bluuebunny/crossref_metadata_2025 huggingface dataset:
Beiträge zur Chemie des Phosphors, 145 [1]. Neue Lithium-hydrogenpolyphosphide durch Metallierung von Diphosphan / Contributions to the Chemistry of Phosphorus, 145 [1]. Novel Lithium Hydrogen Polyphosphides Through Metalation of Diphosphane
Authors: Bäudler Marianne , Heumüller Rudolf
Published: February 2015

In the reaction of P2H4 with n-BuLi the product pattern strongly depends on the stoichiometric ratio and the reaction temperature (-25 °C or -78 °C). The following polyphosphides have been detected by 31P NMR spectroscopy: LiH8P7, LiH4P7, LiH5P8, Li2H2P14, LiH2P7, Li2HP7, Li3P7, LiH4P5, LiH4P3, LiH3P2, and a still unidentified compound LixHyPz.
Cyclisierung von Bis(2,2,2-trifluorethoxy)-1,2-diiminoethan mit Schwefel-, Selen-, Phosphor- und Arsenchloriden / Cyclisation of Bis(2,2,2-trifluoroethoxy)-1,2-diiminoethane with Sulfur, Selenium, Phosphorus, and Arsenic Chlorides
Authors: Roesky Herbert W. , Hofmann Hartmut
Published: February 2015

By the reaction of cyanogen with 2,2,2-trifluoroethanol in the presence of a base catalyst, bis(2,2,2-trifluoroethoxy)-1,2-diiminoethane (1) is obtained. 1 can be easily cyclized with halides to yield five-membered ring compounds. Triethylamine serves as an HCl-acceptor. The building elements of the rings are S 2, 3, Se 4, P 5 and As 6, respectively. 5 reacts with Mg to form the diphosphane 7.
The Electronic Structures of the Group V Series ER3 (E = N→Sb; R=H, Hal). An Intercomparison of Photoelectron Spectra and SCC–Xα Calculations [1]
Authors: Grodzicki Michael , Walther Horst , Elbel Susanne
Published: February 2015

The He I photoelectron spectra o f the group V trihydrides and trihalides are assigned on the basis of a qualitative D3h/C3v-MO model which includes the analogous group III trihalides. Trends and irregularities across the series by varying either the central atoms or the substituents are discussed. U sing experimentally fitted (PES) and optimized parametrization the new SCC -Xα method yields results in excellent agreement with both measured ionisation potentials and dipole m om ents, especially for the heavier homologues. The electronic distribution and the trends in electronic and molecular properties are examined for the model series ER3 (E=N→Sb; R=H,Cl) and AsR′3(R′=H, Hal) within a complete SCC-Xα (and EHT) population analysis. - The PE Spectrum of BiMe3 is presented.
Synthesis, Crystal Structure and Electrochemistry of μ-Acetatodi-μ-hydroxo-bis[(1,4,7-triazacyclononane)ruthenium(III)]-tris-iodide. Characterization of Some Ru(II)—Ru(III) Mixed Valence Species
Authors: Wieghardt Karl , Herrmann Willy , Koppen Martin , Jibril Ibrahim , Hüttner Gottfried
Published: February 2015

A series of mononuclear complexes of ruthenium containing the cyclic triamine ligand 1,4,7-triazacyclononane ([9]aneN3 = L; C6H15N3) have been prepared: [RuIIL (dmso)2Cl]Cl (dmso = dimethyl sulfoxide), [RuIIILX3] (X = C1- , Br-), [RuL2](PF6)2, [RuL(C2O4)I]. Hydrolyses of RuLCl3 under a variety of reaction conditions afford dinuclear species:

[RuIII
2L2(μ-OH)2(μ-CH3CO2)]I3·H2O , [RuIII
2L2(μ-OH)2Cl2](PF6)2, and the mixed-valence species [Ru2L2(μ-Cl)3](PF6)2. The complex [Ru2L2(μ-OH)2(μ-CH3CO2)]I3-H2O has been characterized by a single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic space group P21/c with a = 14.70(1) Å , b = 19.00(1) Å , c = 9.714(7) Å , β = 99.62(7)°, and V = 2674 Å3, dcalcd = 2.37 g cm-3 for Z = 4, and mol wt 952.3. The structure was solved by direct methods using 2519 unique reflections with I > 2σ(I).

Final residuals were R1 = 0.0615 and R2 = 0.075. The structure consists of μ-hydroxo- and μ-acetato- bridged dinuclear cations and iodide anions. The observed diamagnetism and a short Ru-Ru bond distance of 2.572(3) Å are indicative of a Ru-Ru single bond. The electrochemical properties of [Ru2L2(μ-OH)2(μ-CH3CO2)]3+ and [Ru2L2(μ-Cl)3]2+ have been investigated by cyclic voltammetry, and by coulometry. Two one-electron redox processes have been identified for both complexes the first of which exhibits a reversible wave, whereas the second wave at more negative potentials is irreversible. The blue mixed valence species [Ru2L2(μ-OH)2(μ-CH3CO2)]2+ has been characterized in solution.
Chemie polyfunktioneller Moleküle, 80 [1]. Kristall- und Molekülstrukturen der Heteronoradamantane 5-Methyl-2.2.8.8-tetra-ethoxycarbonyl-1.3.7-triarsa-tricyclo[3.3.1.03,7]nonan und 5-Methyl-1.3.7-triarsa-2.8-diselena-tricyclo[3.3.1.03,7]nonan / Chemistry of Polyfunctional Molecules, 80 [1]. Crystal and Molecular Structures of the Heteronoradam antanes 5-Methyl-2.2.8.8-tetra-ethoxycarbonyl-1.3.7-triarsa-tricyclo[3.3.1.03,7]nonane and 5-M ethyl-1.3.7-triarsa-2.8-diselena-[3.3.1.03,7]nonane
Authors: Thiele Gerhard , Rotter Heinz W. , Lietz Martin , Ellermann Jochen
Published: February 2015

The molecular and crystal structures of the nor-heteroadam antanes CH3C(CH2As)3[C(COOCH2CH3)2]2 (1) and CH3C(CH2As)3Se2 (2) have been investigated in order to obtain confirmation of the rare structures deduced earlier from mass, 1H NMR and vibrational spectroscopy. Crystals of 1 are triclinic, space group P1̄-C1
i with a - 769.27(30), b = 1036.09(14), c = 1599.18(17) pm, α = 98.236(10)°, β = 97.987(18)°, γ = 103.633(20)° and Z = 2. On the basis of 1821 unique reflections the structure was refined to a weighted R value of 5.28%. The crystals of 2 are monoclinic, space group P 21/c-C5
2h with a = 1102.73(23), b - 727.49(14), c = 1281.27(42) pm. β = 98.803(21)° and Z = 4. On the basis of 1065 unique reflections the structure was refined to a weighted R value of 5.93%.

