bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthese und herbizide Wirkung von substituierten Phenoxymethylphenoxypropionsäurederivaten/ Synthesis and Herbicidal Effect of Substituted Phenoxymethylphenoxypropionic Acid Derivatives
Authors: Koch Manfred , Bieringer Hermann
Published: February 2015

Compounds are herbicides with high activity. Methods for synthesis are reported.
The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change
Authors: Jochum C. , Gasteiger J. , Ugi I.
Published: February 2015

The principle of minimum chemical distance (PMCD) is derived from the general theory of the BE- and R-matrices, and makes precise the vague classical “principle of minimum structure change”. In fact, the PMCD may be seen as the principle of minimum structure change in mathematical terms. It provides a quantitative measure of chemical similarity of isomeric molecular systems. Its applications lie in the fields of correlations of substructures, elucidation of reaction mechanisms, and evaluation of synthetic pathways as is illustrated by examples. The mathematical foundations of the computer assisted application of the PMCD are presented.
Notizen: Anwendungen der Phasentransfer-Katalyse, 22. Notiz über Fest-Flüssig-Reaktionen von Metallcarbonylen/ Applications of Phase Transfer Catalysis, 22. Note on Solid-Liquid Reactions of Metal Carbonyls
Authors: Dehmlow Eckehard V.
Published: February 2015

Solid NaNO2 and an onium salt react with Fe(CO)5 and Co2[(CO)8] in nonpolar solvents yielding Q[Fe(CO)3NO] and Q[Co(CO)4] (Q = onium cation)
Übergangsmetall- Carbi n - Komplexe, LXXI. Ein neuer Weg zum Carbinkomplex durch Ein-Stufen-Reaktion von Acylmetallat- Komplex mit Thionylchlorid/ Transit ion Metal Carbyne Complexes, LXXI .A New Way to Carbyne Complex by One-Step Reaction of Acylmetallate Complex with Thionylchloride
Authors: Himmelreich Dieter , Fischer Ernst Otto
Published: February 2015

Lithium-pentacarbonyl(diethylaminoacyl)- tungstate reacts with SOCl2 to give trans-tetracarbonyl (chloro) (diethylaminocarbyne) tungsten.
Equilibria between Sulfur Rings in Carbon Disulfide Solution at Elevated Temperatures
Authors: Steudel Ralf , Strauss Reinhard
Published: February 2015

Cyclooctasulfur, S8, dissolved in CS2 reacts at 130-155 °C in sealed ampoules to give S6 and S7 whose concentrations have been determined by HPLC. The half-time of the reaction is independent of the initial S8 concentration and decreases from 232 min at 130 °C to 64 min at 150 °C. After long reaction times equilibrium concentrations are observed which are in agreement with the law of mass action. From the temperature dependence of the equilibrium constants the following reaction enthalpies (at 130-155 °C) have been calculated:

3/4S8⇌S6 ⊿H°=24kJ/mol

7/8S8⇌S7 ⊿H°=21kJ/mol
Neuartige Ge2P4
8–- bzw. Ge2As4
8– -Anionen in Ba2GeP2 und Ba2GeAs2 / New Ge2P4
8-- bzw. Ge2As4
8- -Anions in Ba2GeP2 and Ba2GeAs2
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert
Published: February 2015

The new compounds Ba2GeP2 and Ba2GeAs2 crystallize in the monoclinic system (space group P21/c) with lattice constants:

Ba2GeP2: a = 855.3 ± 0.5 pm, b = 951.5 ± 0.5 pm, c = 748.1 ± 0.5 pm, β = 105.95 ± 0.08°.

Ba2GeAs2: a = 875.7 ± 0.5 pm, b = 970.0 ± 0.5 pm, c = 700.7 ± 0.5 pm, β = 100.03 ± 0.08'.

There are characteristic isolated Ge2P4
8- and Ge2As4
8- anions, which are arranged in sheets.
On Some Ternary Phases in the Systems Nb-Zn-Al and Ta-Zn-Al
Authors: Drašner A. , Blažina Ž.
Published: February 2015

In the systems NbZn2-xALx and TaZn2-xAlx a great number of samples was prepared and investigated by means of X-ray powder diffraction. In both systems at the equiatomic composition two new ternary phases were found. Their crystal structures were determined and found to belong to the Friauf-Laves type (MgZn2 prototype, S. G. P 63/mmc). The unit cell parameters of NbZnAl are a = 506.4 ± 0.2 pm, c = 829.9 ± 0.8 pm, c/a = 1.639, and for TaZnAl a = 503.8 ± 0.2 pm, c = 827.9 ± 0.3 pm, c/a= 1.643. In the system NbZn2-x-Alx, at the composition NbZn1.25Al0.75, a ternary phase of the AuCu3 structure (a= 394.4 i 0.3 pm, S. G. Pm3m) was also observed, while in the system NbZn3-xAlx a single phase region, having the AuCu3 structure, was found to exist up to the composition NbZ2Al. The stability of these Friauf-Laves phases and those found previously in the systems ZrZn2-xAlx and HfZn2-xAlx is discussed in terms of atomic sizes and valence electron concentration.
Synthese und Struktur von [CpFe(CO)2SO2]+ AsF6- / Synthesis and Structure of [CpFe(CO)2SO2]+ AsF6–
Authors: Hartmann Gabriele , Froböse Rolf , Mews Rüdiger , Sheldrick George M.
Published: February 2015

The cationic sulfur dioxide complexes [CpFe(CO)2SO2]+AsF6- (7) and [CpCr(NO)2SO2]+AsF6- (9) are obtained in almost quantitative yield from CpFe(CO)2I(CpCr(NO)2Cl) and AgAsF6 in liquid SO2. With excess transition metal halide dinuclear halogen-bridged cations ([CpFe(CO)2IFe(CO)2Cp]+ and [CpCr(NO)2ClCr(NO)2Cp]+) are formed. The crystal structure of 7 is reported, and the bonding in the complexes is discussed in the light of spectroscopic data.
Darstellung und Struktur des Polyvanadato-periodates Na6[H2V2I2O16]·10H2O / Preparation and Crystal Structure of the Heteropoly Periodate Na6[H2V2I2O16]·10H2O
Authors: Mattes Rainer , Richter Kurt-Ludwig
Published: February 2015

The structure of the heteropoly periodate ion [H2V2I2O16]6- has been determined in its Na salt at -150 °C by single crystal X-ray diffraction with 1909 reflections and refined to F = 0.022 (R′= 0.028). Na6[H2V2I2O16]·10H2O crystallizes in the triclinic space group P1 with a = 11.407(5), b = 8.865(3), c = 6.105(3) Å, α = 82.07(3)°, β = 84.24(4)° γ = 70.23(3)°, V = 574.5 Å3 , Z = 1. The [H2V2I2O16]6- anion consists of edge and corner sharing IO6 octahedra and VO5 square pyramids. The vibrational spectra clearly indicate the presence of VO(terminal)2 groups.
Darstellung und Kristallstruktur von [Ba-4en]Se4·en / Preparation and Crystal Structure of [Ba-4en]Se4·en
Authors: König Theo , Eisenmann Brigitte , Schäfer Herbert
Published: February 2015

