bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Complexes of Cyclophanes, Part XVI On the Donor Properties of Polynuclear Paracyclophanes and their Sulfur Analogues
Authors: Mourad Aboul-fetouh E. , Hucker Joachim , Hopf Henning
Published: March 2015

Visible, 1H NMR and infrared spectra of the charge-transfer (CT) complexes of polynuclear- [2.2]paracyclophanes and their sulfur analogues as electron donors with 2,3-dichloro-5.6-dicyanobenzoquinone (DDQ ), tetracyanoethylene (TCNE) and 9-dicyanom ethylene-2,4,7-trinitrofluorene (DTF) as π-acceptors have been measured. The data indicate an unexpected high basicity of the polynuclear hydrocarbons relative to their sulfur analogues. The types of CT interactions as well as different factors governing the stability of the CT complexes studied are discussed. The effect of temperature on the CT complexes studied are discussed. The effect of temperature on the CT complexes with TCNE is reported.
Synthese und Eigenschaften von 3-Alkoxy(hydroxy)thiazolidin-2,4-dionen / Synthesis and Properties of 3-Alkoxy(hydroxy)thiazolidin-2,4-diones
Authors: Geffken Detlef
Published: March 2015

The reaction of 2-mercaptocarboxylic acids (3 B ) or methyl thioglycolates (3 A ) with 1.1'-carbonyldiimidazole and alkoxyamines produces 3-alkoxythiazolidin-2,4-diones (5). Acid catalyzed methanolysis of the tetrahydropyranyloxy group affords the cyclic N-hydroxy imides (6) which can easily be acylated with 3-chlorophenylisocyanate or dimethylcarbamoyl chloride to give compounds of type 7 or 8.
1.6-Diaminohexan als Schablonenverbindung in der Synthese von Zeolith ZSM-5 / 1.6-Diaminohexane as Template in the Synthesis of Zeolite ZSM-5
Authors: Lermer H. , Unger K. K.
Published: March 2015

A mixture characterized by the molar ratios of H2O/SiO2 = 20, SiO2/Al2O3, = 120, Na2O/SiO2 = 0.3 and 1.6 diaminohexane (DAH) as template was reacted at 182 °C. Dependent on the reaction time, the ratio of OH- /SiO2 and DAH/SiO2 ZSM-5 was crystallised with α-quartz as by-product. The materials were characterized by X-ray diffraction, scanning electron microscopy, infrared spectroscopy, thermogravimetry and differential thermal gravimetry.
Sr3GaSb3 und Sr3InP3, zwei neue Zintlphasen mit komplexen Anionen / Sr3GaSb3 and Sr3InP3, Two New Zintl Phases with Complex Anions
Authors: Cordier Gerhard , Schäfer Herbert , Stelter Michael
Published: March 2015

The new compound Sr3GaSb3 crystallizes in the monoclinic system, space group P21/n (No. 14) with the lattice constants: a = 1176.2(4) pm, b = 1450.9(5) pm, c = 1174.9(4) pm, β = 110.0(1)°. In the structure distorted GaSb4 tetrahedra are connected by common corners, to give strands with groups of four tetrahedra as the repeating unit. The new compound Sr3InP, crystallizes in the orthorhombic system, space group Pnma (No. 62) with the lattice constants: a = 1280.9(5) pm, b = 433.0(2) pm, c =1386.6(5) pm. In the structure distorted InP4 tetrahedra are connected by common corners, to give strands with one tetrahedron as the repeating unit. Both compounds are Zintl phases.
Vibronische Kopplung und dynamisch verzerrte Strukturen in Hexahalogenotelluraten(IV): Ergebnisse aus Tieftemperatur-Röntgenbeugungsuntersuchungen (300—160 K) und aus FTIR-spektroskopischen Experimenten (300—5 K) [1] / Vibronic Coupling and Dynamically Distorted Structures in Hexahalogenotellurates(IV): Low Temperatur X-Ray Diffraction (300—160 K) and FTIR-Spectroscopic (300—5 K) Results [1]
Authors: Abriel Walter , Zehnder Ernst-Jürgen
Published: March 2015

From theoretical considerations a dynamically distorted octahedron as a result of vibronic coupling between the ground state and the first excited state should exist for 14 electron AX6E systems like TeX6
2- . A high symmetry crystal field yielding at least a center of symmetry for the Te position stabilizes this fluctuating structure, otherwise statical distortion will be observed. From X-ray diffraction experiments on antifluorite type compounds A2TeX6 (A = Rb. Cs: X = Cl, Br) the averaged structure (m3̅m symmetry) of the anions was found even at very low temperatures. The thermal parameters are not significantly different from those of similar SnX6
2 compounds. Distortions therefore are very small and are evident from FTIR spectroscopic meas­urements only. Here very broad T1u-deformation vibration bands are observed down to tempera­tures <10 K without splitting: Astatically distorted species could not be frozen out. In contrast to XeF6 for TeX6
2- the energy gap between the threefold, fourfold or sixfold minima of the potential surface (according to the symmetry of one component of the T1u-vibration) is very small and shifted to temperatures lower than reached with the devices used for these experiments.
Synthesis and Structural Systematics of First-Row Transition Metal Complexes with 2-[Bis(benzimidazol-2-ylmethyl)amino]ethanol
Authors: Takahashi Kazuhiro , Nishida Yuzo
Published: March 2015

A nickel(II) complex with (bbimae) (= 2-[bis(benzimidazol-2-ylmethyl)amino]ethanol), [Ni(bbimae)(NCS)2] · H2O (1) and an oxovanadium(IV) complex, [VO(bbimae)(NCS)2] · dma (dma = N.N-dimethylacetamide) (2) have been prepared and their crystal structures determined by X-ray diffraction. Crystal data for 1 at 293 K: a = 13.334(2). b = 17.048(2), c = 10.3829(9) Å, space group P212121, Z = 4, and dcalcd = 1.41 gcm-3. Crystal data for 2 at 293 K: a = 14.099(2). b = 14.998(4), c = 14.051(2) Å, β = 107.634(9)°, space group P21/c, Z = 4, and dcalcd = 1.36 gcm-3. In the nickel(II) complex, (bbimae) functions as a tetradentate ligand, and the geometry around Ni(II) ion is best described as distorted octahedral. The structure is very similar to those of the correspond­ing Co(II) and Mn(II) complexes. In the case of 2, which is also distorted octahedral, (bbimae) is a tridentate ligand without the coordination of the alcohol group. The M-N (benzimidazole) distances are in the range of 1.95-2.18 Å, and also observed for other first-row transition metal complexes with (bbimae). and differ in the order V(IV) < Mn(II) > Co(II) > Ni(II) > Cu(II). consistent with effective ionic radii of the metal ions. Comparison of the structural parameters of these complexes with those of the metal ions in biological systems has supported the usefulness of the tripod-like ligands to synthesis model compounds for biological systems.
Chemie an starren Grenzflächen, 8. [1] Kinetik der Heterogenumsetzung kovalent über Spacer an Aerosil gebundener Aminogruppen (Aminoaerosil) mit homogen gelösten Isothiocyanaten / Chemistry on Rigid Interfaces, 8 . [1] Kinetics of Suspensions of Aminoaerosil (Aerosil Covalently Linked with 3-Aminopropylgroups) with Isothiocyanates in Homogeneous Solution
Authors: Horner L. , Roth W.
Published: March 2015

In aminoaerosil, the products of the reaction of γ-aminopropyltriethoxysilane with aerosil. an intraparticular interaction of the basic amino groups with the acidic silanol groups is observed. This behaviour was established a) by adsorption experiments using n-butylamine on aerosil. resp. aminoaerosil of different support density, and b) by microcalorimetric determination of the adsorption energy of acetonitrile using aerosil and aminoaerosils of different support density as substrates.

