| 21 | Author
| S. Alunni, G. Giulietti | Requires cookie* | | Title
|  | | | Abstract
| Alkoxides, Decomposition, /3-Phenylethylphosphonium Salts Styrene Kinetics /?-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 PPI13 to 85.0 with leaving group P(<-BU)3 in t-BuOK/t-BuOH.. Second order rate constants at 30 °C in Z-BuOK/£-BuOH are 1.1 • 10 _2 lm-1 s~ 1 with leaving group P(w-Bu)3 and 0.96-10~ 2 lm _1 s _1 with leaving group P (cyclohexyl)3. The data are consistent with a mechanism of ^-elimination. | | |
Reference
| (Z. Naturforsch. 38b, 115—116 [1983]; received June 23 1982) | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0115_n.pdf | | | Identifier
| ZNB-1983-38b-0115_n | | | Volume
| 38 | |
23 | Author
| Marianne Baudler, Siegfried Klautke | Requires cookie* | | Title
| Beiträge zur Chemie des Phosphors, 124 [1, 2]  | | | Abstract
| Tri-terJ-butyl-diphosphastiba-cyclopropan, (f-BuP)2Sb(t-Bu) Contributions to the Chemistry of Phosphorus, 124 [1, 2] Tri-ferf-butyl-diphosphastiba-cyclopropane, (£-BuP)2Sb(£-Bu) | | |
Reference
| (Z. Naturforsch. 38b, 121—124 [1983]; eingegangen am 18. Oktober 1982) | | |
Published
| 1983 | | |
Keywords
| Tri-Zer£-butyl-diphosphastiba-cyclopropane, Tri-feri-butyl-diphosphastibirane, Cyclostibaphosphanes, Heterocyclophosphanes | | |
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| default:Reihe_B/38/ZNB-1983-38b-0121.pdf | | | Identifier
| ZNB-1983-38b-0121 | | | Volume
| 38 | |
25 | Author
| Jürgen Köhler, Rudolf Hoppe | Requires cookie* | | Title
| Ein neues kationenreiches Oxogallat [1] Zur Kenntnis von K2Li3Ga04 A New Cation Rich Oxogallate [1] About K2Li3Ga04  | | | Abstract
| The new compound K^LißGaC^ was prepared from binary oxides (powder) and from LiGa02/KOo.48 (colourless transparent single crystals) in a closed Ag cylinder at 600 °C. It crystallizes in the monoclinic space group P2i/c with the constants a = 553.6(2) 6 = 880.4(3) c = 1093.1(4) pm ß = 111.52(3)°. Z — 4, drö = 3.OI7 and dpyk = 2.97 g-cm -3 . [4-circle diffractometer data, 1333 Io (hkl), Mo-Ka, R = 4.95 and i?w = 5.04%, anisotropic refinement.] The new structure type is complicated. The characteristical features are shown using Schlegel projections of the coordination polyhedrons. Extended Schlegel Diagrams, a novel application of graph theory, are used. They describe bijective how the coordination polyhedra are three-dimensionally combined. | | |
Reference
| (Z. Naturforsch. 38b, 130—138 [1983]; eingegangen am 31. August 1982) | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0130.pdf | | | Identifier
| ZNB-1983-38b-0130 | | | Volume
| 38 | |
27 | Author
| S. Blösl, W. Schwarz, A. Schmidt | Requires cookie* | | Title
| Dimethylphosphinatotrichloroantimon(V)-Verbindiingeii Dimethylphosphinatotrichloroantimony(V) Compounds  | | | Abstract
| Trichloroantimony(V) Compounds d,h-/^-Dimethylphosphinato-e-/u-methoxo-f-//-oxo-bis[trichloroantimony(Y)] (1) and bis-(^-dimethylphosphinato)-ia-oxo-bis[trichloroantimony(V)] (2) were prepared by reaction of bis(//-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. | | |
Reference
| Z. Naturforsch. 38b, 143—148 (1983); eingegangen am 21. Oktober 1982 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0143.pdf | | | Identifier
| ZNB-1983-38b-0143 | | | Volume
| 38 | |
29 | Author