Ba metal and Se powder react in dry ethylendiamine (≙ en) in the presence of 222-Crypt to [Ba-4en]Se4·en. The new compound crystallizes in the monoclinic system, space group C2/c with the lattice constants: a = 1187.9(7) pm, b= 1546.9(7) pm, c= 1497.9(7) pm, β = 105.82(8)°. Significant structure units are Se4
2- chain anions.
A 1:1 Host-Guest Complex between 1,4,7,10,13,16-Hexaoxacyclooctadecane ('18-crown-6') and m-Nitroaniline: Mere Stoicheiometry or a Genuine 1:1 Adduct ?
Authors: Weber Gabriela
Published: February 2015

The stoicheiometrically 1:1 adduct of 1,4,7,10,13,16-hexaoxa-cyclooctadecane with m-nitroaniline, C18H30N2O8, Mr = 402.45, crystallises from toluene in red-orange prisms, (probable) space group P1̄, a = 801.8(3), b = 920.4(3), c = 1403.3(4) pm, α = 80.40(4), β = 79.79(4), γ = 85.95(3)°, V = 1.07910 nm3 , Z = 2, dcalc. = 1.238 Mgm-3 . Structure refinement converged at R = 0.060 (Rw = 0.002) for 2915 diffractometer data.
Malonenamidoxim, Nickelkomplexe und deren ßeaktionsprodukte mit Sauerstoff und Kohlendioxid: Vergleichende Strukturuntersuchungen / Malonenamide Oxime, Nickel Complexes, and their Reaction Products with Oxygen and Carbon Dioxide: Comparative Structural Studies
Authors: Endres Helmut , Kadkhodai-Elyaderani Nasser
Published: February 2015

Malonenamide oxime [HONC(NH2)CH2C(NH2)NOH = C3H8N4O2] (1), its bis-chelate complex with Ni(II) [Ni(C3H7N4O2)2] (2) and an ethanol solvate of this complex [Ni(C3H7N4O2)2 · 0.6 C2H5OH] (3) are characterized by X-ray structure analysis, as well as a paramagnetic tris-complex [Ni(C3H7N4O2)2(C3H8N4O2)] (4), which forms a catena structure in the crystal. The molecular structures of two reaction products of 2 with air are described: [Ni(C3H5N4O3)2(H2O)2] · 4 H2O (5) has formed by oxidation of the methylene groups and may be taken as a complex of mesoxalamide oxime; [NiC8H16N8O8] · 6 H2O (6) has a macrocyclic ligand which is a derivative of orthocarbonic acid, formed by addition of carbon dioxide to the oxime groups.
X-Ray Structures and Spectral Properties of 4-Coordinate Copper(II) and Palladium(II) Complexes with a Tridentate ONN-Schiff Base Ligand
Authors: Elias Horst , Hilms Elke , Paulus Helmut
Published: February 2015

The tridentate mono-basic Schiff base N-(2-diethylaminoethyl)salicylaldimine ≙Hsal-en-NEt2 forms complexes 1 = [(sal-en-NEt2)MY] with divalent metals M (Y = halide). The preparation of three copper(II) complexes 1a (Y=Br), 1b (Y=Cl), and 1c (Y=SCN) and one palladium(II) complex 1(1 (Y=Cl) is described and the UV/VIS spectra of these complexes in methanol and chloroform are compared and discussed. The crystals of 1a · CHCl3, 1b · CHCl3, and 1d · CHCl3 are all isotypic and crystallize in the orthorhombic space group Pbca, whereas the solvent-free crystals of 1 b (and also 1 a) are monoclinic with the space group P21/c. The metal is 4-coordinate with an almost planar ONNY donor atom arrangement around the palladium and with a distorted arrangement around the copper. The crystals consist of separate non-bridged complex units and the chloroform is not coordinated.
(CO)13Re3COSi(C6H5)3, ein neuartiger Typ eines metallorganischen Acyl- Komplexes mit dreibindigem Sauerstoff / (CO)13Re3COSi(C6H5)3, A New Type of an Organometallic Acyl Complex with a Three-Coordinate Oxygen Atom
Authors: Rustemeyer Paul , Fischer Ernst Otto , Ackermann Klaus , Schubert Ulrich
Published: February 2015

The reaction of Re2(CO)10 with LiSi(C6H5)3 and subsequent alkylation by CH3FSO3 yields - besides eq-(CO)9Re2C(OCH3)Si(C6H5)3 (1) and (CO)8Re1eq,Re2ax-[C(OCH3)Si(C6H5)3]2Re2 (2) - (CO)13Re3COSi(C6H5)3 (3) in small yields. In this trinuclear complex 3 Rel and Re2 are bridged by a (CeHs^SiCO-group, which is coordinated to Re 1 as an η2-acyl ligand and to Re 2 through oxygen only. Reaction conditions, properties and spectroscopic data of the new compound as well as an X-ray structure of 3 are reported.
Übergangsmetall-Carben-Komplexe, CXXVI [1]. Darstellung und Struktur symmetrischer Hydroxycarben-Anhydrid-Komplexe des Mangans und Rheniums / Transition Metal Carbene Complexes, CXXVI [1]. Preparation and Structure of Symmetrica! Hydroxycarbene Anhydride Complexes of Manganese and Rhenium
Authors: Fischer Ernst Otto , Chen Jiabi , Schubert Ulrich
Published: February 2015

Symmetrical anhydrides of hydroxycarbene complexes of manganese and rhenium, [π-C5H5(CO)2MC(R)]2O, (M = Mn, Re) are prepared by reaction of cationic carbyne complexes [π-C5H5(CO)2MCR]BX4 with the corresponding metal carbonyl acylates Li[π-C5H5(CO)2MC(O)R]. [π-C5H5(CO)2MnC(C6H5)]2O is also obtained by controlled hydrolysis of π-C5H5(CO)2MnCX(Br)Ce6H5. The new complexes are characterized spectroscopically and by an X-ray structure analysis of [π-C5H5(CO)2MnC(C6H5)2O.
Phosphinsubstituierte Chelatliganden, VI [1]. Kristallstrukturen von Tetracarbonyl(diphenylphosphino -N-phenylthioformimidato -P,S )mangan(I) und Tetracarbonyl(diphenylthiophosphoryl-N-phenylthioformimidato-S,S')mangan(I) / Phosphine Substituted Chelate Ligands, VI [1]. Crystal Structures of Tetracarbonyl(diphenylphosphino-N-phenylthioformimidato-P,S)- manganese(I) and Tetracarbonyl(diphenylthiophosphoryl-X-phenylthioformimidato-S.S')- manganese(I)
Authors: Antoniadis Antonios , Hiller Wolfgang , Kunze Udo , Schaal Herberth , Strähle Joachim
Published: February 2015

The phosphinothioformimidato complex

(1) crystallizes triclinic in the space group P1̄ with lattice constants a = 989.4(9) pm, b - 1042.0(8) pm, c = 1088.5(8) pm, α = 91.45(4)°, β = 97.10(4)°, γ = 100.53(5)°. The four-membered chelate ring

is folded over the P-S edge by a dihedral angle of 167.1°. The crystal system of the thiophosphoryl thioformimidato complex