Aminoaerosils react with isothiocyanates according to (I) with formation of covalently linked thiourea groups. Fig. 3 and Fig. 5 (with trimethylamino) show the time-turnover curves of aminoaerosils of different support density with phenylisothiocyanate. The influence of the tem­perature on the thiourea formation is demonstrated in Table III. Depending on the polarity and the size of the ligands R. the isothiocyanates react with different reaction rates with aminoaerosil (Fig. 6). Aminoaerosils with different coverage density, but with an equal molarity of amino groups and varying specific surfaces, react non-uniformly with phenylisothiocyanate (Table IV).

The comparison of the reaction of phenylisothiocyanates a) with heterogeneously by suspended aminoaerosil and b) with n-butylamine in homogeneous solution, both with equal molar amounts of NH2, shows characteristic differences (Fig. 8).

The amount of the covalently linked NH2-groups in aminoaerosils can be determined using Sanger’s reagent.
Purification and Partial Characterization of Rat Liver Lipoxygenase
Authors: Macias Pedro , Pinto M. Carmen
Published: March 2015

Lipoxygenase was purified from rat liver cytosolic fraction by a method involving two successive chromatographic steps on Sephacryl S-200 and Phenyl Sepharose CL-4B. The enzyme has a molecular weight of 96 Kdal and it seems to be composed of two identical subunits. Chromatofocusing of the enzyme revealed a single band of activity at pi 6.3. The enzyme activity of the purified fraction showed maximum activity at pH 7.0 with a Km for linoleic acid of 1.4 μM and is competitively inhibited by the specific lipoxygenase inhibitor nordihydroguaiaretic acid. The purified enzyme shows absorption and fluorescence spectra similar to those of lipoxygenase from other sources. However, the molecular weight of lipoxygenase purified from liver is found to be different from that of the enzyme from polymorphonuclear leukocytes. It is suggested that there are different isoenzymes of lipoxygenases in mammals.
The Space Group of Sodium Nickel Arsenate, NaNiAs04
Authors: Jones Peter G. , Range Klaus-Jürgen , Meister Helmut
Published: March 2015

Abstract The correct space group of NaNiAsO4 is R3̅ and not R3 as previously reported
Darstellung und Charakterisierung des Zwitterions S2C—C(NMe2)2; eine übergangsmetallinduzierte C—C-Kopplung. Komplexchemie der Zwitterionen S2C—C(NR2)2 / Synthesis and Characterization of the Zwitter Ion S2C —C(NMe2)2; a Transition Metal Induced C —C Coupling. Complex Chemistry of the Zwitter Ions S2C —C(NR2)2
Authors: Ziegler Manfred L. , Weber Hannelore , Nuber Bernhard , Serhadle Orhan
Published: March 2015

A transition metal induced C-C coupling by the reaction of W2(N(CH3)2)6, (4) and CS2 yielded the zwitter ion S2C-C(N(CH3)2)2 (1d) besides W2(N(CH3)2)2(CS2)2S4 (5). The com- plex chemistry of the zwitter ions 1d and S2CC(N(CH2)4X)2 (X = CH2, O) has been investigated by their reaction with (η5-C5H5)2Mo2(CO)4 (2) and (η5-C5H5)Mo(CO)3Cl (3). Reaction of the former led to complexes (η5-C5H5)Mo(CO)2(S2CR) (R = N(CH3)2, N(CH2)4X) and the new compounds [(η5-C5H5)Mo(CO)2(S2C-CR2)]+. X-ray structure analyses of 1d and ((η5-C5H5)Mo(CO)2(S2C-C(N(CH2)5)2)]⊕PF6
⊖ (10b) are described.
Übergangsmetallkomplexe von Diazenen, XXIV [1]. Komplexierung und N=N-Spaltung von Diazenen durch Dicarbonylbis(cyclopentadienyl)titan / Transition Metal Complexes of Diazenes, XXIV [1] Complexation and N = N-Cleavage of Diazenes by Dicarbonylbis(cyclopentadienyl)titanium
Authors: Avar G. , Rüsseler W. , Kisch H.
Published: March 2015

Reaction of Cp2Ti(CO)2, Cp=h5-C5H5, with the 1,2-diazenes ROCN = NCOR (R = EtO (1a), tert-BuO (1b), p-MeC6H4O (1c), p-MeC6H4 (1d)) in the molar ratio of 1:1 yiclds five- membered metallacycles 2 by formal 1,4-addition of 1 to the Cp2Ti fragment. When a two-fold excess of Cp2Ti(CO)2 is employed, the initially formed 2 reacts further by N = N-cleavage to give Cp2Ti(NCO)(OR), Cp2Ti(NCO)2 and Cp2Ti(OR)2 resp., in the case of 1a-1c. The bis(p-methyl- benzoyI)diazene (1d) does not afford analogous cleavage products. Dimethyl- and pentamethy- lenediazirine also react by cleavage of the N = N-bond to afford Cp2Ti(NCO)(N=CR2).
Synthesis and Structure of a New 1,5-Anhydro-hex-2-enitol
Authors: Csuk René , Glänzer Brigitte I. , Kratky Christoph , Wagner Ulrike
Published: March 2015

Treatment of methyl 4,6-O-benzylidene-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside with sodium cyanoborohydride/hydrogen chloride gives rise to a very convenient approach of 1,5-anhydro-6-O-benzyl-2,3-dideoxy-D-erythro-hex-2-enitol (2), envisaged to be a precursor for both α-D- and β-L-glycosyl compounds in the pentopyranosyl series. An X-ray analysis revealed 2 to be of space group P21 and to adopt an OH5-conformation.
Carnivora: The Primary Structures of Adult Lion (Panthern leo) Hemoglobins
Authors: Jahan Meeno , Ahmed Aftab , Braunitzer Gerhard , Zaidi Zafar H. , Göltenboth Reinhard
Published: March 2015

Complete amino acid sequences of lion (Panthera leo) hemoglobins are reported. Polyacrylamide gel disc electrophoresis at pH 8.3 and also in the presence of 8 M urea and Triton-X100, RP-HPLC, liquid and gas phase amino acid sequenator. and FAB Mass spectrometer are used. Sequences are aligned with human hemoglobin (Hb A ) and compared with other hemoglobins of felidae.
Biosynthesis of Withanolides in Acnistus breviflorus Chemical Degradation of 14C-Labelled Jaborosalactone A and Withaferin A
Authors: Monteagudo Edith S. , Veleiro Adriana S. , Burton Gerardo , Gros Eduardo G.
Published: March 2015

