bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrolytische Bildung von Perchlorsiloxanen / Formation of Chlorosiloxanes by Hydrolysis
Authors: Quellhorst Heike , Wilkening Andreas , Söger Nicola , Binnewies Michael
Published: February 2015

During the reaction of Si2OCl6 with H2O in the gas phase the intermediate Si2OCl5OH has been observed by mass-spectrometry. Reactive intermediates like this are responsible for the formation of higher chlorosilanes by slow hydrolysis reactions of chlorosilanes and -siloxanes. Reaction products of inter- and intramolecular condensation reactions have been observed by GC-MS-methods.
S-, X-, Q- und W-Band-Pulver-EPR-Untersuchungen an Tetra-n -butylammonium-bis( 1,2-dicyanoethen-1,2-dithiolato)aurat(II), [(n-C4H9)4N]2[AuII(mnt)2] / S, X, Q and W Band Powder-EPR Investigations on Tetra-n-butylammoniumbis( 1,2-dicyanoethylene-1,2-dithiolato)aurate(II), [(n-C4H9)4N]2 [AuII(mnt)2]
Authors: Ihlo Lars , Stößer Reinhard , Hofbauer Wulf , Böttcher Rolf , Kirmse Reinhard
Published: February 2015

Powder-EPR studies at T = 295 K and T = 12 K on the unstable gold(II) complex [(n- C4H9)4N]2[AuII(mnt)2] diamagnetically diluted by the corresponding NiIIcomplex are reported. Due to (i) the small anisotropy of the g and the 197Au hyperfine tensor AAu, and (ii) the large 197Au quadrupole interaction the powder spectra possess a very complex pattern. Using different EPR frequencies - S band (2.4 GHz), X band (9.5 GHz), Q band (35 GHz) and W band (94 GHz) - the spectra could be analyzed successfully. All spectra were simulated with a computer program which diagonalizes the spin-Hamiltonian matrix exactly.
Verdampfungsverhalten von Lanthantrihalogeniden / Evaporation Behaviour of Lanthanum Trihalides
Authors: Oppermann H. , Morgenstern A.
Published: February 2015

The evaporation of LaCl3, LaBr3 and Lal3 was investigated in closed tubes under argon atmosphere and correlated with data in the literature. The enthalpies and entropies of evaporation were derived from the temperature functions of pressure:

ΔH°(v, LaCl3, T) = 48,5 ± 2 kcal/mol, ΔS°(v, LaCl3, T) = 22,0 ± 3 cal/K-mol

ΔH°(v, LaBr3, T) = 48,0 ± 2 kcal/mol, ΔS°(v, LaBr3, T) = 24,0 ± 2 cal/K-mol

ΔH° (v , Lal3, T) = 49,5 ± 2 kcal/mol, ΔS°(v, Lal3,T) = 29,0 ± 2 cal/K-mol
Darstellung und Kristallstruktur von Triammonium-trisulfimid (NH4)3(NSO2)3 / Preparation and Crystal Structure of Triammonium-trisulfimid (NH4)3(NSO2)3
Authors: Leben Christiane , Jansen Martin
Published: February 2015

The preparation and crystal structure of (NH4NSO2)3 (a = 11.720(2), b = 6.156(6), c = 14.030(2) Å ,β = 96.69(8)°) is reported. The structure reveals a chair-conformation o f the anions, which are arranged to form a hexagonal rod stacking. Compared to cyclometatriphosphates the cations are coordinated differently due to the different basicities of the bridging nitrogen and oxygen atoms, respectively
SbCI3, BiCl3 and Na+ Complexes of Maleonitrile-Dithiacrown Ethers: Synthesis, Crystal Structures and DEP-MS Experiments
Authors: Drexler Hans-Joachim , Starke Ines , Grotjahn Manuela , Reinke Helmut , Kleinpeter Erich , Holdt Hans-Jürgen
Published: February 2015

The reactions of MlC3 (M = Sb, Bi) with maleonitrile-dithia-15-crown-5 (mn-15S2O3) and maleonitrile-dithia-18-crown-6 (mn-18S2O4) in MeCN yielded the complexes [MCl3(mn-15S2O3)] {M = S b (l), Bi(2)} and [MCl3(mn-18S2O4)] {M = Sb(3), Bi(4)}, respectively. The pyramidal MCl3 units are coordinated very weakly to the three oxygen and two sulphur donor atoms of mn-15S2O3 in 1 and 2, and to the four oxygen donor atoms of mn- 18S2O4 in 3 and 4. Both mn-15S2O3 complexes, 1 and 2, crystallize isotypically in the m onoclinic space group P2(1)/n with four formula units per unit cell, while the isotypic mn-18S2O4 complexes, 3 and 4, are triclinic, space group P-1, with two formula units per unit cell. In the SbCl3 complexes, 1 and 3, the mean contact distances between the Sb centres and the macrocyclic donor atoms are longer than the corresponding distances in their isostructural BiCl3 analogues, 2 and 4, which may reflect a stereochemical activity of the Sb111 lone pair. Under the conditions of DEP-M S experiments with 1 and 3 the monocationic SbCl2
+ complexes [SbCl2(L)]+ (L = mn-15S2O3, mn-18S2O4) were detected. NaSbCl6 and mn-18S2O4 in MeCN furnished the 2:1 complex [Na(mn-18S2O4)2]SbCl6 {(5)SbCl6). In the complex cation 5 the sodium atom is coordinated sandwich-like through the eight oxygen atoms of two mn-18S2O4 molecules. Compound (5)SbCl6 crystallize in the triclinic space group P -1 with two formula units per unit cell
A Facile Synthesis of Naphthyl-Quinolyl Ethanes and Chromenyl-Quinolyl Ethanes
Authors: Sekar M. , Prasad K. J. Rajendra
Published: February 2015

The reaction of alkaline 2,4-dihydroxyquinoline 1 and 1-tetralone 2 in 2% sodium hydroxide solution with vinyl acetate afforded a brown solid 3, which on treatment with phosphorous oxychloride yielded 2,4-dichloro-3-[l’-(l-chloro-naphth-2-yl)ethyl]quinoline (4). The same reaction of 1 and chromanone 7 with vinyl acetate afforded 2,4-dichloro-3-[l’-(4-chloro- 2-methyl-chromen-3-yl)ethyl]quinoline (9)
EPR-Einkristall-Untersuchungen an (n-Bu4N)2[Cu(dmit)2] im antiferromagnetisch gekoppelten Wirtsgitter (n-Bu4N)2[(dmit)Cu(tto)Cu(dmit)]: Ein Beitrag zur Aufklärung der sogenannten „paramagnetischen Verunreinigung“ im Wirtsgitter / A Single Crystal EPR Investigation on (n-Bu4N)2[Cu(dmit)2] in the Antiferromagnetically Coupled Host Lattice (n-Bu4N)2[(dmit)Cu(tto)Cu(dmit)]: A Contribution to the Nature of the So-called “Paramagnetic Impurities”
Authors: Teschmit Grit , Strauch P. , Barthel A. , Reinhold J. , Kirmse R.
Published: February 2015