(2) is monoclinic with the space group P21/c, and the lattice parameters are a = 1109.5(3) pm, b = 966.0(3) pm, c = 2256.7(3) pm, β=103.11(2)°. The chelate ligand is linked to the metal by two S atoms forming a five-membered ring in the “envelope” conformation with the thiophosphoryl S atom at the apical position.
Ein- und zweikernige Palladiumkomplexe mit CS2 und PR3CS2 als Liganden [1] / Mono- and Binuclear Palladium Complexes with CS2 and PR3CS2 as Ligands [1]
Authors: Bertleff Werner , Werner Helmut
Published: February 2015

The compounds Pd(PPri3)n (n = 2 or 3) and Pd(PMePh2)4 react with CS2 to give the mononuclear complexes (PR3)2Pd(η2 -CS2). In the reactions of Pd(PMe3)4 and Pd(PMe2Ph)4 with CS2 binuclear complexes [(PR3)Pd(S2CPR3)]2 containing bridging phosphoniodithio-carboxylates as ligands are formed. [(PMe3)Pd(S2CPMe3)]2 is also obtained from (PR3)2Pd(η2 -CS2) (PR3 = PPri
3, PMePh2, PPh3) and PMe3. The reactions of Pd(PR3)n with the zwitter ions PMe3CS2 and PMe2PhCS2 lead to binuclear compounds [(PR3)Pd(S2CPR′3)]2 (PR3 = PPri
3, PMe2Ph, PMePh2, PPh3; PR′3 = PMe3, and PR3 = PMePh2; PR′3 = PMe2Ph). [(PMe3)Pd(S2CPMe3)]2 reacts with PMe3 with cleavage of the phosphoniodithiocarboxylate bridges to give (PMe3)2Pd(S2CPMe3). The formation of [(PMe3)Ni(S2CPMe3)]2 from Ni(PMe3)4 and PMe3CS2 is also described.
Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XXVII [1] Fünf- und sechsgliedrige Manganacycloalkane mit Arsen als Donoratom / Preparation and Properties of, and Reactions with Metal-Containing-Heterocycles, XXVII [1] Five- and Six-Membered Manganacycloalkanes with Arsenic as Donor Atom
Authors: Lindner Ekkehard , Starz Karl Anton , Hoehne Sigurd
Published: February 2015

The colourless five-and six-membered arsamanganacycloalkanes

(4a, a′, b, b′) are formed by reductive cycloelimination of (OC)4BrMn-AsPh2-[CH2]n-Cl (3a,b) with sodium amalgam and a one step reaction of (OC)5MnBr (1) with Me2As-[CH2]n-MgCl (2a′,b′), respectively. 3a,b are accessible in substituting CO by the arsanes Ph2As-[CH2]n-Cl (2a,b) in 1. In respect of thermal stability and reactivity 4a,a′, b,b′ are comparable with their phosphorus analogues. 4a crystallizes in the morioclinic space group C2/c with Z = 8 and has an envelope conformation. Into the reactive Mn-Cσ bond SO2 or CO can be inserted to give the cyclic sulfinato-S complexes

(5a,a′,b,b′) and acyl compounds

(6a,b′) respectively.
Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, V [1]. Die Umsetzung von Tricarbonyl-η-6.6-dimethylfulven-chrom(0) mit 7-Methyl- und 7-Methoxycycloheptatrien / Photochemical Reactions of Transition Metal Olefin Complexes, V [1]. The Reactions of Tricarbonyl-η-6,6-dimethylfulvene-chromium(0) with 7-Methyl- and 7-Methoxycycloheptatriene
Authors: Kreiter Cornelius G. , Kurz Hans
Published: February 2015

The stereochemistry of the photo reaction products of tricarbonyl-η-6,6-dimethyl-fulvene-chromium(O) (1) with 7-methyl-and 7-methoxycycloheptatriene was studied by NMR-spectroscopy. Both trienes add to 1, displace a CO ligand, and form substituted dicarbonyl-η3-2-cycloheptadienylene-η5-2-cyclopentadienylidene-propane-chromium(0) complexes. With C7H7CH3 only one isomer (3) is formed with the methyl-group in endo-position and the enyl system encompassing C(1′)-C(3′) of the seven membered ring. C7H7OCH3 yields 3 isomers which were separated by column chromatography. 5 has the same constitution as 3. The isomers 4 and 5 bear the OCH3-group in e^o-position. The enyl system of 4 is located on C(1′)-C(3′), that of 6 on C(3′)-C(5′). 6 rearranges at room temperature to 4.
Studien zum Vorgang der Wasserstoffübertragung, 66 [1]. Untersuchungen zum Mechanismus der elektroreduktiven Spaltung von Aryldisulfonsäurederivaten / Studies to the Occurrence of Hydrogen Transfer, 66 [1]. Investigation of the Mechanism of the Electroreductive Cleavage of Aryldisulfonyl-Derivatives
Authors: Horner Leopold , Schmitt R.-E.
Published: February 2015

Aryl-mono- and -disulfonic acid derivatives (Ar(SO2Y)n n= 1,2; Y = OR, NR, R′) were converted to aryl sulfinic acids by electroreductive fission according to the steps shown in Scheme (1). Determination of the electron-transfer during the electroreduction (Ilkovič, n < 1) indicates the irreversibility of the reaction sequence given. Cyclovoltammetric measurements on benzene-1,4-disulfonicacid-di-n-hexylester indicate that the first reduction step (the formation of the radical anion A or B) is reversible.
Ein nematisches N-Cyclohexylpiperidin / A Nematic N-Cyclohexylpiperidine
Authors: Sucrow Wolfgang , Schatull Wolfgang
Published: February 2015

The preparation of the nematic 4-(4-n-pentyl-1-piperidyl)cyclohexane-1-carbonitrile (1b) via the enamine 2b and the N-Cyclohexylpiperidines 5a-c is described. The nematic range of 1b was found to be 8 °C.
Effiziente Synthese von 1-Aryl-4-oxoazetidin- 2-carbonsäureethylester / Efficient Synthesis of 1 -Aryl-4-oxo-azetidine-2-carboxylicacidethylesters
Authors: Mühlbacher Manfred , Ongania Karl-Hans
Published: February 2015

The dehalogenation of the 1-aryl-3-chloro-4-oxo-azetidine-2-carboxylicacid-ester (3a-d) and (4a-d), which may be obtained by the addition of chloroketene to the aniles (2 a-d) leads to the title compounds in good yield.
π-Olefin-Iridium-Komplexe, XI [1] Das Bis(η4-2.3-dimethylbutadien-1.3)- iridium- Kation und sein Dimethy lsulfoxid - Addukt / π-Olefin Iridium Complexes, XI [1] The Bis(η4-2.3-dimethylbutadiene-1,3)iridium Cation and its Dimethylsulfoxide Adduct
Authors: Müller Jörn , Passon Barbara
Published: February 2015

