bluuebunny/crossref_metadata_2025 huggingface dataset:
Correlation of Zero-Field Splittings and Site Distortions. IX. Fe3+ and Cr3+ in β -Ga2O3
Authors: Büscher R. , Lehmann G.
Published: February 2015

EPR of Fe3+ in distorted tetrahedral sites in single crystals of β-Ga2O3 has been measured for the first time, and the second-order zero-field splitting (ZFS) parameters and principal axes directions were determined. The data for the sixfold coordinated Fe3+ are in good agreement with results from the literature. Comparison of the ZFS patterns with those calculated from the crystal structure data using the superposition model (SPM) shows reasonable agreement in the orientations of the principal axes, but only for the tetrahedral site is a reasonable value of the intrinsic ZFS parameter obtained. Besides large uncertainties in the sizes of the distortions the crystal structure data also appear to be systematically wrong. For Cr3+ in sixfold coordinated sites the discrepancies are even larger, but for this ion a reduced validity of the SPM may also be involved.
Inverse Poincaré Halfmaps
Authors: Kahlert Claus
Published: February 2015

A family of critical curves that lie in the range of a class of Poincaré halfmaps induced by a saddle focus in three-space is investigated analytically. It comprises all "far final points" of the images of invariant curves that are subject to a separating mechanism. The number of branches occurring on a specific critical curve is directly related to the type of separating mechanism present in the halfmap. Moreover, universal properties of the saddle-focus dynamics are demonstrated for the first time.
Thermodynamische Interpretation der Schmelzdiagramme binärer Systeme aus Methylchlorsilanen und Pyridazin bzw. Pyrazin
Authors: Hensen Karl , Gaede Jens
Published: February 2015

By analyzing the cooling curves and the resulting melting point diagrams of the chloromethylsilane- pyridazine and pyrazine systems the existence of the incongruently melting addition compounds CH3SiCl3 • Pyridazine, (CH3)2SiCl2 • (Pyridazine)2, (CH3)3SiCl • (Pyridazine)2, CH3SiCl3 • (Pyrazine)2, (CH3)2SiCl2 • (Pyrazine)2 , (CH3)3SiCl • (Pyrazine)2 was proved. By electro-optical measurements of the turbidity point it was proved that the system (CH3)3SiCl- Pyridazine exhibits a miscibility gap which intersects the liquidus curve of the amine. Based on certain approximations it was possible to fit thermodynamic functions to the experimental results to obtain the excess data of mixing of the corresponding systems. These data allow for a more profound understanding of the Lewis-acid base behaviour of the silanes and amines.

Chloromethylsilanes, Pyridazine, Pyrazine, Phase Diagrams, Addition Compounds, Thermodynamic Excess Functions
An X-Ray Diffraction Study on the Structure of Concentrated Aqueous Caesium Iodide and Lithium Iodide Solutions
Authors: Tamura Yusuke , Okada Isao , Ohtaki Hitoshi , Yamaguchi Toshio
Published: February 2015

X-Ray scattering measurements of 2.78 and 5.56 molal aqueous solutions of caesium iodide and 2.78 and 6.05 molal lithium iodide were carried out at 293 and 343 K Differences in the radial distribution functions (DRDFs) have been obtained between the caesium iodide and lithium iodide solutions of similar composition, the latter being taken as a reference for the data analysis of the former. The DRDFs show a peak arising from Cs - I contact-ion-pairs at 390 pm for all the caesium iodide solutions. The hydration structure of the caesium and iodide ions has been revealed. Effects of the concentration and temperature on the formation of ion-pairs and on the hydration structure of the ions are discussed
Eu2P2S6: Das erste Seltenerd- Thiohypodiphosphat
Authors: Broekner Wolfgang , Becker Robert
Published: February 2015

Europium Hexathiohypodiphosphate Eu2P2S6 with Eu in the oxidation state 2 has been prepared by direct elemental synthesis at high temperatures. Its vibrational spectrum has been recorded. The observed frequencies are assigned on the basis of P2S6
4- units with C2h symmetry in the crystal in analogy to Sn2P2S6 (monoclinic modification II).

DTA-data have been determined and interpreted.
Pressure Effects of Neon and Argon on the 535 nm Thallium Line
Authors: Dygdafa R. S. , Bobkowski R. , Lisicki E. , Szudy J.
Published: February 2015

Experimental studies of collisional broadening and shift of the 535 nm thallium line perturbed by neon and argon were performed using a pressure-scanned Fabry-Perot interferometer. The 535 nm line was excited by irradiation of the thallium vapour with the resonance thallium line (377.68 nm). The present results are compared with previous experimental data obtained by different methods as well as with theoretical ones.
Temperature Dependence of Lithium Isotope Effects in Ion Exchange Electromigration
Authors: Fujii Yasuhiko , Hosoe Morikazu , Makoto Okamoto
Published: February 2015

The isotope separation coefficient of lithium electromigration through a cation exchange membrane is determined at 6, 11, 20 and 40 °C . It is found that this coefficient increases with temperature while the slope of the isotope distribution in the band decreases with increasing temperature. These tendencies are opposite to those usually observed in ion exchange chromatography.
Notizen: Simplest Kinetic Models for Bistability of Antipodal Mixtures
Authors: Gutman I. , Klemm A.
Published: February 2015

Three choices of three rate coefficients out o f the six coefficients occurring in the general second order rate equation for interacting antipodes (e.g. enantiomers) can provide bistability with incomplete demixing. Once choice of two rate coefficients can provide bistability with complete demixing.
X-ray Structural Analysis of Molten LiF — LiCl System
Authors: Okamoto Yoshihiro , Igarashi Kazuo , Mochinaga Junichi
Published: February 2015

The short range structures of molten LiF - LiCl ( 1 : 2 ) and ( 1 :1 ) mixtures with the common cation were investigated by an X -ray diffraction method and compared with those found in the pure melts and the molten alkali halide mixtures with the common anions. In both the mixtures, the nearest neighbor arrangements of the unlike ion pairs were similar to those in the pure melts. On the other hand, the nearest distances between like ions changed by mixing.
Ab initio and Semiempirical Studies on H3C-B=O and H-B=O. Their Structure and Vibrational Spectra
Authors: Raabe Gerhard , Schleker Wolfgang , Straßburger Wolfgang , Heyne Eberhard , Fleischhauer Jörg , Bachler Vinzenz
Published: February 2015

The electronic structure of H3C -BO and H - BO is elucidated employing one determinant ab initio calculations with STO-3G and 4-31G basis sets and the semiempirical MNDO theory. The vibrational spectra of both molecules including various isotopic shifts have been calculated at the 4-31G level. The influence of methyl substitution on the vibrational frequencies, BO stretching force constant, Mulliken charges, and vertical ionization potential is examined and compared with that in the pairs H-CN/H3C-CN and H-NC/H3C-NC , isoelectronic with H-BO/H3C-BO.