| Klaus-Jürgen Range, Heinz-Joachim Hübner | Requires cookie* | | Title
| 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  | | | Abstract
| 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 (AgIn2Se3l, AgIn2Te3l, CuIn2Se3Br, CuIn2Se3I, CuIn2Te3Cl, CuIn2Te3Br, CuInTesI), 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. | | |
Reference
| Z. Naturforsch. 38b, 155—160 (1983); eingegangen am 25. Oktober 1982 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0155.pdf | | | Identifier
| ZNB-1983-38b-0155 | | | Volume
| 38 | |
32 | Author
| Doris Bodenstein, William Clegg, Gerhard Jäger, PeterG. Jones, Horst Rumpel, Einhard Schwarzmann, GeorgeM. Sheldrick | Requires cookie* | | Title
| Darstellung und Kristallstrukturen einiger MSb5013-Verbindungen (M = H30, Na, K) Preparation and Crystal Structure of Some MSbö0i3 Compounds (M = H3O, Na, K)  | | | Abstract
| Crystal Structure, Antimonate(V) The compounds MSbsOi3 (M = H3O, Na, K) have been prepared and characterised by chemical analysis and X-ray structure determination. They are isostructural, space group Cmem, with a = 657.7(2), 657.3(2), 658.4(2); b = 887.3(3), 888.7(2), 888.2(2); c = 1682.6(5), 1651.5(3), 1677.0(3) pm for M = H30, Na, K, respectively. The polymeric structures consist of SbOß octahedra linked via edges and vertices to form an Sb50i3 framework, in which the univalent cations occupy holes. Because these ions display severe disorder, X-ray methods alone would not be sufficient to establish the chemical constitutions. | | |
Reference
| Z. Naturforsch. 38b, 172—176 (1983); eingegangen am 6. Oktober 1982 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0172.pdf | | | Identifier
| ZNB-1983-38b-0172 | | | Volume
| 38 | |
33 | Author
| Moisés Morán, Miguel Gayoso | Requires cookie* | | Title
| Reactions of Dicyanogen and Cyanogen Halides with the Biscyclopentadienyls of Vanadium and Chromium  | | | Abstract
| 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, (/y-C^Hs^M (M = V or Cr), leads to the formation of (/?-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. | | |
Reference
| Z. Naturforsch. 38b, 177—180 (1983); received July 9/September 29 1982 | | |
Published
| 1983 | | |
Keywords
| Cyanogen Halides, Vanadium, Chromium | | |
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| default:Reihe_B/38/ZNB-1983-38b-0177.pdf | | | Identifier
| ZNB-1983-38b-0177 | | | Volume
| 38 | |
34 | Author
| Hans-Jörg Deiseroth, Han Fu-Son | Requires cookie* | | Title
| Cs6Ga2Se6, ein ternäres Selenogallat(III) mit isolierten [Ga2Se6] 6 --Ionen Cs6Ga2Se6, a Ternary Selenogallate(III) with Isolated [Ga2Se6] 6_ Ions  | | | Abstract
| Cs6Ga2Se6 can be prepared from mixtures of Cs2Se and Ga2Se3. The transparent single crystals of the moisture sensitive compound (m.p. 685 °C) crystallize in the monoclinic system with a = 848.0(5), b = 1364.4(5), c = 1111.5(5) pm, ß = 126.22(5)° (T = —150 °C, Z — 2, space group P2i/c). The gallium atoms pairwisely occupy selected tetrahedral holes between layers formed by the cesium and selenium ions. This structural principle leads to the formation of double tetrahedral isolated [Ga2Se6] 6-ions. | | |
Reference
| Z. Naturforsch. 38b, 181—182 (1983); eingegangen am 15. Oktober 1982 | | |
Published
| 1983 | | |
Keywords
| Cesium Selenogallate, Crystal Structure, Thermal Properties | | |
