bluuebunny/crossref_metadata_2025 huggingface dataset:
Some Kinetic and Equilibrium Isotope Effects in the Isobutylphenone Eno land Enolate Ion System
Authors: Chiang Y. , Kresge A. J. , Walsh P. A.
Published: February 2015

The following kinetic isotope effects were determined for acid-catalyzed ketonization of isobutyrophenone enol and enolate ion through rate-determining hydron transfer from catalyst to substrate: enol, kH/kD = 3.30±0.07 (hydronium ion catalysis), kH/kD = 4.0 + 2.8 (acetic acid catalysis); enolate ion, kH/kD= 1.00 + 0.21 (hydronium ion catalysis), kH/kD = 3A \ +0.20 (acetic acid catalysis), kH/kD = 7.48±0.23 (water catalysis). The magnitude of these isotope effects, when assessed in terms of the free energies of reaction for the processes in which they occur, are consistent with Melander-Westheimer- Bigeleisen theory. An equilibrium isotope effect of KH/KD = 5.88±0.32 was also determined for the ionization of isobutyrophenone enol as an oxygen acid.
Ionization Energy and Level Shifts of Multiply Charged Ions in Nonideal Plasmas
Authors: Ebeling W. , Kilimann K.
Published: February 2015

The Bethe-Salpeter equation for plasmas containing ions with higher charges is solved by perturbation methods. The lowering of the ionization energy as well as the energy level shifts due to nonideality effects are calculated. It is shown that multiply charged ions lead to an essential amplification of nonideality effects. An estimate for the modification of transition rates is given.
Phase Correction in Microwave Fourier Transform Spectroscopy
Authors: Heineking N. , Dreizler H.
Published: February 2015

We report on our experience with the adaptation of phase correction techniques to microwave Fourier transform spectroscopy. The performance of this yet uncommon technique is based on theoretical considerations and compared to other methods.
A Computer Simulation Study of Supercooled Liquid and Amorphous-Solid Methanol
Authors: Marchi Massimo , Klein Michael L.
Published: February 2015

The constant-pressure molecular dynamics technique has been used to study the structural consequences of cooling liquid methanol. We employed a periodically replicated system of 250 molecules interacting with an intermolecular potential fitted to thermodynamic properties of the liquid. Plots of the enthalpy and volume against temperature exhibit a distinct change in slope around 160 K; a feature that is identified with the onset of structural arrest, occurring on the picosecond time-scale, in the supercooled liquid. The corresponding glass transition in real methanol occurs around 103 K. The main structural feature that accompanies the structural arrest is the appearance of a splitting in the primary peak of the radial distribution function for methyl groups. This observation contrasts strongly with the behaviour of atomic systems where such splittings arise only in the second peaks of distribution functions. The calculations are discussed in the light of recent neutron scattering data on glassy methanol.
Die Änderung des elektrischen Widerstands bei der reversiblen Reaktion GdBrHx
GdBrH2 (0.67 <̳ x <̳ 1.0) / The Change of Electrical Resistivity during the Reversible Reaction GdBrHx <
GdBrH2 (0.67<̳ x<̳ 1.0)
Authors: Bauhofer W. , Mattausch Hj. , Simon A.
Published: February 2015

The electrical resistivity of GdBrHx (0.67 <̳ x <̳ 1.0) and GdBrH2, has been measured as a function of temperature and environment (H2, vacuum). A two-electrode dc method and a contactless microwave technique were used. Both methods indicate a metal-to-semiconductor transition for the reaction GdBrHx

GdBrH2.
14N Quadrupole Coupling in the Rotational Spectra of Cyclopropylamine and Cyclopropyl Cyanide
Authors: Böttcher Olaf , Heineking Nils , Sutter Dieter Hermann
Published: February 2015

The 14N hyperfine structure in the rotational spectra of cyclopropylamine and cyclopropyl cyanide has been reinvestigated by microwave Fourier transform spectroscopy. The observed quadrupole coupling constants in units of MHz are: Xaa = 2.3338(18), Xbb = 1.7874(20), Xcc = −4.1209(20) for cyclopropylamine and Xaa = −3.4536(35), Xbb= 1.7468(51), Xcc= 1.7068(51) for cyclopropyl cyanide.
The Rotational Zeeman Effect of 1,2,4-Trifluorobenzene
Authors: Stolze W. H. , Sutter D. H.
Published: February 2015

The rotational Zeeman effect of 1,2,4-trifluorobenzene has been studied for 8 low-J rotational transitions in magnetic fields between 1.9 and 2.4 Tesla. The observed susceptibility anisotropics and molecular g-values are: (2χaa−χbb−χcc) = 37.85(69) • 10−6 erg G−2 mole−1, (2χbb−χcc−χaa) = 56.85(54) • 10−6 erg G−2 mole−1, gaa= −0.0393(3), gbb= −0.0277(3), and gcc = 0.0042(2). The Zeeman parameters have been used to derive the molecular electric quadrupole moments and vibronic ground state expectation values for the electronic second moments. The observed out-of-plane quadrupole moment is discussed with reference to an additivity scheme proposed earlier. The observed out-of-plane component of the molecular magnetic susceptibility tensor is in excellent agreement with the value predicted earlier from the CNDO/2-π-electron density alternation at the ring atoms.
Submillimeter Wave Spectrum of HS34SH
Authors: Mittler P. , Winnewisser G. , Yamada K. M. T.
Published: February 2015

The rotational spectrum of 34S-substituted disulfane, HS34SH, has been measured between 60 and 420 GHz, yielding for the first time the rotational constants A = 146694.949 MHz, B = 6779.018 MHz and C = 6776.339 MHz, together with a complete set of J4 and J6 distortion constants.
Internal Cation Mobilities in Molten (Na,Ag)NO3 Remeasured by the Column Method
Authors: Ichioka Kazunori , Okada Isao , Klemm Alfred
Published: February 2015

Internal mobility ratios bNa/bAg in molten (Na, Ag)NO3 have been measured with the column-method. From these, the densities and conductivities the internal mobilities have been calculated. Contrary to results obtained with other methods, over the investigated range of concentration and temperature, bAg is greater than bNa. The various methods are discussed.
14N-and D-Hyperfine Structure in the Rotational Spectrum of Pyrrolidine
Authors: Ehrlichmann H. , Grabow J.-U. , Dreizler H.
Published: February 2015

We present an analysis of the rotational spectra of the normal and the N-deuterated pyrrolidine measured by microwave Fourier transform spectroscopy. The quartic centrifugal distortion con­ stants and the 14N coupling constants have been determined with higher accuracy. In addition the D hyperfine structure could be analyzed.
Molekülinterne Dipolorientierung und dielektrische Absorption in verdünnter Lösung bei Mikro-und Submillimeterwellen. V.Acetyl-Verbindungen
Authors: Klages Gerhard
Published: February 2015

The dielectric loss of sixteen molecules, eleven with the acetyle group in aromatic bonds and five in aliphatic bonds, has been measured in very dilute solutions of cyclohexene at 20 °C. Five of these molecules are investigated in decalene solutions, too. The measurements have been made at wavenumbers in the range 0.08 to 140 cm -1 above 8 cm -1 making use of a pumped molecular laser. They are supplemented by the data of a Fourier transform spectrometer up to 300 cm -1. All microwave spectra of loss factor ε″ are analysed in terms of three absorption areas using the two variable Mori formalism. On the other hand, Lorentz curves are fitted to the FIR absorption spectra of α(v̄).