As judged from a comparison of the force constants for stretching the XY bonds in the H3C -XY and H-XY molecules, the XY bond is “softened” upon methyl substitution. This effect is found to decrease in the order H3C-BO>H3C-CN>H3C-NC.

For XY=BO the difference between the first ionization potentials of H-XY and H3C-XY is found to be somewhat smaller than for XY = CN but slightly higher than for the isonitril compounds (XY = NC).
Magnetic Surfaces and Localized Perturbations in the Wendelstein VII-A Stellarator
Authors: Wobig H.
Published: February 2015

The critical dependence of plasm a confinement in low-shear stellarators, such as Wendelstein VII-A, on the external rotational transform can be explained on the basis of magnetic surface destruction. External symmetry-breaking perturbations generate islands on the low order rational magnetic surfaces. The islands are largest at t = 1/2 and t = 1/3. Confinement is optimum in close proximity to these values. In o rd er to study the structure of surfaces under the influence of perturbations, a mapping procedure is used instead of field line integration. It is found that the neighbourhood of low-order rational surfaces is particularly robust against surface destruction. The reason is that in this vicinity only rational surfaces with large m and n exist (t = m/n). On these surfaces the external perturbation only generates small islands.

In W VII-A the current leads to the helical windings are one symmetry-breaking perturbation , and there might also be others. It is possible to avoid field errors of this kind in future stellarators.
Effect of Vacuum Magnetic Well on Magnetohydrodynamic Stability in Heliotron-E-like Configurations with High Shear
Authors: Herrnegger F.
Published: February 2015

An analysis of n ≥ 1 free-boundary modes in Heliotron-E-like configurations using the stellarator expansion code STEP is given. It is shown that an axisymmetric quadrupol field improves the stability properties of these high-shear equilibria. The corresponding vacuum quadrupole field is used to find vacuum field configurations with an average magnetic well of (ΔV' / V')min = -4 % .
Selective Non-Excitation of Water or Fat Protons in Magnetic Resonance Imaging
Authors: Braun M. , Jung W. I. , Lutz O. , Oeschey R.
Published: February 2015

Nuclear magnetic resonance imaging (MRI) of water and fat protons has been performed with a 1.5 T whole body imager. The highly selective excitation, necessary for the discrimination of the two proton species, has been achieved by different four and five pulse excitation schemes which had to be adapted to the needs of MRI and completed to imaging sequences. Their ability to produce well separated water and fat distribution images of test objects is demonstrated. The special features of the method such as signal-to-noise ratio, insensitivity to rf-field inhomogeneities, ease of implementation and data handling are discussed and compared to existing spectral separation techniques.
Investigations of the Reversible Energy Transfer in Concentrated Dye Solutions
Authors: Bojarski C. , Żurkowska G.
Published: February 2015

In the system rhodamine 6G (donor)/rhodamine B (acceptor) the reverse energy transfer considerably increases the donor fluorescence quantum yield, particularly in the high concentration region. These experimental results confirm a theoretical model with no adjustable parameters.
AComparative Study of Approximate Treatments of the Density Polarization in CN-
Authors: Koniński Marek , Nalewajski Roman F.
Published: February 2015

The simple perturbative description of the main polarization effects in molecular systems is tested and calibrated using the modified Hamiltonian MNDO SCF results for the cyano group CN- perturbed by positive or negative point charges. The relative importance of various polarization channels is examined and the reliability of the MNDO predictions is investigated by testing them against the respective ab initio modified Hamiltonian results. It is shown that the δ-function approximation of the point-charge perturbative potential leads to semiquantitatively correct density relaxation patterns, already within one-channel approximation.
Nuclear Magnetic and Quadrupole Resonance Studies of Phase Transitions in Crystalline (NH4)2SbF5 and (ND4)2SbF5
Authors: Kobayashi Ataru , Yoshioka Yoshichika , Nakamura Nobuo , Chihara Hideaki
Published: February 2015

(NH4)2SbF5 undergoes two successive phase transitions at 169 and 292 K, both of which are of typical lambda-type and without thermal hysteresis. Proton and fluorine spin-lattice relaxation time measurements showed that the isotropic reorientation of the NH4
+ ions is highly excited below the lower transition point with an activation energy of 15.5 kJ mol-1 and that the uniaxial reorientation of the square pyramidal SbF5
2- anion is excited above about 200 K with an activation energy of 42.0 kJ mol-1. There is strong cross relaxation between the proton and the fluorine over the whole temperature range of the measurements. The 121Sb and 123Sb nuclear quadrupole resonance frequencies show an anomalous temperature dependence; each resonance frequency assumes a minimum at around 100 K and increases on heating, reaches a maximum at the lower transition point, decreases drastically in the middle temperature phase and then fades out just below the upper transition point. The anomalous increase in the resonance frequencies stems from the reorganization of the N - H ... F type hydrogen bonds with the progress of the lower phase transition. The lower and the upper transition temperatures shift to 173.0 and 290.1 K, respectively, on deuteration of the ammonium ion.
Cis and Gauche Propanal: Microwave Spectra and Molecular Structures
Authors: Randell Jeremy , Cox A. Peter , Hillig Kurt W. ii , Imachi Misako , LaBarge Marabeth S. , Kuczkowski Robert L.
Published: February 2015

The microwave spectra of twelve isotopic species of cis propanal (CH3CH2CHO) and six isotopic forms of the less stable gauche rotamer have been studied to determine accurate structural parameters for both conformers. The following bond lengths (Å) and angles (°) were derived:
An ESR Investigation of Synthetic Pyrite Crystals
Authors: Siebert D. , Dahlem J. , Fiechter S. , Hartmann A.
Published: February 2015

Synthetic pyrite crystals doped with halogen (CI, Br) or manganese (Mn) were investigated by ESR at 78 K with an X-band spectrometer and a TE102 cavity with 100 kc field modulation. The crystals were preferably measured with the directions 〈100〉, 〈110〉, and 〈111〉 parallel to the static magnetic field HO. The ESR spectrum of Mn-doped crystals showed a sextet which can be explained by a spin-Hamiltonian for an electron spin S = 1/2 in interaction with the nuclear spin I = 5/2 of the Mn nucleus for axial symmetry. Due to the observed spin and due to the orientation of the paramagnetic centers the spectra were assigned to Mn2+ in the low spin state which resides on cation site in the FeS2, lattice. In halogen-doped crystals four pairs of lines can be interpreted by the interaction of the two isotopes of I = 3/2, 79Br, 81Br and 35Cl, 37Cl, respectively, with an electron spin S = 1/2. According to the observed symmetry of the ESR signals the paramagnetic centers can be explained as (S-X)2- radicals (X = CI, Br) which substitute for the (S2)2- dumb-bells of pyrite. All crystals evoked extremely narrow ESR lines, especially the halogen-doped crystals with linewidths down to 0.03 mT. Excellent agreement between measured and calculated spectra up to the finest details has been obtained.
Prediction of Isotope Effects for Anticipated Intermediate Structures in the Course of Bacterial Denitrification
Authors: Morgenstern M. A. , Schowen R. L.
Published: February 2015