The complex [L2IrCl] (L = η4-2,3-dimethylbutadiene- 1,3) reacts with AgBF4 in CH2Cl2 to yield [L2Ir]+BF4
- (1). If 1 is dissolved in dimethylsulfoxide (DMSO) the stable adduct [L2Ir(DMSO)]+BF4
- (2) can be isolated. In 2 the DMSO ligand coordinates to iridium via oxygen. The compounds 1 and 2 were characterized by elemental analysis, infrared, and 1H NMR spectra.
Über Oxoplumbate(IV). Die Kristallstruktur von TT-Li2PbO3 [1] .On Oxoplumbates(IV) The Crystal Structure of LT-Li2PbO3 [1]
Authors: Brazel Berthold , Hoppe Rudolf
Published: February 2015

For the first time single crystals of LT-Li2PbO3 have been prepared by decomposition of K2Li6[Pb2O8] [Incompletely closed Ag cylinders, sealed in Supremax-glass ampoule, vacuum, 690 °C, 100 d]. The structure determination [533Io(hkl); four-circle-diffractometer PW 1100, ω - scan, Mo - Kα, R = 4,86%, Rw = 4,93% confirms space group C2/c with a = 544.52(7), b = 926.12(7), c = 547,56(8) pm, β = 111.216(13)°, Z = 4, drö = 6.94 g · cm-3, dpyk = 6.89 g · cm-3. The NaCl-type structure variant is characterized by alternating layers of Li(2)+ and Li(l)+/Pb4+ cations. All atoms have octahedral coordination. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.
Cyclische Diazastannylene, XVI [1]. Ringe und Käfige mit Ge(II), Sn(II) und Pb(II) / Cyclic Diazastannylenes, XVI [1]. Rings and Cages with Ge(II), Sn(II) and Pb(II)
Authors: Veith M. , Grosser M.
Published: February 2015

1,3-Di-tert-butyl-2,2-dimethyl-1,3,2,4λ2-diazasilagermetidine (1) and its lead analogue (3), which have been synthesized from the dichlorides of germanium and lead and the dilithium salt of bis(tert-butylamino)dimetliylsilane, are compared with the corresponding tin compound 2 in their reactivity towards tert-butylamino. There is a clear dependence of the reaction rate on the nature of the element. The norcubane-like cage Ge3(NtBu)4H2 (5 a) and the cubane-like cages Ge4(NtBu)4 (6a) and Pb4(NtBu)4 (6c) result from these reactions. When 3 is treated with bis(methylamino)dimethylsilane, [(Me2Si)2(MeN)3Pb]n (7) precipi­tates from the reaction mixture. Sn3(NtBu)4H2 (5b) can be transformed into Sn3(NtBu)4Ge (8a) and Sn3(NtBu)4Pb (8b) when heated at high temperatures with 1 or 3, respectively. In these polycyclic compounds two low-valent elements of group IV are simultaneously present in one cage unit. As can be shown, 8b is less stable to bond cleavage than 8a and undergoes redistribution reactions at elevated temperatures to form Sn4(NtBu)4 (6b), Sn2Pb2(NtBu)4 (9). SnPb3(NtBu)4 (10) and Pb4(NtBu)4 (6c).
Synthese und Struktur des Tetraschwefel-pentastickstoff-hexafluoroarsenats / Synthesis and Structure of Tetrasulfurpentanitrogen-hexafluoroarsenate
Authors: Isenberg Wilhelm , Mews Rüdiger
Published: February 2015

The preparation of S4N5 + MF6- (5 a, b M = As, Sb) by decomposition of S3N3F2 + MF6- and by Cl- exchange in S4N5Cl with AgAsF6 is described. The structure of 5a was de­termined from single crystal X-ray data.
Synthese und Kristallstrukturen einiger Tetramethylstibonium-Hydrogendicarboxylate / Synthesis and Crystal Structures of Some Tetramethylstibonium Hydrogendicarboxylates
Authors: Milewski-Mahrla Beatrix , Schmidbaur Hubert
Published: February 2015

Reactions of pentamethylantimony (CH3)5Sb with carboxylic acids in the molar ratio 1:2 afford one equivalent of methane and essentially quantitative yields of crystalline tetramothylstibonium hydrogendicarboxylates. Six new compounds of this series have been synthesized using benzoic, o-phthalic, salicylic, 4-ethoxy-salicylic, oxalic, and malic acid, and characterized by analytical and spectroscopic data. An ionic structure with strong hydrogen bonds in the anionic components is proposed.

The crystal structures of the hydrogen-dibenzoato (1), hydrogen-ortho-plithalato (2) and 4-ethoxy-hydrogen-salicylate (3) were determined by single crystal X-ray diffraction. The compounds can be described as having ionic lattices with some donor-acceptor inter­actions between the stibonium centers and the carboxylate oxygen atoms. The anions are characterized by strong hydrogen bonds O...H...O. Thus, the (CH3)4Sb-tetrahedron in 1 is distorted by two benzoate oxygon atoms (at 304(2) and 340(2) pin). The cation in 2 is largely undistorted and the anion has a hydrogenphthalate hydrogen bond of d(O...H...O) = 232 pm. The cation-anion contact in 3 is as short as d(Sb-O) = 289 pm rendering the Sb atom pentacoordinate.
Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von P(C6H5)4SeOCl3, P(C6H5)4SeOBr3 und As(C6H5)4SeOBr3
Authors: Krebs Bernt , Schaffer Andreas , Hucke Marita
Published: February 2015

The novel oxotribromosolcnate(IV) SeOBr3- anion was prepared from the reaction of stoichiometric quantities of SeOBr2 and bromide in acetonitrile solution, and it was isolated as the tetraphenylphosphonium and -arsonium salts in crystalline form. For the synthesis of the analogous SeOCl3- as P(C6H5)4SeOCl3, SeCl4 was reacted in the presence of a small quantity of H2O with P(C6H5)4Cl in acetonitrile. Complete X-ray structural analyses of P(C6H5)4SeOCl3 (space group P1̄, a = 10.981(3), b = 11.0511(3), c = 10.358(3) Å, α = 73.77(2)°, β = 83.33(2)°, γ = 80.51(2)°, V = 1187.9(6) Å3) and of P(C6H5)4SeOBr3 (space group P 21/c, a = 11.719(4), b = 16.088(4), c = 13.124(4) Å, β = 94.72(3)°, V = 2400(1) Å3) show dimeric centrosymmetric Se2O2Cl6
2- and Se2O2Br6
2- anions being present in the solid. In the anions two square-pyramidal (Ψ-octahedral) SeOHal4 groups are connected through a common Hal-Hal edge. The axial oxygen ligands (So-O: 1.597(4) and 1.584(0) Å) cause a pronounced stereochemical trans-activation of the inert pairs at the Se atoms. As(C6H5)4SeOBr3 is isotypic with P(C6H5)4SeOCl3.
Ein Heteropolyanion als Einschlußverbindung / A Heteropolyanion with Clathrate Character
Authors: Fuchs Joachim , Thiele Axel , Palm Rosemarie
Published: February 2015