Single-crystal EPR investigations on the paramagnetic CuII impurity present in the binuclear antiferromagnetically coupled complex (n-Bu4N)2[(dmit)CuII(tto)CuII,(dmit)] (dmit = dimercaptoisotrithion, tto = tetrathiooxalate) identify the mononuclear S =½ complex [CuII(dmit)2]2− as being responsible for the observed EPR spectra. The 63Cu hyperfine structure data as well as the data obtained from density functional theory (DFT) and extended Hückel theory molecular orbital (EHT-MO) calculations were used to characterize the spin-density distribution of the copper complex.
Neutronen- und Röntgenbeugungsuntersuchungen an Pulvern und Einkristallen von Strukturverwandten des Berliner Blaus: CsMnIICrIII(CN)6 · D2O , NMe4MnII(Cr0,06,Mn0,94)III(CN)6 · 8 H2O , NMe4MnIICoIII(CN)6 · 8 H20 , Mn3
II[MnIII(CN)6]2 · 15 H2O und Cd3[FeIII(CN)6]2 · 15 H2O / Neutron and X-Ray Diffraction Studies on Powders and Single Crystals of Compounds Structurally Related to Prussian Blue: CsMnIICrIII(CN)6 · D2O, NMe4MnII(Cr0,06Mn0,94)III(CN)6 · 8 H2O, NMe4MnIICoIII(CN)6 · 8 H2O, Mn3
II[MnIII(CN)6]2 · 15 H2O and Cd3[FeIII(CN)6]2 · 15 H2O
Authors: Ziegler Bernd , Witzel Michael , Schwarten Martin , Babel Dietrich
Published: February 2015

The results of a Rietveld refinement of CsMnCr(CN)6 · D2O neutron powder data (a = 1084.3(1) pm, F4̄3m, Z = 4) and of a neutron single crystal structure refinement of tetragonal NMe4MnII(Cr0,06Mn0,94)III(CN)6 · 8 H2O (a = 1065.8(21), c = 1064.6(26) pm, P4/n, Z = 2) at ambient temperature are reported. Single crystal X-ray analyses of the isostructural octahydrate NMe4MnCo(CN)6 · 8 H20 (a = 1062.1 (1), c = 1046.2( 1) pm) and of gel-grown crystals of cubic Mn3
II[MnIII(CN)6]2 - 15 H2O (a = 1062.6(3) pm, Fm3̄m, Z = 4/3) and Cd3[Fe(CN)6]2 · 15 H2O (a = 1067.7(3) pm) were performed as well. The latter “Prussian Blues” are highly disordered and intermediate with respect to cyano-bridging between the above three-dimensional cesium and one-dimensional tetramethylammonium compounds.
Über das Octastannandiid R*6Sn8[Na(THF)2 ]2 und zur möglichen Existenz des Octastannans R*6Sn8 [1] / On an Octastannanediide R*6Sn8[Na(THF)2]2 and the Possible Existence of an Octastannane R*6Sn8 [1]
Authors: Wiberg Nils , Lemer Hans-Wolfram , Wagner Susanne , Nöth Heinrich , Seifert Thomas
Published: February 2015

The black, air and moisture sensitive octastannanediide R*
6Sn8[Na(THF)2]2 (4) (R* = SitBu3) is prepared by reaction of Sn[N(SiMe3)2]2 with R*Na in tBuOMe at -78°C. Red brown octastannane R*6Sn8 (5) is formed by thermolysis of the tristannacyclopropene R*4Sn3 in benzene at 100 °C. According to the result of the X-ray structural analysis, 4 contains a Sn8 cubane with six Sn atoms each connected with R* and two at the end of a space diagonal connected with Na(THF)2. A preliminary X-ray structure analysis shows 5 to adopt the same Sn8 cubane structure as 4 with two bare Sn atoms at the end of a space diagonal.
Structure and Conformation of Tetra-meso-, Octa-β-, and Dodecasubstituted 22,24-Dihydroporphyrins (Porphyrin Dications)
Authors: Senge Mathias O. , Kalisch Werner W.
Published: February 2015

A comparative crystallographic analysis of the conformation of porphyrin diacids with various substituent types reveals considerable differences in the degree of nonplanarity and distortion modes. Diacids of 5,10,15,20-tetraarylporphyrins generally exhibit typical saddledistorted macrocycles with displacements of the Cb positions in the range of 0.7-1.0 Å. Adding peripheral substituents, i.e., using dodecasubstituted porphyrins for the diacid formation yields similar distortion types albeit with larger out-of-plane displacements. As a result of the combined effect of both peripheral (interaction between the Cb and Cm substituents) and core (interaction between the four inner hydrogen atoms) steric strain the maximum Cb displacements reach 1.3-1.5 Å. Quite a different situation is observed for the diacids of 2,3,7,8,12,13,17,18-octaalkylporphyrins. Here, macrocycles with pair-wise displacement of neighboring pyrrole rings and significant NH pyramidalization and those with classic saddle distortion are found. Generally, octa- β-substituted porphyrin diacids show smaller degrees of nonplanarity; Cb displacements ranged from 0.06 to 0.72 Å. On the basis of the overall degree of conformational distortion (⊿24 = average deviation of the 24 macrocycles atoms from the mean plane), the three different types of porphyrin macrocycles studied differ considerably in their degree of conformational flexibility. For several porphyrin crystal structures with different counterions and/or solvate molecules were obtained. Taking into account results from the literature 2,3,7,8,12,13,17,18-octaethyl-22,24-dihydro-5,10,15.,20-tetraphenylporphyrin (13) shows the smallest degree of flexibility (⊿24 = 0.61-0.63 Å; four different X-ray structures), while 22,24-dihydro-5,10,15,20-tetraphenylporphyrin (1) is more flexible (Z⊿24 = 0.42-0.52 Å; four structures). The largest flexibility is observed for 2,3,7,8,12,13,18-octaethyl- 22,24-dihydroporphyrin (7) (⊿24 = 0.02-0.33 Å; four structures).
Metallkomplexe mit biologisch wichtigen Liganden, CXXI [1]. Orthopalladierte Enolate aus N-(Diphenylmethylen)-Schiff-Basen von a-Aminosäureestern als ambivalente 1,3-Dipole in [2+3]-Cycloadditionsreaktionen. Strukturen einer Reihe von Cycloaddukten
Authors: Schreiner Bernhard , Urban Reinhold , Zografidis Anastassios , Sünkel Karlheinz , Polborn Kurt , Beck Wolfgang
Published: February 2015