Vibrational-analysis methods have been used to estimate the equilibrium 14N/15N isotope effects to be expected for conversion of nitrite anion to thirteen possible intermediate-state and productstate structures [HONO, NO+ , NO, NO-, FeNO, ON*NO2, O*NNO2, O2NNO2, ONO*N, O*NON, ONNO, *NNO, N*NO] in the reduction of nitrite ion to nitrous oxide denitrifying bacteria. The results, taken in combination with previous experimental isotope-effect and tracer studies of the Pseudomonas stutzeri and related systems, are consistent with a suggestion that a second nitrite anion enters the enzyme-catalytic cycle at the stage of a nitrosyl-ion intermediate but re-emerges after entry of the reducing electrons; the product nitrous oxide is then formed by disproportionation of enzymically generated hyponitrous acid. The calculations are consistent with contributions, under different experimental conditions, of several different transition states to limiting the rate of the enzymic reaction. These transition states (and the corresponding experimental conditions) are the transition states for N -O fission in the generation of a mononitrogen electrophilic species from nitrite anion (high reductant, high nitrite concentrations), for attack of nitrite on this electrophile (high reductant, low nitrite concentrations) and for electron transfer to a dinitrogen-trioxide-like species (low reductant concentration).
1H NMR and Thermal Studies of CH3NH3Br in a Metastable Solid Phase Newly Found above 483 K
Authors: Tansho Masataka , Nakamura Daiyu , Ikeda Ryuichi
Published: February 2015

By differential thermal analysis a new high-temperature solid phase of methylammonium bromide was found between 483 K and its “melting point” (510 K). 1H NMR absorption measurements revealed the presence of rapid 3D translational self-diffusion and overall rotation of methylammonium cations in this phase. These cationic motions are quite analogous to those of methylammonium iodide in its ionic plastic phase. Surprisingly, this plastic-like phase is metastable, the stable phase in the same temperature range being liquid.
CdSe Photoanodes for Electrochemical Photovoltaic Conversion
Authors: Kochev K. , Popkirov G. , Ivanova K. , Quint R. , Getoff N.
Published: February 2015

The paper presents experimental results obtained with a polycrystalline n-CdSe photoanode produced as recently described. The photoelectrochemical studies (I-V and C-V measurements), using a polysulfide electrolyte, indicate a relatively high efficiency of 6.8%.
YBa2Cu3O7–x:Transport Properties and Defects at High Temperature
Authors: Chiodelli G. , Campari-Viganò G. , Flor G.
Published: February 2015

Electrical resistivity measurements were carried out on polycrystalline YBa2Cu3O7-x at temperatures 300 < T < 1023 K and oxygen partial pressures 5 ·10-7 ≤ po2 ≤ 1 atm. The samples, equilibrated in the range from 5 ·10-4 to 1 atm, show metallic behaviour, the one equilibrated at po2 = 2 ·10-5 shows a transition between metallic and semiconducting behaviour at 920 K, and that equilibrated at po2 = 5 ·10-7 shows semiconducting behaviour: for the latter the relevant resistivity is due to the oxygen-ion migration. The isotherms log σ vs. log po2 (in the temperature range from 723 to 1023 K) show slopes of about 1/6 at 723 K (orthorhombic phase) and about 1/2 at 1023 K (tetragonal phase). These results are discussed in terms of appropriate defect models.
Laser Tandem Mass Spectrometry in a Time of Flight Instrument
Authors: Weinkauf R. , Walter K. , Weickhardt C. , Boesl U. , Schlag E. W.
Published: February 2015

We present a new laser tandem mass spectrometry technique in a reflectron time of flight (TOF) instrument. A first pulsed laser performs the multiphoton ionization and the primary photodissociation. A newly designed ion source permits a high mass resolution in the space focus of the 12 cm long first linear TOF, where then the secondary excitation can take place. For high resolution applications the pure secondary or pure metastable mass spectrum of a preselected precursor ion can be recorded using a new reflectron scanning technique. It is also possible to obtain the whole secondary mass spectrum with one cycle using a new postacceleration method. Several techniques for ejection of interfering ions are shown. The features of our techniques are demonstrated at various primary fragments of benzene.
Neue Cyclophosphazene mit Metallen der III. Hauptgruppe als Ringbausteine / New Cyclophosphazenes with Metals of Main Group III as Building Blocks
Authors: Hasselbring Reinhard , Roesky Herbert W. , Heine Andreas , Stalke Dietmar , Sheldrick George M.
Published: February 2015

Acylic silylated phosphazenes of the type HN(PR2NSiMe3)2 (1) react quantitatively with molecules MMe3 (M = Al, Ga, In) under ring formation and CH4 evolution. The ring compounds N(PPh2NSiMe3)2AlMe2 (2 a) and N(PPh2NSiMe3)2InMe2 (4 a) have been investiga­ ted by X-ray structure determination. 2a and 4a crystallize in the space groups P 1̄ and P 31, respectively; they show different conformations regarding the cyclohexane framework. NMR spectroscopy of the nuclei in the chelating phosphazene ligand indicates decreasing Lewis acidity of the metal containing fragments in the series AlMe2 ≥ GaMe2 > InMe2.
Umsetzungen von 2-chlor- und 2-organoaminosubstituierten 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinan-4-onen mit Aziden / Reactions of 2-Chloro- and 2-Organoamino-Substituted 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinane-4-ones with Azides
Authors: Neda Ion , Kaukorat Thomas , Schmutzler Reinhard
Published: February 2015

The reaction of 5,6-benzo-2-chloro-1,3-dimethyl-1,3,2-diazaphosphorinane-4-one (1) with trimethylsilyl azide led to the substituted cyclotriphosphazene (3). A monomeric reaction product was not observed by NMR spectroscopy. The diazaphosphorinane 2, with the 2-chloroethyl substituent bonded to the nitrogen atom in a-position to the carbonyl group, did not react with trimethylsilyl azide. An attempt to prepare 3 from N,N'-dimethylanthranilamide 5 and hexachlorocyclotriphosphazene 4 failed, as did the attempt to react 5 with phosphorus pentachloride. The reaction of 5,6-benzo-2-{bis(2-chloroethyl)amino}-1,3-dimethyl- 1.3.2-diazaphosphorinane-4-one (7) and of the related compound 9, bearing only one 2-chloroethyl substituent, with 4-nitrobenzoyl azide furnished, in a normal Staudinger fashion, the monomeric products 8 and 10. In the case of 10, intramolecular P=O···H interaction was demonstrated by IR spectroscopy.
Strukturen sterisch überfüllter Moleküle, 39 [1,2]
Authors: Bock H. , Meuret J. , Bats J. W. , Havlas Z.
Published: February 2015