Several attempts to synthesize CH3C(CH2As)3Te2 failed.
Formaldehydkomplexe / Formaldehyde Complexes
Authors: Berke Heinz , Birk Reiner , Hüttner Gottfried , Zsolnai Laszlo
Published: February 2015

The synthesis of formaldehyde complexes (OC)2L2FeCH2O(L=P(OEt)3 (2b), L = P(OiPr)3 (2c)) and CpRe(CO)2CH2O (3) is reported. A(OC)2[P(OMe)3]2FeCH2O compound (2a) reacts with CO,PPh3 and C2H4 substituting the CH2O ligand. CH3I and H2 also cause elimination of formaldehyde with oxidative addition to the Fe(CO)2[P(OMe)3]2 fragment. HI adds to 2c to give a iodomethyl complex 5, which has been characterized by an X-ray structure determination.
Mesosubstituierte Porphyrine und mesosubstituierte Eisenporphyrine, 2 [1] / meso-Substituted Porphyrins and meso-Substituted Iron Porphyrins, 2 [1]
Authors: Volz Heinrich , Herb Georg
Published: February 2015

Pyrryl-heptadecyl-carbinol and Pyrryl-9-anthracenyl-carbinol are cyclised in acidic medium to the corresponding meso-tetra-substituted porphyrins. The meso-tetra-substituted porphyrins are transfered to the iron complexes.
Dikationether, 3 [1]. Substitutionen an Bis(acridinium)ethern und 9-Trifloxyacridinium-Salzen mit Halogeniden, Pseudohalogeniden und Schwefel-Nucleophilen / Dication Ethers, 3 [1]. Substitution Reactions on Bis(acridinium) Ethers and 9-Trifloxyacridinium Salts by Halides, Pseudohalides and Sulfur Nucleophiles
Authors: Singer Berndt , Maas Gerhard
Published: February 2015

9-Trifloxyacridinium salts 3a, b and 9,9′-oxy-bis(acridinium ) salts 4a, b which are easily obtained from the 9-acridones 2 a, b react readily with halides, pseudohalides and sulfur nucleophiles to give 9-substituted acridinium ions. This reaction represents an efficient alternative to the commonly used transformation of 9-chloroacridinium into other substituted acridinium salts; the two-step conversion of the carbonyl com pound into a (pseudo)halide-substituted carbenium ion or into a thione may be generally applicable to ketones which can be transformed either into trifloxy carbenium ions or into dication ethers.
The Effect of Substituents on the Photochemical Reaction between Naphthalenedicarbonitrile and Methylbenzenes
Authors: Albini Angelo , Fasani Elisa , Montessoro Ezio
Published: February 2015

The photochemical reaction between 1,4-naphthalenedicarbonitrile (NDN) and toluene in acetonitrile is extended to bibenzyl (4), 3- and 4-fluorotoluene (8, 7), and 3- and 4-m ethoxytoluene (9, 10). The product distribution obtained with com pounds 4, 7 and 10 is similar and includes 4-benzyl-1-naphthalencarbonitriles (1a -c), 1-benzyl-1,2-dihydro-1,4-naphthalenedicarbonitriles (5a-c), cis 2-benzyl-1,2-dihydro-1,4-naphthalenedicarbonitriles (2a-c) (with com pound 10 also the trans isomer 12), 12-substituted 6,11-dicyano-5,11-methano-5,6,11, 12-tetrahydrodibenzo[ a,e]cyclooctenes (3a, b) (not obtained with com pound 10), besides the hydrocarbons arising from the coupling o f the respective benzyl radicals (products 6a-c). With com pound 9 the only process observed is reduction of NDN to 1,2-dihydronaphthalene-1,4-dicarbonitrile (11). The results obtained fit into the previously proposed mechanistic scheme, involving electron and proton transfer follow ed either by in cage radical coupling to form products 2, 3, 5 and 12 or radical escape leading to products 1 and 6. The effect of substituents on the various phases of the reaction is discussed.
ESR- und ENDOR-Untersuchungen von p-Benzosemichinon-Diarylthallium-Ionenpaaren / ESR- and ENDO R-Investigations of p-Benzosemiquinone-Diarylthallium Ion Pairs
Authors: Stegmann Hartmut B. , Ulmschneider Karl B. , Schuler Paul , Jülich Thomas , Scheffler Klaus
Published: February 2015

Diarylthallium hydroxides react very smoothly in organic solvents with hydroquinones to stable paramagnetic complexes. This reaction has been investigated with two ligands and several organometallic compounds in 8 different solvents. In basic solutions clearly two paramagnetic species can be detected by ESR spectroscopy. One component exhibits a large doublet splitting assigned to the thallium counterion and the second radical does not show any metal coupling. The relative concentrations of both radicals depend strongly on the solvent and the temperature. Therefore, a slow equilibrium betw een a contact ion pair and a solvent separated ion pair is assumed. The thermodynamic parameters are determined to ⊿H = 0.8 kcal/mol, ⊿G293 = -0.1 kcal/mol, ⊿S = 3.04 cl/mol.

The proton and thallium coupling constants as well as the g-value of the contact ion pair show a rem arkable temperature dependence. The signs of proton splitting constants are determined by ENDOR-TRIPLE investigations. The change of the electronic structure of the radical anion by formation of a contact ion pair is discussed. For interpretation of these results we assumed a fast equilibrium between different conformations of the contact ion pair according to behaviour of comparable aroxyl radicals. Therefore, the systems investigated allow a simultaneous observation of solvent separated and different contact ion pairs.
Chemical Examination of the Seeds of Cassia spectablis
Authors: Singh Mithilesh , Singh J.
Published: February 2015

Tetratriacontanyl palmitate, tetratriacontanyl nonadecanoate and 2″-O-glycoside of 5-acetonyl- 7-hydroxy-6-glucosyl-2-methyl chromone have been isolated from the seeds of Cassia spectablis.
Heterocyclen-Synthesen mit 4.4-Bis(trifluormethyl)-1,3-diazabuta-1,3-dienen, III [1]. Synthese trifluormethyl-substituierter Sechsring-Heterocyclen durch Umsetzung mit Enolethern, Enaminen und Heterokumulenen / Synthesis of Heterocyclic Compounds from 4.4-Bis(trifluorom ethyl)-1,3-diazabuta-1,3-dienes, III [1]. Synthesis of Trifluoromethyl Substituted Six Membered Ring Systems by Reaction with Enolethers, Enamines, and Heterocumulenes
Authors: Burger Klaus , Waßmuth Ulrike , Forster Barbara , Penninger Stefan
Published: February 2015