Enolates of ortho-palladated N-(diphenylmethylene) Schiff bases from glycine esters (R3P)Pd[(C6H4)(C6H5)C=N-C(R')=CO2R] were isolated and have been shown to be ambivalent 1,3-dipoles in [2+3] cycloadditions. Tetracyanoethene, dimethyl acetylene dicarboxylate, dimethyl azodicarboxylate, thiobenzophenone, thione-S, 4-phenyl-l,2,4-triazoline-3,5-dione, diphenyl-ketene and phenylisocyanate are added at the palladium and the enolate (a-C) carbon atoms, whereas methyl propiolate, methyl acrylate, and the methyl esters of maleic and fumaric acid form [2+3] cycloadducts with the «-carbon and the imino carbon atoms of the enolates under mild conditions. The structures of seven cycloadducts were determined by X-ray diffraction analyses.
Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-(n-Bu4N)2[ReBr4(NCS)(SCN)], trans-(n-Bu4N)2[ReBr4(NCS)(SCN)] und trans-(n-Bu4N)2[ReBr4(NCSe)(SeCN)]
Authors: Homolya L. , Preetz W.
Published: February 2015

The crystal structures of cis-(n-Bu4N)2[ReBr4(NCS)(SCN)] (1) (monoclinic, space group P21/n, a = 11.203(3), b = 11.738(5), c = 35.218(7) Å, β = 93.434(4)°, Z = 4), trans-(n-Bu4N)2[ReBr4(NCS)(SCN)] (2) (monoclinic, space group P21/n, a = 11.644(7), b = 13.695(3), c = 29.028(8) Å, β = 95.96(4)° Z = 4) and trans-(n-Bu4N)2[ReBr4(NCSe)(SeCN)] (3) (monoclinic, space group P21/n, a = 11.894(2), b = 13.737(2), c = 28.869(7) Å, β = 96.98(10)° 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), 1.75 (2) and 1.75 (3), fd(ReS) = 1.32 (1) and 1.37 (2) and fd(ReSe) = 1.20 mdyn/Å (3).
Darstellung und Kristallstruktur von Hexacaesium-hexatelluridodigermanat( III) (Cs6Ge2Te6)
Authors: Friede Bernd , Jansen Martin
Published: February 2015

The new compound hexacaesium hexatellurido digermanate(III), Cs6Ge2Te6, has been prepared by reacting the elements in a stoichiometric ratio at 923 K in an evacuated silica glass tube. The title compound crystallizes as black columns and is isostructural to K6G e2Te6 (C2/c, a = 17.027(2), b = 14.237(1), c = 10.104(1) Å, β = 96.701(8)°, Z = 4 (5130 reflections, R1 (I > 2 σ (I)) = 0.042). The structure ist composed of isolated distorted Te6 octahedra, with Ge-Ge dumbbells at the centres. The caesium cations are arranged between the isolated Ge2Te6 octahedra. The Ge-Ge bond lengths in A6Ge2Te6 (A = alkali metal) increase significantly as the counter ions are varied from sodium to caesium.
Schwingungsspektren und Normalkoordinatenanalyse der Tetrahalogeno-closo-1,2-diphosphahexaborane P2B4X4, X = Cl, Br / Vibrational Spectra and Normal Coordinate Analysis of the Tetrahalogeno-closo-1,2-diphosphahexaboranes P2B4X4, X = Cl, Br
Authors: Lorenzen V. , Preetz W. , Keller W. , Haubold W.
Published: February 2015

High resolution vibrational spectra of the tetrahalogeno-closo-1,2-diphosphahexaboranes P2B4X4, X = Cl, Br have been measured at low temperatures (20 - 60 K). The boron-halogen stretching vibrations are observed below 370 cm-1 while the P-P valence vibrations are found at 414 (Cl) and 372 cm-1 (Br). Due to the presence of the boron isotopes 10B and 11B the P-P stretching vibrations and the cage modes in the region of 550 to 1200 cm-1 are split. Based on the crystallographic data of P2B4C14 normal coordinate analyses have been performed. Using a set of 16 force constants (e.g. fd(PP) = 1.35 (X = Cl) and 1.20 (Br), fd(BB) = 1.30 / 1.65 (Cl) and 1.45 /1.60 (Br), fd(BX) = 4.40 (Cl) and 3.53 (Br) mdyn / Å) a good agreement of observed and calculated frequencies has been achieved.
Synthesis and Structural Characterization of [Me4N]2[W2O2(μ-S)(η2-S2)4]·MeCN, a Novel Oxo-thiotungstate(VI)
Authors: Rahman A. B. M. Shamsur , Boller H. , Klepp K. O.
Published: February 2015

Orange red crystals of the new compound [Me4N]2[W2O2 (μ-S2)(η2 -S2)4] MeCN were obtained from the reaction of a solution of [Me4N]2[WOS3] in MeCN with solid AuCN at room temperature. They are monoclinic, space group P21/n, with a = 9.264(2), b = 17.736(3), c = 18.742(5) Å, ß = 95.19(1)°; Z = 4. The crystal structure was determined from single crystal diffractometer data (MoKα-radiation) and refined to R = 0.050 (2955 reflections, 221 variable parameters). It is characterized by binuclear complex anions [(S2)2OWSWO(S2)2]2- with close to C2 symmetry. Each metal center is surrounded by two end-on coordinating disulfide groups at distances ranging from 2.37 to 2.42 Å which together with a bridging sulfur atom (d̄w-s = 2.445 Å) occupy the equatorial positions of a pentagonal bipyramid whose apices are defined by a terminal oxygen atom (d̄w-o
~ 1 -725 Å) and one sulfur atom of the neighboring component at a distinctly larger distance (d̄w-s
~ 2.82 Å).

Infrared spectra of the complex (KBr powder) showed ν(W-O) and ν(W-S) of bridging W-S-W at 931 (vs) and 454 (m) cm - 1, respectively, ν(W-S) of the WS2 unit appeared in the range between 465 and 438 cm -1. The mass spectrum of the anion showed the molecular mass at m/z 688 for [W2O2 S9]- as well as peaks for other fragments.
Syntheses and Evaluation of the Analgesic Activity of Some 4-Acetyl- 4-phenylpiperidine and 4-Hydroxy-4-phenylpiperidine Derivatives
Authors: Saify Zafar Saeed , Khan Khalid Mohammed , Haider Syed Moazzam , Zeeshan  , Shah Syed Tasadaque Ali , Saeed Muhammad , Shekhani Mohammed Saleh , Voelter Wolfgang
Published: February 2015

Synthesis and analgesic activity of 4-phenylpiperidine derivatives is a topic of high actuality. A s part of a programme towards obtaining new potential analgesics, ten derivatives of 4- acetyl-4-phenylpiperidine and ten derivatives of 4-hydroxy-4-phenylpiperidine were synthesised and characterized through spectroscopic techniques. All derivatives along with the parent compounds were evaluated for analgesic activity in the acetic acid-induced writhing assay and tail-flick test in mice. All derivatives of 4-acetyl-4-phenylpiperidine except one com pound exhibited more or less protection against mice writhing, whereas all the compounds proved to be inactive in the tail-flick test at doses of 50 and 100 mg/kg body weight.
Darstellung und Charakterisierung von Rubidiumhydrogencyanamid/Synthesis and Characterization of Rubidium Hydrogen Cyanamide
Authors: Becker Michael , Jansen Martin
Published: February 2015