Administration of [2-14C]mevalonolactone to excised leaves of Acnistus breviflorus produced labelled withaferin A and jaborosalactone A. Degradation of the labelled withanolides allowed isolation of C-26, and in the case of withaferin A of C-1, both derived from C-2 of mevalonolactone. The relative specific activity of these carbon atoms was consistent with our previous results indicating the partial cleavage of the side chain of a sterol precursor in the biosynthetic process leading to the withanolides.
Wirkung von Glia-Maturationsfaktor (GMF) und Adhäsionsfaktor (ADF) auf Kulturen leukämischer Zellen / Effect of Glia Maturation Factor (GMF) and Adhesion Factor (ADF) on Cultures of Leukaemic Cells
Authors: Busse E.
Published: March 2015

GMF was isolated from the glia of different brain parts of calf. Its influence on the input of 3H-TdR was tested in leukaemic and non-malignant lymphocites. GMF isolated from the diencephalon proved to be the most effective one. The used substance of reference was DBcAMP. The cAMP contents of leukaemic cells were lower than those of non-malignant cells, whereas the level of cGMP was higher in the first ones. We found both in non-malignant cultures and in cultures of leukaemic cells that the impact of GMF and AdF elevated the cAMP value and reduced cGMP. The adhesion of cAMP to the nuclei of leukaemic was reduced in comparison with non-malignant cells. The nuclei of leukaemic cells showed increased adhesive capacity after pre-incubation with GMF and AdF. The adhesive capacity of non-malignant nuclei remained unchanged. The adenylcyclase activity (AC) was diminished in leukaemic cells. It could not be stimulated by means of catecholamines. GMF and AdF produced a slight increase of the basal Ac activity in cultures of leukaemic cells only. But isoproterenol led to a distinct increase of the Ac activity in leukaemic cells when incubation with those two factors preceded it.
The Structure of the Tetraphenyldithioimidodiphosphinate Ion
Authors: Cea-Olivares Raymundo , Nöth Heinrich
Published: March 2015

The potassium 18-crown-6 ether salt of the title anion has been prepared. It crystallizes in the monoclinic system, space group C2/c, with four molecules in the unit cell. The anion possesses a crystallographically imposed C2 symmetry. The PN bond length of the anion is shorter and the PS bond longer than in the neutral molecule [Ph2P(S)]2NH , while the PNP bond angles are essentially the same.
Anwendung der 15N-NMR-Spektroskopie zur Charakterisierung reaktiver, koordinativ ungesättigter Zinn-, Bleiund Phosphor-Stickstoff-Verbindungen / Application of 15N-NMR Spectroscopy to the Characterization of Reactive, Coordinatively Unsaturated Tin-, Lead- and Phosphorus-Nitrogen Compounds
Authors: Stader Carin , Wrackmeyer Bernd
Published: March 2015

The basic INEPT pulse sequence proved most useful for recording 15N NMR spectra at natural abundance of bis(amino)stannvlenes (1). -plumbylenes (2) and of imino-amino-λ2-phosphanes (3), where the nitrogen atoms carry bulky substituents like Me3Si-, t-Bu-, 2.4.4-trimethyl-2- pentyl-groups (t-Oct-groups) or are part of the 2.2.6.6-tetramethylpiperidinyl group. The sensitiv­ity of this technique is proved by the observation of 117/119Sn or 207Pb satellites owing to spin-spin coupling constants 1J(117/119Sn15N) and 1J(117/119Pb15N), respectively. NMR data of bis[bis(trimethylsilyl)methyl]tin (4) are reported in order to corroborate the arguments for the interpretation of the δ(15N) and 1J(119Sn15N) data. The 15N NMR data of the λ2-phosphanes (3) indicate a bonding situation similar to that in triazenes.
Synthese einer chiralen Thienamycin-Vorstufe / Synthesis of a Chiral Thienamycine Intermediate
Authors: Martin Hubert , Herrmann Rudolf , Ugi Ivar
Published: March 2015

A key intermediate of Kametani’s total synthesis of racemic thienamycine has now been prepared in chiral form via a 1.3-dipolar cycloadduct of a chiral nitrone and benzyl crotonate.
μ-Nitridokomplexe von Wolfram(V) / μ-Nitrido Complexes of Tungsten(V)
Authors: Fenske Dieter , Godemeyer Thomas , Dehnicke Kurt
Published: March 2015

W2NCl7 has been prepared by the reaction of tungsten pentachloride with the bromide of Millon's base, [Hg2N]Br, in boiling CCl4. The product forms a dark brown, moisture sensitive crystal powder (μeff = 0.7 B.M. at 21 °C). With phosphoryl chloride, the complex W2NCl7·2 POCl3 is formed. The reaction with chlorine leads to the mixed-valenced W(V)/W(VI) complex W2NCl8 (μeff = 0.5 B.M. at 22 °C), which reacts with tetraphenylphosphonium chloride in CH2Cl2 to form (PPh4)2[W2NCl10] ·2CH2Cl2. The reactions of W2NCl7 with PPh4Cl in molar ratios in CH2Cl2 solution lead to several complexes; one of them was identified bv X-ray diffraction methods to be (PPh4)2[W3Cl9(μ3-N)(0)(μ2-NCl)]2 ·1,5 CH2Cl2, which forms black crystals. The compound crystallizes monoclinically in the space group P21/n with two formula units per unit cell (7318 observed, independent reflexions, R = 0.083). The lattice dimensions are (20 °C): a = 994.4; b = 2673; c = 1518.2 pm; β = 101.00°. The compound consists of PPh4
⊕ cations and centrosymmetric anions [W3Cl9(μ3-N)(O)(μ2-NCl)]2
2⊕. The tungsten atoms form a scalene triangle with WW bond lengths of 282 and 278 pm, respectively. The hypothenuse of this triangle is a nearly linear W - N -W bridge with WN distances of 199 and 182 pm. One of the WW edges is bridged by a μ-NCI group with WN bond lengths of 196 und 189 pm. respectively.
Lineare Oligophosphaalkane, XX [1]: Alkalimetall-und Trimethylsilylderivate PH-funktioneller Methylenbisphosphane / Linear Oligophosphaalkanes, XX [1]: Alkali Metal and Trimethylsilyl Derivatives of PH-Functional Methylenebisphosphanes
Authors: Gol Franjo , Hasselkuß Gerd , Knüppel Peter C. , Stelzer Othmar
Published: March 2015

The synthesis of the trimethylsilyl derivatives of the PH-functional methylenebisphosphanes, R2-n(Me3 Si)nP-CH2 -PR(SiMe3) (R = Me, iPr, tBu, Ph, 2.4.6-Me3C6H2 ; n = 0.1) is reported. In the Li-phosphides R2-nLinP - CH2 - PLiR used as reactive intermediates, a monomer-oligomer association equilibrium causes a rapid Li-exchange as indicated by the solvent and temperature dependent 31P{1H} and 7Li NMR spectrum of (iPr)2 P-CH2 -P(iPr)Li in various solvents (Et2O, THF and MTHF) in the temperature range from 30 to -110 °C. For the syntheses of the Me-and Ph-substituted PH-functional methylenebisphosphanes R2P-CH2 -PRH and RHP-CH2 -PRH (R = Me, Ph) the chlorophosphane CKP -CH2 -PCl2 is used as a starting material. Bifunctional substituents (Ph -N̍-N̍ -Ph and Me -N̍-CO-N̍-Me) are employed for the first time as protecting groups to block one or two PCl-functions in Cl2P-CH2-PCI2,. Cleavage of the PN-bonds in the five membered ring systems

(R = Me, Ph) with HCl affords the P-substituted methylenebis-chlorophosphanes RClP-CH2 - PClR in satisfactory yields.