Regiochemistry and site specifity of [4+2] cycloaddition reactions of 4,4-bis(trifluoromethyl)-1,3-diazabuta-1,3-dienes with enolethers, enamines and heterocumulenes are described. IR, 1H , 13C, and 19F NMR data of the compounds obtained are discussed.
Synthese und Struktur- und Konformationsanalyse von Triphenylphosphonium-bis(diphenylarsino)methylid
Authors: Schmidbaur Hubert , Nußstein Peter , Müller Gerhard
Published: February 2015

Triphenylphosphonium -diphenylarsinomethylide (1) and -bis-(diphenylarsino)methylide (2) are easily available through transylidation processes using Ph3P = CH2 and Ph2AsCl as the starting materials in the appropriate molar ratio. Analytical and spectroscopic data are presented for both ylides. The structure of 2 was studied in detail by single-crystal X-ray diffraction. The basic PCAs2 skeleton is found to deviate strongly from planarity. The Ph2As-substituents adopt a cis/trans conformation relative to the ylidic P = C bond with the directions of the lone pairs of electrons at the arsenic atoms in the heavy atom plane as expected for a maximum compensation of the electrostatic vectors. For 1, a cis-conformation of the lone pair of electrons and a large PCAs angle are predicted on the basis of NMR analogies with the phosphorus homologues. Single bond rotational barriers appear to be much lower for 1 and 2, however, than for the corresponding phosphino-substituted ylides.
Beiträge zur Chemie des Bors, 153 [1] Die Kristall- und Molekülstruktur eines 1.3.2-Dioxaborolan-2-yl-1.3.2-dioxaborolans
Authors: Nöth H.
Published: February 2015

The structure of the title com pound 5 has been investigated by X-ray crystallography in order to discern between two structural alternatives. 5 crystallizes in the monoclinic space group P21/c, and almost planar B-B bonded dioxaborolane rings are present in the molecule. 5 possesses a crystallographically imposed center of inversion, and approaches the point group symmetry D2h-
Zur Kenntnis der Verbindungen MCl5· NSCl, (MCl5)2 · N2S2, S4N4Cl[MCl6] und N(SCl)2[MCl6] von Niob und Tantal
Authors: Hanich Jürgen , Dehnicke Kurt
Published: February 2015

The pentachlorides MCI5 (M = Nb, Ta) react with trithiazyl chloride in CCl4 suspension to form the donor-acceptor com plexes MCl5-NSCl and (MC15)2 • N2S2. With excess (NSCl)3 the ionic com pounds S4N4Cl[MCl6] are obtained. Reaction of the complexes MCl5 - NSCl with SCl2 give another ionic species N(SCl)2[MCl6] whereas thermal cleavage is found to result in the formation of (MCl5)2 • N2S2. All products were characterized by their IR spectra.
Darstellung und Charakterisierung von Biscyanophthalocyaninatoferraten(III)
Authors: Küppers H. , Kennedy B. J. , Murray K. S.
Published: February 2015

The preparation of bis-cyanophthalocyaninatoferrates(III) with different bulky cations is described. The redox behaviour was studied by cyclic voltammetry, and the results confirmed by appropriate chemical reduction and oxidation reactions. Reactions with bases and acids as well as the redox reactions are governed by the strong trans-efiect of CN- favouring the formation of the monocyano or mixed ligand monocyano complexes. The ESR and Mössbauer spectra as well as the magnetic susceptibility studies (4 .2 -300 K) indicate a low-spin Fe(III) complex with a pseudooctahedral 2T2-groundstate. The IR and Resonance Raman (RR) spectra were investigated. By comparison with similar electronic Raman transitions in the low-temperature Raman spectra of K3[Fe(CN)6] and Na2[Fe(CN)5NO] • 2H2O the RR-enhanced band at 525 cm-1 in the 80 K RR-spectrum is assigned to the intraconfigurational Raman transitions between the groundstate spin-orbit split components Г7g →Г7g, Г6g(D4h*) yielding the spin-orbit coupling parameter ζFe = 350 cm-1. In the FIR-spectrum the F e-C-stretching vibration (a2u) is localized at 350 cm -1 as confirmed by comparison with the FIR-spectra FeXPc(2-) (X = F. Cl. Br, I). The UV - VIS spectrum was measured together with those of the bis-cyano complexes of Fe(II) and Co(III). The splitting of the Q-band (a2ueg) is discussed. Extra-bands at 540. 610 and 775 nm are assigned to Pc →Fe-electron transfer. A comparison with the spectra of the H2S04 adduct and the phthalocyanine- π-cation radical is presented.
Bis(trimethylsilyl)-phosphaethene und Tris(trimethylsilyl)silyl-fluorphosphane
Authors: Haase Martin , Klingebiel Uwe , Skoda Lutz
Published: February 2015

Phosphaethenes of the type (Me3Si)2C = P -NRSiMe3 R = C10H15 (7), CMe3 (8), 2.4.6-Me3C6H2 (10)), LiF, and Me3SiF are obtained in the reaction of the aminodifluorophosphanes (3-5) with the lithium salt of tris(trimethylsilyl)methane (1). 10 is isolated as by-product. The main product is F2PC(SiMe3)3 (9). The lithium salt of tris(trimethylsilyl)silan (2) reacts with 3 -6 to give the thermally stable substitution compounds (Me3Si)3Si -PF-NRSiMe3 (11-14). The fluorosilylphosphane Me3Si(CMe3)P -SiFMe - N(SiMe3)2 (15) is formed in the reaction of Me3Si(CMe3)PLi and F2SiMeN (SiMe3)2.
Änderung der Selektivität in katalytischen Mehrkomponenten-Systemen über die Konzentrationen, Steuerung metallkatalysierter Reaktionen, XIII. Mitteilung [1]
Authors: Bartik Tamas , Behler Ansgar , Heimbach Paul , Ndalut Paulo , Sebastian Jörg , Sturm Harald
Published: February 2015

By applying the method of inverse titration [1,2] the influence of increasing concentrations of added effectors to organic and metalorganic chemical systems on the product selectivity can easily be identified. o a Wittig-type system we added LiI (change of stereoselectivity) and also triphenylphosphanoxide (removal of salt-effect). To a catalytic N(0)/butadiene system we added triphenylphosphite and then morpholine and vice versa. Ni:P(OC6H5)3: morpholine in a ratio 1:1:0,1 yields more than 90% cyclodimers but in a ratio 1:0,1:20 more than 90% n-octa-1,3,6- trienes. The co-oligomerisation of two butadienes with one 2,5-dimethyl-3-aza-hex-3-en in the system Ni/triphenylphosphane/butadiene/Schiff base/toluene/effector (1:1:66:33:66:~0,1) leads - within the 2 : 1-cooligomers - by adding di-n-propyl-borane to a pure octadienylated Schiff base 11 or by adding morpholine largely to an octatrienylated amine 12 (~85% 12 and ~15% 11).
Cycloalkylidenselenoketene durch Pyrolyse von 1,2,3-Selenadiazolen — Untersuchungen mit der temperaturabhängigen PE-Spektroskopie und Matrix-IR-Spektroskopie [1]
Authors: Schulz Reinhard , Schweig Armin
Published: February 2015