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| default:Reihe_B/38/ZNB-1983-38b-0181.pdf | | | Identifier
| ZNB-1983-38b-0181 | | | Volume
| 38 | |
35 | Author
| W. Preetz, H. Schulz | Requires cookie* | | Title
| Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [0s02(ox)2] 2 -und [0s02(mal)2] 2 - Vibrational Fine Structure on the Electronic Absorption Spectra of [0s02(ox)2] 2 -and [0s02(mal)2] 2  | | | Abstract
| Bisoxalato-osmate(VI), Bismalonato-osmate(VI), UV-VIS Spectra, Vibrational Fine Structure The complexes (TBA)2[Os02(ox)2] and (TBA)2[0s02(mal)2] have been prepared and characterized. The IR and Raman frequencies are assigned according to point group D2h. The electronic absorption spectra measured on thin films of the solid complex salts on silica discs at 10 K show well resolved vibrational fine structure. Two very weak bands (e: 4-58) in the visible region are assigned to d-d transitions from the singlet ground state ag 2 (dxy) to a triplet and singlet term of the equivalent ji* orbitals b2g/b3g (dxz, dyz). The two more intense band systems (e: 500-1500) in the UV region are attributed to CT transitions from b2u/b3u n orbitals of tbe oxo ligands to the lowest unoccupied orbitals b2g/b3g of the central ion. These electronic transitions couple with vs(0s — 0) as indicated by the main progression of about 700 cm -1 . In comparison to the vibrational ground state this lowered frequency is caused by population of antibonding n levels. The loosening of the 0s = 0 bonds in the excited state is demonstrated by high anharmonic constants (—2.5 to —10.5 cm -1) and the estimated bond lengthening of about 12 pm. Moreover the vibrational fine structure of the malonato complex shows many combination modes of i's(0s = 0) with other symmetric fundamentals. Due to lower site symmetry in the solid state the CT transitions of the malonato compound are split into 2 components with a spacing of about 200 cm-1 . | | |
Reference
| Z. Naturforsch. 38b, 183—189 (1983); eingegangen am 11. Oktober 1982 | | |
Published
| 1983 | | |
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| default:Reihe_B/38/ZNB-1983-38b-0183.pdf | | | Identifier
| ZNB-1983-38b-0183 | | | Volume
| 38 | |
36 | Author
| Reinhold Tacke, Hartwig Lange, Anke Bentlage, WilliamS. Sheldrick, Ludger Ernst | Requires cookie* | | Title
| 2.2.5.5-Tetraorganyl-1.4-dioxa-2.5-disilacyclohexane 2,2,5,5-Tetraorganyl-l,4-dioxa-2,5-disilacyclohexanes  | | | Abstract
| The 2,2,5,5-tetraorganyl-l,4-dioxa-2,5-disilacyclohexanes 2a-2c were prepared by condensation of the corresponding (hydroxymethyl)diorganylsilanes 1 a-1 c. The constitu-tion of the heterocycles was confirmed by elemental analyses, cryoscopic measurements, mass spectrometry, and NMR-spectroscopic (X H, 13 C) investigations. The molecular struc-ture of 2 b was determined by X-ray diffraction analysis. | | |
Reference
| Z. Naturforsch. 38b, 190—193 (1983); eingegangen am 11. Oktober 1982 | | |
Published
| 1983 | | |
Keywords
| l, 4-Dioxa-2, 5-disila-cyclohexane Ring System, Synthesis, Structure | | |
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| default:Reihe_B/38/ZNB-1983-38b-0190.pdf | | | Identifier
| ZNB-1983-38b-0190 | | | Volume
| 38 | |
37 | Author
| JaapN. Louwen, RonaldR. Andréa, DerkJ. Stufkens, Ad Oskam | Requires cookie* | | Title