The compounds have been characterized by 1H, 13 C{1H} and 31P{1H} NMR spectroscopy. With-in homologous substitution series of methylenebisphosphanes, e.g. R2P-CH2-PR2-nHnthe coupling constants 2J(PP) seem to reflect conformational changes at the PCP-skeleton.
Synthese und Kristallstruktur von t-Butyloxyzinn(II)chlorid / Synthesis and Crystal Structure of t-Butyloxytin(II) Chloride
Authors: Zybill Chr. , G. Müller G.
Published: March 2015

t-Butyloxytin(II) chloride (1) is prepared from SnCl2 and KO-z-Bu at -60 °C in tetrahydrofuran. Above -30 °C a reversible dismutation into SnCl2 and [(t-BuO)2Sn] is observed in THF. For this process Δ G = +38 kJ/mol is estimated from NMR data. Compound 1 is a centrosymmetric dimer in the solid state with bridging O atoms (Sn-O 2.153(2)/2.156(2) Å, O-Sn-O 73.0(1)°, Sn-O-Sn 107.0(1)°). Due to the acute intraring bond angles at Sn. the O···O distance across the four-membered ring is relatively short (2.563(3) Å). The dimers are very loosely connected to chains by bridging THF molecules.
Synthese und Eigenschaften einiger Silylethinylsilane; Molekülstruktur von Tetrakis(trimethylsilylethinyl)silan / Synthesis and Properties of Some Silylethynylsilane; Molecular Structure of Tetrakis(trimethylsilylethynyl)silane
Authors: Schmidbaur Hubert , Ebenhöch Jan
Published: March 2015

Trimethylsilylethine (1) has been prepared from C2H2, sodium and Me3SiCl in anisole. The product can be converted into a Grignard reagent Me3SiC≡CMgCl using iPrMgCl. This reagent yields the compounds Me3SiC≡CSiH3, (Me3SiC≡C)2SiH2, (Me3SiC≡C)3SiH, and (Me3SiC≡C)4Si (2-5) when treated with equivalent amounts of H3SiBr, H2SiBr2, HSiCl3, or SiCl4. respectively. The new silanes have been characterized by NMR data. The crystal structure of (Me3SiC≡C)4Si has been determined by single crystal X-ray diffraction. It shows the expected tetrahedral geometry at he central silicon atom with four linear SiC≡CSi linkages.
Synthese, Eigenschaften und Struktur neuer 1,1-Diphosphonsäuren / Synthesis, Properties and Structure of New 1,1-Diphosphonic Acids
Authors: Blum Helmut
Published: March 2015

The synthesis of 3-tert-alkyl-3-oxo-1-arninopropane-1,1-diphosphonic acids and of 3-tert-alkyl-3-oxo-prop-1-ene-1,1-diphosphonic acids as two new groups of metal complexing agents and their chemical properties are described. Evidence is given for their suggested structures. In addition, the first known example of a diphosphonic acid with a cyano group attached to the geminal carbon atom was prepared from 3-oxo-1-aminoalkane-1,1-diphosphonic acids and 3-terr-alkyl-3-oxo-1-hydroxypropane-1,1-diphosphonic acids from 3-oxo-1-aminopropane-1,1-diphosphonic acids.
Struktur und Schwingungsspektrum des Kaliumundecawolframats Kg6H4W11O38· 11H2O / Structure and Vibrational Spectrum of the Potassium Undecatungstate K6H4WnO38 -11 H2O
Authors: Lehmann Thomas , Fuchs Joachim
Published: March 2015

The title compound crystallizes in the triclinic space group P1̅ with lattice parameters a = 13.129 Å, b = 14.156 Å, c = 14.843 Å and α= 88.34°, β = 74.43°, γ = 70.86°. The polyanion evidently is the predominant species in pseudometatungstate phases the exact composition of which has not previously been determined.
Die Kristallstrukturen von Ph3PNPh, [Ph3PN(H)Ph][AuI2] und von 2,3-Bis(triphenylphosphoranimino)maleinsäure-N-methylimid / The Crystal Structures of Ph3PNPh, [Ph3PN(H)Ph][AuI2] and of 2,3-Bis(triphenylphosphoranimino)maleic Acid-N-methylimide
Authors: Böhm Eberhard , Dehnicke Kurt , Beck Johannes , Hiller Wolfgang , Strähle Joachim , Maurer Andreas , Fenske Dieter
Published: March 2015

[Ph3PN(H)Ph][AuI2] (2) is formed by the reaction of AuI with N-Phenyl-iminotriphenylphosphorane, Ph3PNPh in a toluene suspension. 2,3-Bis(triphenylphosphinimino)maleic acid-N-methylimide (3) has been prepared by the Staudinger reaction of 2,3-bis(azido)maleic acid-N-methylimide with PPh3 in THF solution in the form of red crystals. Crystal structure determinations of three iminophosphoranes were carried out by X-ray methods.

Ph3PNPh (1): space group P21/c, Z = 4, 2176 independent observed reflexions, R = 0.057. Lattice dimensions (-30 °C): a = 1126.4, b = 1148.6, c = 1476.0 pm; β = 97.21°. The compound forms monomeric molecules with P=N = 160.2 pm and an PNC angle of 130.4°.

[Ph3PN(H)Ph][AuI2] (2): space group P1̄, Z = 2, 1780 independent observed reflexions, R = 0.057. Lattice dimensions (18 °C); a = 824.9, b = 1022, c = 1476.2 pm; α = 89.23°, β = 87.41°, γ = 85.65°. The compound consists of ions [Ph3PN(H)Ph]⊕ with P=N = 162.4 pm and PNC = 129.3°, and anions [AuI2]⊖ with Au-I = 261.9 and 259.3 pm, IAuI = 176.8°.