The gas-phase pyrolysis of cyclohexeno-1,2,3-selenadiazole and cycloocteno-1,2,3-selenadiazole has been investigated by variable temperature photoelectron spectroscopy and matrix IR spectroscopy. The ring contracted, highly reactive products cyclopentylidenselenoketene (cyclopentylidenmethanselone) and cycloheptylidenselenoketene (cycloheptylidenmethanselone) - which had not been found in liquid phase thermolysis experiments - have been detected. Additionally HeI photoelectron and IR spectra of analogous ketenes and thioketenes are presented for comparative reasons.
Germanium-haltige Heterocyclen, VI [1] Ph8Ge5O6, ein Germoxan aus bicyclisch verknüpften (GeO)4-Ringen
Authors: Häberle Karl , Dräger Martin
Published: February 2015

The title compound 1,3,3,5,7,7,10,10-octaphenyl-2,4,6,8,9,11-hexoxa-1,3,5,7,11-pentagermabicyclo[3.3.3]undecane is synthesized from PhGeCl3/Ph2GeC l2 and AgNO3 in aqueous acetone. The 13C NMR phenyl signals for bridges and bridge-heads are in the expected ratio of intensity 3:1. The crystal structure of Ph8Ge5O6 ·1/2 acetone has been determined and refined to R = 0.062. The asymmetric unit contains two independent bicyclic Ph8Ge5O6 cages and one disordered crystal acetone. The total symmetry of both Ph8Ge5O6 molecules is near to D3, the symmetry of the individual 8-membered rings (GeO)4 is near to C2 (distances Ge -O 172-180, Ge -C 191-195 pm, angles Ge - O - Ge 128.0-133.8, O - Ge - O 107.5-110.6°).
Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XXIII [1] Synthese und dynamisches Verhalten von Dicarbonyl(η-dien)-bis(trimethylphosphan) chrom(0) und Dicarbonyl(η-dien)-bis(trimethylphosphit)chrom(0)
Authors: Kreiter Cornelius G. , Kotzian Michael , Schubert Ulrich , Bau Robert , Bruck Michael A.
Published: February 2015

Cr(CO)2[P(CH3)3]2(η-diene) (9-14) and Cr(CO)2[P(OCH3)3]2(η-diene) complexes (15-20) were prepared photochemically in high yields from Cr(CO)4[P(CH3)3]2 (1) or Cr(CO)4[P(OCH3)3]2 (2), respectively, with the dienes 1,3-butadiene (3), trans-1,3-pentadiene (4), 2-methyl-1,3- butadiene (5), trans,trans-2,4-hexadiene (6), 2-methyl-1,3-pentadiene (7), and 2-ethyl-1,3- butadiene (8). The stereochemistry of 9-20 was determined by IR and N M R spectroscopy. In the case of dicarbonyl-η-trans-1 ,3-pentadiene-bis(trimethylphosphane)chromium(0) (10) and the corresponding trans,trans-2,4-hexadiene complex 12 the X-ray crystal and molecular structure analyses confirm the spectroscopic conclusions. The distorted octahedral complexes are obtained exclusively as af-isomers. They show a hindered, degenerate isomerization with an intramolecular mutual exchange of the donor ligands. Trigonal prismatic transition states and distorted octahedral intermediates are appropriate models for the explanation of the degenerate isomerization. The activation barriers for the ligand movement were determined by dynamic 31P-NMR spectroscopy. The mobility of the ligand spheres distinctly depend on the position of the alkyl groups of the diene ligands. A methyl group in 1E-position increases the barrier of the ligand movement by ≈ 16 kJ/mol, in 2-position the barrier is lowered by ≈ 5 kJ/mol. This effect is caused by steric interactions between the alkyl groups and the donor ligands in the transition or ground state.
Diastereomere Organophosphorverbindungen, II [1] Molekül- und Kristallstrukturen von [CH3(t-C4H9)P(S)]2 und [CH3(t-C4H9)P(S)]2S
Authors: Wunderlich Hartmut , Wussow Hans-Georg
Published: February 2015

Syntheses, separation of diastereomers, NMR studies and molecular properties in solution are reported for [CH3(t-C4H9)P (S)]2 (1 and 2), and [CH3(t-C4H9)P(S)]2S (3) in the preceding paper [1], For further characterization the crystal structures of the diastereom eric disphosphane disulphides (1 and 2) as well as of the related sulphane (3) have been determ ined. 1 is triclinic (space group P1̄; Z = 1), 1792 independent reflections yielded R = 0.03. 2: monoclinic (P21; Z = 2), 973 reflections, R = 0.07. 3: orthorhombic (Pbca; Z = 8), 2607 reflections, R = 0.05. Molecules of 1 and 2 are diastereomers. The configuration of 1 is meso (point symmetry 1̄-Ci , all ligands trans) whereas 2 is an enantiomeric form of the prepared racemic mixture (S atom s and methyl gauche, t-butyl trans). The distance P - P is 226.6(1) and 226.9(3) pm, respectively. Molecules of 3 are enantiomers in racemic crystals (S atoms and t-butyl close to gauche). The molecule is bent by an angle P -S -P of 104.78(5)°.
Fulvene mit inverser Ringpolarisation, 17 [1] Heptafulvene und Heptafulvenradikalkationen: Ringverengung durch Abspaltung eines C1-Fragments bei der Einelektronen-Oxidation von Bis(dimethylamino)dibenzoheptafulven
Authors: Daub Jörg , Pirzer Erika , Trieschmann Christa , Merz Andreas
Published: February 2015

Disubstituted dibenzoheptafulvenes 4 are obtained from dibenzocycloheptene 8 via the carboxylic acid amide 10, and are characterized by spectroscopic methods and cyclic voltammetry. These dibenzoheptafulvenes are nonplanar, geometric enantiomorphy is shown by 1H-NMR of 12-dim ethyl-am ino-12-siloxydibenzoheptafulvene 4c. Oxidation o f 12,12-bis(dim ethylamino)dibenzo[a,d]-heptafulvene 4a with Ag(I), I2 or Cu(II) leads to the radical cation 7. In solution 7 is converted to dibenzocycloheptatriene and anthracene amidinium salts 18 and 19. The ratio o f these two amidinium salts depends on the reaction conditions. H-radical trapping from the medium is proposed for the formation of 18, while 19 must be formed under elimination of a C1-unit.
Untersuchungen zum Redox-System Bis-(pyridin-2,6-dicarbothioato)-ferrat(II) /-ferrat(III) [1]
Authors: Hildebrand U. , Lex J. , Taraz K. , Winkler S. , Ockels W. , Budzikiewicz H.
Published: February 2015

