmmn, no. 59, a = 989.7, b = 1333.7, c = 903.7 pm). The compound is a versatile starting material for many substances containing the [BioHio]2- entity and its derivatives. The closo-[B10H10]2- cluster is a bicapped square antiprism which is only slightly distorted. Its deviation from D4d symmetry is smaller than that of the B10 cages in every other compound containing this entity that have been structurally characterised. The presence of additional (N )H ---B3 interactions in form of multiple-centre bonds between the cations and the anions, which were postulated earlier and which should influence the cage symmetry, could not be confirmed. At 55 °C, the transition into a high temperature phase was investigated by X-ray powder diffraction. The high temperature phase crystallises in the tetragonal crystal system (a = 946.9, c = 1351.0 pm).
Cyclische Silylhydrazine - Kristallstrukturen isomerer fünf- und sechsgliedriger Ringe / Cyclic Silylhydrazines - Crystal Structures of Isomeric Five- and Six-Membered Rings
Authors: Gellermann Eike , Klingebiel Uwe , Witte-Abel Henning , Schäfer Martina
Published: February 2015

The lithium derivative of di(isopropyl)aminofluorosilylhydrazine cyclizes with formation of a five-membered silylhydrazine ring system (1). The analogous reaction of di(tert-butyl)- fluorosilylhydrazine gives the six-membered silylhydrazine ring system (2 ). 1 isomerizes thermally to the six-membered cyclic silylhydrazine 3. LiF-elimination from lithiated (Me3C)2- SiFNHNHSiF(CHMe2)2 leads to the formation of the six-membered cyclic silylhydrazine 4, [(Me2HC)2Si-NH-NSiF(CMe3)2]2. Symmetrical six-membered tetra(fluoro)silylhydrazine rings, (F2SiNRNR)2 (5: R = SiMe3, 6: R = SiMe2CMe3) are obtained in the reaction of bis(trifluorosilyl)hydrazines with dilithium-bis(silyl)hydrazides, whereas a five-membered unsymmetrical silylhydrazine (7: (RNSiF2)2N-NR'2, R = SiMe2CMe3, R′ = SiMe3) is formed in the reaction of R(SiF3)N-N(SiF3)R and R'(Li)N-N(Li)R'. In the reaction of the same fluorosilylhydrazine with dilithiated N,N'-diphenylhydrazide the unsymmetrical six-membered ring 8 is obtained. The crystal structures of 1, 2 and 3 are reported.
Structural and Spectral Studies of 2-Pyridineformamide Thiosemicarbazone and its Complexes Prepared with Zinc Halides
Authors: Castiñeiras Alfonso , Garcia Isabel , Bermejo Elena , West Douglas X.
Published: February 2015

Reduction of 2-cyanopyridine by sodium in dry methanol in presence of thiosemicarbazide produces 2-pyridineformamide thiosemicarbazone, HAm4DH. The crystal structure of HAm4DH, which has a number of intermolecular interactions involving its five NH hydrogen atoms, has been solved. Crystal structures of the complexes prepared by reaction of HAm4DH with zinc(II) chloride, bromide and iodide have also been obtained. Neutral HAm4DH is coordinated via the pyridyl nitrogen, imine nitrogen and thione sulfur atoms, and each complex is five-coordinate with two halogen ligands. The structures of the three complexes are best described as square pyramidal with [Zn(HAm4DH)l2] having the largest distortion toward a trigonal bipyramid.
Synthesis of Halfsandwich Ruthenium Complexes of Sulfinic Acid Esters [1]
Authors: Schenk Wolfdieter A. , Kuhnerta Nikolai
Published: February 2015

A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR'3)2(SO2R)] (R = Me, CH2Ph, C2H4Ph, Ph, 4-C6H4Me; PR'3 = PMe3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(CO )(PPh3)(SO2R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [R"3O]X (R" = Me, Et; X = BF4 , PF6) gave ruthenium complexes of sulfinic acid esters, [CpRu(L)(L′)(S(O)(OR″)R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I- or SMe- dealkylate the coordinated sulfinic acid esters.
A Synthesis, Antimicrobial Activity and Heterocyclic Ring Transformation of 5-(Pyrazol-5-yl)-1,3,4-oxadiazole-2(3H)-thiones
Authors: Shaw A. S. , Abdallah M. A. , Zayed M. E. M.
Published: February 2015

The synthesis and antimicrobial activity of a series of the title thiones were examined. Reaction of such thiones with hydrazonoyl halides, resulted in ring transformation to give 5-acylhydrazono derivatives of 1,3,4-thiadiazoles. The mechanisms of the studied reactions are discussed.
Crystal Structure and Magnetic Properties of a (μ-Hydroxo)(μ-acetato) Dicopper(II) Complex
Authors: Kavlakoglu E. , Elmali A. , Elerman Y. , Fuess H.
Published: February 2015