(Ph3P)2N2C4O2 (NMe) (3): space group P1̄, Z = 2, 4972 independent observed reflexions, R = 0.050. Lattice dimensions (-90 °C): a = 904.7, b = 993.8, c = 2017.4 pm; α = 101.55°, β = 96.39°, γ = 105.81°. The compound forms monomeric molecules with syn-conformation of the two NPPh3 groups. Bond lengths: P=N = 157.1; 155.3 pm, bond angles: PNC = 133°; 136°
Synthese und Hochdruckverhalten quaternärer Chalkogenidhalogenide M2M′X3Y (M = Zn, Cd; M′ = Al, Ga, In; X = Se, Te; Y = CI, Br, I) / Synthesis and High-Pressure Behaviour of Quaternary Chalcogenide Halides M2M′X3Y (M = Zn, Cd; M′ = Al, Ga, In; X = Se, Te; Y = Cl, Br, I)
Authors: Range Klaus-Jürgen , Handrick Karin
Published: March 2015

Quaternary chalcogenide halides M2M′X3Y (M = Zn, Cd; M′ = Al, Ga, In; X = Se, Te; Y = Cl, Br, I) can be synthesized by heating stoichiometric amounts of the binary components MX. MY2, and M′2X3 in evacuated sealed quartz ampoules. In the case of aluminium and gallium compounds, a mixture of the M′ and X elements rather than the binary compounds has been used. The products are typical tetrahedral compounds, crystallizing with either the defect wurtzite-type or the defect zinc-blende-type structure. At 25 kbar, and 1400 °C, Cd2InSe3Cl, Cd2InSe3Br, and Cd2InSe3I transform from the defect wurtzite-type structure to quenchable high-pressure phases with defect NaCl-type structure. The retransformation to the ambient-pressure phases proceeds via intermediates having the defect zinc-blende-type structure. Some aspects of the apparent non-stoichiometry in the high-pressure phases are discussed
Darstellung und Kristallstruktur von [(NH3)5Rh(H7O4)Rh(NH3)5](S2O6)2,5 · H2O (1). Ein gemischtes Aquopentamminrhodium(III)-hydroxopentamminrhodium(III)- dithionat mit einer neuartigen μ-H7O4-Struktureinheit / Preparation and Crystal Structure of [(NH3)5Rh(H7O4)Rh(NH3)5](S2O6)2,5 · H2O (1). A Mixed Aquopentaamminerhodium(III)-hydroxopentaamminerhodium(III) Dithionate with a Novel μ-H7O4 Structural Unit
Authors: Frank Walter , Stetzer Thomas , Heck Ludwig
Published: March 2015

The title compound 1 can be obtained from an aqueous solution of aquopentaammine rhodium(III) dithionate and hydroxopentaammine rhodium(III) dithionate. The crystal structure has been determined from single crystal X-ray diffraction data and refined to R = 0.035 for 4390 unique reflections. Crystal data: monoclinic, space group P21/c, a = 1300.9(5) pm. b = 1472.3(6) pm. c = 1478.8(9) pm, β = 106.20(4)°, Z = 4.

In the crystal dinuclear rhodium cations with point group symmetry 1 (C1) are found. A central μ-H3O2-bridge is formed by strong hydrogen bonding between aquo and hydroxo ligands; this bridge is additionally coordinated by two molecules of water. The entire bridging system is therefore H7O4
-(H3O2
- · 2 H2O). O-O distances characterizing the strength of the three hydrogen bonds within this new kind of structural unit are O(H2O-Rh 1)-O(HO-Rh2): 248 pm. O(H2O-Rh 1)-O(H2Oa): 273 pm, O(HO-Rh2)-O(H2Ob): 287 pm. The hydrogen atoms involved in these bridges have been located. The small difference in the Rh 1-O(H2O) - (205.4(3) pm) and Rh2-O(OH)- (204.3(3) pm) distances indicates that the entire H7O4
-- moiety serves as a μ-bridging unit between Rh 1 and Rh 2
Reaktionen des organischen Donors Tetra(methylthio)tetrathiafulvalen mit Kupfer-und Goldhalogeniden: (TTM-TTF) (CuI)2, (TTM-TTF)+[CuCl2]-, (TTM-TTF)2+ [AuCl4]2
- und C4H6S4AuCl2 / Reactions of the Organic Donor Tetra(methylthio)tetrathiafulvalene with Halides of Copper and Gold: (TTM-TTF)(CuI)2, (TTM-TTF)+ [CuCl2]-, (TTM-TTF)2+ [AuCl4]2
- and C4H6S4AuCl2
Authors: Brunn Karl , Endres Helmut , Weiss Johannes
Published: March 2015

(TTM-TTF)(CuI)2. {TTM-TTF = Tetra(methylthio)-tetrathiafulvalene}. the product of the reaction of TTM-TTF with CuI in an I2, atmosphere, is monoclinic C2/m, a = 7.928(2). b = 13.272(1), c = 10.523(2) Å, β 107.82(2)° V = 1054 Å3 Z = 2, dc = 2.42 g cm-3,μ = 56.8 cm-1, final Rw = 0.027 for 964 reflections and 59 variables. The donor acts as a bridging chelate ligand by coordination of the SCH3-groups to Cu.

(TTM-TTF)+(CuCl2]- is triclinic P1̄, a = 7.253(1), b = 7.657(1), c = 10.256(1) Å, α = 89.63(1), β = 89.98(1), 3̄̄μ1̄γ = 73.26(1)°, V = 470 Å3 Z = 1, dc = 2.07 g cm-1, μ = 22.95 cm-1, final Rw = 0.029 for 1871 reflections and 104 variables. Stacks of the (TTM-TTF)+ radical cations with intrastack S···S-contacts of 3.792(2) Å.

(TTM-TTF)2+[AuCl4]2
- and C4H6S4AuCl2 were obtained as products of the reaction of TTM-TTF with AuCl3 in acetonitrile. (TTM-TTF)2+[AuCl4]2
- is monoclinic, C2, a = 14.799(2), b = 11.513(2), c = 8.034(3) Å, β = 97.05(3)°, V = 1359 Å3, Z = 2, dc = 2.61 g cm-3, μ = 121.6 cm-1, final Rw = 0.028 for 1581 reflections and 140 variables. Stacks of the oxidized donor with intrastack S···S-contacts of 3.683(6) Å. C4H6S4AuCl2 is monoclinic. P21/n, a = 10.722(2), b = 14.054(3), c = 14.877(2) Å, β = 108.03(2)°, V = 2132 Å3, Z = 8, dc = 2.80 g cm-3, μ = 149.8 cm-1, final Rw = 0.029 for 3053 reflections and 212 variables. The molecules are arranged in stacks which shortest S···S-contacts of 3.269(3) Å
Spectroscopic Evidence for Pseudorotation of Seven-Membered Chalcogen Rings in Solution [1]
Authors: Steudel Ralf , Papavassiliou Maria , Jensen Detlef , Seppelt Konrad
Published: March 2015

The 77Se NMR spectrum of 1,2-Se2S5 exhibits one singlet at 1077.3 ppm indicating pseudorotation in solution; the same conclusion is reached from the solution Raman spectrum of S7 showing characteristic line broadening compared to the solid state spectrum
Reaktionen koordinierter Liganden, IV [1] Cyclotriphosphankomplexe (RP)3[Cr(CO)5]m (m = 1, 2, 3) durch Dehalogenierung von RPBr2Cr(CO)5 mit Magnesium / Reactions of Coordinated Ligands, IV [1]. Cyclotriphosphane Complexes (RP)3[Cr(CO)5]m (m = 1, 2, 3) by Dehalogenation of RPBr2Cr(CO)5 with Magnesium
Authors: Hinke Anna-Margarete , Hinke Axel , Kuchen Wilhelm
Published: March 2015