The structure of the blue pigment obtained from the culture medium of Pseudomonas putida upon addition of Fe++ and the nature of its redox reactions has been elucidated.
Thiation Reactions, II Thiation of Certain o-Diazaketones
Authors: El-Kateb A. A. , Shabana R. , Osman F.H.
Published: February 2015

Diazoketones 2 and 4 react with the thiation agent 1 to give 1 ,2 ,3-thiadiazole derivatives 3, 5 and 6 , respectively. The action of 1 on 3-diazooxindole (8 ) yields the dimeric dithione 9. Structural assignments are based on analytical. Chemical and spectroscopic results.
Preparation of 3β-Acetoxy-5β-pregnan-20-one from 3α-Acetoxy-5β-cholan-24-oic Acid Aimed at the Isotopic Labelling of the Pregnane Side Chain
Authors: Deluca Mónica E. , Seldes Alicia M. , Garraffo Hugo M. , Gros Eduardo G.
Published: February 2015

3α-Acetoxy-5β-cholan-24-oic acid was transformed into 3β-acetoxy-5β-pregnan-20-one by a sequence of reactions that involves inversion o f the configuration at C-3 and degradation of the side chain of the bile acid. The procedure would allow the introduction of a label at C-21 of the final compound.
Bis(triphenylphosphan)iminiummonothionitrat
Authors: Seel F. , Kuhn R. , Simon G.
Published: February 2015

The title compound (1) has been prepared by the reaction of PNP-perthionitrate with triphenylphosphane in acetone or acetonitrile.
Anmerkungen zur Strukturbestimmung von Pentacarbonyl[Z-butenyl- (methoxy)carben]chrom [1]
Authors: Schubert Ulrich , Dötz Karl Heinz
Published: February 2015

Redetermination o f the structure of the title complex revealed that some unusual bond lengths originally reported for this structure [1], are due to an overlooked disorder of the carbene ligand. Rerefinement with a disordered structural model results in normal bond lengths.
Bromoselenate(II): Darstellung, Struktur und Eigenschaften von [P(C6H5)4]2SeBr4 und [P(C6H5)4]2Se2Br6 / Bromoselenates(II): Preparation, Structure and Properties of [P(C6H5)4]2SeBr4 and [P(C6H5)4]2Se2Br6
Authors: Krebs Bernt , Schäffer Andreas , Pohl Siegfried
Published: February 2015

The novel anion SeBr4
2- was prepared by dissociation of SeOBr2 with formation of SeBr2 and subsequent reaction with bromide in acetonitrile solution; it was isolated as the crystalline tetraphenylphosphonium salt. The X-ray structure analysis of [P(C6H 5)4]2SeBr4 (space group P 1̄ , a = 14.190(3), b = 15.125(3), c = 10.383(2) Å , α = 92.69(2), β = 100.89(2), γ = 92.04(2)° Å , V = 2182.2 Å3) shows the structure to contain monomeric SeBr4
2- anions with a square planar coordination of Se(II). The mean Se -Br bond length in the anion is 2.598 Å .

[P(C6H5)4]2Se2Br6 was obtained from the reaction of SeBr4 (which is in equilibrium with SeBr2, Se2Br2, and Br2, in solution) and bromide in acetonitrile. It crystallizes in the space group P 1̄, with a = 1 0 . 9 3 3 ( 4 ) , = 11.154(4), c = 10.344(4) Å , α = 79.26(3), β = 72.63(3), y = 81.35(3)°, γ = 1176.7 Å3 (at -120 °C), and contains a novel type of centrosymmetric Se2Br6
2- ions with square planar Se-coordination. The mean terminal and bridging Se -Br bond lengths are 2.442 and 2.799 Å , resp. Vibrational spectra are reported and discussed.
Isolation and Crystal Structure of (Hexamethylbenzene)gallium(I) Tetrachlorogallate(III), a Mono(arene) Complex of Gallium(I)
Authors: Thewalt Ulf , Zafiropoulos Theodore , Schmidbaur Hubert
Published: February 2015

Ga2Cl4 reacts with hexamethylbenzene in benzene to give (hexamethylbenzene)gallium (I)- tetrachlorogallate(III), (CH3)6C6G a+GaCl4
- , in high yield. The complex crystallizes in the rhombohedral space group R 3 m with four formula units per cell. Cell constants are a = 12.449(3) Å and α = 91.01(2)°. In the structure tetrameric clusters can be identified containing two crystallographically independent formula units, one having 3 m and the other three having m symmetry. In both types of (arene)Ga+ cations the Ga atoms are symmetrically positioned over the arene ring, 2.43(3) and 2.51(3) Å , respectively, away from the ring plane. Four (arene)Ga+ cations and four GaCl4
- anions are aggregated in such a way that the Ga1 atoms are surrounded by six or seven chlorine atoms, respectively, at distances in the range 3.16(1) to 3.67(1) Å . The four hexamethylbenzene molecules form an efficient cover around the inorganic [Ga+GaCl4
-]4 framework. Between the tetrameric clusters there are no contacts of the Ga1···Cl Type.
Synthese und Struktur von Oxo-phthalocyaninato-molybdän(IV) / Synthesis and Structure of Oxo-phthalocyaninato-molybdenum(IV)
Authors: Börschel Volker , Strähle Joachim
Published: February 2015

Oxo-phthalocyaninato-molybdenum (IV), PcMoO, was obtained in form of violet crystals by the reaction of Mo(CO)6 with phthalodinitrile in toluene at 180 °C in a sealed tube. It crystallizes isotypically with the monoclinic form of PcTiO in the space group P21/c: a = 1344.1(3). b = 1329.2(2), c = 1404.1(3) pm, β = 103.81(1)°, Z = 4. The structure is built up by monomeric molecules in which the Mo atom exhibits a square pyramidal coordination. It is located 69 pm above the plane of the phthalocyaninato ligand and forms a short bond of 166.8 pm to the O atom. The Mo-N distances range from 206.8 to 211.2 pm. In the IR spectrum ν(Mo = O) is observed at 965 cm-1. Partial oxidation of PcMoO with I2 yields semi-conducting PcMoOIx (x = 1 .4-2.6) with electrical conductivity of 10-5 to 10-4 S/cm.
Dimethyl(phenylchalkogeno)bismutane — Moleküle mit Bismut-Schwefel, -Selen und -Tellur-Bindungen / Dimethyl(phenylchalcogeno)bismuthanes — Molecules with Bismuth-Sulfur, -Selenium and -Tellurium Bonds
Authors: Wieber Markus , Sauer Ingbert
Published: February 2015