[Cu2(L)(O2CMe)] · H2O (L = 1,3-Bis(2-Hydroxy-1-napthylideneamino)propan-2-ol) was synthesized and its crystal structure determined. (C27H23N2O5Cu2).H2O , monoclinic, space group P21/c, a = 11.795(3), b = 17.988(5), c = 12.005(6) Å, β = 109.99(3)°, V = 2393(2) Å3, Z = 4. Two copper(II) ions in a square-planar coordination are bridged by alkoxide and acetate oxygen atoms to form a dinuclear unit. The metal coordination sphere is four-coordinate, planar with an NO3 donor set. The dihedral angle between the two coordination planes is 6.34(9)°. The copper(II) centers are separated by 3.492(2) Å and weakly antiferromagnetically coupled (-2J = 163.6 cm-1 ), which follows from temperature-dependent magnetic susceptibility measurements in the temperature range 4.6 to 310 K. The Cu-O-Cu angle is 133.5(1)° in the super-exchange pathway. The weak antiferromagnetic coupling of the complex is interpreted in terms of countercomplementary effects of the different bridging ligands which participate in the super-exchange interaction. The magnetic moment at 310 K is ca. 2.7 B. M., but 0.2 B. M. at 4.6 K. The magnetic susceptibility is at a maximum near 140 K and decreases rapidly as the temperature is lowered to liquid helium temperature.
Lanthanide Complexes with Carbacylamidophosphates: The First Registration of Chelate Coordination of the Neutral Ligand Form in the Structure of Di-(N,Nf-tetramethyl-NM -benzoylphosphoryl- triamide)cerium(III) Nitrate
Authors: Gubina Katerina E. , Ovchynnikov Vladimir A. , Amirkhanov Vladimir M. , Fischer Helmut , Stumpf Rüdiger , Skopenko Viktor V.
Published: February 2015

The coordination compounds of the general formula Ln(HL)2(NO3)3, (where Ln = La - Eu (without Pm), HL = C6H5C(O)NHP(O)[N(CH3)2]2, N,Nʹ-tetramethyl-Nʺ-benzovlphosphoryl-triamide) have been synthesized and characterized by means of IR, UV-VIS, 1H, 31P NMR spectroscopy, and X-ray analysis. The complexes are isostructural according to X-ray powder diffraction studies. The crystal structure of the cerium(lll) complex has been determined. Crystal data: monoclinic, P21/c, with a = 10.503(9), b = 15.62(2), c = 21.91(2) Å, β = 99.56(8)°, Z = 4, V = 3546(6) Å3, R1= 0.0550, wR2 = 0.1383 for 6970 unique reflections used. The complex has a molecular structure. Neutral phosphoryltriamide ligands are coordinated to the metal ion in a bidentate manner via phosphoryl and carbonyl oxygen atoms with formation of six membered chelate rings. The coordination polyhedron of the Ce atom is a sphenocorona; C.N. = 10 (4 O[HL] + 6 O [NO3
-]).
Zum System Bi2O3 /Bi2Se3/BiCl3,I. Das Zustandsdiagramm Bi2O3/Bi2Se3/BiCl3/On the System Bi2O3/Bi2Se3/BiCl3, I. The Phase Diagram Bi2O3/Bi2Se3/BiCl3
Authors: Schmidt P. , Oppermann H.
Published: February 2015

The phase relations in the quaternary system Bi/Se/O/Cl have been studied and the existence of several new compounds in the pseudotemary area Bi2O3/Bi2Se3/BiCl3 has been established by solid state and chemical vapour transport reactions. The phase diagram is derived from X-ray powder diffraction and thermal analysisdata, and from measurements of the decomposition pressure behaviour. Three new quaternary phases with different compositions exist in the system: Bi4O4SeCl2, Bi10O12SeCl4 and Bi22O28SeCl8.

By estimation of the thermodynamic data of the quaternary phases it is possible to calculate complex heterogeneous chemical equilibria between all the binary, ternary and quaternary compounds of the phase diagram. As a result, we can describe thermodynamically the observed phase relations and the direction of thermal decomposition of the respective compounds.
Mono-and Dinuclear triphos-Metal(II)-Complexes with N itriles as Co-Ligands
Authors: Mann Susanne , Hüttner Gottfried , Zsolnai Laszlo , Heinze Katja , Jacob Volker , Antelmann Björn , Driess Alexander , Schiemenz Berthold
Published: February 2015

The triphos ligand CH3C(CH2PPh2)3 reacts with Co(BF4)2 (aq) or Fe(BF4)2 (aq) in the presence of nitriles RCN to produce the pentacoordinate [triphosCo(NCR)2](BF4)2 (1) or the hexacoordinate [triphosFe(NCR)3](BF4)2 (2). With α,ω-dinitriles NC-X-CN dinuclear compounds [triphosFe(NC-X-CN)3Fetriphos](BF4)4 (X = (CH2)3 (3a) X = o-C6H4 (3b) are formed. The compound [triphosFe((CH3)2C=C(CN)2)3Fetriphos](PF6)4 (3c) is obtained from FeCl2 by addition of the triphos ligand, the dinitrile and NaPF6.

All compounds are characterised by the usual analytical techniques including X-ray analy­ses. It is observed that the quadruply positively charged compounds 3 tend to associate the respective anions in pockets formed by the three segments of the Fe(NC-X-CN)3Fe bridg ing units.
Thermal Decomposition of Prussian Blue Analogues of the Type Fe[Fe(CN)5NO]
Authors: Inoue Hidenari , Narino Shuichi , Yoshioka Naoki , Fluck Ekkehard
Published: February 2015

The structure and properties of the thermal decomposition products of Fe[Fe(CN)5NO] · x H2O (x = 5 ~ 6) have been studied by Mössbauer and FT-IR spectroscopy, X-ray diffraction, and conductivity measurements. The valence state and coordination environment of the iron ions change dramatically when the nitrosyl ligand is eliminated by heat-treatment under vacuum at 200 °C. The dark blue product obtained by heat-treatment under vacuum at 250 °C is characteristic of the mixed-valence state in Prussian blue analogues. The electrical conductivity of the dark blue product is higher by a factor of 103 than that of the starting material because of the mixed-valence state between Fe(III)[Fe(II)(CN)5] and Fe(II)[Fe(III)(CN)5]. Heat-treatment under vacuum at 350°C yields a new product Fe(II)[Fe(II)(CN)4] the crystal structure of which is different from that of the starting material. The electrical conductivity of the decomposition product obtained at 350 °C is about 105 times higher than that of the starting material.