The synthesis of RbHCN2 was carried out by reaction of cyanamide with rubidium amide in liquid ammonia. The crystal structure has been determinedo by x-ray powder methods (orthorhombic, P21,21,21, a = 7.299(1), b = 9.435(1), c = 9.420(1) Å; Z = 8). The anion is slightly bent (174°) and exhibits two different bond lengths (C-N: 1.17, HN-C: 1.31 Å).
Über die Struktur von synthetischem Tinsleyit K[Al2(PO4)2 (OH)(H2O)]·H2O/The Structure of Synthetic Tinsleyite K[Al2(PO4)2(OH)(H2O )]·H2O
Authors: Dick Stefan
Published: February 2015

Synthetic tinsleyite K[Al2(PO4)2(OH)(H2O)]·H2O has been obtained by the reaction of gibbsite with a potassium-phosphate solution of pH = 7 at 423 K within five days. A single crystal X-ray structure analysis has shown that synthetic tinsleyite is isotypic with the mineral leucophosphite K[Fe2(PO4 )2(OH)(H2O )]·H2O. Crystal data: monoclinic space group P21/n,a = 949.9(2), b = 950.3(2), c = 953,5(2) pm, β = 103,26(3)°, Z = 4. The structure of tinsleyite consists of tetranuclear A I4O2 units formed by a central pair of edge sharing AlO6 octahedra, to which two additional AlO6 octahedra are attached sharing corners. These units are crosslinked by phosphate ions to a three dimensional framework structure with tunnels along [010], occupied by potassium cations. While one type of water molecules is attached to Al, a second type is fixed in the structure by hydrogen bonds only. As a consequence two steps for thermal loss of water at 341 K and 471 K are observed.
Bis(N-tnmethylsilylamino)titanium Dichlorides Bearing Two Identical or Two Different Amino Groups
Authors: Wrackmeyer Bernd , Weidinger Jürgen
Published: February 2015

N-Trimethylsilylaminotitanium trichlorides, Me3Si(R)N-TiCl3 [R = tBu (2a), SiMe3 (2b), 9-borabicyclo[3.3.1 ]nonyl (9-BBN) (2c)] react with the corresponding plumbylenes 1a - c or with the lithium amides LiN(R)SiMe3 to give the bis(amino)titanium dichlorides 3a - c, and 4 - 6. The titanium dichlorides 4-6 are the first examples, in which the titanium atom bears two different amino groups. The compounds were characterised by a consistent set of 1H, 13C, 14/15N and 29Si NMR data.
Preparation and Characterization of [C6H5CH2 NH3]2PbI4, [C6H5CH2CH2SC(NH2)2]3 PbI5 and [C10H7CH2NH3]PbI3 Organic-Inorganic Hybrid Compounds
Authors: Papavassiliou G. C. , Mousdis G. A. , Raptopoulou C. P. , Terzis A.
Published: February 2015

The preparation, crystal structures, optical absorption spectra, and photoluminescence spectra of the title compounds are reported. The compounds were prepared in single crystal form. [C6H5CH2NH3]2PbI4 consists of anionic perovskite sheets of corner-sharing Pbl6 octahedra, which alternate with the C6H5CH2NH3
+ sheets. [ C6H5CH2CH2SC(NH2)2]3 PbI5 consists of zig-zag chains of anionic corner sharing PbI6 octahedra separated by C6H5CH2CH2SC(NH2)2 cations. [C10H7CH2NH3]Pbl3 consists of twin chains of edge-sharing PbI6 octahedra separated by C10H7CH2NH3 cations. The compounds are thus low-dimensional systems. The excitonic spectra were observed in all cases, even at room temperature, and the possibility of organicinorganic excitonic interactions is discussed.
Thermisches Verhalten von festem LaAlCl6 und chemischer Transport von LaCl3 mit AlCl3/Thermical Behaviour of Solid LaAlCl6 and Chemical Transport of LaCl3 with AlCl3
Authors: Oppermann H. , Quoc H. Dao , Morgenstern A.
Published: February 2015

The thermodynamical data of solid aluminium lanthanum chloride LaAlCl6 have been obtained by determination of the decomposition equilibria from total pressure measurements. The melting diagram was determined by DTA. The chemical transport of LaCl3 with AlCl3 is suggesting the existence of the gaseous complex LaAl3Cl12. The data are:

ΔH(LaAlCl6
f,298) =-427,1 ±2,5 kcal/mol, S°(LaAlCl6,f,298) = 61 ±2,5 cal/K-mol,

Δ(LaAl3Cl12,g ,298) =-712 ± 7 kcal/mol, S°(LaAl3Cl12,g,298) = 205 ± 3 cal/K-mol.
Nitriles in Heterocyclic Organic Synthesis: Synthesis of Pyrano[2,3-h]coumarines, Pyrano[3,2-c]coumarines, and their Derivatives
Authors: Hafiz I. S. Abdel , Hussein A. M. , Mahmoud V. F. F.
Published: February 2015

Several new 4H-pyrano[2,3-h]coumarines 5a-e were prepared by the reaction of 7-hydroxycoumarine with cinnamonitriles 1. Also, the reaction of 7-hydroxycoumarine with a mixture of aliphatic aldehydes and malononitrile afforded compounds 5f,g. Similarly, 4-hydroxycoumarine was reacted with the same reagents to give compounds 9a-g. The reaction of 9 g with different nucleophilic reagents afforded the pyrimido[4′,5′:6,5]pyrano[3,2-c]coumarin-4-one derivatives 10-12, 4-methyl-2-(ethoxymethylenamino)4H-pyrano[3,2-c]coumarine-3-carbonitrile (13) and pyrazolo[3′,4′;6,5]pyrano[3,2-c]coumarine (14) respectively.
Neuuntersuchung der Kristallstruktur von α-ICl / Novel Investigation on the Crystal Structure of α-ICl
Authors: Minkwitz Rolf , Berkei Michael
Published: February 2015

The redetermination of the crystal structure of α-iodine monochlorideα-ICl, is described. It crystallises monoclinically in the space group P21/c with a = 1216.2(1), b = 428.6(1), c = 1188.9(1) pm, ß = 117.50(1)° and eight formula units per unit cell.
A Facile Synthesis of Quino[2,3-a]carbazoles
Authors: Balamurali R. , Prasad K. J. Rajendra
Published: February 2015

Condensation of 1-oxo-1,2,3,4-tetrahydrocarbazoles 1a-e and o-aminoacetophenone 2 under acid catalysis afforded a new class of quino[2,3-a]carbazoles 3a-e in good yields. A plausible mechanism for the product formation is also proposed.
Wechselwirkungen in Molekülkristallen, 166 [1, 2]. Polyiod-Moleküle I2C=CI2, (IC)4S, (IC)4NH, (IC)4N-CH3 und HCI3: Strukturbestimmung nach Kristallzüchtung oder durch Dichtefunktionaltheorie-Berechnung / Interaction in Molecular Crystals, 166 [1, 2], Polyiodo Molecules I2C=CI2, (IC)4S, (IC)4 NH, (IC)4N-CH and HCI3: Structure Determination Following Crystallization or by Density Functional Theory Calculation
Authors: Bock Hans , Holl Sven , Krenzel Volker
Published: February 2015