1,4-Bis(trimethylsiloxy)benzene has been crystallized both by vacuum sublimation and from «-heptane solution, which each yielded colourless plates with identical monoclinic unit cell dimensions (P2/n, Z = 4). The conformation of C[ symmetry shows the two (H3C)3SiO-substituents to be conrotationally twisted around the O-( C6H4)-O axis by dihedral angles o f ± 60°. According to the photoelectron spectroscopic ionisation pattern and its Koopmans’ assignment, IEV
n = -εJ
AM 1, by AM 1 eigenvalues, the gas phase structure should also be of C, symmetry. The results of geometry-optimized MNDO , AM 1 or PM 3 calculations for the monosubstituted derivative H5C6-OS i(CH3)3 are compared with respect to the quality of their fit to the measured data.
Kristallstruktur zweier Zinkthiocyanat-Hexamethylentetramin-Addukte, Zn(SCN)2 · (C6H12N4)2 und {Zn(SCN)2 · C6H12N4 · 2H2O}n, mit unterschiedlich koordinierten Zinkionen / Crystal Structure of Two Zinc Thiocyanate Hexamethylenetetramine Adducts, Zn(SCN)2 · (C6H12N4)2 and {Zn(SCN)2 · C6H12N4 · 2H2O}n with Differently Coordinated Zinc Ions
Authors: Pickardt Joachim , Gong Gill-Taik , Wischnack Sabine , Steinkopff Christina
Published: February 2015

Crystals of the adducts Zn(SCN)2 · (C6H12N4)2 (1), and {Zn(SCN)2 · C6H12N4 · 2H2O}n (2) were obtained by crystallization from aqueous solutions containing hexamethylenetetrami­ne, potassium thiocyanate and zinc nitrate or zinc sulfate, resp., under identical conditions, as two totally different products. 1 crystallizes orthorhombically, space group P nmm, Z = 2, a = 622.4(5), b = 1152.3(7), c = 1394.0(9) pm; 2 is monoclinic, space group C2/c, a = 984.4(3), b = 1217.0(5), c = 1257.4(6) pm, and β = 111.69(5)°. The crystal structure of 1 contains discrete molecules of the complex, in which the zinc ion is tetrahedrally coordinated by two NCS ligands, and two hexamethylenetetramine molecules, which act as monodentate ligands. In 2 however, the zinc ions are octahedrally coordinated. A “supramolecular” structure is form­ed: The hexamethylenetetramine molecules act as bridging bidentate ligands and connect [Zn(H2O)2(NCS)2] units forming zig-zag chains. Adjacent chains are interconnected via hydrogen bonds. The formation of the two compounds with different coordination may be due to the fact, that the educts Zn(NO3)2 · 4H2O and ZnSO4 · 7H2O contain Zn(H2O)4 and Zn(H2O)6 moieties, resp., and that these species are retained in solution.
Einkernige Ruthenium(III)-Komplexe des Typs LRuX3 (X = Cl-, NCO-, NCS-, N-
3; L = 1,4,7-Trimethyl-1,4,7-triazacyclononan) / Mononuclear Ruthenium (III) Complexes of the Type LRuX3 (X = Cl-, NCO-, NCS-, N-
3; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane)
Authors: Schneider Ralf , Jüstel Thomas , Wieghardt Karl , Nuber Bernhard
Published: February 2015

The chloro ligands in [LRuCl3] (1), the crystal structure of which has been determined, are readily substituted in aqueous solution by NCO-, NCS-, and N-
3 with formation of LRuIIIX3 complexes. [LRu(N3)3] is very thermolabile and light sensitive and forms diamagnetic [LRuII(N3)2(N2)]. The thiocyanate species probably contains N- and S-coordinated NCS-ligands: [LRu(N̲CS)2(S̲CN)]. The electrochemistry of the new complexes is reported.
Synthese, IR-Spektrum und Kristallstruktur von 1.3.5-Trichlortriazinium-hexachloroantimonat, [HC3N3Cl3]SbCl6 / Synthesis, IR Spectrum and Crystal Structure of 1.3.5-Trichlortriazinium Hexachloroantimonate, [HC3N3Cl3]SbCl6
Authors: Weller Frank , Schmock Fritjof , Dehnicke Kurt , Findeisen Kurt
Published: February 2015

1,3,5-Trichlortriazinium hexachloroantimonate has been prepared by the reaction of CCl2 = N-COCl with antimony pentachloride in boiling dichloromethane. The compound was characterized by IR spectroscopy and by a crystal structure determination. [HC3N3Cl3]SbCl6 crystallizes in the monoclinic space group P21/n with four formula units per unit cell. 2503 observed unique reflections, R = 0.029. Lattice dimensions at 19 °C: a = 1314.1(1), b = 958.2(1), c = 1329.1(1) pm, β = 117.113(5)°). The compound forms ion pairs via a linear N-H ··· Cl bridge, thus distorting the SbCl6
- ion from octahedral geometry. The C3N3 skeleton of the [HC3N3Cl3]+ ion is nearly planar, but the hydrogen atom lies about 30 pm out of this plane.
The Crystal Structure of the Tetrameric Adduct of Antimony Trichloride and Phosphoryl Isothiocyanate, [SbCl3·OP(NCS)3]4
Authors: Sienkiewicz Alexander V. , Kapshuk Anatoliy A.
Published: February 2015

The crystal and molecular structure of the tetrameric complex of the composition [SbCl3·OP(NCS)3]4 synthesized from SbCl3 and OP(NCS)3 in CCl4 waso determined by X-ray crystallography [143 m space group, cubic system with a = 13.927(4) Å]. The complex exhibits a tetranuclear "cage" structure with a [Sb4O4] core which consists of μ3-bridging oxygen and six coordinate antimony(III) atoms; the Sb-O distance, 3.060 Å, is exceptionally long.
Darstellung, 11B-, 13C-NMR-und Schwingungsspektren von Cyanomethylhexahydro-closo-Hexaborat(Hexaborat(1-), [B6H6(CH2CN)]– sowie Kristallstruktur von [P(C6H5)4][B6H6(CH2CN)] / Preparation, 11B, 13C NMR and Vibrational Spectra of Cyanomethylhexahydro-closohexaborate(1-), [B6H6(CH2CN)]- and the Crystal Structure of [P(C6H5)4][B6H6(CH2CN)]
Authors: Franken A. , Preetz W.
Published: February 2015