Compounds RPBr2Cr(CO)5 (R = Me, Et, i-Pr. t-Bu, c-Hex. (-)Menthyl. Ph) and RPBr2W(CO)5 (R = (-)Menthyl, Ph) are obtained from M(CO)5THF and organodibromophosphane. Dehalogenation of the chromium complexes with magnesium in THF leads to (RP)3[Cr(CO)5]m (m = 1. 2, 3) with m depending on the bulkiness of R. When dissolved in THF the binuclear complexes (m = 2) are gradually converted into mononuclear compounds. The isomeric structure of the cyclotriphosphane complexes is deduced from their 31P{1H} NMR spectra.
Synthese von [LRe(CO)3]+-Komplexen mit makrocyclischen Liganden Die Kristallstrukturen von 1,4,7-Triazacyclononan-tricarbonylrhenium( I)-thiocyanat und 1,4,7-Trithiacyclononan-tricarbonylrhenium( I) -bromid-hemihydrat / Synthesis of [LRe(CO)3]+ Complexes with Macrocyclic Ligands The Crystal Structures of 1,4,7-Triazacyclononane-tricarbonyl-rhenium(I) Thiocyanate and of 1,4,7-Trithiacyclononane-tricarbonyl-rhenium(I) Bromide Hemihydrate
Authors: Pomp Christa , Drüeke Stefan , Küppers Heinz-Josef , Wieghardt Karl
Published: March 2015

The tridentate macrocyclic ligands 1,4,7-triazacyclononane, its thia analogue 1,4,7-trithiacyclononane, 1-oxa-4,7-diazacyclononane, and N,N′,N″-trimethyl-1 ,4,7-triazacyclononane react with Re(CO)5Br in dimethylformamide to yield colorless, air-stable [LRe(CO)3]Br complexes (L = tridentate macrocycle). With Mn(CO)5Br only the cyclic amines react to afford yellow-orange [LMn(CO)3]Br complexes whereas 1,4,7-trithiacyclononane does not give stable complexes of manganese. The crystal structures of [([9]aneN3)Re(CO)3](NCS) and [([9]aneS3)Re(CO)3]Br · 1/2 H2O have been determined. The former crystallizes in the orthorhombic space group P bca (a = 12/763(4), b = 12.662(5), c = 17.472(9) Å; Z = 8); whereas the latter crystallizes in the monoclinic space group P21/c (a = 9.444(1). b = 11.797(2), c = 28.095(3) Å. β = 90,86(1); Z = 8).
Darstellung von 1,2,3,4-Tetramethyl-1,4-diboracyclohexen-2 und Umlagerung zum 1,2,3,4,5-Pentamethyl-2,3-dihydro-1,3-diborol / Synthesis of 1,2,3,4-Tetramethyl-1,4-diboracyclohexene-2 and Rearrangement to 1,2,3,4,5-Pentamethyl-2,3-dihydro-1,3-diborole
Authors: Uhm J.-K. , Römich H. , Wadepohl H. , Siebert W.
Published: March 2015

Reaction between Cl2AlCH2CH2AlCl2 and BCl3 leads to Cl2BCH2CH2BCl2, in which halogen exchange is achieved by Bl3 to yield I2BCH2CH2BI2 (5). Redox reaction between butyne-2 and 5 results in the formation of 1,4-diiodo-2,3-dimethyl-1,4-diboracyclohexene-2 (1a) and iodine. Methylation of 1 a with AlMe3 leads to the title compound 1 d , established by 1H, 11B, 13C NMR. Heating of 1 d in toluene at 160 °C in a sealed tube results in an intramolecular isomerization to give 1,2,3,4,5-pentamethyl-2,3-dihydro-1,3-diborole (2d) in 90% yield.
Metallorganische Verbindungen der Lanthanoide, 41 [1]. Die Kristall-und Molekülstruktur von (C5Me5)2HoCl(THF) / Organometallic Compounds of the Lanthanides, 41 [1]. The Crystal and Molecular Structure of (C5Me5)2HoCl(THF)
Authors: Schumann H. , Loebel J. , Helm D. van der , Hossain M. B.
Published: March 2015

The title compound (1) is obtained as brownish crystals by reaction of HOCl3 with NaC5Me5 in tetrahydrofuran. The structure of 1, which has two slightly different independent molecules per asymmetric unit, has been elucidated by X-ray analysis. The crystals are triclinic with a = 1686.2(8) pm, b = 1816(1) pm, c = 846.5(4) pm, α = 92.02(7)°, β = 92.47(9)°, γ = 63.21(5)°, space group P1̄, D(calcd) = 1.560 g/cm3, and R = 0.0286, for 6219 observed reflections with I > 3σ(I).
Derivatives of Khellinonequinone and their Aflatoxigenic Activity
Authors: Hishmat O. H. , Mabrouk S. S. , Nasef A. M. M. , Shayeb N. M. A. , Ismail S. A.
Published: March 2015

Nitration of khellinone leads to the formation of a small amount of 3-nitrokhellinone and 5-acetyl-6-hydroxybenzofuran-4.7-dione (khellinonequinone) as a main product. The latter compound reacts with primary amines to give the corresponding imino compounds. Reaction of khellinone with o-phenylenediamine involves condensation followed by cyclisation. While on the other hand treating with phenyl hydrazines gives the phenyl hydrazone. The pyrazolobenzofuran derivative was obtained by the action of hydrazine hydrate on khellinonequinone. Finally the reaction with malononitrile leads to the formation of the ylidene derivative. Two quinone derivatives showed a weak effect on mycelial growth and aflatoxin formation.
Über Verbindungen subvalenter Hauptgruppenmetallkationen mit Dithiolaten, 1. Mitteilung. Das dimorphe Blei(II)-l,l-dicyanoethylen-2,2-dithiolat: Darstellung und Kristallstrukturen / Compounds of Subvalent Main Group Metal Cations with Dithiolates, 1. Contribution. Dimorphie Lead(II) l,l-Dicyanoethylene-2,2-dithiolate: Preparation and Crystal Structures
Authors: Hummel Hans-U. , Meske Hermann
Published: March 2015

By reaction of Pb(CH3COO)2 · 3H2O with Na2S2C=C(CN)2 · 3H2O in water, α-PbS2C=C(CN)2 is obtained. Hydrothermal conditions give small crystals of the α-and β-phase. The crystal structures of the two phases have been determined. The α-phase is monoclinic with space group P21/n and a = 11.879(5), b = 12.027(5), c = 4.655(1) Å, β = 96.94(3)°, Z = 4. The compound contains PbS2C4N2 molecules with Pb-S = 2.66 and 2.90 Å. Two molecules are connected to dimers with Pb···Pb = 4.44 Å. The β-phase also crystallizes monoclinically, space group C2/c, a = 9.613(1), b = 13.579(1), c -16.052(2) Å, β = 98.36°, and Z = 12. There are two independent lead positions, with the metals integrated in PbS2C = C(CN)2 groups with a stereochemically active lone-pair, and dimers Pb2(S2C4N2)2 with Pb···Pb distance = 3.80 Å.
Kristallstruktur von Triphenylmethyliodsulfan (C6H5)3CSI [1] / Crystal Structure of Triphenylmethyliodosulfane (C6H5)3 CSI [1]
Authors: Minkwitz Rolf , Preut Hans , Sawatzki Jürgen
Published: March 2015