Tetrabutylammoniumdodecatungstophosphate, [N(C4H9)4]3PW12O40 exists in two different forms. The anion of the first one represents the regular “Keggin-Structure” (α-type) with Td-Symmetry. The second isomer, crystallizing in the triclinic space group P1̄ with lattice parameters a = 13.897 Å, b = 15.410 Å, c = 19.535 Å, α = 95.11°, β = 92.88°, γ = 90.46° contains a neutral W12O36 moiety with centrosymmetric tungsten and oxygen positions built from tetragonal-pyramidal WO5 units. In the central cavity a disordered PO4
3- anion is enclosed. For the new isomer the term γ-type is proposed.
Kristallstrukturen von zwei Modifikationen des Mo(IV)-Komplexsalzes [(Et2PS2)3Mo3S(S2)3]+(Et2PS2)- / Crystal Structures of Two Modifications of the Mo(IV) Complex Salt [(Et2PS2)3Mo3S(S2)3] + (Et2PS2)-
Authors: Meyer Beate , Wunderlich Hartmut
Published: February 2015

Tris(diothyldithiophosphinato)-tris-μ-disulfido-μ3-thiotriangulo-trimolybdenum(IV)-di-ethyldithiophosphinate, [(et2PS2)3Mo3S(S2)3+(et2PS2)-, crystallizes in two orthorhombic modifications with crystallographic parameters of A: a = 20.651(3), b=10.152(2), c = 19.019(2) Å, Pca21, Z = 4 and B: a = 20.128(2), b= 15.655(2), c = 12.608(1) Å, Pinna, Z = 4. Both crystal structures were determined from 2886 (A) and 3414 (B) X-ray data with R factors of 0.058 and 0.045, respectively. The Mo atoms form a trinuclear Mo3S(S2)3 cluster with local symmetry close to C3V in both modifications which differ in the packing of anions and cations and in the conformation of the ethyl groups. The av. distance Mo-Mo is 2.737 Å, the coordination number of the Mo atoms is 7 within the cluster and 9 on inclusion of the S atoms of the dithiophosphinato group.
Über eine Hochdruckmodifikation des SrAl2 / On a High Pressure Modification of SrAl2
Authors: Cordier Gerhard , Czech Erwin , Schäfer Herbert
Published: February 2015

SrAl2, forming at standard conditions the KHg2 structure type, transforms at ~60 kbar and 1050 °C to a high pressure modification with the MgCu2 structure (a = 832.5(5) pm).
Study of the Complexes of the Ascorbic Acid-Iron(III) System
Authors: Martinez P. , Uribe D.
Published: February 2015

The blue complex of L-ascorbic acid with Fe3+ ions has been obtained and isolated. Various spectrographic and analytical techniques have been used to study this complex. A kinetic study was also carried out on L-ascorbic acid oxidation by Fe3+ by means of the stoppod flow technique for rapid processes.
Boron Chelates and Boron-Metal Chelates, X [1]. 3-(2-Hydroxyphenyl)-2,2-diphenyl-1-oxa-3-azonia-2-borata-naphthalene-methanol (1/1): Synthesis, Spectroscopic Investigations and Crystal Structure
Authors: Allmann Rudolf , Hohaus Eberhard , Olejnik Stanislaw
Published: February 2015

The title compound, C25H20BNO2 · CH3OH, was examined by UV, IR, 1H, and 13C NMK spectroscopy as well as by thermogravimetry and X-ray structure analysis (Pbnb, a = 8.815, b = 17.309, c=28.992 Å, R= 5.5%). These investigations show the six-membered chelate ring (chelate A) to exist as formulated in [2] and not as a five-membered chelate ring B. One methanol molecule connects two chelate molecules by hydrogen bonds, resulting in an overall ratio of chelate to methanol of 1 : 1.
Sila-Pharmaka, 26. Mitt. [1]. Darstellung und Eigenschaften potentiell curarewirksamer Silicium-Verbindungen, III / Sila-Pharmaca, 26th Communication [1]. Preparation and Properties of Silicon Compounds with Potential Curare-Like Activity, III
Authors: Tacke Reinhold , Linoh Haryanto , Attar-Bashi Moayad T. , Sheldrick William S. , Ernst Ludger , Niedner Roland , Frohnecke Joachim
Published: February 2015

The potentially curare-like silicon compounds 8a-8f wore synthesized and investigated with respect to their structure-activity relationships. The conformations of the com­pounds in the solid state and in solution were studied by X-ray diffraction analysis (8a-8e) and 1H NMR spectroscopy (8a-8f), respectively. The muscle relaxing properties of 8a-8f were investigated on the mouse. The observed structure-activity relationships are not in accordance with the classical “14 Å model” for neuromuscular blocking agents.
Notizen: Übergangsmetallketen-Verbindungen, X [1]. Der Ketenidligand als Synthesebaustein für Sulfine / Compounds of Transition Metal Ketenes, X [11 The Ketene Ligand as a Synthetic Tool for Sulfines
Authors: Kreißl Fritz R. , Sieber W. , Wolfgruber M.
Published: February 2015

The η2-ketenido (η5-C5H5)(CO)[P(CH3)3]W[O=C=C-C6H4CH3-(4)] reacts with thionyl chloride forming a sulfine O = S = C(COCl)C6H4CH3-(4).
Notizen: Einkristall-Daten der Hochdruck-Hochtemperaturphase von CaSi2 / Structural Refinement of the High Pressure-High Temperature Phase of CaSi2
Authors: Evers Jürgen , Oehlinger Gilbert , Weiss Armin
Published: February 2015

The high pressure-high temperature phase of CaSi2 is a representative of the α-ThSi2 type of structure. Single crystals grown at 40 kbar and 1000 °C enabled a structural refinement which leads to interatomic distances Si-Si: 229.9(1) pm (1 × ) and 240.0(1) pm (2 × ), Ca-Si: 309.4(4) pm (4 x ) and 323.9(4) pm (8 × ), Ca-Ca: 400.3(3) pm (4 × ) and 428.3(3) pm (4 × ).
31P-NMR-Untersuchungen an linearen Thiophosphorylphosphazenen / 31P NMR Investigations on Linear Thiophosphorylphosphazenes
Authors: Schilling Gerhard , Rabener Claus W. , Lehr Wendel
Published: February 2015

The 31P NMR spectra of PCl3=N[PCl2 = N]nPCl2=S (n = O-2) undergo significant changes in ν/2 and 4JPP when the temperature is lowered. The effects are discussed in terms of T1 relaxation effects which may re­flect the mobility of phosphorus in compounds 1-3.