The fast relaxation process of the aliphatic compounds is suggested to be due to intramolecular reorientation of the acetyle group itself, since in acetyle cyclohexene the remaining part of the molecule is rigid. To the contrary, the acetyle group is not able to reorientate swiftly, if bounded to aromatic rings. Presumably, it is fixed by mesomeric interaction with the dipole in the plain of the ring. However, 2-methyl acetophenone and 1-acetyle naphthone show some quick dipole reorientation, which coincides with a steric hindrance of the group in entering the plain of the ring.
Planetary Compositions - Clues from Meteorites and Asteroids
Authors: Scott Edward R. D. , Newsom Horton E.
Published: February 2015

We review the chemical and mineralogical properties of primitive meteorites and chemical data for the Sun, Comet Halley and interplanetary dust particles. Regardless of where meteorites formed, concentrations of rock-forming elements in solar nebular solids could not have varied simply with distance from the Sun. Thus compositional differences between neighboring planets and the chemical and mineralogical diversity of chondritic asteroids may have been caused by local variations in the compositions of planetesimals, rather than transport of planetesimals over large heliocentric dis­ tances. Chemical variations were partly caused by differential transport and preferential agglomer­ ation of various presolar and solar grains and aggregates, and the production from these aggregates of diverse types of chondrules, refractory inclusions and other chondritic components in brief, local high temperature events in the nebula. These processes were just as important in controlling solar system chemistry as effects due to changes in ambient nebular temperatures and pressures. Differ­ ences between the Fe/Si ratios of the Sun, CI chondrites, interplanetary dust particles and Comet Halley suggest that planetesimals in the outer solar system had diverse relative concentrations of rock-forming elements.
Study Butte: A Chaotic Chondrite Breccia with Normal H-Group Chemistry
Authors: Fredriksson K. , Jarosewich E. , Wlotzka F.
Published: February 2015

The Study Butte (SB) H-group chondrite is an accretionary, well-indurated, multicomponent breccia of exceptional complexity. It contains practically all previously described types of chondrules (in two discrete populations according to Fe/Mg and Al/Ca distributions) and fragments (including CAI’s and also some which were not observed before, e.g. an “andesite”); furthermore it is gas-rich. According to currently popular definitions, it can be ascribed to petrographic type 3 based on overall texture, presence of glass in chondrules and the wide spread of pyroxene and olivine composition (PMD 30), although about 2/3 have nearly constant Fa 17 (PMD 4) in the normal H-range. In addition, Al and Ca in individual chondrules with normal H-olivines, Fa 16-20, are negatively correlated, as usual in chondrules from H 4.5 chondrites [3], but are positively correlated in other chondrules. Thus SB has the properties of both “equilibrated” and “unequilibrated” chondrites. However, in spite of the multitude and complexity of components, the bulk composition is that of normal H-chondrites. A great variety of multi-stage accretion and chondrule formation, break-ups, heating and compaction processes in a quasi closed system are clearly indicated; no clues to preceding nebular processes have been recognized. After the descriptive and analytical data a “Model”, based upon bulk composition, for the formation of chondrules and chondrites is presented.
Gold-Alkalimetallsysteme, III. Hochdrucksynthese und Kristallstruktur von Rb3Au7 [1] / Gold-Alkali Metal-Systems, III. High Pressure Synthesis and Crystal Structure of Rb3Au7 [1]
Authors: Range Klaus-Jürgen , Grosch Georg H. , Rau Franz , Klement Ulrich
Published: February 2015

The intermetallic compound Rb3Au7 could be synthesized from the elements at 4 kbar, 700 °C in a modified Belt-type apparatus. The structure (Cmmm; a = 5.579(1), b = 13.267(5), c = 7.265(2) Å; Z = 2; R = 0.035, Rw = 0,031) comprises three crystallographically independent Au atoms, arranged in layers along the c-axis. The shortest interatomic distances are Au -Au = 2.633Å, Au -Rb = 3.438Å and Rb -Rb = 3.622Å.
Cs2SnTe4, ein Polytelluridostannat(IV) mit Kettenstruktur 1
∞[SnTe2-
4] / Cs2SnTe4, a Polytelluridostannate(IV ) with Chain Structure 1
∞[SnTe2-
4]
Authors: Sheldrick W. S. , Schaaf B.
Published: February 2015

The cesium polytelluridostannate(IV) Cs2SnTe4 has been prepared by methanolothermal reaction of Cs2CO3 with Sn and Te at 190 °C. The crystal structure contains chain anions 1
∞[SnTe2-
4] in which individual SnTe4 tetrahedra are linked via Te -Te bonds of length 2.814(3) Å. Weak Te∙∙∙Te secondary bonds of length 3.631(3)-3.663(3) Å connect neighbouring chains into a framework structure. Nine Te atoms from three chain anions participate in the coordination sphere of the cesium cation.
Kristallstruktur des „supramolekularen“ Silber(I)thiocyanat-Cyclam-Komplexes [Ag(SCN)·(C10H24N4)1/2] / Crystal Structure of the “Supramolecular” Silver(I)thiocyanate Cyclam Complex [Ag(SCN)·(C10H24N4)1/2]
Authors: Pickardt Joachim , Shen Jing
Published: February 2015

Colourless crystals of the 1,4,8,11-tetraazacyclotetradecane (cyclam) silver(I) thiocyanate complex [Ag(SCN) · (C10H24N4)1/2] were obtained by diffusion of a solution of cyclam in ethanol into an aqueous solution of K[Ag(SCN)2], The crystals are tetragonal, space group P42/n, Z = 8, a = b - 1256.0(4), c = 1185.5(9) pm. The SCN groups act as μ3 ligands, the S atoms of two SCN groups bridge two neighbouring Ag ions, which are only 297.5 pm apart, forming butterfly-like Ag2S2 moieties, the N atoms of the SCN groups form bonds to Ag atoms of adjacent Ag2S2 moieties. Two Ag2S2 units are again connected by cyclam molecules which act as two-dentate bridging ligands. Thus a complicated three-dimensional “supramolecular” structure results.
Ein neues Inselpolyborat: Das Heptaboration in einem Silberikosadiborat / A New Polyborate: The Heptaborate Ion in a Silver Icosadiborate
Authors: Timper Ulrich , Heller Gert
Published: February 2015