By reaction of [B6H6]2- with chloroacetonitrile in dichloromethane the cyanomethylhexahy-dro-closo-hexaborate(1-), [B6H6(CH2CN)]- is formed. The com pound has been separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [P(C6H5)4][B6H6(CH2CN)] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1 with a = 7.503(3), b = 12.0949(8), c = 14.6572(11) Å α = 79.399(6)°, β = 79.19(2)°, γ = 89.2(2)°. The 11B NMR spectrum is consistent with a mono hetero substituted octahedral B6 cage. In the 13C NMR spectrum of Cs2[B6H5(CH2CN)] a singlet at 131.9 ppm (CN) and a quartet at 2.97 ppm with 1J(C,B) = 54.7 Hz (CH2) are observed. The IR and Raman spectra exhibit a very strong CN stretching band at 2218 cm-1.
Cycloadditionen, XXII [1]. Synthese und thermische Reaktion von S-(Alkyl/Aryl)- 2.3-butadienthiosäure-estern / Cycloadditions, XXII [1]. Synthesis and Thermal Reaction of S-(Alkyl/Aryl)-2,3-butadienethioates
Authors: Himbert Gerhard , Fink Dieter
Published: February 2015

While the S-alkyl- or S-phenyl-2,3-butadienethioates 4 a-c are synthesized via the usual “Wittig ylide way”, the corresponding 2-methyl-2,3-butadienethioates 9 a-d and the 2-methyl-4.4-diphenyl-2,3-butadienethioates 9 e,f are obtained by condensation of the allenic acids 7 a,b with the thiols and thiophenols 8 in the presence of dicyclohexylcarbodiimide (DCC) and a catalytic am ount of 4-dimethylaminopyridine (DMAP). In contrast to N- or O-phenyl 2,3- butadienamides or -esters, resp., the phenyl derivatives of 4 and 9 do not undergo the intram olecular Diels-Alder reaction, but by heating, all representatives of 4 only decompose, while 9 a-d and 9 e,f rearrange to 3-alkyl(aryl)thio-2-cyclobuten-1-ones 12a-d and to 3-arylthio- 1-naphthols 14a, b, resp. Heating of the cyclobutenone 12d in the presence of N-methylaniline furnishes the 2-butenanilide 16. On reacting 1-phenylthio-1-propyne 17 with diphenylketene 18, the diphenylacetate 19 is isolated, where the naphthol derivative 14a represents the ester moiety.
Crystal Structure of Lead(II) Complexes with 2,2'-Iminodiethanol
Authors: Sienkiewicz Alexander V. , Kokozay Vladimir N.
Published: February 2015

The lead(II) complexes of 2,2'-iminodiethanol (H2Dea)Pb2(Dea)(NO3)2(DMF), Pb2(HDea)2Cl2 and [Pb2Br6](H3Dea)2(DMF=N,N-dimethylformamide) have been synthesized from the com­ponents and characterized by X-ray crystallography. Both mono- (HDea) and doubly (Dea) deprotonated HN(CH2CH2OH)2 are coordinated via oxygen and nitrogen atoms in Pb2(Dea)(NO3)2(DMF) and Pb2(TIDea)2Cl2. The nitrate complex contains three- and two- coordinate lead(II) atoms linked by μ2-bridging oxygen atoms, whilst in the chloride complex four- and two-coordinate metal atoms are also associated by μ2-bridging oxygen atoms. In [Pb2Br6](FI3Dea)2 the nearest coordination environment of metal atoms consists of bromine atoms only, while the H3Dea+ cations are not coordinated to lead atoms at all. The structural differences between the coordination environments of the lead atoms are discussed in connec­tion with the inert pair effect. All compounds possess ionic type crystal structures.
Darstellung und Struktur dreier verschiedener Bis(ethylendiamin)-kupfer(II)-tetraborate / Preparation and Structure of Three Different Bis(ethylenediamine) Copper(II) Tetraborates
Authors: Shakibaie-Moghadam Mahmood , Timper Ulrich , Heller Gert
Published: February 2015

Three different bis(ethylenediamine) Copper(II) tetraborates have been prepared: Cu(en)2[B4O5(OH)4] · 2B(OH)3 (A), 2{Cu(en)2B(OH)3 · H2O[B4O5(OH)4]} · H2O (B) and {Cu(H2O)2[B4O5(OH)4]2}(μ-H2O){Ag(en)2} · (μ-H2O){Na(H2O)2) (C).

The crystal structure analyses of A (monoclinic, P21/c, a = 1282.5(1), b = 1020.8(1), c = 1510.5(2) pm; β = 96.66(1)°, Z = 4), B (monoclinic, Pc, a = 1254.4(1), b = 914.1(1), c = 1594.2(2) pm; β = 94.79(1)°, Z = 2) and C (triclinic, P1, a = 846.3(3), b = 917.9(3), c = 928.1(7) pm; α = 93.71(6)°, β = 104.79(3)°, γ = 103.23(2)°; Z = 1) show that all compounds contain the tetraborate ion [B4O5(OH)4]2-. In A and B, there are tetraborate ions and boric acid molecules. The coordination sphere of the Cu2+ ion is Jahn-Teller distorted, coordinated by 2 en groups with 4 Cu-N distances between 196 and 206 pm, as well as by 2 OH groups with Cu-O distances of 251 to 274 pm.

In C, the Cu2+ ion is surrounded by 6 OH groups, and the Ag+ ion by 2 en and 2μ-H2O molecules.
Strukturen der mehrkernigen nickelthiolato-komplexe [(μ-SMe)2(Ni(MeNHCS2))2] und cyclo-[(μ-SMe)2Ni]6 / Structures of Two Polynuclear Nickel-Thiolato-Complexes [(μ-SMe)2(Ni(MeNHCS2))2] and cyclo-[(μ-SMe)2Ni]6
Authors: Schulbert Klaus , Mattes Rainer
Published: February 2015