Bei 31P-NMR-Untersuchungen an linearen Phosphorylphosphazenon der allgemeinen Struk­tur PCl3=N[PCl2=N]nPCl2=O (n=O-3) ha­ben wir eine höchst augenfällige Abhängigkeit der Parameter Kopplungskonstante, chemische Verschiebung und Halbwertsbreito ν/2 von Lö­sungsmittel und Temperatur festgestellt [1]. Die Änderungen von ν/2 betroffen dabei vor allem die ondständige PCls-Gruppo. Es konnte gezeigt werden, daß dieser Effekt wahrschein­lich durch Relaxation über den Spinrotations- Mechanismus (T1SR) zustande kommt. Um weiteres Untersuchungsmaterial in die Hände zu bekommen und um damit zu erkennen, in wel­chen Grenzen die beschriebenen Effekte auftreten, wurden nun auch die entsprechenden Thioanaloga in die Untersuchungen mit einbe­zogen.
On the Chemistry of Ingenol, III [1] Synthesis of 3-Deoxy-3-oxoingenol, Some 5-Esters and of Ethers and Acetals of Ingenol
Authors: Sorg Bernd , Hecker Erich
Published: February 2015

3-Deoxy-3-oxoingenol (3) was prepared from ingenol-5,20-acetonide (25) by oxidation and subsequent removal of the acetonide. 3 was acylated to give homologous 5,20-diacylates 5-9. From these the 5-monoacylates 14, 15 and 17 were obtained in only moderate yields. Therefore the 20-silyl ether 10 (prepared from 3) was acylated. After smooth removal of the silyl ether the homologous 5-acylates 16. 18 and 19 resulted in good yield. The 5,20-dibutyrate 6 and all 5-acylates prepared (14-19) showed no irritant activity on the mouse ear. The 3-oxo-5-acylates 14-19 could not be reduced to give ingenol-5-acylates (24). Therefore various ingenol derivatives, 29-32, with suitable protected hydroxyl functions as well as the corresponding 5-clecanoates 35-38 were synthesized. The protecting groups of the derivatives 35-38 could however not be cleaved off to yield ingenol-5- decanoate (24)
Regioselektivität der Baeyer-Villiger- Oxidation substituierter Adamantanone / Regioseleetivity in Baeyer-Villiger-Oxidations on Substituted Adamantanones
Authors: Duddeck Helmut , Kaiser Manfred
Published: February 2015

Very high regioselectivities in Baeyer-Villigeroxidations of some 4-substituted adamantanones with strongly electron-withdrawing substituents X are observed. If the substitutents have smaller inductive effects, regioselectivities are much lower and the substituents' stereochemical position is of significance. Generally, the axial epimers are less reactive, since their Criegeeintermediates suffer severe 1,3-diaxial steric interactions
Na6CoS4 - ein Thiocobaltat mit isolierten CoS4-Anionen / Na6CoS4 - A Thiocobaltate with Isolated CoS4 Anions
Authors: Klepp Kurt , Bronger Weif
Published: February 2015

Na6CoS4 crystallizes in the hexagonal space group P 63mc with a = 890.9(2) pm and c = 687.8(2) pm, Z = 2. The crystal structure was determined from four circle diffractometer data and refined to a conventional R-value of 0.020. Na6CoS4 is isotypic with Na6ZnO4. The crystal structure can be derived from a h.c.p. arrangement of S atoms. Co atoms occupy tetrahedral voids, the resulting CoS4-tetrahedra being almost regular with an average Co-S distance of 235 pm. Na atoms occupy tetrahedral and octahedral voids in the ratio 1:1.
Characterisation of a Binary Transition Metal Complex of a Purine 3′ -Nucleotide, {[Cu3(3′ -GMP)2(3′ -GMPH)2(H2O)5]·7H2O}n. [1]. Phosphate-only Binding of Copper(II)
Authors: Sheldrick W. S.
Published: February 2015

{[Cu3(3′-GMP)2(3′-GMPH)2(H2O)5]·7H2O}n (1) was isolated from an aqueous solution of Cu(NO3)2 and guanosine 3′-monophosphate at a pH of 4.4. 1 is monoclinic space group C 2 with a = 29.140(7), b = 6.865(5), c = 16.980(7) Å, β = 90.31(3)°, Z = 2, Dc = 1.81 g·cm-3. The structure was refined to R - 0.065 with i?w = 0.060 for 2642 independent reflections. It is disordered about a crystallographic diad axis with one of the copper atoms Cu(2) sited on this axis. This and the other independent copper atom Cu(l) both display square pyramidal geometries. Cu(l) binds N(7) of a guanine base, two phosphate O atoms of nucleotide molecules not symmetry-related to one another and two water oxygens. The guanine base involved in this coordination adopts a syn-conformation relative to the ribose ring with χCN= -118.5°. Cu(2) is coordinated by four phosphate O atoms of different nucleotide molecules and one water oxygen. The second guanine base, which is not involved in metal binding, displays the anti-conformation relative to the ribose ring.
Darstellung und Eigenschaften von Fe[ClC(COOEt)2]3 / Synthesis and Properties of Fe[ClC(COOEt)2]3
Authors: Petz W. , Kremer S.
Published: February 2015

Fe2(CO)9 reacts with Cl2C(COOEt)2 to give the paramagnetic complex Fe[ClC(COOEt)2]3 in high yield. The magnetic and spectroscopic properties of this complex are discussed.
Röntgenstrukturuntersuchungen an Trimethylsilylaluminiumverbindungen / X-Ray Crystal Study of Trimethylsilylaluminium Compounds
Authors: Rösch Lutz , Altnau Gerald , Krüger Carl , Tsay Y.-H.
Published: February 2015

Structure, Tris(trimethylsilyl)aluminium, Sodium-tetrakis(trimethylsilyl)aluminate The crystal and molecular structures of three trimethylsilylaluminium compounds -tris(trimethylsilyl)aluminium coordinated to a diethylether molecule (1), sodium-tetrakis-(trimethylsilyl)aluminate coordinated to two toluene molecules (2b) and unsolvated sodium-tetrakis(trimethylsilyl)aluminate (2a) -have been determined by X-ray structure analysis. In all three compounds the aluminium is tetrahedrally coordinated, the Al-Si-distances lying between 2.44 and 2.49 Å. (1) is monomeric and (2a) and (2b) form linear chains resulting from contact-ion pair interactions.
Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, XXXVII [1]. Neue Synthesewege zu cyclischen N-Silylharnstoffen und thioharnstoffen / Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules, XXXVII [1]. New Syntheses of Cyclic N-Silylureas and -thioureas
Authors: Maringgele Walter
Published: February 2015

N-Silylated Ureas and Thioureas, Silicon Tetrachloride, Bis(dimethylamino)dimethylsilane N,N′-Diorganylureas react with silicon tetrachloride to give the 1,3,5-triaza-2-silacyclo-hexan-4,6-diones 1-4, in case of N,N′-dicyclohexylurea to give dicyclohexylcarbodiimide. By reacting bis(diethylamino)dimethylsilane with N,N′-diorganylureas and thioureas, resp., one obtains 1,3,5-triaza-2,4-disilacyclohexan-6-ones 6, 10, 13-15, 1-oxa-3,5-diaza-6-silacyclohexan-4-ones 5, 9, 1,3,5-triaza-2-silacyclohexan-4,6-diones 7, 11, 1,3-dioxa-5-aza-2,6-trisilacyclohexanes 8,12, 1,3,5-triaza-2,4-disilacyclohexan-6-thiones 16-25 or the organylamino-diethylamino-dimethylsilanes 26-28. The compounds were characterized analytically and spectroscopically.
Metallkomplexe der Liganden 1.4.7-Triazacyclononan-N.N′.N″ -tris-2-ethansulfonat (TES) und 1.4.7-Triazacyclononan-N.N′.N″ -trisethylacetat (TEA). Die Kristallstrukturen von Na[Ni(TES)(H2O)]·5H2O und Na[Cu(TES)]·3H2O / Transition Metal Complexes Containing the Ligands 1,4,7-Triazacyclononane-N,N′,N″-tris-2-ethanesulfonate (TES) and 1,4,7-Triazacyclononane-N,N′,N″-tris-ethylacetate (TEA). The Crystal Structures of Na[Ni(TES) (H2O)]·5H2O and of Na[Cu(TES)]·3H2O
Authors: Wieghardt Karl , Bossek Ursula , Guttmann Martina , Weiss Johannes
Published: February 2015