The structures of tri-and tetraiodo-substituted carbon compounds are determined either expe­rimentally by X-Ray Structure Analysis or, because crystallization of tetraiodothiophene could not be achieved, approximated by Density Functional Theory optimization of structural data from a donor/acceptor complex. The structures show noteworthy details such as a second po­lymorph of tetraiodoethene crystallized by sublimation or herringbone crystal packing patterns of tetraiodopyrrole derivatives. All molecular geometries are discussed and compared based on relativistic density functional theory calculations with 6 -31G* basis sets including iodine pseudopotentials. They reproduce even finer structural details due to van der Waals repulsion of the bulky iodo substituents. Natural Bond Orbital (NBO) charge distributions suggest positive partial charges at all iodine centers with the strongest polarization Cδ㊀ → Iδ㊉ in HCI3, which contains well over 97% iodine.
Orthoamide, LV [1]. C7H7N3O6 - Tris(diformylamino)methan („Formylaalen“) - ein Orthoameisensäureamid-Derivat mit sechs Formylgruppen / Orthoam ides, LV [1]. C7H7N3O6 - Tris(diformylamino)methane ( “Formylaalen”) - an Orthoformic Acid Amide Derivative with Six Formyl Groups
Authors: Kantlehner Willi , Ziegler Georg , Ciesielski Michael , Scherr Oliver , Vettel Markus
Published: February 2015

The preparation of tris(diformylamino)methane (3), a hitherto unknown derivative of orthoformic acid, is described. In the presence of a Lewis acid the orthoamide 3 formylates activated aromatic compounds.
Wechselwirkungen in Molekülkristallen, 168 [1,2]. σ-Donator/Akzeptor-Komplexe {HCl3···Xe⊖ }(X⊖ = Cl, Br⊖ , I⊖ ) von Triiodmethan in Tetraphenylphosphoniumhalogeniden / Interaction in Molecular Crystals, 168 [1, 2]. σ-Donor/Acceptor Complexes {HCl3 ···X⊖} (X⊖ = Cl⊖ , Br⊖ , I⊖ ) of Triiodomethane in Tetraphenylphosphonium Halides
Authors: Bock Hans , Holl Sven
Published: February 2015

Three donor/acceptor complexes between halide anion donors and the triiodomethane acceptor with tetraphenylphosphonium countercations, {(H5C6)4P⊕ X⊖ ··· I3CH)} (X⊖ = Cl⊖ , Br⊖, I⊖ ) could be crystallized and their structures determined at low temperature. Their crystal packing motifs are donor/acceptor layers of halide anion/triiodomethane patterns and phenyl/ phenyl interacting tetraphenylphosphonium cation chains. Structure comparison and discussion are based on literature-known analogous adducts with organoammonium salts as well as the phenyl/phenyl interactions in the numerous tetraphenylphosphonium salts registered in the Cambridge Structural Database. The results add novel facets to the selforganization phenomena observed on crystallization of halogen compounds and halide salts.
New Magnesium Compounds RE2Cu2Mg (RE = Y, La -Nd, Sm, Gd -Tm, Lu) with Mo2FeB2 Type Structure
Authors: Mishra Ratikanta , Hoffmann Rolf-Dieter , Pöttgen Rainer
Published: February 2015

The title compounds were synthesized by reaction of the elements in sealed tantalum tubes in a water-cooled sample chamber in a high-frequency furnace. These magnesium intermetallics crystallize with the tetragonal Mo2FeB2 type structure, space group P4/mbm. The lattice pa­ rameters of all compounds were refined from X-ray powder data. Single crystal X-ray data yielded a = 792.09(6), c = 396.31(8) pm, wR2 = 0.0396, 315 F2 values for La2Cu2Mg, a = 778.30(5), c = 384.04(5) pm, wR2 = 0.0954, 214 F2 values for Nd2Cu2Mg, and a = 762.65(5), c = 374.09(3) pm, wR2 = 0.0566, 186 F2 values for Y2Cu2Mg with 12 variable parameters for each refinement. The RE2Cu2Mg structures can be described as an intergrowth of distorted A1B2 and CsCl related slabs of compositions RECu2 and REMg. Chemical bonding in La2Cu2Mg was investigated on the basis of extended Hückel calculations and compared to isotypic La2Cu2ln. This structure was also refined from single crystal X-ray data: P4/mbm, a = 780.8(2), c = 400.1(2) pm, wR2 = 0.0351, 211 F2 values and 12 variable parameters.
Kinetics of the Substitution of Norbornadiene in Tetracarbonyl(norbomadiene)molybdenum(0) by 2,2'-Bipyridine
Authors: Kayran Ceyhan , Okan Eser
Published: February 2015

The kinetics of the thermal substitution of norbornadiene (nbd) by 2,2'-bipyridine (2,2'-bipy) in (CO)4Mo(C7H9) was studied by quantitative FT-IR and UV-VIS spectroscopy. The reaction rate exhibits first-order dependence on the concentration of the starting complex, and the observed rate constant depends on the concentration of both leaving nbd and entering 2,2'-bipy ligand. The mechanism was found to be consistent with the previously proposed one, where the rate determining step is the cleavage of one of the two Mo-olefin bonds. The reaction was performed at four different temperatures (35 -50 °C) and the evaluation of the kinetic data gives the activation parameters which now support states.
The Stannides RERhSn (RE = Ho - Yb) and ScTSn (T = Pd, Pt) - Structure Refinements and 119Sn Mössbauer Spectroscopy
Authors: Mishra Ratikanta , Pöttgen Rainer , Hoffmann Rolf-Dieter , Trill Henning , Mosel Bernd D. , Piotrowski Holger , Zumdick Markus F.
Published: February 2015

The stannides RERhSn (RE = Ho -Yb) and ScTSn (T = Pd, Pt) were prepared by reaction of the elements in sealed tantalum tubes in a high-frequency furnace, by arc-melting, or by a tin-flux technique in quartz tubes. The rhodium based stannides crystallize with the ZrNiAl type structure, space group P6̄2m. The four structures were refined from single crystal X-ray data: a = 754.5(3), c = 377.1(1) pm, wR2 = 0.0357, 233 F2 values for HoRhSn, a = 753.3(1), c = 372.16(8) pm, wR2 = 0.0721, 233 F2 values for ErRhSn, a = 753.7(3), c = 369.0(2) pm, wR2 = 0.0671,233 F2 values for TmRhSn, and a = 753.17(5), c = 366.53(4) pm, wR2 = 0.0566, 180 F2 values for YbRhSn with 14 parameters for each refinement. ScPdSn and ScPtSn adopt the HfRhSn type, a superstructure of ZrNiAl, space group P6̄2c: a = 747.5(1), c = 710.2(1) pm, for ScPdSn, and a = 738.37(9), c = 729.47(9) pm, wR2 = 0.0452,369 F2 values, 18 variables for ScPtSn. Structural motifs in these stannides are transition metal centered trigonal prisms formed by the rare earth and tin atoms. While these prisms are regular in the rhodium based stannides, significant distortions occur in ScPdSn and ScPtSn. The formation of the superstructure can be ascribed to packing reasons. The shortest interatomic distances occur between the transition metal (T) and tin atoms. These atoms form three-dimensional [FSn] networks in which the rare earth atoms fill distorted hexagonal channels. The series RERhSn displays a somewhat unique behavior. The a lattice parameter is more or less independent of the rare earth element, while the c lattice parameter shows the expected lanthanoid contraction. 119Sn Mössbauer spectroscopic data of the rhodium stannides show signals at isomer shifts varying from 1.77 to 1.82 mm/s subject to quadrupole splitting between 0.75 to 0.82 mm/s.
Phytol And Glycerol Derivatives From The Marine Green Alga Codium Iyengarii Of The Karachi Coast (Arabian Sea)
Authors: Ali Muhammad Shaiq , Saleem Muhammad , Ahmad Viqar Uddin , Shameel Simin
Published: February 2015