Dimethyl(phenylchalcogeno)bismuthanes of the general formula (CH3)2BiEC6H5(E = S, Se, Te), the first m olecules with a Bi -Se or a Bi-Te-bond, respectively, were synthesized in good yields by reactions of tetramethyldibismuthane and diphenyldichalcogenides. At room temperature - these thermolabile compounds react quantitatively - with increasing rate in the series S-Se-Te to give CH3Bi(EC6H5)2 and Bi(CH3)3.
Beiträge zur Chemie des Phosphors, 147 [1] 31P-Kernresonanzspektrum und Struktur von Hexaethyl-octaphosphan(6), P8Et6 / Contributions to the Chemistry of Phosphorus, 147 [1] 31P NMR Spectrum and Structure of Hexaethyloctaphosphane(6), P8Et6
Authors: Bäudler Marianne , Därr Eberhard , Binsch Gerhard , Stephenson David S.
Published: February 2015

Hexaethyloctaphosphane(6) (1) was proven to possess the structure of a 2,3,4,6,7,8-hexaethylbicyclo[3.3.0]octaphosphane by a complete analysis of its 31P {1H } NMR spectrum. The chemical shifts and coupling constants yielded inform ation about the configuration and conformation of 1.
Complexes of Bis(phenyldithiocarbazato)mckel(II) with Triphenylphosphane and Some Ditertiary Phosphanes
Authors: Aly A. A. M. , Kamal M. M. , El Meligy M. S. , El Said A. I.
Published: February 2015

Mixed ligand complexes of bis(phenyldithiocarbazato)nickel(II) with triphenylphosphane and a number of ditertiary phosphanes have been synthesised. The complexes were characterised on the basis of molar conductance, magnetic moment values, electronic and IR spectra. Out of the five prepared com plexes the mixed ligand complexes with triphenylphosphane and bis(diphenylphosphino) m ethane are paramagnetic, the mixed ligand complexes with bis(diphenylphosphino) ethane, -propane, and -butane are diamagnetic. The complexes were assigned octahedral, square planar or square pyramidal structures. The biological activities of the complexes were also tested.
Cyclo-thiazenokomplexe von Molybdän und Wolfram. Die Kristallstruktur von AsPh4[WCl4(N3S2)] / Cyclo-thiazeno Complexes of Molybdenum and Tungsten. The Crystal Structure of AsPh4[WCl4(N3S2)]
Authors: Kynast Ulrich , Conradi Elke , Müller Ulrich , Dehnicke Kurt
Published: February 2015

The dark brown cyclo-thiazeno com plexes [MoCl3(N3S2)]2 and [WCl3(N3S2)]2 are obtained by quantitative reactions of MoNCl3 with (NSCl)3 and of WOCl4 or WSCl4 with excess (NSCl)3, respectively. They are diamagnetic, thermally stable up to 200 °C, and only slightly sensitive towards moist air, but react explosively with aqueous bases. According to the IR spectra [MoCl3(N3S2)]2 is dimerized via chloro bridges whereas the tungsten com pound is associated via the γ-nitrogen atoms of the cyclo-thiazeno ligand. By reaction with [AsPh4]Cl or [PPh4]Cl in CH2Cl2, the compounds EPh4[MCl4(N3S2)] are obtained (E = P, As; M = Mo, W). The crystal structure of AsPh4[WCl4(N3S2)] was determined from X-ray diffraction data (1845 observed reflexions, R = 0.045). It crystallizes in the monoclinic space group P21/c with four formula units per unit cell. The lattice constants are a = 1352.4, b = 968.4, c = 2393.8 pm and β = 115.1°. The com pound is built up from AsPh4
⊕ cations and [WCl4(N3S2)]⊖ anions in which the W atoms are coordinated in a distorted octahedral fashion by four Cl and two N atoms of the N3S2 ligand. The WN bond lengths (182 and 188 pm) correspond to douple bonds. The WN3S2 ring is planar and has SN bond lengths between 154 and 161 pm.
Dioxobis(Carboxylato)Chromium(VI) and Oxo(Carboxylato)Chromium(III): Reactions of CrO3 with Carboxylic Acid Anhydrides
Authors: Kapoor Ramesh , Sharma Ramneek , Kapoor Pratibha
Published: February 2015

Reactions of carboxylic acid anhydrides [(RCO)2O where R = CH3, C2H5, n-C3H7 and CHCl2] with excess of chromium (VI) oxide at low temperatures yield chromyl carboxylates, CrO2(OOCR)2. These compounds are non-conducting in polar organic solvents. IR spectra suggest the presence of both unidentate and bidentate carboxylato groups and discrete Cr = 0 units. The 1H NMR spectra show the presence of only one type of carboxylato group.

Reactions of carboxylic acid anhydrides with CrO3 in equimolar ratio yield reduced chromium(III) com pounds o f the type CrO(OOCR) at room temperature. Their millimolar solutions in C6H5NO2, CH3NO2 and CH3CN are non-conducting. IR spectra, magnetic susceptibility and some other properties have been investigated. Both types of compounds are polymeric in nature having covalent structures.
Alternativ-Liganden, XVIII [1]: Neue Komplexe M(CO)3L mit Tripodliganden des Typs RSi(OCH2EMe2)3 (M = Cr, Mo, W; R = Me, Ph; E = P, As) / Alternative Ligands, XVIII [1]: Novel Complexes M(CO)3L with Tripod Ligands of the Type RSi(OCH2EMe2)3 (M = Cr, Mo, W; R = M e, Ph; E = P, As)
Authors: Grobe Joseph , Le Van Norbert Krummen und Duc
Published: February 2015

Tripod ligands of the type RSi(OCH2EMe2)3 (R = Me, Ph; E = P, As) (compounds 3a, b and 4a, b) have been prepared by reacting RSiCl3 with Me2ECH2OH (2a, b) in the presence of NMe3. 2a, b are obtained from Me2EH (1a , b) and paraformaldehyde. Replacement of the cycloheptatriene ligand in M(CO)3CHT com pounds (M = Cr, Mo, W) yields the new complexes fac-M(CO)3[RSi(OCH 2EMe2)3] (5a, b-10a, b). The ligand properties of 3a, b and 4a, b have been studied by determining the effects of coordination on the spectroscopic data (νco , 1H, 31P NMR).
Über bicyclische Acyloxyfluoroborane 1.5-Difluoro-3.7-dialkyl-2.4.6.8.9-pentaoxa-1.5-diborabicyclo(3.3.1)nonadiene: Darstellung, Molekül- und Kristallstruktur / New Bicyclic Acyloxyfluoroboranes 1.5-Difluoro-3.7-dialkyl-2.4.6.8.9-pentaoxa-1.5-diborabicyclo(3.3.1)nonadienes: Synthesis, Molecular and Crystal Structure
Authors: Binder Herbert , Matheis Walter , Deiseroth Hans-Jörg , Fu-Son Han
Published: February 2015