The X-ray crystal structure analysis of the silver icosadiborate hydrate, Ag2O · 11 B2O3 · 5 C2H4(NH2)2 · 20H2O (triclinic, P1̄, a = 842.4(1), b = 868.5(1), c = 2160.6(2) pm; α = 79.5(1), β = 85.4(1), γ = 86.4(1)°, Z = 1), shows that the unit cell contains two anions of heptaborates [B7O9(OH)5]2-, two anions of tetraborates [B4O5(OH)4]2-, and eight molecules of crystal water as well as probably one cation of disilver(I)-tris(ethylenediamino) [(Hen)+Ag+(en) Ag+(enH)+] and two cations of ethylenediammonium (HenH)2+.
Darstellung und spektroskopische Charakterisierung der Trihalogenphosphonium-Salze PHal3X+MF6- (Hal = Cl, Br; X = H, D; M = As, Sb) / Preparation and Spectroscopic Characterization of the Trihalogenophosphonium Salts PHal3X+MF6- (Hal = Cl, Br; X = H, D; M = As, Sb)
Authors: Minkwitz Rolf , Bäck Birgit
Published: February 2015

PHal3X+MF6- (Hal = Cl, Br; X = H, D; M = As, Sb) are prepared at 213 K by protonation of the phosphortrihalides in the superacidic media XF/MF5. The salts are characterized by 31P, MS, IR and Raman spectroscopy.
Perfluorbenzyl-Stickstoff-Derivate / Perfluorobenzyl Nitrogen Derivatives
Authors: Knitter Gerd , Behrens Ulrich , Lork Enno , Mews Rüdiger
Published: February 2015

In the HgF2-assisted addition of Cl2 and Br2 to C6F5CN the compounds C6F5CF=NX (3, 5: X = Cl, Br) and C6F5CF2NX2 (2, 4: X = Cl, Br) are formed. Photochemical decomposition of the dibromoamine (4) gives the diazene C6F5CF2- N=N - CF2C6F5 (6) in 31% yield. The structure of 6 has been determined by X-ray diffraction.
Synthese und Komplexierung des 4.5-Cycloocta-2,3-dihydro-1,2,3-trimethyl-1,3-diborols / Synthesis and Complexation of 4,5-Cycloocta-2,3-dihydro-1,2,3-trimethyl-1,3-diborole
Authors: Fenner Ulrich , Pritzkow Hans , Siebert Walter
Published: February 2015

Redox reactions of cyclooctyne and 1,1-bis(diiodboryl)ethane lead to 4,5-cycloocta-2,3-dihydro-1,3-diiodo-2-methyl-1,3-diborole (1a), which is methylated with AlMe3 to give 4,5-cycloocta-2,3-dihydro-1,2,3-trimethyl-1,3-diborole (1b). Complexation of 1b with the complex fragments (C5H5)Co, (C8H12)Ni, (C5H5)Ni, and (OC)3Co leads to the corresponding metal complexes 2b, 3b, 4b, and 5b. Their constitutions are derived from spectroscopic data and confirmed for 2b and 4b by X-ray structure analyses. 2b contains a C-H-B 3c/2e bond, its hydrogen atom could be located. [(C8H12)Ni(1b)] (3b) is the first example for a (C8H12)Ni complex having a C-H-B interaction.
Structures and Magnetic Properties of Dinuclear Iron(III) Complexes
Authors: Elmali Ayhan , Elerman Yalcin , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: February 2015

The compounds [FeL1(MeOH)Cl]2 (1), [FeL2Cl]2 (2) and [FeL3Cl]2 (3), with L1 for N-2-hydroxy-4-chlorophenylsalicylaldimin, L2 for N-2-hydroxyphenyl-3-hydroxy-2-naphthaldimin, and L3 for N-2-hydroxy-4-chlorophenyl-3-hydroxy-2-naphthaldimin, have been synthesized. 1 crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a = 7.347(1), b = 21.390(1), c = 9.555(2) Å, β = 104.92(1)° with Z = 2. The crystal structures of 2 and 3 were reported previously. In all structures, two identical [FeL] fragments, related by an inversion center, are connected by two bridging oxygen atoms to form a binuclear unit in the supported condition. Magnetic susceptibility measurements in the range 4.2 < T < 286.5 K re­vealed the diiron (III) centers of 1, 2, and 3 to be weakly antiferromagnetically coupled with spin exchange coupling constants J1 = -7.7(1) cm-1, J2 = -6.5(1) cm-1, and J3 = -10.9(1) cm-1, respectively.
Zur Chemie der Roccellsäure / On the Chemistry of Roccellic Acid
Authors: Huneck Siegfried , Schmidt Jürgen , Porzel Andrea
Published: February 2015

The isomerization of roccellic acid to threo-roccellic acid has been investigated. Reduction of dimethyl roccellate with LiAlH4 gave the corresponding diol which yielded on oxidation with Jones' reagent two isomeric γ-lactones. 1-Methyl roccellic amide has been transformed by a photochemical reaction to the δ-lactone acaranoic acid. Two copper complexes of roccellimide have been prepared.
Zur Kristallchemie der Oxoplatinate. Eine neue Phase der Zusammensetzung Sr4-ϰNaϰPtO6 (ϰ = 0,33) / On the Crystal Chemistry of Oxoplatinates. A New Phase of the Composition Sr4-ϰNaϰPtO6 (ϰ = 0,33)
Authors: Tams G. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Sr3.67Na0.33PtO6 were prepared by heating oxide mixtures in closed silver tubes and investigated by X-ray single crystal techniques. It crystallizes with trigonal symme­try, space group D6
3d-R3̅c (Nr. 167) with a = 9.6617, c = 11.6580 Å, Z = 6. Sr3.67Na0.33PtO6 belongs to the Sr4PtO6 type and is isotypic to K4CdCl6. One point position characterized by a trigonal prismatic O2- coordination is occupied by Na+ and Sr2+ statistically. The crystal structure is discussed with respect to the related compounds Sr3CuPtO6 and Ca3. 5Cu0.5PtO6.
Ein Beitrag zur Kristallchemie der oxidischen Alkali-Erdalkali-Edelmetall-Perowskite. Synthese und Kristallstruktur von NaBa4Cu0,5Pt1,5O8 / A Contribution to the Crystal Chemistry of Alcaline Alealine Earth Precious Metal Perovskites. Synthesis and Crystal Structure of NaBa4Cu0,5Pt1,5O8
Authors: Tams G. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of the phase NaBa4Cu0,5Pt1,5O8 were prepared in closed silver tubes. The black and moisture sensitive crystals were investigated by four-circle diffractometer X-ray tech­niques. They show trigonal symmetry, space group D2
3-P321, a = 10.0644, c = 8.3811 Å, Z = 3 and belong to the perovskites. The typical M2C9; double octahedra are occupied by Pt4+ and Cu2+ in a different manner. Na+ is partly in and out of the centres of trigonal prisms of oxygen. These features will be discussed with respect to the underoccupied point position O(3).
Das erste Oxocuprat/-Arsenat mit Kupfer in gemischter Valenz: Cu(Mg2,56Cu0,44)Cu(AsO4)3 / The First Oxocuprate/Arsenate Containing Mixed Valent Copper:Cu(Mg2,56Cu0,44)Cu(AsO4)3
Authors: Osterloh D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cu(Mg2.56Cu0.44)Cu(AsO4)3 have been prepared by CO2-LASER technique and investigated by X-ray diffraction methods. The light blue crystals show monoclinic sym­metry, space group C6
2h-C2/c, a = 11.897, b = 12.855, c = 6.688 Å, β = 113.06°, Z = 4. The structure type is characterized by AsO4 tetrahedra, dumb-bell-like coordinated Cu(I), twisted CuO4 square polygons and octahedra statistically occupied by Mg/Cu2+.
Unexpected Formation of 1-Amino-4,4,5,5-tetramethyl-3- (5,5,6,6-tetramethyl-1,4,5,6-tetrahydropyridazin-3-yl)pyrrolidin-2-one
Authors: Voss Jürgen , Röske Rüdiger , Adiwidjaja Gunadi
Published: February 2015