The reactions of N-substituted dithiocarbamic acid esters and nickel acetate yield, by partial degradation of the esters, the polynuclear nickel thiolato complexes cyclo-[(μ-SMe)2Ni]6, 1 and [(μ-SMe)2(Ni(MeNHCS2))2, 2. Their crystal structures have been determined. The Ni coordination spheres are comprised of four sulfur atoms in a planar arrangement. 1 is a second, highly symmetrical modification of the already known cyclic hexamer Ni6(SMe)12. In 2 two Ni(PhNHCS2) moieties are bridged to dimers by thiolato groups. Two of these dimers are connected to a tetramer by weak axial Ni-S interactions. Crystal data for 1: monoclinic, space group P21/n, a = 986.1(2), b = 1308.1(3), c = 1228.6(2) pm, β = 96.07(3)°, Z = 2, R = 0.072, Rw = 0.062, 3797 reflections. 2: orthorhombic, space group Pnma, a = 1790.0(4), b = 1806.7(4), c = 934.4(2) pm. Z = 4, R = 0.061, Rw = 0.051, 2079 reflections
Verbindungen mit dem 5,6-Benzo-l,3,2-diazaphosphorinan-4-on-Ringsystem: Synthese von 2-Chlor-, 2-N,N-dimethylamino-und 2-Bis-(2-chlorethyl)amino- substituierten Derivaten mit drei-und vierfach koordiniertem Phosphor / Compounds Involving the 5,6-Benzo-l,3,2-diazaphosphorinane-4-one Ring System: Synthesis of 2-Chloro-, 2-N,N-dimethylamino-and 2-Bis-(2-chloroethyl)amino- Substituted Derivatives with Three-and Four-Coordinated Phosphorus
Authors: Sonnenburg Ralf , Neda Ion , Fischer Axel , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reaction of methylisatoic anhydride with 2-(aminomethyl)pyridine, 3-(aminomethyl)- pyridine, 3-dimethylamino-1-propylamine, 3-diethylamino-1-propylamine and 3-dibutylamino- 1-propylamine furnished the N-substituted N'-methylanthranilic amides 1-5. In the reaction of 1-5 with phosphorus trichloride the 3-substituted 5,6-benzo-1-m ethyl-1,3,2-diazaphosphorinane- 4-one derivatives 6 to 10 were obtained. The possibility of intramolecular donoracceptor interaction between the nitrogen atom of the R2N group and the λ3P atom is suggested on the basis of 1H NMR studies. The reaction of 9 with dimethylamino-trimethylsilane furnished the 2-dimethylamino-substituted product 11. In the reaction of 6, 7 and 10 with bis-(2-chloroethyl)amine hydrochloride/triethylamine the expected substitution products 12 to 14 were obtained. 5,6-Benzo-2-[bis-(2-chloroethyl)amino]-1-methyl-3-(3-picolyl)-1,3,2-diazaphosphorinan- 4-one 13 reacted with (COD)PtCl2 to give the czs-dichloro-platinum(II) complex 15. The characterisation of 1-15 is based on the 1H-, 13C-, and 31P-NMR spectra, mass spectra and X-ray structure determinations of the precursor compounds 1 and 3
Synthese von Alkin-, Alkinyl-und Vinyliden-Rhodium-Komplexen ausgehend von Alkinyltriphenylsilanen [1] / Synthesis of Alkyne, Alkynyl and Vinylidene Rhodium Complexes from Alkynyltriphenylsilanes [1]
Authors: Baum Matthias , Windmüller Bettina , Werner Helmut
Published: February 2015

Compound [RhCl(PiPr3)2]n (1) reacts with RC≡CSiPh3 to give the rhodium(I) complexes trans-[RhCl(RC≡CSiPh3)(PiPr3)2] (2-5) of which 2 (R = CH3) and 5 (R = C6H5) rearrange thermally to yield the vinylidene isomers trans-[RhCl(=C=C(SiPh3)(R)(PiPr3)2] (6,7). The reaction of 2 and 4 (R = CH2OMe) with NaC5H* affords the cyclopentadienyl complexes [C5H5Rh(RC≡CSiPh3)(PiPr3)] (8,9). The square-planar alkynylrhodium(I) compounds trans-[Rh(C≡CSiPh3)(L)(PiPr3)2] (12,13) are obtained from 10 or 11 on treatment with NaN(SiMe3)2; they react with cyclopentadiene to give [C5H5RhH(C≡CSiPh3)(PiPr3)] (14). Five- and six-coordinate bis(alkynyl)hydridorhodium(III) complexes

[RhH(C≡CSiPh3)(C≡CSiR3)(PiPr3)2] (15,16) and

[RhH(C≡CSiPh3)(C≡CSiR3)(py)(PiPr3)2] (17,18) are prepared from 12 and 13 by oxidative addition of HC≡CSiR3 (R = CH3, C6H5). The reaction of 12 with Me3SiC≡CCO2Et leads to the formation of trans-[Rh(C≡CSiPh3)(Me3SiC≡CCO2Et)(PiPr3)2] (19).
NaK9Tl13: Eine neue Verbindung an der Zintl-Grenze mit isolierten, von Thallium besetzten Tl17-Ikosaedern / NaK9Tl13: A New Compound at the Zintl Border with Isolated Tl12 Icosahedra, Centered by Tl Atoms
Authors: Cordier Gerhard , Müller Volker
Published: February 2015

NaK9Tl13 (a = 1152.0(1) pm, Im 3, Z = 1, R1 -0.029, wR2 = 0.0724) has been prepared from the elements and characterized by single crystal X-ray diffraction. The title compound contains isolated Tl12 icosahedra, which are centered by Tl atoms. The icosahedra are in an α-W-type arrangement.
Notizen: Zinnorganische Fluoride als Fluorierungsreagenzien für Chloride von Hauptgruppenelementen - Quantitatives Recycling des Fluorierungsreagenzes / Tinorganic Fluorides Function as Fluorinating Reagents for Chlorides of Main Group Elements - Quantitative Recycling of the Fluorinating Reagent
Authors: Roesky Herbert W. , Herzog Axel , Keller Klaus
Published: February 2015

PF3 is obtained in high purity by reacting PCl3 with Me3SnF. Alternative fluorinating reagents for this reaction are Ph3SnF and (i-C4H9)3SnF. The reaction with the isobutyl derivative is less complicated since the resulting chloride is a liquid in contrast to Ph3SnCl being a solid. PCl5, MeCOCl, SiCl4, Me3SiCl, and SOCl2 react with Me3SnF to give also the corresponding fluorides. The resulting chlorides are easily converted again to the fluorides. A quantitative recycling of the fluorinating reagent is therefore achieved.
Strukturen ladungsgestörter Moleküle, 47 [1 , 2 ] Dinatrium- und Dikalium-Nitranilate: Die Cyanin-Verzerrung der Kohlenstoff-Sechsringe / Structures of Charge-Perturbed Molecules 47 [1,2] Disodium and Dipotassium Nitranilates: The Cyanine Distortion of the Six-Membered Carbon Ring
Authors: Bock Hans , Nick Sabine , Näther Christian , Bats Jan W.
Published: February 2015