The ethyl acetate soluble part of a methanolic extract of the marine green alga Codium iyengarii, collected from the Karachi coast of the Arabian Sea, afforded four new derivatives of glycerol named : codioside A,B,C,D (1-4), a new derivative of frans-phytol named codioester (5) and rrans-phytol (6). The structures of 1 -5 were elucidated with the aid of acid hydrolysis, methylation, GC-MS, and spectroscopy. The structure of 1 was confirmed through the HMBC NMR technique and the structures of compounds 2 -4 were based on the assignments made for 1
Group 12 Metal Complexes of 2-Formylpyrrole-(4PL1) and 2-Acetylpyrrole-N(4)-phenylthiosemicarbazone (4Pl2), as Examples form Different Donor Modes. Crystal and Molecular Structures of [Hg(4PL1- H)Br]2 and [Zn(4PL2)2Br2] · 2 EtOH
Authors: Carballo Rosa , Castiñeiras Alfonso , Pérez Teresa
Published: February 2015

The reactions of 4N-phenyl-2-[ 1 -(pyrrol-2-yl)methylidene]-hydrazine carbothioamide (4PL1) and 4N-phenyl-2-[l-(pyrrol-2-yl)ethylidene]-hydrazine carbothioamide (4PL2) with Group 12 metal halides afford complexes of types [M(L)2X2] [M = Zn, L = 4PL1 or 4PL2, X = Cl, Br or I; M = Cd, L = 4PL1, and X = Cl, or L = 4PL2 and X = Cl, Br or I] and [M(L)X2] [M = Cd, L = 4PL1, X = Br or I; M = Hg, L = 4PL1 or 4PL2, X = Cl, Br or I]. The new compounds were characterized by elemental analysis, FAB mass spectrometry, IR spectroscopy, and, in the case of sufficiently soluble compounds, 1H, 13C and, when appropriate, 113Cd or 199Hg NMR spectrometry. The structures of [Hg(4PL1-H)Br] and [Zn(4PL2)2Br2] · 2 EtOH were also studied by single-crystal X-ray diffractometry. In [Hg(4PL1-H)Br] crystallized from the mother liquor of its synthesis, 4PL1 behaves as a monodeprotonated S,N-bidentate ligand. Otherwise, with Hg(II), Zn(II) and Cd(II), 4PL1 and 4PL2 both behave as neutral S-monodentate ligands.
Thermisches und kalorisches Verhalten von festem LaAl3Br12 und chemischer Transport von LaBr3 mit AlBr3 / Thermical and Calorical Behaviour of Solid LaAl3Br12 and Chemical Transport of LaBr3 with AlBr3
Authors: Oppermann H. , Quoc H. Dao , Zhang-Preβe M.
Published: February 2015

The thermodynamical data of solid Lanthanum Aluminium Bromide LaAl3Br12 have been obtained by determination of the decomposition equilibria from total pressure measurements. For different compositions LaBr3/AlBr3, the barogram of the binary system LaBr3-AlBr3 was constructed and from this and DTA the melting diagram was determined. The chemical trans­ port of LaBr3 with AlBr3 is suggesting the existence of two gaseous complexes LaAl3Br12 and LaAl2Br9.

The data are:

ΔH°B(LaAl3Br12,f,298) =-587,2 ± 7 kcal/mol, S°(LaAl3Br12,f,298) = 179,3 ± 7 cal/K·mol;

ΔH°B(LaAl3Br12,g,298) =-548,7 ± 5 kcal/mol, S°(LaAl3Br12,g,298) = 239,4 ± 6 cal/K·mol;

ΔH°B(LaAl2Br9,g,298) =-619,7 ± 5,5 kcal/mol, S°(LaAl2Br9,g,298) = 212,0 ± 7 cal/K·mol.

From solution calorimetric measurements follows the enthalpy of formation of the solid com­plexes: ΔH°B(LaAl3Br12,f,298) =-590,9 ± 3 kcal/mol.
Spectroscopic and Magnetostructural Evidence for the Formation of [Cu0.5Co0.5(H2Tea)X] Mixed-Crystal Compounds from Zerovalent Cu and Co Salts in the Presence of Triethanolamine (H3Tea -Triethanolamine; X = SCN, Cl)
Authors: Makhankova Valeriya G. , Vassilyeva Olga Yu. , Kokozay Volodymyr N. , Skelton Brian W. , Van Albada Gerard A. , Reedijkc Jan
Published: February 2015

Mixed crystals [Cu0.5Co0.5(H2Tea)(SCN)] (1), [Cu0.5Co0.5(H2Tea)Cl] (2) (H3Tea = triethanolamine) have been obtained by the open-air reaction of metallic copper with cobalt(II) chloride/cobalt(II) thiocyanate and triethanolamine in non-aqueous solvents, like dmf, dmso, CH3OH and CH3CN. The simultaneous presence of copper and cobalt in the mixed crystals was unambiguously determined by atomic absorption, EPR and electronic spectroscopy. Details of 1 have been studied structurally, and a preliminary report of the structure of 2 is also given. The mononuclear species 1 and 2 contain crystallographically indistinguishable Cu(II) and Co(II) ions in virtually identical trigonal bipyramidal sites. The molecules are linked together by O-H···O hydrogen bonds to give chains. The values of the temperature independent μeff of 3.50 and 3.48 μB for 1 and 2 (in the range of T = 20 - 280 K), respectively, agree with the 1:1 molar ratio of the metals in both samples.
Polysulfonylamine, CXLII [1]. Ein supramolekulares Monomer-Dimer-Paar: Starke und schwache Wasserstoffbrücken in den Kristallstrukturen von Pyridinium-dimesylamid und 4,4´-Bipyridindiium-bis(dimesylamid) / Polysulfonylamines, CXLII [1]. A Supramolecular Monomer-Dimer Pair: Strong and Weak Hydrogen Bonding in the Crystal Structures of Pyridinium Dimesylamide and 4,4´-Bipyridinediium Bis(dimesylamide)
Authors: Moers Oliver , Lange Ilona , Wijaya Karna , Blaschette Armand , Jones Peter G.
Published: February 2015