The title compound 3 is formed on reaction of octamethyldispiro[2.1.2.1]octane-4,8-dione (1) with hydrazine. Its structure is established by X -ray diffraction analysis.
Verbindungen an der Zintl-Grenze: Darstellung und Kristallstruktur von Na17Ga29ln 12 und K17In41 / Compounds at the zintl border: preparation and crystal structure of Na17Ga29ln 12 and K17In41
Authors: Cordier Gerhard , Müller Volker
Published: February 2015

Na17Ga29ln12 (a = 2178.5(5) pm, Fd3m, Z = 8, R = 0.081) and K17In41 (a = 2424.1(5) pm, Fd3m, Z = 8, R = 0.060) have been prepared from the elements and characterized by single crystal X -ray methods. Na17Ga29ln12 is a ternary variant of K17In41. The crystal structure of Na17Ga29ln12 contains Ga12 icosahedra (In 12 icosahedra in K17In41) and truncated In12 tetrahedra which are four-capped and centred by additional Ga atoms (In atoms in K17In41). The packing of icosahedra and truncated tetrahedra leads to interpenetrating Samson polyhedra. The Ga12 icosahedra (In12 icosahedra in K17In41) take the Cu positions of the MgCu2 type, the In12 clusters take the positions of the Mg atoms of this structure type. The alkali atoms in Na17Ga29In12 and K17In41 occupy the deltahedral faces of the icosahedra and form pentagonal dodecahedra
Organometallische Oxide: Die Kristallstruktur von [(η-C5H5)Ti]8(μ-O)12 / Organometallic Oxides: The Crystal Structure of [(η-C5H5)Ti]8(μ-O)12
Authors: Heshmatpour Felora , Wocadlo Sigrid , Massa Werner , Dehnicke Kurt , Bottomley Frank , Day Robert W.
Published: February 2015

The structure of the complex [(η-C5H5)Ti]8(μ-O)12 has been determined in a crystal of [η-C5H5)Ti]8(μ-O)12 - 6 CH3CN (space group P1̄, Z = 1, lattice dimensions at -4 0 °C: a = 1083.9(3). b = 1292.9(1), c = 1304.0(2) pm, a = 61.18(1)°, β = 71.73(2)°, γ = 70.35(2)°, structure solved using 2164 observed unique reflections, R = 0.043). The Ti atoms occupy the corners of an approximate cube. The 12 oxygen atoms are at the mid point of the edges connecting the Ti atoms. Two pairs of the 12 Ti-O-Ti bridge angles are 147.9(3)° and 148.6(3)°, the remaining eight bridge angles are between 162.4(3)° and 163.9(3)°. The Ti-O distances are between 179.5(5) and 181.8(5) pm with an average of 180.5(5) pm. Each Ti atom is capped by an η5-cyclopentadienyl ligand. The same subane-like unit has been found in [(η-C5H5)Ti]4(μ2-Se)3(μ-Se)3-[(η-C5H5)Ti]8(μ2-O)12 Et3N THF
Synthesen, 121Sb-Mößbauer-Spektren und Strukturen von [SbF3(18-Krone-6)], [SbF3(18-Krone-6)]·CH3CN und [(SbF3)2(12-Krone-4)] / Synthesis, 121Sb-Mößbauer Spectra and Structures of [SbF3(18-Crown-6)], [SbF3(18-Crown-6)]·CH3CN, and [(SbF3)2(12-Crown-4)]
Authors: Becker Irina , Windhaus Marcus , Mattes Rainer
Published: February 2015

The crown ether complexes SbF3(18-crown-6) (1), SbF3(18-crown-6) · CH3CN (2) and (SbF3)2(12-crown-4) (3), have been prepared by reactions of SbF3 and the corresponding crown ether. They have been characterized by IR. Raman and 121Sb-Mößbauer spectroscopy, and by X-ray structure determinations. The s electron density at the Sb atom is diminished in these complexes. 1 and 2 show a symmetrical half-sandwich structure, with coplanar O atoms and Sb-O distances ranging from 298 to 321 pm. 3 has a band-like structure. The two metal centers adopt different stereochemistries. The Sb-O distances are in the range from 269 to 325 pm. One oxygen atom of 12-crown-4 has a bridging function. Crystal data for 1: space group P212121, a = 823,1(1), b = 1146,1(2), c = 1807,0(3) pm, Z = 4; 2: space group P21/c, a = 1257,7(3), b = 828,9(2), c -1895,5(5) pm, β = 93,68(2). Z = 4; 3: space group P21/c, a = 805,6(1), b = 2143,1(4), c = 836,4(2) pm, β = 90,98(1), Z = 4.
Uber die Reaktionen von Molekülen (R2CS)2 (R = CF3, CI) und Cl2CS mit XeF+MF6
- (M = As, Sb) und Kristallstruktur von [1] / On the Reactions of Molecules (R2CS)2 (R = CF3, Cl) and Cl2CS with XeF+MF6
- (M = As, Sb) and Crystal Structure of (CF3) [1]
Authors: Minkwitz Rolf , Bäck Birgit , Preut H ans
Published: February 2015

XeF+MF6
- (M = As, Sb) reacts with ((CF3)2CS)2 and Cl2CS to form the corresponding monofluorinated sulfonium hexafluorometalates. The salts have been characterized by vibrational and 19F NMR spectroscopic measurements.

crystallizes in the monoclinic space group C2/c with a =o 14.791(10), b = 11.093(6), c - 10.356(6)Å, β = 119.83° and Z = 4. With a value of 1.51(1) Å d (S-F) is comparable to the SF-bond distance in

.
Monomeres [(Me3Si)2CH]2Al-Te-Al[CH(SiMe3)2]2 mit gewinkelter Al-Te-Al-Gruppe / Monomeric [(Me3Si)2CH]2Al-Te-Al[CH(SiMe3)2] 2 with a Bent Al-Te-Al Group
Authors: Uhl Werner , Schütz Uwe
Published: February 2015

Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 with an Al-Al bond and Et3P+-Te- give under mild conditions the title compound R2Al-Te-AlR2 (R = CH(SiMe3)2) 2 in high yields. Due to the high steric shielding 2 is monomeric even in the solid state with an angled Al-Te-Al group (110.4°) and an Al-Te bond length of 254.9 pm as expected for a Al-T e single bond with the atoms in low coordination numbers. A hindered rotation of the bulky substituents is observed in solution probably caused by steric restrictions similar that in ana­logous compounds with Al-S-Al or Al-CH2-Al groups.
5-Alkoxy(Aralkoxy)-3,6-dihydro-2H-1,3,4-oxadiazin-2-one(thione) aus 2-Hydroxycarbonsäure-hydrazonid-estern / 5-Alkoxy(Aralkoxy)-3,6-dihydro-2H-1,3,4-oxadiazin-2-ones(thiones) from 2-Hydroxycarbohydrazono Esters
Authors: Geffken Detlef , Holst Carsten
Published: February 2015

The sulfhydrolysis of the glycolimidates 3 affords 2-hydroxy thiocarboxylic O-esters (4), which on treatment with phenylhydrazine give glycolohydrazonates of type 5. Under suitable conditions the reaction of 5 with phosgene or 1,1′-thiocarbonyldiimidazole produces 3,6-dihydro-2H -1,3,4-oxadiazin-2-ones(thiones) 6 as stable compounds.
Stabile und instabile Produkte bei der Reaktion von 2.2-Diphenyl-1,2-dihydrochinolinnitroxid-Radikalen mit Stickstoffmonoxid / Stable and Unstable Products on the Reaction of 2.2-Diphenyl-1,2-dihydroquinolinenitroxide Radicals with Nitric Oxide
Authors: Weber Horst , Grzesiok Andreas , Sustmann Reiner , Korth Hans-Gert
Published: February 2015

The stable 2,2-diphenyl-1,2-dihydroquinolinenitroxide radicals 1 react with nitric oxide (NO) to form the stable nitro compounds 2 and 3 as main products. The stable dinitro compounds 6 and 1,2-dihydroquinolines 7 are formed in minor yield as side-products accom­panied with the unstable N-nitroso compounds 4 and 5, which further decompose to form the stable products mentioned above. The proposed mechanism of the reaction is discussed in terms of homolytical processes and is supported by PM 3 calculations.
Elektronentransfer und Ionenpaar-Bildung, 34 [1 - 3] Einkristallstruktur des Solvens-separierten Radikalionenpaares [9,9′-Bianthryle·⊖][Na⊕(DME)3] / Electron Transfer and Ion Pair Formation, 34 [1-3] Single Crystal Structure of the Solvent-Separated Ion Pair [9,9′-Bianthryle·⊖][Na⊕(DME)3]
Authors: Bock Hans , John Andreas , Näther Christian , Havlas Zdenek
Published: February 2015

The one-electron transfer to large π-delocalized hydrocarbons provides an interesting possibility to crystallize solvent-separated ion-pair salts containing optimally solvated cations. Accordingly, the reduction of 9.9′-bianthryl in aprotic 1.2-dimethoxyethane (DME) solution at a sodium metal mirror allows to grow dark blue, brick-like crystals of its radical anion and threefold DME-solvated sodium cation. The structure of the radical anion is very similar to that recently published for the neutral molecule. According to AM 1 enthalpy hypersurface calculations based on the structural data, the torsion angle between 60° and 120° is determined by the lattice packing and the negative charge is -π-delocalized predominantly within only one anthracene subunit. The counter cation [Na⊕(DME)3], reported only three times so far, shows a sixfold propeller-like coordination of approximate D3 skeletal symmetry with contact distances Na⊕···O between 232 and 243 pm and angles ≮ONa⊕O varying between 69° and 159°. Due to the small repulsion between the chelating DME molecules, the isodesmically calculated Na⊕ solvation enthalpy is more negative than that of the analogous tetrahydrofuran complex [Na⊕(THF)6] - as confirmed by the laboratory experience that salts of less stable anions are preferentially crystallized from a strongly cation solvating DME solution.
Die Kristallstruktur des Lithium-Benzamidinats {Li3[C6H5 - C(NSiMe3)2]3 · NC - C6H5} / The Crystal Structure of the Lithium Phenylamidinate {Li3[C6H5 - C(NSiMe3)2]3 · NC - C6H5}
Authors: Goesmann Helmut , Fenske Dieter
Published: February 2015

Single crystals of the title compound have been prepared by the reaction of benzonitrile with LiN-(SiMe3)2 in hexane and subsequent evaporation of the solvent. Space group P21/n, Z = 4, structure solution with 7945 observed unique reflections. R = 0.052. Lattice dimensions at -70 °C: a = 1485.2(9); b = 2486.9(11); c = 1568.9(8) pm; β = 91.06(4)°. The compound forms a trimeric ion ensemble in which two of the lithium cations are coordinated by three nitrogen atoms of two phenylamidinate an ions, the other one by four nitrogen atoms of two chelating phenylaminidate anions and in addition by the nitrogen atom of a benzonitrile molecule.
1,3-Di-terf-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-thione, a Severely Helically Distorted Thionolactone-Bridged Biaryl
Authors: Bringmann Gerhard , Wuzik Andreas , Schupp Olaf , Peters Karl , Peters Eva-Maria
Published: February 2015

The title compound 2c, a potentially useful synthetic intermediate in stereoselective biaryl synthesis, has been prepared from the oxolactone 1c, by treatment with Lawesson′s reagent. An X-ray structure analysis reveals its strongly helically distorted structure, the overall molecular distortion even slightly exceeding that of the corresponding oxo compound 1c.
Über die Reaktionen von (CH3)4N+I-, (CH3)4
N+ICl2
-, (CH3)4N+ICl4
- und (CH3)4N+Cl- mit Trifluormethylhypochlorit CF3OCl / The Reactions of (CH3)4N+I-, ( CH3)4N+ICl2
-, (CH3)4N+ICl4
- and (CH3)4N+Cl- with Trifluoromethylhypochlorite CF3OCl
Authors: Minkwitz Rolf , Bröchler Raimund
Published: February 2015