Crystals of lemon yellow dipotassium nitranilate and of yellow disodium nitranilate di­hydrate have been grown and their structures determined at 290 and 200 K. The six-member- ed, O2N-disubstituted rings show a pronounced cyanine distortion with all four CO bonds identical and the two (OCC(NO2)CO)⊖ chains connected by single CC bonds of each 156 pm length. In the anhydrous K⊕ salt, the ring is planar, but in the Na⊕ hydrate salt it exhibits a twist conformation. Quantum chemical calculations allow to reproduce the structure in every detail, demonstrate strong charge alternation along the cyanine chains with considerable delocalization into the O2N acceptor substituents, and suggest that the rather long connecting CC bonds contain positively charged carbon centers on both ends. In addition, metal ion coordination effects as well as the rather high pKa value of nitranilic acid are rationalized.
Squamaron, ein Naphthochinon aus der Flechte Squamarina cartilaginea / Squamarone, a Naphthoquinone from the Lichen Squamarina cartilaginea
Authors: Himmelreich U. , Huneck S. , Feige G. B. , Lumbsch H. T.
Published: February 2015

The structure of the orange pigment from the lichen Squamarina cartilaginea has been elucidated by NMR spectroscopical methods as 2,6.8-trihvdroxy-3-methyl-7-ethyl-1.4-naph­thoquinone
Triacylglycerols, Fucosterol, Diacylglyceroglycolipids and Fucoxanthin from Fucus virsoides
Authors: Falsone G. , Cateni F. , Vrech E. , Birkofer L. , Lucchini V. , Wagner H. , Seligmann O. , Lokar L. Coassini
Published: February 2015

From the marine brown macroalga Fucus virsoides J. AG. (Fucales, Phaeophyceae), a mixture of triacylglycerols 1 -3, fucosterol 4, a mixture of galactosyldiacylglycerols 5-8 and fucoxanthin 9 have been isolated. Normal phase column flash chromatography was effective for the isolation of the marine compounds. FAB-MS, CI-MS spectrometry, 1H NMR, 13C NMR, 1H-1H COSY and 1H-13C COSY experiments were useful in providing informations for their structure elucidation
Bis(triorganotelluronium)hexasulfide / Bis(triorganotelluronium)hexasulfides
Authors: Wieber Markus , Habersack Ralph
Published: February 2015

The reaction of triorganolelluronium chlorides R3TeCl (R = Me, Ph, 4-tBu-C6H4) with Na2Sx, (x = 4 - 6) yields the corresponding bis(triorganotelluronium) hexasulfides (R3Te)2S6 regardless of the employed sodium polysulfide or the size of the lelluronium cation. All compounds are thermally stable and insensitive to moisture or air. (Ph3Te)2S6 was structurally characterized by X-ray crystallography (monoclinic, space group P21/c). Each tellurium atom is connected to both ends of the hexasulfide chain.
Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et2PbFe(CO)4]2
Authors: Herberhold Max , Tröbs Volker , Milius Wolfgang , Wrackmeyer Bernd
Published: February 2015

Complexes of the types R3Pb-Fe(CO)2Cp [R=Me (a). Et (1b), iPr (lc), iBu (Id)]. R2Pb[Fe(CO)2Cp]2 [R=Me (2a), Et (2b)], iPr2(Br)Pb-Fe(CO)2Cp (3c) and [R2PbFe(CO)4]2 [R=Me (4a), Et (4b). iPr (4c)], as well as the spiro-complexes Pb[Fe(CO)4PbR2]2 [R = Me (5a). Et (5b). iPr (5c)] and Pb[Fe(CO)4]4 (6) were studied by multinuclear magnetic resonance spectroscopy (1H. 13C, 207Pb NMR). For the first time, coupling constants 1J(207Pb57Fe) were determined, covering a range between 33.5 (6) and 117 Hz (4a). The magnitude of the geminal coupling constants ∣2J(207Pb207Pb) ∣ in the spiro-compounds 5 decreases from 1090.0 Hz (5a) to 377.0 Hz (5c). The signs of the coupling constants nJ(207Pb13C(R)) (n = 1, 2) and nJ(207Pb1H(R)) (n = 2, 3) were determined by various 2D NMR experiments. Among all known Pb(IV) compounds the lowest 207Pb nuclear magnetic shielding was found in Pb[Fe(CO)4]4 (6): δ207Pb +3586.6. According to the single crystal X-ray structure determination of 4b (orthorhombic; space group Pbca; a = 967.4, b = 1367.7, c = 1772.4 pm), the Pb2Fe2 ring is planar with bond angles FePbFe = 102.8° and PbFePb = 77.2°, and there is a relatively short transannular distance of 340.8 pm between the two lead atoms.
Synthese und Struktur von Kalium-4,4-difluor-[1,3,2]dithiazetidinid-1,l,3,3-tetraoxid und Rubidium-4,4,5,5-tetrafluor-[1,3,2]dithiazolidinid-1,1,3,3-tetraoxid / Syntheses and Structure of Potassium-4,4-difluoro-[1,3,2]dithiazetidinide-1,1,3,3- tetraoxide and Rubidium-4,4,5,5-tetrafluoro-[ 1,3,2]dithiazolidinide-1,1,3,3-tetraoxide
Authors: Jüschke Ralf , Henkel Gerald , Sartori Peter
Published: February 2015

Reactions of perfluoroalkane-1,n-bis(sulfonylfluorides) (n = 1-2) (1-2) with liquid ammonia in tetrahydrofuran (TH F) lead to the cyclic ammonium imides 3-4. These cyclic imides 3-4 can easily be transform ed to other salts using the corresponding hydroxides. X -ray structure analyses (T = 150 K) were perform ed for the potassium 4,4-difluoro-[1,3,2]dithiazetidinide-1,1,3,3-tetraoxide 5 and rubidium -4,4,5,5-tetrafluoro-[1,3,2]dithiazolidinide-1,1,3,3-tetraoxide 6. Cylic imides of the type 3, 5 have not been reported previously. Their formation and their nmr-data are discussed.
Röntgenstrukturuntersuchungen an Elpasolith-verwandten Hexacyanokomplexen [N(CH3)4]2A[M(CN)6] (A = Rb, Tl; M = Cr, Fe) / X-Ray Structure Investigations of Elpasolite Related Hexacyano Complexes [N(CH3)4]2A[M(CN)6] (A = Rb, Tl; M = Cr, Fe)
Authors: Schwarten Martin , Ziegler Bernd , Witzei Michael , Babel Dietrich
Published: February 2015

Single crystals were prepared and X -ray structure determinations performed of the hexagonal com pounds (R3̄m, Z = 3) [N(CH3)4]2RbCr(CN)6 (a = 895.9, c = 2176.4 pm), [N (CH3)4],TlCr(CN)6 (a = 894.0, c = 2168.4 pm), [N(CH3)4],RbFe(CN)6 (a = 886.7, c = 2149.9 pm ) and of monoclinic [N(CH3)4]2TlFe(CN)6 (C2/c, Z = 4; a = 1511.4, b = 884.8, c = 1525.9 pm , β = 110.0°). The structure of the hexagonal complexes is closely related to that of cubic elpasolites, showing, however, orientational disorder of the tetramethylammonium groups. Within the monoclinic TIFe-compound this group has fixed orientation, which makes some of the Fe-CN-Tl bridges bent, contrary to the linear M-CN -A array within the hexagonal compounds. Details and relations are discussed with respect to similar hexacyano complexes.
Notizen: A New Lithium Amide with Bulky Substituents -Molecular Structure of N-Lithio-N-trimethylsilyl-9-amino- 9-borabicyclo[3.3.1]nonane; Competition between N-Li and BN(pp)π Interactions
Authors: Wrackmeyer Bernd , Schwarze Bernd , Weidinger Jürgen , Milius Wolfgang
Published: February 2015