The syntheses of two new, potentially hexadentate ligands with an N3O3 donor set is reported: 1,4,7-triazacyclononane-N,N′,N″-tris-2-ethanesulfonate (TES) and 1,4,7-triazacyclononane- N,N′,N″-tris-ethylacetate (TEA). Complexes of the divalent transition metals Co(II), Ni(II), Cu(II) containing these ligands have been prepared. The kinetics of the reactions of [Con(TEA)H2O]2+ and [CoII(TCTA)]-(TCTA= 1,4,7-triazacyclononane- N,N′N″-tris-acetate) with [FeIII(CN)6]3-, respectively, have been measured. A stable binuclear [Co(TEA)(CN)6Fe]- species has been characterized in solution whereas the reaction of [Co(TCTA)]- with [Fe(CN)6]3- yields [CoIIITCTA] and [Fe(CN)6]4- via an outer-sphere electron transfer reaction (k = 5,9 × 103 1 mol-1 sec-1; 25 °C, I = 0,26 M). Na[Ni(TES)H2O]·5H2O crystallizes in the triclinic space group P1̄ (Ci
1-No 2) with cell constants a = 806,7(4), b = 1468,4(8), c = 2317,9(8) pm, α = 72,36(4)°, β = 83,48 (3)°, γ = 81,99(4)°, and Z = 4. The nickel(II) center is in a distorted octahedral environment of a pentadentate TES ligand (N3O2) and a coordinated H2O. Na[Cu(TES)] 3H2O crystallizes in the triclinic space group P1̄ (Ci
1-No 2) with cell constants a = 747,3(3), b - 1082,6(5), c = 1459,3(9) pm, α = 81,13(5)°, β = 84,75(4)°, γ = 79,39(3)°, and Z = 2. The copper(II) center is in a distorted quadratic pyramidal environment of a pentadentate TES ligand. Each of the complex anions contains one uncomplexed CH2-CH2-SO3-group.
Reactions of Alkylamino- and Dialkylaminotriphenylphosphonium Halides with Halogens and Interhalogen Compounds; Formation of Alkylaminotriphenylphosphonium Polyhalides
Authors: Zimmer Hans , Jayawant Madhusudan , Amer Adel , Ault Bruce S.
Published: February 2015

Alkylamino-and cycloalkylaminotriphenylphosphonium halides react with elemental halogens or interhalogen compounds to afford alkylamino-or cycloalkylaminotriphenyl-phosphonium trihalides. The stability of these trihalides depends on the cation as well as the trihalide anion. The assignment of a trihalide structure to these compounds was based on elemental analysis and on IR-and Raman spectroscopic evidence. Most stable are the tribromide and [IX2]⊖ salts. During all reactions involving N-alkylamino-and N-cyclo-alkylaminotriphenylphosphonium halides and elemental halogens an N-halogenation of the cation was not observed.
Styrene Forming Elimination Reaction from β-Phenylethylphosphonium Salts+
Authors: Alunni S. , Giulietti G.
Published: February 2015

β-Phenylethylphosphonium salts in RO-/ROH give styrene in amount depending on the steric requirements of the nucleophile and of the salt. The % of styrene formed increases from 22.9 with leaving group PPH3 to 85.0 with leaving group P(<-BU)3 in t-BuOK/t-BuOH. Second order rate constants at 30 °C in t-BuOK/t-BuOH are 1.1 · 10-2lm-1s-1 with leaving group P(n-Bu)3 and 0.96- 10-2 lm-1s-1 with leaving group P (cyclohexyl)3. The data are consistent with a mechanism of β-elimination.
Tetraalkyldibismutane/Tetraalkyldibismutanes
Authors: Breunig Hans Joachim , Müller Ditmar
Published: February 2015

The tetraalkyldibismutanes R2BiBiR2 (R = Et, Pr, iPr, Bu) were synthesized by reactions of 1,2-dibromoethane with sodium dialkylbismutides, which were produced by cleavage of the corresponding trialkylbismutanes with sodium in liquid ammonia. The dibismutanes were isolated in good yields as air sensitive red liquids. Spectral data of dibismutanes and some bismutanes are compared with data of their antimony analogues. 1H NMR spectra reveal, that the methylene protons in Et4Bi2 as well as the methyl groups in iPr4Bi2 are diastereotopic.
Das Zustandsdiagramm Thallium(I)iodid-Thallium(I)selenid und die Kristallslruktur der Verbindungsklasse Tl6X4Y/The System Thallous Iodide -Thallous Selenide and the Structure of the Tl6X4Y Compounds
Authors: Blachnik R. , Dreisbach H. A. , Engelen B.
Published: February 2015

The system TlI-Tl2Se was investigated by DTA, X-ray and metallographic methods. At the Tl2Se corner of the system a solid solution up to 25 mol% TlI is observed, which decomposes peritectically at 681 K. Two new compounds Tl5ISe2 and Tl6I4Se were found. The latter is isotypic to a class of compounds found in the TlX-TI2S systems [2]. The crystal structure of Tl6Cl4S was determined. It is based on the TlCl structure (CsCl-type) in which 1/5 of the Tl or Cl atoms, resp., are substituted by Tl2S in a regular manner. The coordination of the anions (Cl, S) is very similar to the coordination of Cl in TlCl or S in Tl2S resp.
Dimethylphosphinatotrichloroantimon(V)-Verbindiingen/ Dimethylphosphinatotrichloroantimony(V) Compounds
Authors: Blösl S. , Schmidt A.
Published: February 2015

d,h-μ-Dimethylphosphinato-e-μ-methoxo-f-μ-oxo-bis[trichloroantimony(V)] (1) and bis-(μ-dimethylphosphinato)-μ-oxo-bis[trichloroantimony(V)] (2) were prepared by reaction of bis(μ-dimethylphosphinato-0,0′)-bis[tetrachloroantimony(V)] with antimony(V)-chlo-ride/water 1:1 and antimony(V)-chloride/water/methanol 1:1:1, resp. The crystal and molecular structure of 2 was determined by X-ray analysis. The vibrational spectra of 1 and 2 are discussed. The mass spectrum of 2 was measured and the fragmentation classified.
Alkylammonium-chloroantimonate(III) Struktur und Schwingungsspektren/Alkylammoniumchloroantimonates(III). Structure and Vibrational Spectra
Authors: Ensinger U. , Schwarz W. , Schmidt A.
Published: February 2015

The crystal and molecular structures of triethylammonium tetrachloroantimonate(III) (1) and tris[methylammonium] hexachloroantimonate(III) (2) were determined by X-ray analysis. In compound 1, SbCl3 molecules are bridged by Cl ions to form chains. The coordination of Sb by Cl atoms yields a distorted tetragonal-pyramidal structure. In compound 2 there are chains of SbCL4
- ions, again through bridging by Cl ions. One Cl ion has no contacts to Sb. The cations of 1 and 2 form hydrogen bonds with the anionic components.
Hochdrucksynthese quaternärer Chalkogenidhalogenide AB2X3Y (A = Cu, Ag; B = In; X = S, Se, Te; Y = Cl, Br, I)/High Pressure Synthesis of Quaternary Chalcogenide Halogenides AB2X3Y (A = Cu, Ag; B = In; X = S, Se, Te; Y = Cl, Br, I)
Authors: Range Klaus-Jürgen , Hübner Heinz-Joachim
Published: February 2015