Trimeric alkoxydifluoroboranes (F2BOR), react with carboxylic acid anhydrides to form bicyclic acyloxyfluoroboranes of the 1.5-difluoro-3.7-dialkyl-2.4 .6 .8 .9-pentaoxa-1.5-diborabicyclo- (3.3.1)nonadiene type. A X-ray crystal structure determ ination of 6a is reported.
Darstellung und Eigenschaften von Cyclo-1λ6-metalla-3,5-ditha-2,4,6-triazenen / Synthesis and Properties of Cyclo-1λ6-metalla-3,5-dithia-2,4,6-triazenes
Authors: Anhaus Jens , Siddiqi Zafar A. , Schimkowiak Jürgen , Roesky Herbert W. , Lueken Heiko
Published: February 2015

The metallacycles [Cl3MS2N3]2 (M = Mo, W) 1a and 2a have been obtained from reactions of S4N4 with Mo2Cl10 and WCl6, respectively, and from S3N3Cl3 with the hexacarbonyls M(CO)6. The adducts Cl3MS2N3 · CH3CN 1b and 2b are formed with acetonitrile, and the salts [Ph4As+][Cl4MS2N3
-] 1c and 2c with addition of Ph4AsCl. Reactions of Mo2Cl10 and WCl6, respectively, with related S -N com pounds lead predominantly to 1a and 2a; Mo2Cl10 reacts with S3N2Cl2 to give 1a , and with [Me3SiN]2S to give [Cl3MoN]x, while WCl6 yields Cl4WNSCl with S3N2Cl2, and 2a with [Me3SiN]2S. [Cl3MoN ]x does not react with S4N4, but [Cl3WN]x forms 2a. Reactions of VCl4 and VOCl3 with [Me3SiN]2S give [Cl2V S2N3]x, 3. 2c has also been obtained by the reaction of [Ph4As+][Cl5WNSCL-] with [Me3SiN]2S. The oxidation states of the metal atoms are +6 for 1a-c and 2a-c, and +5 for 3, respectively; as determined by 51V and 95Mo NMR spectroscopy and magnetic susceptibility measurements. The UV/VIS spectra of 1b , 1c , 2b, c and 3 are discussed. The electrical conductivity of 3 is reported.
Darstellung und Röntgenstrukturanalyse eines Komplexes aus 1,3-Dioxan und Silberhexafluorarsenat — [Ag(1,3-C4H8O2)3](AsF6) / Preparation and X-Ray Structure Analysis of a Complex from 1,3-Dioxane and Silver Hexafluoroarsenate — [Ag(1,3-C4H8O2)3](AsF6)
Authors: Jones Peter G. , Roesky Herbert W. , Liebermann Johannes , Sheldrick George M.
Published: February 2015

Excess 1,3-dioxane 1 reacts with AgAsF6 2 to yield a complex [Ag(1,3 -C4H8O2)3](AsF6) 3, which was characterized by X-ray structure determination. Crystals of 3 are monoclinic, P21/n, a = 939.9(2), b = 1814.0(3), c = 1147.6(3) pm , β = 92.98(2)°, Z = 4, R = 0.049 for 2825 reflections with F > 4σ(F). 3 is a chain polymer with two bridging and one terminal dioxane ligands; Ag-O bond lengths are 242-249 pm. A weak Ag ··· F contact completes a disordered octahedral coordination at silver. No ring opening of 1 occurs on reaction with 2.
Linear GoId(I) Derivatives with Bulky Phosphine and Imidazolato Ligands. X-Ray Crystal Structure of 1-(C6H11)3PAu-2-i-Pr-Imidazole · C6H6
Authors: Bovio Bruna , Bonati Flavio , Burini Alfredo , Pietroni Bianca Rosa
Published: February 2015

By reaction of a 1-unsubstituted imidazole (im H) with alkali and R3′PAuCl under phase transfer conditions or in MeOH solution R3′PAu (im-N) compounds were obtained where R′ = C6H11 or t-Bu, and imH was imidazole, 2-i-Pr-, 4-NO2-imidazole or benzimidazole. When the Ph3Sb (or Ph3As) homologue was reacted, polymeric [μ-(2-methylimidazolato-N,N′)gold(I)]n was obtained, together with (Ph3Sb)2AuCl.

The X-ray crystal structure of 1-[(C6H11)3PAu]-2-i-Pr-imidazole confirmed that the gold atom is linearly coordinated (177.0(1)°), with Au - N 2.019(5) and Au -P 2.255(2) Å .
On the Circumambulatory Rearangement of Cyclopentadienylphosphanes — Retention versus Inversion at the Migration Phosphorus
Authors: Schoeller Wolfgang W.
Published: February 2015

According to a quantum chemical analysis based on energy optimized MNDO calculations the 1.5-sigmatropic reaction of cyclopentadienylphosphanes can occur via a transition state either with retention or inversion of configuration at phosphorus, depending on the ligands within the PR2 fragment. Electropositive R favour inversion and electronegative R retention of configuration at phosphorus. In addition, given the same ligand R, retention (over inversion) comes to the fore with increasing atomic number of the central atom at the MR2 unit, i.e. in the order M = N < P < As < Sb.
Ein Beitrag zum Mechanismus der singulett-angeregten Photo-Isomerisierung des Homofulven-Systems / On the Mechanism of the Singulet Excited Photo-Isomerization of the Homofulvene System
Authors: Brune Hans-Albert , Lach Peter , Schmidtberg Günter
Published: February 2015

Syntheses of the four at the cyclopropane part alkyl-substituted homofulvenes 6-endo-Ethyl-1,2,3,5-tetramethyl-4-methylenebicyclo[3.1.0]hex-2-ene (endo-1a), 6-exo-Ethyl-1,2,3,5-tetramethyl-4-methylenebicyclo[3.1.0]hex-2-ene (exo-1a), 6-ercdo-Isopropyl-1,2,3,5-tetramethyl- 4-methylenebicyclo[3.1.0]hex-2-ene (endo-1b) and 6-exo-Isopropyl-1,2,3,5-tetramethyl-4-methylenebicyclo[ 3.1.0]hex-2-ene (exo-1b) are reported. Following singulet excitation endo-1a, endo-1b and exo-1b underwent photo-isomerization to 6-Ethyl-1,2,3,4-tetramethyl-5-methylenecyclohexa- 1,3-diene (2a) and 6-Isopropyl-1,2,3,4-tetramethyl-5-methylenecyclohexa-1,3-diene (2b) resp. It is demonstrated, that C-6 - the top of the cyclopropane ring in 1 - is transferred to C-6 - adjacent to the exo-methylene substituent - in the 5-methylenecyclohexa-1,3-diene system 2. A mechanism is suggested.
The Electron Spectra of a Blue S-Tetrazine Derived Betaine and its Protonated Forms A Comparison with the Radical Anion 1,5-Dimethyl-5-oxoverdazyl-3-olate
Authors: Vogler Helmut , Neugebauer Franz A .
Published: February 2015