The fluorinating properties of CF3OCl have been demonstrated by the reactions with different iodate salts like (CH3)4N+I-, (CH3)4N+ICl2
- and (CH3)4N +ICl4
- . At -70°C all reactions give hexafluoroiodate(V ) salts IF6
- . In contrast, the reaction of CF3OCl with (CH3)4N+Cl+ yields (CH3)4N+OCF3
-. The products have been characterized by vibrational and NMR spectra.
Synthese und Röntgen-Strukturuntersuchung von Rb4Cd(VO)(V2O7)2Cl und Tl4Cd(VO)(V2O7)2Cl / Synthesis and X-Ray Structure Analysis of Rb4Cd(VO)(V2O7)2Cl und Tl4Cd(VO)(V2O7)2Cl
Authors: Mertens B. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (I) Rb4Cd(VO)(V2O7)2Cl und Tl4Cd(VO)(V2O7)2Cl have been prepared by flux techniques. The compounds were examined by X-ray analysis. They crystallize with tetragonal symmetry, space group C1
4-P4 with (I): a=9.142(1); c=5.525(1), (II): a=9.150(1), c=5.405(1) A, Z = 4. Both compound belong to the K4CuV5O15Cl-Type. V (l) forms V2O7 double tetrahedra, connected by square V(2)O5 pyramids and CdO4Cl2 octahedra. The short V(2)-O distance indicates a vanadyl group.
Synthese und Kristallstruktur von [Se3N2Cl]+SbCl6
- / Synthesis and Crystal Structure of [Se3N2Cl]+SbCl6
-
Authors: Lau Carsten , Neumüller Bernhard , Dehnicke Kurt
Published: February 2015

Chloro-Cycloselenazenium Hexachloroanti-monate(V), Synthesis, Crystal Structure [Se3N2Cl]+SbCl6
- has been prepared as red crystals by the reaction of the nitride chloride Se2NCl5 with antimony(III) chloride in dichloromethane. It was characterized by a crystal structure determination. Space group PI, Z = 2, 4396 observed unique reflections, R = 0.030. Lattice dimensions at -80 °C: a = 698.2, b = 699.7, c = 1510.5 pm, α = 89.45°, β = 86.18°, γ = 68.22°. The structure consists of two symmetry-independent cations and two symmetry independent anions, which differ only slightly from each other. The cations contain Se3N2 five-membered rings, which deviate very little from planarity as shown by fol­ ding angles of 14° and 18°. The Se-N bond distances are between 171.4 and 176.4 pm suggesting double-bond constituents.
3-Hexyne Complexes of Molybdenum(II) and Tungsten(II). Crystal Structures of [WI2(CO)(PPh3 )2 (η2-EtC2 Et)] and [WI2(CO){Ph2P(CH2)3PPh2}(η2-EtC2Et)]
Authors: Al-Jahdali Mutlaq , Baker Paul K. , Drew Michael G. B.
Published: February 2015

Treatment of [Ml2(CO)3(NCMe)2] (M = Mo, W) with two equivalents of EtC2Et in CH2CI2 at 0°C yields the bis(3-hexyne) complexes [MI2(CO)(NCMe)(η2-EtC2Et)2] (1 and 2). Complexes 1 and 2 react with two equivalents of PPh3 in CH2CI2 to give the complexes [Ml2(CO)(PPh3)2 (η2-EtC2Et)] (3 and 4). The molecular structure of 4 (M = W) has been crystallographically determined and has a pseudo-octahedral geometry with the two PPh3 ligands trans to each other with the two cis-iodo-ligands, which together with the carbonyl and 3-hexyne ligand are occupying the equatorial plane. Reaction of 1 and 2 with an equimolar amount of Ph2P(CH2)nPPh2 (for M = Mo, n =1; for M = W, n = 1 to 6 ) in CH2CI2 affords the mono(3-hexyne) complexes [Ml2(CO){Ph2P(CH2)nPPh2}(η2-EtC2Et)] (5 - 11). The tungsten complex [Wl2(CO){Ph2P(CH2)3PPh2}(η2-EtC2Et)] (8 ) has also been crystallographically characterised and has cis-phosphorus atoms in the equatorial plane with the carbonyl and one of the iodo-ligands, with the other iodo-ligand and the 3-hexyne occupying the axial sites.
1,2,4-Diazaphosphole und 1,2,4-DiazaarsoIe: Ringstruktur und Struktur wasserstoffbrücken-gebundener Paare und Helices/1,2,4-Diazaphospholes and 1,2,4-Diazaarsoles: Ring Structure and Structure of Hydrogen-Bonded Pairs and Helices
Authors: Polbom Kurt , Schmidpeter Alfred , Märkl Gottfried , Willhalm Angela
Published: February 2015

Among the large family of azaphospholes 1,2,4-diazaphospholes feature a particularly stable ring system. 3,5-Unsubstituted and 3,5-equally substituted 1,2,4-diazaphospholes and -diazaarsoles are best made from 1,3-bis(dimethylamino)-2-phospha/arsaallyl chlorides and hydrazines. This way four examples for single crystal X-ray structure investigations were prepared: The unsubstituted 1,2,4-diazaphosphole 2 and -diazaarsole 4, the N-substituted 1 -(2-pyridyl) 1.2.4-diazaphosphole 1, and the C-substituted 3,5-di-tert-butyl 1,2,4-diazaphosphole 3. They all possess planar rings with small angles at P (86°) and As (81°). The N-unsubstituted molecules are connected to each other by NH···N hydrogen bonds forming in case of the isotypic compounds 2 and 4 a helix along a crystallographic axis and in case of compound 3 for steric reasons a dimer. The structures of the aggregates found are compared to those of pyrazoles.
Metal Complexes of Heteroarenes, X [1].η1-Coordination of Phosphinine: Synthesis and Structure of cis-Dichloro-bis(2,6-dimethyl-4-phenyl-phosphinine)platinum
Authors: Elschenbroich Christoph , Voß Steffen , Harms Klaus
Published: February 2015

Cis-Dichloro-bis(2 ,6 -dimethyl-4 -phenyl-η1-phosphinine)platinum (3) has been prepared by ligand substitution from cis -dichloro(2,5-cyclooctadiene)platinum and characterized by spectroscopy (1H , 13C, 31P NMR, IR, UV-Vis), CV and X-ray diffraction (space group P21/c, a = 14.998, b = 16.540, c - 11.506 Å, α = γ = 90°, β = 92.46°, Z = 4). In line with findings for similar P hybridization states, the Pt-P bond length (221 pm) in 3 equals that in η1 -phosphaalkene Pt complexes and falls short of the respective parameters in Pt phosphane species. The stretching frequencies νPtCl and the bond length Pt-Cl indicate that phosphinines and phosphaalkenes, relative to phosphanes, adopt a lower position on the trans-influence scale. This gradation is also suggested by the coupling constants 1J(195Pt,31P).
Copper Complexes with the Ligand [Cp2MoH2]
Authors: Brunner Henri , Muschiol Manfred , Neuhierl Thomas , Nuber Bernhard
Published: February 2015