The crystal structure of (C6H5)3CSI is reported. It is the first structure determination of an iodine sulfane. (C6H5)3CSI crystallizes in the monoclinic space group P21/c with a - 1226.4(7) pm, b = 1398.8(18) pm, c = 941.6(8) pm, β = 96.38(8)° and Z = 4. The sulfur-iodine bond length is 240.6(4) pm corresponding to the sum of the covalent radii with 237 pm. The molecules are linked via short I···S contacts of 321.0(4) pm such that a zig-zag chain is formed.
Methyl(trifluormethyl)haIogensulfonium-Salze [1] Halogen = F, CI, Br, I Methyl(trifluoromethyl)halosulfonium Salts [1] / Methyl(trifluoromethyl)halosulfonium Salts [1] Halogen = F, Cl, Br, I
Authors: Minkwitz Rolf , Werner Arnulf
Published: March 2015

The preparation and spectroscopic characterization of the halosulfonium salts CH3(CF3)SHal+ A-(Hal = F, Cl, Br, I, A- = AsF6
-, SbF6
-, SbCl 6
-) is reported. The compounds are synthesized by the reaction of the sulfane CH3SCF3 with XeF+MF6
-, Cl2F+AsFf6
-, Cl2/AsF5, Cl2/SbCl5 , Br2/AsF5 , or I3
+MF6
- (M = As, Sb), resp., at low temperatures.
La2TaO4Cl3 — ein neues Oxochlorotantalat mit TaO5-Baugruppen / La2TaO4Cl3 - a New Oxochlorotantalate with TaO5 Building Units
Authors: Schaffrathü U. , Gruehn R.
Published: March 2015

The compounds La2TaO4CL3 and Ce2TaO4CL3 have been prepared by reacting SECL3 with SETaO4 (SE = La, Ce) in evacuated silica ampoules. Single crystals of La2TaO4CL were obtained by chemical transport reaction (1100→1000 °C) using chlorine as transport agent. The crystal structure of La2TaO4Cl3 has been refined with single crystal data (Pmmn; a = 15.528(1) Å. b = 3.9395(2) Å, c = 18.132(2) Å; Z = 6; R = 8.53%, Rw = 6.10%). Main building units are TaO5 trigonal bipyramides and two- or threefold capped trigonal prisms around La.
Radikalionen, 79 [1, 2] ESR-Nachweis von Tetra(methylthio)thiophen- und Tetra(methylthio)ethen-Radikalkationen bei der oxidativen Schwefelung von H3CS-C=C-SCH3 mit S2Cl2/AlCl3 und H3CSCl/AlCl3 / Radical Ions, 79 [1, 2] ESR Evidence for Tetra(methylthio)thiophene and Tetra(methylthio)ethene Radical Cations During the Oxidative Sulfuration of H3CS-C=C-SCH3 by S2Cl2/AlCl3 and H3CSCl/AlCl3
Authors: Bock H. , Rittmeyer P.
Published: March 2015

Di(methylthio)acetylene H3CS-C≡C-SCH3 reacts with S2C12 in AlCl3/H2CCl2 solution to the tetra(thiomethyl)thiophene radical cation (H3CS)4C4S·⊕ and with H3CSCl to the tetra(thiomethyl)ethene radical cation (H3CS)2C·=⊕C(SCH3)3. Their ESR spectra are assigned by compari­son with literature data or those of analogous products obtained from other acetylene derivatives R-C≡C-R with R = SCH2CH3, CH3, C6H5 as well as based on HMO arguments. The possible course of the oxidative sulfuration is discussed.
Sr5Al2Sb6 und Ba5In2Sb6: Zwei neue Zintlphasen mit unterschiedlichen Bänderanionen / Sr5Al2Sb6 and Ba5In2Sb6: Two New Zintl Phases with Different Chain Anions
Authors: Cordier Gerhard , Stelter Michael
Published: March 2015

The compound Sr5Al2Sb6 crystallizes in the orthorhombic system (space group Pnma (No. 62)) with the lattice constants: a = 1212.4(4) pm, b = 1034.1(4) pm, c = 1340.9(5) pm. AlSb4 tetrahedra are connected via common edges and corners to chains. Every second terminal Sb atom of the chain is connected to another Sb atom, such that end-on Sb2 groups and terminal Sb alternate. The compound Ba5In2Sb6 crystallizes in the orthorhombic system (space group Pbam (No. 55)). The lattice constants are: a = 1530.7(6) pm, b = 1335.8(5) pm, c = 478.6(2) pm. In the structure, InSb4 tetrahedra are connected via common corners and Sb2 groups to form double chains. Both compounds are classified as Zintl phases.
Mannich Reaction with 5,5-Dimethyl-3-phenylamino-2-cyclohexen-1-one
Authors: Hamama W. S. , Hammouda M. , Afsah E. M.
Published: March 2015

Mannich reaction of the title compound 1 with morpholine, piperidine or piperazine gave the keto-bases 2-4, respectively. Whereas, such reaction with primary amines afforded the quinazolinones 5 and 6. Compound 1 reacts with isonicotinic acid hydrazide and formalin to give 7. Schmidt reaction of 4 and 5a gave 8 and 9, respectively. Reduction of the latter afforded the 9H-pyrimido[5,4-ḇ]azepine ring system 10. The reaction of 1 with formalin was investigated.
Notizen: Die Kristallstruktur von Rb2Ca(N3)4 · 4 H2O / The Crystal Structure of RB2Ca(N3)4 · 4 H2O
Authors: Mautner Franz A. , Krischner Harald , Kratky Christoph
Published: March 2015

The crystal structure of Rb2Ca(N3)4 · 4H2O has been determined by single crystal X-ray methods. The compound is isotypic with K2Ca(N3)4 · 4 H2O and crystallizes in the orthorhombic space group Ccca, Z = 4, a = 1949.1(12) pm, b = 1099.5(3) pm, c - 622.2(1) pm.
Bildung wasserlöslicher Histidin-Platin- Komplexe aus metallischem Platin und Histidin / Formation of Water Soluble Histidine Platinum Complexes from Metallic Platinum and Histidine
Authors: Ehrenstorfer-Schäfers Eva , Hartl Helmut , Beck Wolfgang
Published: March 2015

Metallic Platinum dissolves under oxygen atmosphere in aqueous histidine solution. About 0.1 to 0.3 μmol of a water soluble histidine platinum complex per ml solution have been found by atomic absorption spectroscopy.
Gemischte Borsäureester von Aminoalkoholen und Diolen / Mixed Esters of Boric Acid with Amino Alcohols and Diols
Authors: Heller Gert , Seeger Karlheinz
Published: March 2015

B(OC2H5)3 reacts with diols to give 2-ethoxy-1,3-dioxa-2-boracycloalkanes (1-4) which, on aceotropic distillation in toluene with amino alcohols, give mixed boric acid esters of the type

(5-8, a-g). The structures of these compounds are discussed on the basis of IR and Raman spectra and MS, 1H, and 11B NMR data, and with reference to an X-ray investigation published previously.