N-Lithio-N-trimethylsilyl-9-amino-9-borabicyclo[3.3.1]nonane (2) was prepared from the reaction of N-trimethylsilyl-9-amino-9-borabicyclo-[3.3.1]nonane (1) with rert-butyl lithium; 2 crystallizes as a trim er with a planar N3Li3 ring. The nitrogen atoms are tetrahedrally coordinated, but should be treated as sp2 hybridised, because the BN double bond, typical of aminoboranes, is retained.
Darstellung und Kristallstrukturanalyse von K3BiO3 und Rb3BiO3 / Synthesis and Crystal Structure Determination of K3BiO3 and Rb3BiO3
Authors: Zoche Nicola , Jansen Martin
Published: February 2015

K3BiO3 and Rb3BiO3 have been synthesized for the first time by solid state reactions of the respective binary compounds. K3BiO3 was obtained from Bi2O3 and K2O at 550 °C, Rb3BiO3 from Bi2O3 and Rb2O at 650 °C. The compounds were structurally examined by single-crystal X -ray investigations (K3BiO3: I 4̅ 3 m, a = 1070.15(2) pm, Z = 8; Rb3BiO3: P 21 3, a = 875.48(2) pm, Z = 4). The structures reveal “isolated” BiO3
3- groups. While K3BiO3 is isostructural to Na3BiO3, Rb3BiO3 has the same crystal structure as Cs3BiO3.
Synthese, Struktur und Reaktivität von 2-Amino- und 2-Imino-2,3-dihydro-1H-1,3,2-diazaborolen / Synthesis, Structure and Reactivity of 2-Amino- and 2-Imino-2,3-dihydro-1H-1,3,2-diazaboroles
Authors: Weber Lothar , Dobbert Eckhard , Rausch Andreas , Stammler Hans-Georg , Neumann Beate
Published: February 2015

The 2-halo-2,3-dihydro-1H-1,3,2-diazaboroles

(1a′: R = tBu, X = Br; 1b: R = 2,6-Me2C6H3; X = I) were converted into the 2-amino-2,3-dihydro-1H-1,3,2- diazaboroles

(2a: R = tBu; 2b: 2,6-Me2C6H3) by treatment with dry gaseous ammonia. Similarly reaction of 1a′ with 2,6-dimethylaniline or tBuNH2 afforded the corresponding derivates

(3; R1 = 2,6-Me2C6H3; 4; R1 = tBu). The treatment of 1a′ with the ethylene diamine adduct of lithium acetylide led to the formation of

(5). Lithiation of 2 a and subsequent silylation gave 6 (R1 = SiMe3), which was transformed to the diborolylamine

(7) upon exposure to 1a′. Borolylketimine

(8 ) and borolylcarbodiimide

(9) resulted from 1a′ and Ph2C=NSiMe3 or Me3SiN=C=NSiMe3, respectively. All the new compounds were characterized by elemental analyses as well as spectroscopic data (IR, 1H, 11B, 13C NMR, MS). Heterocycle 5 was also subjected to an X-ray diffraction analysis.
Isoperadione: A New Triterpenoid from Salvia bucharica
Authors: Ahmad Viqar Uddin , Zahid Muhammad , Ali Muhammad Shaiq , Ali Zulfiqar , Alam Naseer , Tareen Rasool Bakhsh , Iqbal Muhammad Zafar
Published: February 2015

A new isomer of peradione (2) named as isoperadione (1) has been isolated along with peradione (2) and perovskone (3) from the hexane soluble part of Salvia bucharica. The structures of 1 - 3 were elucidated with the aid of modern spectroscopic techniques.
Synthese und Eigenschaften von 1,3-Diisopropyl-4,5-dimethylimidazolium- 2-carboxylat. Ein stabiles Carben-Addukt des Kohlendioxids [1] / Synthesis and Properties of 1,3-Diisopropyl-4,5-dimethylimidazolium -2-carboxylate. A Stable Carbene Adduct of Carbon Dioxide [1]
Authors: Kuhn Norbert , Steimann Manfred , Weyers Gerd
Published: February 2015

The reaction of 2,3-dihydro-l,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (5) with CO 2 gives the imidazolium-2-carboxylate 6. The compound can be transformed into the salts of its corresponding Broenstedt acid 8 . The cationic acid chloride 10a is obtained from 6 and thionylchloride. Chemical properties and spectroscopic data indicate 6 to be less basic than its anionic counterparts, e. g. PhCO2
- . The X-ray structure of 6 is reported.
Crystal and Molecular Structure of Two Tetradentate “Oxime-and-Amide” Ligands
Authors: Fritsky Igor O. , Karaczyn Aldona , Kozłowski Henryk , Głowiak Tadeusz , Prisyazhnaya Elena V.
Published: February 2015

Syntheses and X-ray structure analyses of two new tetradentate ligands with “oxime-and-amide” donor systems (N,N′-bis(2-hydroiminopropionyl)-1,2-diaminoethane and N,N′-bis(2- hydroxyiminopropionyl)-1,4-diaminobutane) were performed. The overall conformation of both ligands is distinctly different from that reported earlier for N,N′-bis(2-hydroxyiminopropionyl)- 1,2-diaminopropane. The number of methylene groups critically influences the ligand geometry and may have distinct impact on the co-ordinating ability of the ligands.
Metallation of Calix[4]arene with Thulium Diiodide, TmI2(DME)3: Molecular Structure of [(5,11,17,23-Tetra-tert-butyl-25,27-dioxo-26,28- dimethoxycalix[4]arene)thulium(III)iodide(diethyl etherate)]
Authors: Fedushkin Igor L. , Weydert Marc , Fagin Anatoly A. , Nefedov Sergei E. , Eremenko Igor L. , Bochkarev Mikhail N. , Schumann Herbert
Published: February 2015

[(5,11,17,23-Tetra-tert-butyl-25,27-dioxo-26,28-dimethoxycalix[4]arene)thulium(III)-iodide( diethyl etherate)] 1 is obtained by deprotonation of 5,11,17,23-tetra-tert-butyl-25,27- dihydroxy-26,28-dimethoxy-calix[4]arene with 2 equivalents of Tml2(DME)3 in THF.