Quaternary compounds AB2X3Y (A = Cu, Ag; B = In; X = S, Se, Te; Y = Cl, Br, I) could be synthesized at high pressures and temperatures. The crystal structures found are defect-zincblende (AgIn2Se3I, AgIn2Te3l, CuIn2Se3Br, CuIn2Se3I, CuIn2Te3Cl, CuIn2Te3Br, CuInTe3I), spinel (AgIn2S3Cl, AgIn2S3Br, AgIn2Se3Cl, AgIn2Se3Br, AgIn2Se3l) and defect-rocksalt (AgIn2Te3Cl, AgIn2Te3Br). A second form of CuIn2Se3l is intermediate between the zincblende and spinel structure. A survey of the different reaction pathways of AB-B2X3 mixtures at high pressures and temperatures is given.
Photochemisches Verhalten von (CF3S)2CS in Inertgasmatrix/Photochemical Behavior of (CF3S)2CS in Rare Gas Matrix
Authors: Schlosser Karl , Willner Helge
Published: February 2015

Infrared spectra have been recorded of (CF3S)2CS in the gas and solid phase as well as isolated in noble gas matrix; the Raman spectra of the liquid have also been taken. The analyses of the spectra show that this compound consists of a complex mixture of conformers. By photolysis in a matrix with light of wavelength > 300 nm the distribution of the conformers changes and with light of wavelength > 530 nm this change can be reversed. The threshold for photochemical decomposition in the matrix is about 300 nm. The decomposition products consist of an equimolar mixture of CF3SCF3 and CS2.
Reactions of Dicyanogen and Cyanogen Halides with the Biscyclopentadienyls of Vanadium and Chromium
Authors: Morán Moisés , Gayoso Miguel
Published: February 2015

The oxidative addition of dicyanogen, (CN)2, and of the cyanogen halides, XCN (X = Cl, Br or I), to the biscyclopentadienyl compounds of vanadium and chromium, (η-C5H5)2M (M = V or Cr), leads to the formation of (η-C5H5)2MX(CN) (X = CN, Cl, Br, I; M = V or Cr). The synthesized compounds have been characterized by elemental analyses, IR and EPR spectra, and determinations of the magnetic moments.
He(I) and He(II) Photoelectron Spectra of Some L3MCo(CO)4 Complexes (M = Si, Ge, Sn, Pb and L = Cl, Br and CH3)
Authors: Louwen Jaap N. , Andréa Ronald R. , Stufkens Derk J. , Oskam Ad
Published: February 2015

The He(I) and He(II) photoelectron spectra of L3MCo(CO)4 complexes (M = Si, Ge, Sn, and Pb and L = Cl, Brand CH3) are reported. Bands attributable to the metal-cobalt bond, cobalt 3d and CO orbitals are assigned in agreement with a qualitative MO model. Relativistic effects and He(I)/He(II) intensity ratios prove to be important in assigning these ultraviolet photoelectron spectra.
Hydroxyl Radical-Induced Oxidation of Ethanol in Oxygenated Aqueous Solutions. A Pulse Radiolysis and Product Study
Authors: Bothe Eberhard , Schuchmann Man Nien , Schulte-Frohlinde Dietrich , Sonntag Clemens von
Published: February 2015

γ-Radiolysis of N2O-saturated water or photolysis of aqueous H2O2 provided a source of OH radicals. These radicals react with ethanol by preferentially abstracting an H atom at C-1. In the presence of oxygen these radicals are converted into the corresponding peroxyl radicals.

The a-hydroxyethylperoxyl radicals decay by first order kinetic(k=k1 + k2 [OH-]) acetaldehyde and HO2
˙/H+ + O2 ⨪ being the products (k1 (20 °C) = 50 ± 10 s-1 , Ea = 66 ± 7 kJ·mol-1 , k2= (4± 1) X 109 M-1 s-1). In competition (favoured by low pH, low temperature and high dose rate) they also decay by second order kinetics (2k3 = (7 ± 2) x 108 M-1 s-1). The most important route in the bimolecular decay leads to acetaldehyde, acetic acid and oxygen (ca. 75%). This route might largely be concerted (Russell mechanism), but there might also be a contribution from the disproportionation of oxyl radicals within the solvent cage. There is also a concerted route that leads to two molecules of acetic acid and to hydrogen peroxide (ca. 10%). Another pathway (ca. 15%) yields two oxyl radicals and oxygen. The former may either decompose into formic acid and methyl radicals (ca. 5%) or rearrange into 1,1-dihydroxyethyl radicals (ca. 10%). These radicals add oxygen and the resulting peroxyl radicals rapidly decompose into acetic acid and HO2
˙. The reaction of a-hydroxyethylperoxyl radicals with HO2
˙/O2⨪ radicals appears to be slow (k≈107 M-1s-1).
Stereochemistry and Tautomerism of Amino Acid Antagonists: α,γ-Diketo Acids and Esters and their Cyclisation Products
Authors: Sheldrick W. S. , Trowitzsch W.
Published: February 2015

X-ray structural analyses of two α,γ-diketo esters and one α,γ-diketo acid, which are amino acid antagonists, have shown them all to be present in the solid state in the α,β-unsaturated γ-keto enolic form. The structures of the esters β-acetyl-pyruvic acid methyl ester (1) and 2-oxo-cyclopentyl-glyoxylic acid ethyl ester (3) are stabilized by intra-molecular O···H(-O) hydrogen bonds involving the enol proton. In the case of camphor oxalic acid (4) an intramolecular O···H-O hydrogen bond between the γ-keto oxygen and the acid proton is observed. The bond lengths and angles in 1 indicate a significant contribution from the mesomeric β,γ-unsaturated enol form. For comparison purposes the structure of the γ-enol methyl ether of 1, (4-methoxy-2-oxo-pentene)carboxylic acid methyl ester (2) has also been determined. The X-ray structures of the cyclization products of respectively an α,γ-diketo acid and an α,γ-diketo ester are reported.
ESR-Untersuchungen des Adrenalon-Semichinons und analoger Verbindungen/ESR-Investigations of Adrenalone-Semiquinones and Related Compounds
Authors: Stegmann Hartmut B. , Stolze Klaus , Schelfler Klaus
Published: February 2015

The autoxidation of adrenalone and other 4-acyl-catecholamines in the presence of diorganothalliumhydroxide are investigated by ESR-spectroscopy. On the basis of the counterion splitting and the proton coupling constants as well as the g-values a semi-quinone structure was established. By comparing several monosubstituted o-benzosemi-quinones an increment system for the assignment of the different proton coupling constants was developed. The agreement between experimental and calculated values is good for all compounds investigated. Prolonged autoxidation of adrenalone yields a stable para-magnetic secondary product.