The reaction of CuCl with [CP2MoH2] yields the complex [Cu(Cp2MoH2)2Cl]. An X-ray structure analysis shows that the coordination of the copper(I) ion by two [CP2MoH2] ligands and the chloride ion is pseudo-trigonal planar. The hydride ligands were located by using difference Fourier methods. A manifold of reactions took place when an aqueous solution of CUSO4 was treated with a solution of [Cp2MoH2] in dichloromethane in a 1:2 molar ratio. The X-ray structure analysis established a polymeric structure of the complex [Cu(Cp2MoH2)2Cu(Cp2MoH2)SO4]n with two different copper centers.
Wechselwirkungen in Molekülkristallen, 153 [1 - 3]. Wirt/Gast-Einschlußverbindungen von N,N'-Ditosyl-p-phenylendiamin-Derivaten: Die Kristallstrukturen von N,N'-Di(4-ethyl-benzosulfuryl)-p-phenylendiamin und seinen Aggregaten mit Aceton und Cyclopentanon / Interactions in Molecular Crystals, 153 [1 - 3]. Host/Guest-Inclusion Compounds of N,N'-Ditosyl-p-phenylenediamine Derivatives: The Crystal Structures of N,N'-Di(4-ethyl-benzosulfuryl)-p-phenylenediamine and its Aggregates with Acetone and Cyclopentanone
Authors: Bock Hans , Nagel Norbert , Eller Peter
Published: February 2015

A class of novel inclusion compounds based on the hydrogen-bonded host lattice of N,N′- ditosyl-p-phenylenediamine is the starting point for the investigation of derivatives such as N,N′- di(4-ethyl-benzosulfuryl)-p-phenylenediamine. Structures of both the guest-free compound and of its clathrates with acetone as well as cyclopentanone suggest a considerable enthalpy of formation contribution from the conformational change of the sulfonamide backbone on adaption of the guest molecules. The host channels of the N,N′-ditosyl-p-phenylenediamine inclusion compounds are compared to those of the ethyl derivative elongated by two H2C substituent units, and the crystal packing in its cyclopentanone clathrate with an unexpected type of bulged channels is emphasized.
Darstellung chiraler heterocyclischer β-Aminosäureester / Preparation of Chiral Heterocyclic Esters of β-Amino Acids
Authors: Aurich Hans Günter , Gentes Christian , Sievers Ulrich
Published: February 2015

Chiral β-amino alcohols were successively prone to N-benzylation, O-allylation and oxidation of the resulting benzylamino group to give nitrones 3 which on hydrolysis afforded chiral hydroxylamines HO-NH-CH(R)-CH2-O-CH2-CH=CH2 ((S)-4: R = Me, Bn, iPr. (R)-4: R = Et). Swern oxidation of methyl 2,2-dimethyl-3-hydroxypropionate (16) and treatment of the resulting aldehyde 17 with hydroxylamines (S)-4b (R = Bn) or (R)-4d (R = Et) provided nitrones 18 that underwent an intramolecular 1,3-dipolar cycloaddition on heating yielding the bicyclic β-amino-acid esters 19b and ent-19d, respectively.Reductive cleavage of the N,0- bond of compounds 19 afforded the eight-membered ring compounds 20b and ent-20d, respectively.

N-Benzylalaninol (22) was treated with /3-bromo-methacrylate to give the amino alcohol 23. Swern oxidation and subsequent treatment with N-ferf-butylhydroxylamine provided the bicyclic ester 26a (R = t-Bu) via the corresponding nitrone 24. Oxime 25 was prepared in an analogous way as 24 with unsubstituted hydroxylamine. It underwent an intramolecular 1.3- dipolar cycloaddition yielding 26b on heating in toluene. Reduction of 26a afforded the pyrrolidine-carboxylic ester 27a.
Reaktionen von Isochinolinium-Salzen mit Hydroxylamin-Derivaten, 2. Mitteilung N-(Alkyl)- und N-(Aryl)-substituierte Verbindungen / Reactions of Isoquinolinium Salts with Hydroxylamine Derivatives, 2nd Communication N-(Alkyl) and N-(Aryl) Substituted Compounds
Authors: Möhrle H. , Nießen R.
Published: February 2015

The N -alkyl- and N -aryl-isoquinolinium salts 7, 15-17 reacted with free hydroxylamine in pyridine to give the isoquinoline-2-oxide (9) as final product. The intermediate dioximes 8 were isolated and characterized by derivatisation with acetic anhydride to the oxime ester nitrile 10. From the reaction o f 8 with trifluoroacetic anhydride/triethylam ine 3-amino-isoquinoline- 2-oxide (12) resulted after hydrolysis. Due to the electronic influence the 5-nitroisoquinolinium salts 1 -3 react faster than the 5-hydroxy derivative 20. but with the same course of conversion via dioximes to amine oxides. An optimized method for preparation of the amine oxides was developed .
Cyanothioacetamide and its Derivatives in Heterocyclic Synthesis: A New Route for the Synthesis of Several Pyridine and Thieno[2,3-b]pyridine Derivatives and their Biological Evaluation
Authors: Eldin Sanaa M.
Published: February 2015

Several new pyridine and thieno[2,3-b]pyridine derivatives were synthesized via the reactions of some pyridinethiones, obtained by the action of acetylacetone on some thiocarboxamidocinnamonitriles, with halogenated esters and ketones. Structures were established based on elemental and spectral data. All the synthesized compounds were tested for their biological activity.
Reaktionen von [(η5-C5R5)2WH2] mit Boranen / Reactions of [(η5-C5R5)2WH2] with Boranes
Authors: Braunschweig Holger , Kollann Carsten
Published: February 2015

Reactions of [Cp2WH2] with B(C6F5)3 and Me2NB(CF3)2, respectively, leads to the formation of the zwitterions [CpWH3{η5-C5H4B(C6F5)3}] (1) and [CpWH2{η5-C5H4B(NHMe2)(CF3)2}] (2). [Cp*
2WH2] reacts with B(C6F5)3 and tBuBCl2 to give the saltlike compounds [Cp*
2WH3][B(C6F5)4] (3) and [Cp*
2WH3][tBuBCl3] (4).
Ligandenaustauschreaktionen von NiCl2 (PPh3)2 mit O(S)⌒N⌒S-Liganden / Ligand Exchange Reactions of NiCl2(PPh3)2 with O(S )⌒ N ⌒ S Ligands
Authors: Sawusch Stefan , Schilde Uwe
Published: February 2015

Ligand exchange reactions of NiCl2(PPh3)2 with O (S )⌒N⌒S ligands were studied. Oxidation products of O⌒N⌒S ligands have been characterized and their structures determined: 3-methyl-4H-benzo[b] [ 1,4]thiazin-2-yl-phenylmethanone / 2-methyl-benzo[d] [ 1,3]thiazole (mixed crystal); [2-iminoisopropyl-thiophenolato(2-)](triphenyl-phosphane)-nickel(II); 1 -phenyl-3-methyl-4-(benzoyl-thiobenzoylhydrazono)-pyrazol-5-thione; [ 1 -phenyl-3-methyl- 4-(benzoyl-thiobenzoylhydrazono)-pyrazol-5-thionato](triphenyl-phosphane)-nickel(II).
Bis[1,3-bis(diphenylmethylsilylamido)propane]zirconium: A Spirocyclic Complex Containing a Sterically Demanding Chelating Amido Ligand
Authors: Garcia-Yuste Santiago , Hellmann Konrad W. , Gade Lutz H. , Scowen Ian J. , McPartlin Mary
Published: February 2015