| He(I) and He(II) Photoelectron Spectra of Some L3MCo(CO)4 Complexes (M = Si, Ge, Sn, Pb and L = Cl, Br and CH3)  | | | Abstract
| 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. Rela-tivistic effects and He(I)/He(II) intensity ratios prove to be important in assigning these ultraviolet photoelectron spectra. | | |
Reference
| Z. Naturforsch. 38b, 194—202 (1983); received October 3 1982 | | |
Published
| 1983 | | |
Keywords
| Metal-Metal Bond, UPS, Cobalt Complexes, Relativistic Effects, Ionization Potentials | | |
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| default:Reihe_B/38/ZNB-1983-38b-0194.pdf | | | Identifier
| ZNB-1983-38b-0194 | | | Volume
| 38 | |
39 | Author
| Dieter Weber, Karl Peters, Hans Georg, Schnering, Ekkehard Fluck | Requires cookie* | | Title
| Kristallstruktur yon Pyrrolidinium-bis(diisopropylphosphinoyl)phosphid, einem System mit zweifach koordiniertem Phosphor Crystal Structure of Pyrrolidinium-bis(diisopropylphosphinoyl)phosphide, a System with Bicoordinated Phosphorus  | | | Abstract
| Pyrrolidinium-bis(diisopropylphosphinoyl)phosphide crystallizes triclinically in the space group Pi with a = 1019.6(8), b = 1271.5(4), c = 999.5(7) pm, a = 100.90(5)°, ß = 91.24(5)°, y = 99.10(5)° and Z = 2 formula units. The mean P-P bond length is 212.2 pm and hence shorter than in derivates in which the electron pairs of the bicoordi-nated phosphorus atom are bonded to one or two M(CO)5-groups. Additional p.-z-d* bonding explains the shortening of the P-P bond. | | |
Reference
| Z. Naturforsch. 38b, 208—211 (1983); eingegangen am 13. Oktober 1982 | | |
Published
| 1983 | | |
Keywords
| Pyrrolidinium-bis(diisopropylphosphinoyl)phosphide, Crystal Structure, NMR Spectra | | |
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| default:Reihe_B/38/ZNB-1983-38b-0208.pdf | | | Identifier
| ZNB-1983-38b-0208 | | | Volume
| 38 | |
40 | Author
| Eberhard Bothe, Nien Man, Dietrich Schuchmann, Schulte-Frohlinde, Clemens Von Sonntag | Requires cookie* | | Title
| Hydroxyl Radical-Induced Oxidation of Ethanol in Oxygenated Aqueous Solutions. A Pulse Radiolysis and Product Study  | | | Abstract
| y-Radiolysis of N20-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-l. In the presence of oxygen these radicals are converted into the corresponding peroxyl radicals. The a-hydroxyethylperoxyl radicals decay by first order kinetics (k = ki + k2 [OH -]) acetaldehyde and H02/H+ + 01 being the products (ki (20 °C) = 50 ± 10 s" 1 , Ea = 66 ± 7 kJ-mol -1 , k2= (4± 1) X 10 9 M -1 s -1). In competition (favoured by low pH, low tem-perature and high dose rate) they also decay by second order kinetics (2k3 = (7 ^ 2) x 10 8 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 mech-anism), 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 H02/02 radicals appears to be slow (k» 10 7 M-is-i). | | |
Reference
| Z. Naturforsch. 38b, 212—219 (1983); received September 28 1982 | | |
Published
| 1983 | | |
Keywords
| Pulse Conductometry, Peroxyl Radicals, Oxyl Radicals, Radical Rearrangements, Radiation Chemistry | | |
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| default:Reihe_B/38/ZNB-1983-38b-0212.pdf | | | Identifier
| ZNB-1983-38b-0212 | | | Volume
| 38 | |
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