In order to study packing arrangements and hydrogen bonding networks, low-temperature X-ray structures were determined for pyH+(MeSO2)2N- (M, orthorhombic, space group P212121, Z′ = 1) and 4,4′-bipyH2
2+ ·(MeSO2)2N- (D, monoclinic, C2/c, Z′ = 0.5). The structures consist of ionic formula entities assembled by N+-H···N- hydrogen bonds; the dication in D displays crystallographic C2 symmetry and has its two pyridyl moieties twisted by 43.9°. According to the packing architectures, D represents a supramolecular dimer of the monomeric congener M. In particular, the (MeSO2)2N- ions of the M structure are associated via short C(sp3) - H···O contacts to form a diamondoid network, whereas in D a topologically congruent framework is constructed from weakly hydrogen-bonded [(MeSO2)N-]2 nodes. Hexagonal channels in the anion substructures each include two adjacent stacks of monomeric pyH+ or “dimeric” 4,4-bipyH2
2+ cations that are linked to the channel walls by the strong hydrogen bond(s) and a set of short Car-H···O contacts. All C - H···O taken into consideration have normalized parameters d(H···O) ≤ 270 pm and θ(C - H···O) ≥ 115°.
Synthesis and Structural Studies of 5, 11, 17, 23-Tetrahydroxyresorc[4]arenes
Authors: Gerkensmeier Thorsten , Agena Ceno , Iwanek Waldemar , Fröhlich Roland , Kotila Sirpa , Näther Christian , Mattay Jochen
Published: February 2015

Hydroxyresorc[4]arenes are bowl-shaped calixarene compounds. Herein we report the synthesis and the results of X-ray diffraction examinations of six hydroxyresorc[4]arenes, one of them could be crystallized in two conformations. All compounds co-crystallize with different solvent molecules, linked together by hydrogen bonds. It is known that hydroxyresorc[4]arenes are capable of forming large aggregates, a number of different compounds have been prepared, some of them could be crystallized and investigated by single crystal methods. Most of the compounds tend to form polarity-induced double layers.
Notizen: Metallkomplexe mit biologisch wichtigen Liganden, CXXXIX [1], Ein Ferrocenylen-verbrücktes Pseudohexapeptid Fe[C5H4CH 2OGlyValOMe(Val-Boc)]2 / Metal Complexes of Biologically Important Ligands, CXXXIX [1]. A Ferrocenylene Bridged Pseudohexapeptide Fe[C5H4CH 2OGlyValOMe(Val-Boc)]2
Authors: Dialer Harald , Steglich Wolfgang , Beck Wolfgang
Published: February 2015

The reaction of the α-chloro tripeptide Boc- Val-DL-Gly(Cl)-ValOMe with 1,1′-bis(hydroxymethyl) ferrocene gives a ferrocenylene bridged pseudohexapeptide which was characterized by its analytical, spectroscopic and ms data.
Thermal Catalytic Hydrosilylation of Conjugated Dienes with Triethylsilane in the Presence of Tricarbonyl(o-xylene)Metal (Metal = Cr, Mo, W) Complexes
Authors: Kayran Ceyhan , Rouzi Pazilaiti
Published: February 2015

The thermal catalytic hydrosilylation of 1,3-butadiene (1), trans-2-methyl-1,3-pentadiene (2), 2,3-dimethyl-1,3-butadiene (3), and isoprene (4), with triethylsilane were studied in the presence of M(CO)3 (o-xylene) (M = Cr, Mo, W) complexes in polar and nonpolar solvents such as tetrahydrofuran, hexane and toluene. Mo(CO)3 (o-xylene) was found to be the only active catalyst for the hydrosilylation of 3 with triethylsilane, which gave 1-triethylsilyl-2,3-dimethyl- 2-butene (3a). as hydrosilylated product in tetrahydrofuran. The product was identified by means of 1H and 13C-NMR and GLC. The same catalyst, Mo(CO)3 (o-xylene), decomposed to Mo(CO)6 without giving hydrosilylated products of 1, 2 and 4 in tetrahydrofuran. M(CO)3(o-xylene) (M = Cr, Mo, W) complexes were found to be stable for about 6 h in hexane and toluene, and showed no catalytic activity for the hydrosilylation of 1, 2, 3 and 4.
CsCu3Dy2S5 und CsCu3Er2S5 : Zwei isotype quaternäre Sulfide der Lanthanoide mit Kanalstrukturen / CsCu3Dy2S5 and CsCu3Er2S5: Two Isotypic Quaternary Sulfides of the Lanthanides with Channel Structures
Authors: Lauxmann Petra , Schleid Thomas
Published: February 2015

Orthorhombic single crystals of CsCu3Dy2S5 (a = 397.54(4), b = 1414.8(1), c = 1685.7(2) pm) and CsCu3Er2S5 (a = 394.82(4), b= 1410.9(1), c = 1667.2(2) pm; both Cmcm, Z = 4) are obtained as by-products (pale yellow or pink transparent needles) in attempts to synthesize CuMS2 (M = Dy and Er) through the oxidation of elemental copper, dysprosium and erbium, respectively, with sulfur (molar ratios: 1:1:2 ) in the presence of equimolar amounts of cesium chloride (CsCl) as fluxing agent at 900 °C within fourteen days from torch-sealed evacuated silica tubes. Their crystal structure contains octahedral [MS6]9- units (d(M-S) = 269 - 282 pm) which share edges and vertices to form layers 2
∞{(M2S5)4-} parallel (010). These are three-dimensionally interconnected along [010] by two crystallographically different Cu+ cations in tetrahedral coordination of S2- anions (d(Cu-S) = 227 - 269 pm) according to 3
∞{(Cu3M2S5)- }. Thereby a likewise layered substructure 2
∞{(Cu3S5)7-} is formed parallel (010) by edge- and vertexlinking of all [CuS4]7- tetrahedra. Large channels within the 3
∞{(Cu3M2S5)-} network spread along [100] and suit well to take up the highly coordinated Cs+ cations, which are surrounded by eight plus one S2- anions at distances between 340 and 358 pm (8x) with the ninth ligand 420 - 421 pm apart in the shape of (2+1)-fold capped trigonal prisms.
Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
Authors: Wilton-Ely James D. E. T. , Mitzel Norbert W. , Hofreiter Stefan , Schmidbaur Hubert
Published: February 2015

Treatment of the ligand l,3,5-tris[(diphenylphosphanyl)methyl]trimethylbenzene (P3) with (tetrahydrothiophene)gold(I) chloride results in the symmetrical trigold complex [(P3)(AuCl)3]. In the presence of sodium methoxide, [(P3)(AuCl)3] reacts with thiocresol (HSC6H4Me-4) and 2-mercaptoquinoline (2-HSQn) to provide the complexes [(P3)(AuSC6H4Me-4)3] and [(P3)(AuSQn)3], respectively. Reaction of [(P3)(AuCl)3] with KSCN also yields the expected product [(P3)(AuSCN)3], however, treatment with 2-10 molar equivalents of NaSMe re­sults only in the unsymmetrical cationic complex [(P3)Au3(SMe)2]Cl. Reaction between [(P3)(AuOTf)3] (prepared in situ from [(P3)(AuCl)3] and AgOTf) and sodium sulfide yields the complex [(P3)Au3S]+OSO2CF3
- , the first example of a trigoldsulfonium unit coordinated to a tridentate phosphine. The tetrafluoroborate salt is obtained from [(P3)(AuCl)3] and Na2S·9 H2O in the presence of NaBF4. The structure of [(P3)(AuSMe)2]Cl has been determined and reveals that in the solid the two methylthiolate units bridge the three gold atoms, but the structure of the cation is fiuxional in solution according to NMR data.
Borane Activators for Nickel Catalysts for Olefin Polymerization
Authors: Lassahn Paul-Gerhard , Janiak Christoph , Oh Jae-Seung
Published: February 2015