The striking similarities of the hypsochromic shifts of the longest wavelength absorption observed in the serie 1-3 and 4 -6 are rationalized by means of simple molecular orbital theory.
Die Belousov-Zhabotinskii-Reaktion mit Ascorbinsäure / The Belousov-Zhabotinskii Reaction of Ascorbic Acid
Authors: Blume Rüdiger , Bader Hans Joachim
Published: February 2015

In small ranges of concentration ascorbic acid yields oscillations in the Belousov-Zhabotinskiitype reaction [substrate/bromate/cerium (sulfuric acid)]. During the reaction ascorbic acid is oxidized and decomposed. The oxidation respectively bromination of the resulting compounds, as oxalic acid, threonic acid, glyceric acid and pyruvic acid, also leeds to oscillatory chemical reactions in the same range of concentration as ascorbic acid.
Improved Preparation of 5,6-Dialkoxy-1,1-dimethylindenes, Precocene Analogues Lacking the Pyranyl Oxygen Atom [1]
Authors: Camps F. , Coll J. , Colomina O. , Messeguer A .
Published: February 2015

The use of methanesulfonic acid as solvent and catalyst in the cyclocondensation of 1,2-dialkoxybenzenes with 3-methylbut-2-enoyl chloride to afford indanones 3, thus allowing the preparation of indenes 4 with improved overall yields, is reported. Additionally, structure of dimeric compound 7 a, formed in high yield by thermal treatment of 4a has been determined by com bination of spectroscopic means and selective deuterations.
Elektronenreiche Olefine, 8 [1] Unsymmetrisch substituierte elektronenreiche Olefine mit 1.3-Dithiol-2-yliden, Benzthiazolin-2-yliden-, Benzselenazolin-2-ylidenund 1.3.4-Thiadiazolin-2-yliden-Einheiten / Electron-rich Olefins, 8 [1] Unsymmetrically Substituted Electron-rich Olefins with 1.3-D ithiol-2-yliden-, Benzthiazolin-2-yliden-, Benzselenazolin-2-ylidenand 1.3.4-Thiadiazolin-2-yliden-Units
Authors: Krasuski Witold , Regitz Manfred
Published: February 2015

2-(1-Piperidinyl)-1.3-dithioles (6a-c) can be condensed with benzthiazolium- and benzselenazolium perchlorates (7a-d) to the electron-rich olefines 8a-i. By the same synthetic principle the 2-(3.5-diaryl-Δ4-1.3.4-thiadiazolin-2-yliden)-1.3-dithioles 10a-e such as the unsymmetrically substituted bis(3.5-diaryl-Δ4-1.3.4-thiadiazolin-2-ylidenes) (12a-d) are acessible. The olefines 8c and h undergo [2 + 2]-cycloaddition reaction to form the cyclobutenes 16a-d, which isomerize spontaneously by electrocyclic ring opening to the 1.3-butadienes 17a-d.
Kaempferol 3-O-[β-D-Glucopyranosyl(1-2)β-D-galactopyranoside], a New Flavonoid from Lilium candidum L.
Authors: Nagy E. , Seres I. , Petri G . Verzár- , Neszmélyi A.
Published: February 2015

From perianth of Lilium candidum L. a new flavonoid, lilyn has been isolated by column chromatography and identified by 1H and 13C NMR spectroscopy as 3-O-[β-D-glucopyranosyl (1-2)β-D-galactopyranoside]-kaempferol.
Neue zweikernige Pd-Komplexe mit Organophosphorliganden / Novel Dinuclear Complexes of Pd with Phosphorus Ligands
Authors: Fenske Dieter , Bensmann Walter
Published: February 2015

Pd(PPh3)4 reacts with [2.3-bis(diphenylphosphino)- N-methylmaleimide]-palladium (II) chloride to form new dinuclear Pd-complexes. The structures were studied by X-ray crystal structure analysis.
Reduction of Carbonyl Compounds by Catalytic Hydrogen Transfer from 1,4-Butanediol
Authors: Marčec Radovan
Published: February 2015

Hydrogen transfer from appropriate hydrogen donors to unsaturated substrates catalysed by transition metal complexes offers some advantages over hydrogenation with molecular hydrogen [1], These reactions have been carried out mainly with stoichiometric or excess amounts o f primary or secondary alcohols [2-7], hydroaromatic com pounds [8] and formic acid [9] as hydrogen donors.

Although bis primary diols exhibit relatively high propensity for hydrogen donation [10, 11], little attention has been paid to the em ployment of these com pounds as the source of hydrogen in hydrogenation reactions. The aim of the present investigation was to examine the potential use of 1,4-butanediol as the source of hydrogen in the catalytic reduction of carbonyl com pounds, using ruthenium (II) complexes as homogeneous catalysts.
Ein neues Peptidalkaloid aus Discaria febrifuga Mart / A New Peptide Alkaloid from Discaria febrifuga Mart
Authors: Morel Ademir , Herzog Rolf , Biermann Jakob , Voelter Wolfgang
Published: February 2015

On the basis of spectroscopic investigations (1H NMR, UV , IR and MS spectroscopy), elemental analysis and degradation reaction the structure of a new alkaloid, discarine F, from the bark extract of Discaria febrifuga Mart is elucidated.
Hierarchical Structure of Slow Manifolds of Reacting Flows
Authors: Bykov Viatcheslav , Neagos Alexander , Klimenko Alexander , Maas Ulrich
Published: February 2015

Nowadays the mathematical description of chemically reacting flows
uses very often reaction mechanisms with far above hundred or even
thousand chemical species (and, therefore, a large number of partial
differential equations must be solved), which possibly react within
more than a thousand of elementary reactions. These chemical kinetic
processes cover time scales from nanoseconds to seconds. An analogous
scaling problem arises for the length scales. Due to these scaling
problems the detailed simulation of three-dimensional turbulent flows
in practical systems is beyond the capacity of even today's
super-computers. Using simplified sub-models is a way out of this
problem. The question arising in mathematical modeling of reacting
flows is then: How detailed, or down to which scale has each process
to be resolved (chemical reaction, chemistry-turbulence-interaction,
molecular transport processes) in order to allow a reliable
description of the entire process. Both the chemical source term and
the transport term have one important property, namely, they cause the
existence of low-dimensional attractors in composition space. When
these manifolds can be constructed (described) and parametrized by
a small number of variables, it can be used to reformulate and reduce
the mathematical description for modeling reacting flows. In this work
the hierarchical nature of these low-dimensional manifolds of slow
motions is discussed. It is demonstrated how this important feature of
reacting flows is accounted for by the standard model reduction
methods (like e.g. PEA and QSSA methods) as well as by recently
developed concepts of model reduction. The use of the hierarchical
nature for identification of the low-dimensional manifolds to devise
hierarchical modeling concepts (e.g. for turbulent reacting flows) is
additionally discussed.