Lithiation of the diamine CH2(CH2NHSiMePh2)2 using n-butyl lithium and subsequent reaction with zirconium tetrachloride yielded the bis(chelate)-amidozirconium complex [Zr{CH2(CH2NSiMePh2)2}2]- The spirocyclic molecule has a distorted tetrahedral coordination at the zirconium centre with overall C2 symmetry broken only by the relative orientation of four phenyl rings. The bulky diphenylmethylsilyl substituents at the amido-N functions as well as the ligand backbone sterically protect the metal centre and render it inert towards conproportionation with zirconium chloride.
Synthesis and Oxidation of Ruthenium Allyl Thioether Complexes Bearing Phosphite and Phosphonite Coligands [1]
Authors: Steinmetz Bernhard , Hagel Michael , Schenk Wolfdieter A.
Published: February 2015

Halfsandwich ruthenium thiolate complexes bearing electron-withdrawing phosphite or phosphonite ligands were prepared from [CpRu(PPh3)2(SR)] (R = Ph, CH2Ph, Me) and triphenylphosphite or (S,S)-bis(binaphthylphosphonito)ethane (bbpe), respectively. Reaction with 1-bromo-3-methyl-2-butene in the presence of NH4PF6 gave the corresponding allylthioether complexes [CpRu(PR'3)2(S(R)CH2CH=CMe2)]PF6. Treatment with an excess of dimethyldioxirane (DMD) transformed the triphenylphosphite derivatives into diastereomeric (oxiranylmethyl) sulfoxide complexes with 18 - 80% de. NMR monitoring of the reaction revealed that the oxidant attacks the sulfur atom and the C=C double bond with comparable rates. Similar oxidation of the bbpe complexes gave mixtures of four diastereoisomers with ratios of (64 : 15 : 13 : 8 ) and (51 : 24 : 15 : 10), respectively.
Notizen: Role of the Hydroxymethyl Group for the Inhibitory Activity of Penienone
Authors: Kimura Yasuo , Mizuno Takashi , Kawano Tsuyoshi , Shimada Atsumi
Published: February 2015

Penienone was isolated from the culture filtrate of Penicillium sp. No. 13 and completely inhibited hypocotyl elongation and root growth of lettuce seedlings at a concentration of 300 mg/l. In order to elucidate the active site of penienone, three derivatives were prepared and tested for their inhibitory activity against the growth of lettuce seedlings. The results indicated that hydroxymethyl group in the molecule of penienone was essential to exhibit the remarkable inhibitory activity against the growth of lettuce seedlings.
Carbene Adducts of Dimethylcadmium
Authors: Arduengo Anthony J. , Goerlicha Jens R. , Davidson Fredric , Marshall William J.
Published: February 2015

The first examples of carbene-cadmium complexes are reported from the reactions of a variety of imidazol-2-ylidenes or imidazolin-2-ylidenes with dimethylcadmium. Four new carbene complexes are characterized by NMR spectroscopy (1H , 13C and 113Cd). The cadmium centers are strongly shifted downfield (100 -150 ppm) by interaction with the carbenes. X-ray structures are reported for three carbene-cadmium 1:1 adducts. The cadmium centers exhibit distorted trigonal-planar geometries in which the carbene ligands have an average 18.2 pm longer bond distance to cadmium compared to the methyl groups. The planes of cadmium coordination are twisted with respect to the plane of the imidazole ring. The more basic imidazolin-2-ylidene is shown to displace imidazol-2-ylidenes from the cadmium center.
Synthesis and Structure of 2,2,-Bis(2,2,5-trimethyl-pyrrolidinyl)methane
Authors: Hommer Herbert , Nöth Heinrich , Ponikwar Werner , Rojas-Limab Susana
Published: February 2015

Reaction of 2,5,5-trimethyl-Δ1-pyrrolidine-N-oxide with methyl lithium yields 2,2′-bis(1-hydroxy- 2,2,5-trimethyl-pyrrolidinyl)methane which is reduced by Raney nickel/hydrogen to the corresponding amine. Both molecules are present in the meso-configuration in the solid state. While the hydroxylamine derivative shows intermolecular O-H···O bridge bonding no intermolecular N···H-N interaction is observed for the amine.
Synthesis and Properties of Biagra . A 5-(2,3-Dihydro-7-benzofuryl) Analog of Viagra®
Authors: Voeltera Wolfgang , El-Abadelahb Mustafa M. , Sabrib Salim S. , Khanfar Monther A.
Published: February 2015

The synthesis and spectral properties (IR, MS, NMR) of a substituted 5-(2,3-dihydro-7- benzofuryl)pyrazolo[4,3-d]pyrimidin-7-one (2), an analog of Viagra® (1), are described. The generally applicable route involves interaction of 2,3-dihydro-7-benzofuranoyl chloride (3) with 4-amino-l-methyl-3-propyl-5-pyrazolecarboxamide (4), and the resulting bis-amide (5) is cyclized to the corresponding substituted pyrazolo[4,3-d]pyrimidin-7-one (6). Chlorosulfonylation of 6, followed by treatment with 1-methylpiperazine, furnished the title compound 2 (named Biagra). Preliminary experiments “associated with the erectile process” on rats lend evidence of greater potency of Biagra (2) as compared to Viagra® (1).
The Molecular and Electronic Structure of Tris(dimethylarsino)amine (Me2As)3N
Authors: Jockisch Alexander , Schmidbaur Hubert
Published: February 2015

The molecular structure of tris(dimethylarsino)amine has been determined by X-ray diffraction methods. The compound has a planar AS3N core unit with a paddle-wheel conformation of the three Me2As groups. This structure was also confirmed by density functional calculations.
Some Organic-Inorganic Hybrid Compounds Based on iso– Thiuronium Cations and Lead Halide Anions
Authors: Papavassiliou G. C. , Mousdis G. A. , Koutselas I. B.
Published: February 2015

Using 1-chlorodecane (C10H21CI), benzyl chloride (C6H5CH2CI), a,a'-dichloro-p-xylene (CICH2C6H4CH2CI), 4-phenylbenzyl chloride (C6H5C6H4CH2CI), 2-bromomethyl-naphthal-ene (C10H7CH2Br), 4-bromomethyl-7-methoxycoumarin (C10H7O3CH2Br), 2-bromomethyl-anthraquinone (C14H7CH2Br), 9-chloromethyl-anthracene (C14H9CH2CI), thiourea and halides as starting materials, the organic-inorganic hybrid compounds [C10H21SC(NH2)2]2Pbl4, [C6H5CH2SC(NH2)2]4Pb3l10 [(H2N2)CSCH2C6H4CH2SC(NH2)2]0.5PbI3, [C6H5C6H4CH2S-C(NH2)2]PbI3, [C10H7CH2SC(NH2)2]Pbl3, [C14H7 O2CH2SC(NH2)2]Pbl3, [C14H9CH2SC(NH2)2]PbI3, and [C14H9CH2SC(NH2)2]PbBr4, were prepared and characterized analytically and spectroscopically.