The presence of a boron ← nitrogen coordination is proposed in all cases.
Über hexakoordinierte gemischte Halogeno-Anionen des Te(IV): Kristallographische und Raman-spektroskopische Untersuchungen an Rb2TeBr3,5Cl2,5 / On Hexacoordinated Mixed Halogeno Anions of Te(IV): Crystallographic and Raman Spectroscopic Investigation of Rb2TeBr3,5Cl2,5
Authors: Abriel Walter , Ehrhardt Hartmut
Published: March 2015

The title compound contains the anions [TeBr3Cl3]2- and [TeBr4Cl2]2- in a 1:1 ratio. The corresponding point symmetries, detected by Raman spectroscopic methods, are 3 m and 4/mmm, respectively. The crystal structure analysis exhibits a random distribution of these anions: K2PtCl6- type, space group Fm3̅m with a = 10.4602(5) Å and Z = 4, final R = 0.036 from 178 F0 (MoKα).
Komplexe des 1-Thia-4,7-diazacyclononans (L) mit Blei(II), Indium(III), Thallium(I) und (III) Kristallstruktur von [LPb][PbBr4] / Complexes of 1-Thia-4,7-diazacyclononane (L) with Lead(II), Indium(III), Thallium(I) and (III) Crystal Structure of [LPb][PbBr4]
Authors: Hoffmann Peter , Hermes Franz-Josef , Mattes Rainer
Published: March 2015

The reaction of 1-thia-4,7-diazacyclononane (C6H14N2S = L) with salts containing Tl(I) and (III), In(III) and Pb(II) ions yields 1:1 complexes, which can be crystallized as halide or Perchlorate salts. The structure of [LPb][PbBr4] (5) has been determined: Crystal data: orthorhombic, space group P212121, a = 853.2(6), b = 1000.1(4), c = 1860(1) pm, Z = 4. Pb2+ in the [LPb]2+ cation is seven-coordinated by the tridentate ligand and a square of four Br- ions. The Pb-S distance, 286.0(5) pm, is rather short, the lone pair stereochemically activ. The PbBr4
- ions are polymeric with octahedrally coordinated lead(II) atoms.
Notizen: Preparation and ESR Spectra of Manganese(III) Complexes with 2-[Bis(benzimidazol-2-ylmethyl)- amino] ethanol
Authors: Nishida Yuzo , Oshino Naoko , Tokii Tadashi
Published: March 2015

Manganese(III) complexes with 2-[bis(benz-imidazol-2-ylmethyl)amino]ethanol were prepared. Based on the analytical data, IR, magnetic and ESR (“16-line ESR signal” was observed in the frozen state) properties, these complexes are assumed to be of the binuclear structure with μ-oxo and di-μ-acetato bridges.
Enthalogenierung von Bis(diisopropylamino-chlorboryl)methan: Lösungsmittelabhängige Bildung eines 1,2,4,5-Tetraborinan-und eines 1-Aza-2,4-diborolidin-Derivats / Dehalogenation of Bis(diisopropylamino-chloroboryl)methane: Solvent-dependent Formation of a 1,2,4,5-Tetraborinane and of a 1-Aza-2,4-diborolidine Derivative
Authors: Fisch Herbert , Pritzkow Hans , Siebert Walter
Published: March 2015

Dehalogenation of bis(diisopropylamino-chloroboryl)methane 1 b with sodium/potassium alloy in petroleum ether yields the 1,2,4,5-tetraborinane 2b (38%), whereas in tetrahydrofuran the five-membered 1-aza-2,4-diborolidine derivative 3a (36%) is formed. The constitution of 2b and 3a follows from spectroscopic data and has been confirmed by X-ray structure analyses.
Alkali-Polyketenenolat, ein Polyacetylen-Derivat / Alkali-Polyketene-Enolate, a Polyacetylene Derivative
Authors: Fritz Heinz P. , David Peter
Published: March 2015

An alkali-polyketene-enolate was made from polyketene by using aqueous bases MOH (M = Li, Na, K, Rb, Cs). The structure is proposed on the basis of IR and 13C NMR spectra, the paramagnetic properties were investigated by EPR spectroscopy. AC conductivity measurements show a maximum conductivity of 10-2 S cm- 1 (at 115 °C), where marked ionic participation is expected. Doping of the polyacetylene backbone with iodine gives no increase of conductivity; CV measurements indicate the presence of triiodide anions.
Komplexe von Silber(l)-Salzen mit Naphthalino(cyclo)phanen, Strukturbestimmung von (rac-[2](1,5)Naphthalino[2]- paracyclophan)-silber(I)-perchlorat / Complexes of Silver(I) Salts with Naphthalino(cyclo)phanes, Structure Determination of (rac-[2](1,5)Naphthalino[2]- paracyclophane)silver(I) Perchlorate
Authors: Schmidbaur H. , Bublak W. , Haenel M. W. , Huber B. , Müller G.
Published: March 2015

The 1:1 complexes of Ag[GaCl4 ] with anti-[2.2](1 ,4)naphthalinophane and of Ag[ClO4 ] with [2](1.4)naphthalino[2]paracyclophane and rac-[2](1,5)naphthalino[2]paracyclophane have been prepared and characterized by elemental analyses and IR spectra. The crystal structure of the last compound, ([2](1,5)naphthalino[2]paracyclophane)silver(I) Perchlorate, has been determined by X-ray methods. It crystallizes in the centrosymmetrical space group P21/n with cell dimensions a = 12.495(2), b = 8.546(1), c =16.196(2) Å, β = 101.27(1)°. Both enantiomers of the ligands are present in the unit cell and related by centrosymmetry. Each silver atom is connected with the naphthalin systems of two ligands and with two Perchlorate anions, one of which is chelating, while the other is only monodentate. The cation/anion chains are linked through the organic ligands in such a way that a sheet structure is formed. The benzene rings of the cyclophanes are not involved in the metal coordination, the naphthaline rings are μ3 -bonded to the silver atoms, which are not ring-centered.
Synthese neuer 1λ6- und 1λ4,2,4,6-Thiatriazine aus S,S-Diorganosulfodiimiden / Synthesis of Novel 1λ6- and 1λ4,2,4,6-Thiatriazines from S,S-Diorganosulfodiimides
Authors: Haake Manfred , Jürgler Winfried
Published: March 2015

From S,S-diorganosulfodiimides 1a-e with diphenylcyanimidocarbonate (2) via condensation products 3a-e and 6a-d novel heterocycles were obtained. In DMF 3a-c react with aliphatic amines to form 1λ4,2,4,6-thiatriazines 4a-e and 5a, b. With HCl 6a-d can be cyclized to give 1λ6,2,4,6-thiatriazine hydrochlorides 8a-d. These are thermally converted into 1λ4,2,4,6-thiatriazines 4a, f, g. Condensation of 6a with orthoesters and paraformaldehyde affords 1λ6,2,4,6- thiatriazines 9a, b and 10a, whereas 3a, e undergoes ring closure with methyl hydrazine to 1,2,4- triazoles 11a, e.
Synthese und Reaktionen von [1.4]Diazepino[6.5-c]chinolinen / Syntheses and Reactions of [1.4]Diazepino[6.5-c]quinolines
Authors: Gündel Wolf-H. , Bohnert Sabine
Published: March 2015

Three routes for the preparation of [1.4]diazepino[6.5-c]quinolines (1) have been studied. The best yields resulted by starting from the amides of N-(3-quinolylcarbonyl)-N-alkyl-amino acids (5). Quaternization to 9, intramolecular cyclization under the influence of base to 10, oxidation to 11 and debenzylation by catalytic hydrogenation gave 1.