Activation of Ni(acetylacetonate)2 and Ni(2-ethylhexanoate)2 with B(C6F5)3 and B(C6F5)3/ triethylaluminium leads to highly active catalyst systems for the vinyl polymerization of nor­bomene.
Improved Synthetic Route to Unsymmetrically Substituted Phosphinimino-phosphonium Salts. Crystal Structure of Tri-n-butyl- [tris(diethylamino)phosphinimino]phosphonium Chloride
Authors: Bartsch R. , Freytag M. , Goller S. , Jones R G. , Schmutzler R.
Published: February 2015

The title compound was prepared from tri-n-butyl-chlorophosphonium chloride and N-tri-methylsilyl-tris(diethylamino)-phosphinimine. A low temperature X-ray crystal structure de­termination revealed PN bond lengths of 156.1(2) and 158.0(2) pm, with a PNP angle of 149.36(17)°.
The Gold Sulfates MAu(S04)2 (M = Na, K, Rb)
Authors: Wickleder Mathias S. , Büchner Oliver
Published: February 2015

The evaporation of a solution of Au(OH)3 and Na2So4 in conc. sulfuric acid led to yellow single crystals of NaAu(SO4)2 (monoclinic, P21/n, Z = 2, a = 469.1, b = 845.9, c = 831.2 pm, β = 95.7°). Analogous procedures with K2SO4 or Rb2SO4 instead of Na2SO4 yielded single crystals of KAu(SO4)2 (monoclinic, C2/c, Z = 4, a = 1109.8, b = 724.2, c = 941.1 pm, β = 118.4°) and RbAu(S04)2, respectively, (triclinic, P1̄, Z = 1, a = 423.6, b = 497.5, c = 889.0 pm, a = 76.4°, β = 88.4°, γ = 73.5°). Although the crystal structures of the three sulfates are not isotypic they show similar structural features: The gold atoms are coordinated by four oxygen atoms in a square planar manner. These oxygen atoms belong to four SO4
2- ions which link the [AUO4] units to infinite chains according to 1
∞[Au(SO4)4/ 2]- . These chains are connected via the monovalent cations which show coordination numbers of 6 (Na+), 10 (K+) and 12 (Rb+), respectively.
Accuracy of Whole-Genome Prediction Using a Genetic Architecture-Enhanced Variance-Covariance Matrix
Authors: Zhang Zhe , Erbe Malena , He Jinlong , Ober Ulrike , Gao Ning , Zhang Hao , Simianer Henner , Li Jiaqi
Published: February 2015

Obtaining accurate predictions of unobserved genetic or phenotypic values for complex traits in animal, plant, and human populations is possible through whole-genome prediction (WGP), a combined analysis of genotypic and phenotypic data. Because the underlying genetic architecture of the trait of interest is an important factor affecting model selection, we propose a new strategy, termed BLUP|GA (BLUP-given genetic architecture), which can use genetic architecture information within the dataset at hand rather than from public sources. This is achieved by using a trait-specific covariance matrix (T), which is a weighted sum of a genetic architecture part (S matrix) and the realized relationship matrix (G). The algorithm of BLUP|GA (BLUP-given genetic architecture) is provided and illustrated with real and simulated datasets. Predictive ability of BLUP|GA was validated with three model traits in a dairy cattle dataset and 11 traits in three public datasets with a variety of genetic architectures and compared with GBLUP and other approaches. Results show that BLUP|GA outperformed GBLUP in 20 of 21 scenarios in the dairy cattle dataset and outperformed GBLUP, BayesA, and BayesB in 12 of 13 traits in the analyzed public datasets. Further analyses showed that the difference of accuracies for BLUP|GA and GBLUP significantly correlate with the distance between the T and G matrices. The new strategy applied in BLUP|GA is a favorable and flexible alternative to the standard GBLUP model, allowing to account for the genetic architecture of the quantitative trait under consideration when necessary. This feature is mainly due to the increased similarity between the trait-specific relationship matrix (T matrix) and the genetic relationship matrix at unobserved causal loci. Applying BLUP|GA in WGP would ease the burden of model selection.
RIG: Recalibration and Interrelation of Genomic Sequence Data with the GATK
Authors: McCormick Ryan F , Truong Sandra K , Mullet John E
Published: February 2015

Recent advances in variant calling made available in the Genome Analysis Toolkit (GATK) enable the use of validated single-nucleotide polymorphisms and indels to improve variant calling. However, large collections of variants for this purpose often are unavailable to research communities. We introduce a workflow to generate reliable collections of single-nucleotide polymorphisms and indels by leveraging available genomic resources to inform variant calling using the GATK. The workflow is demonstrated for the crop plant Sorghum bicolor by (i) generating an initial set of variants using reduced representation sequence data from an experimental cross and association panels, (ii) using the initial variants to inform variant calling from whole-genome sequence data of resequenced individuals, and (iii) using variants identified from whole-genome sequence data for recalibration of the reduced representation sequence data. The reliability of variants called with the workflow is verified by comparison with genetically mappable variants from an independent sorghum experimental cross. Comparison with a recent sorghum resequencing study shows that the workflow identifies an additional 1.62 million high-confidence variants from the same sequence data. Finally, the workflow’s performance is validated using Arabidopsis sequence data, yielding variant call sets with 95% sensitivity and 99% positive predictive value. The Recalibration and Interrelation of genomic sequence data with the GATK (RIG) workflow enables the GATK to accurately identify genetic variation in organisms lacking validated variant resources.
Die Rechtsprechung des BGH zu Bearbeitungsentgelten für Darlehensverträge – Rück- und Ausblick
Authors: Piekenbrock Andreas
Published: February 2015

Die Rechtsprechung des für das Bankrecht zuständigen XI. Zivilsenat des BGH im Jahre 2014 war wesentlich durch die Entscheidungen zu Bearbeitungsentgelten für Verbraucherdarlehensverträge geprägt, die inzwischen als AGB-rechtswidrig angesehen werden. Da der Senat die Verjährung möglicher Rückforderungsansprüche nach § 199 Abs. 1 BGB bis Ende 2014 ausgeschlossen hat, sieht sich die Kreditwirtschaft hoher Forderungen ihrer Kundschaft ausgesetzt. Der Beitrag analysiert die bisherige Rechtsprechung, erörtert mögliche Folgefragen und prüft Handlungsoptionen für die Zukunft.