Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 8

August 1980

Volume 19, Issue 8

Pages 575–658

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Physicochemical Principles and Applications of Supercritical Fluid Chromatography (SFC). New analytical methods (19) (pages 575–587)

      Dr. Ulrich van Wasen, Dipl.-Chem. Issam Swaid and Prof. Dr. Gerhard M. Schneider

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198005753

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      The use of highly compressed gases in the critical temperature range as mobile phases has many advantages in the separation of nonvolatile or thermally unstable substances. Typical applications are for the separation of oligomers and in the petroleum industry.

    2. Valence Changes at High Pressure in Systems Containing Lanthanoids (pages 587–593)

      Prof. Dr. A. Jayaraman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198005871

      A transformation strongly reminiscent of alchemy occurs on the pressure-in-duced valence change in SmS, for the originally dull, black substance glitters like gold once the electronic transition has taken place. As a novel feature, the valence state of Sm fluctuates rapidly between two electronic configurations. Phases having so-called homogeneously mixted valence states may prove to be particularly effective catalysts.

    3. Liquid Metals and Liquid Semiconductors (pages 593–606)

      Prof. Dr. Friedrich Hensel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198005931

      Electrical properties resembling those of crystalline or amorphous semiconductors are found for molten ionic CsAu and covalent Se as well as some expanded metals. Changes in chemical interaction, and hence in the close-range order of liquid structure, with temperature, density, or concentration are of fundamental significance for the (continuous) transition to “semiconducting” behavior.

    4. The Influence of Density and Temperature on the Properties of Pure Molten Salts (pages 606–619)

      Dr. Klaus Tödheide

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006061

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      Studies on the statistical and dynamic structure of fused salts and their relationship with macroscopic properties provide a consistent, even if incomplete picture. This applies in particular to the transition from an insulator to an ionic conductor on compression of a vaporized salt.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Unusually Rapid cis-trans Isomerization of a Tetrasilylated Ethylene: Generation of Free Radicals During the Rotation (page 620)

      Prof. Dr. Hideki Sakurai, Dipl.-Chem. Hiromi Tobita, Dr. Mitsuo Kira and Dr. Yasuhiro Nakadaira

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006201

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      A radical mechanism for the fast cis-trans isomerization of (1) is suggested by results obtained with the parent compound. By H abstraction (e.g. from the solvent) it forms the (Me3Si)2CH[BOND]C(SiMe3)2 radical, detectable by ESR spectroscopy.

    2. Synthesis and Rearrangement of Azulenesulfonium Salts (pages 621–622)

      Dipl.-Ing. Manfred Müller, Dr. Siegmar Braun and Prof. Dr. Klaus Hafner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006211

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      4-Functionalized azulenes have become accessible via the sulfonium salt (1), X = SMemath imageBFmath image. On rearrangement of this salt to (3) the dihydro derivative (2) can be isolated, whose formation is of interest in connection with the Sommelet rearrangement.

    3. Dimerization of Propylene with Catalysts Exhibiting Activities Like Highly-Active Enzymes (pages 622–623)

      Prof. Dr. Borislav Bogdanović, Ing. (grad.) Bernd Spliethoff and Prof. Dr. Günther Wilke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006221

      The most active synthetic homogeneous catalysts yet obtained are solutions of EtAlCl2 and (π-C3H5)NiBrP(C6H11)3 which effect the dimerization of propylene. The catalysts are about 1000 times as active as was determined in 1963 under unfavorable experimental conditions. The turnover number/s extrapolated to room temperature is ca. 60 000; compare 100 for hexokinase, 80 000 for catalase, and 600 000 for carboanhydrase.

    4. Solubility of Nonvolatile Biochemical Substances in Compressed Carbon Dioxide (pages 623–624)

      Dr. Ziad Alwani

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006231

      The extraction of natural products with compressed carbon dioxide has already found industrial application. Studies on the model substance α-tocopheryl acetate showed that its solubility (i) increases in liquid and supercritical CO2 with increasing pressure and (ii) changes comparatively little when CO2 is warmed at constant pressure from subcritical to supercritical temperature.

    5. Dianion and Tetraanion of [24] Paracyclophanetetraene—New Unusual Perimeter Systems (pages 624–625)

      Dr. Walter Huber, Prof. Dr. Klaus Müllen and Dr. Olof Wennerström

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006241

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      The existence of peripheral ring currents in the dianion and the tetraanion of (1) is manifested in the NMR spectra. In the case of (1), the dianion, and the tetraanion, H-3 (outer) absorbs at δ = 7.37, 9.26, and 4.48, respectively, and H-4 (inner) at 7.37, −7.07 (!), and 12.76, respectively. From the viewpoint of bonding theory, it is particularly surprising that perimeter conjugation extends beyond the benzene units.

    6. Lithiated Allyl N,N-Dialkylcarbamates as Homoenolate Equivalents; Synthesis of Protected 4-Oxoalkanoates (pages 625–627)

      Priv.-Doz. Dr. Dieter Hoppe, Rudolf Hanko and Alfons Brönneke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006251

      Thumbnail image of graphical abstract

      New homoenolate equivalents are now also accessible from substituted allyloxy derivatives (1) by direct metalation; the device employed is acidification of the γ-protons by the protecting group.

    7. A New Preparation of 4-Aminobutyramide (page 627)

      Dr. Axel Kleemann, Dr. Wolfgang Leuchtenberger, Dr. Jürgen Martens and Horst Weigel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006271

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      The first high-yield synthesis of the biologically important title compound(3) and the intermediate (2) uses the inexpensive starting materials hydrocyanic acid and acrylamide (1).

    8. (6R, 7R)-( – )-7-Hydroxy-3-oxabicyclo[4.3.0]non-1-en-9-one, A Readily Accessible and Highly Versatile Intermediate (page 628)

      Prof. Dr. Klaus Weinges, Dipl.-Chem., Dipl.-Biol. Herbert von der Eltz and Dipl.-Chem. Dao Tran-Viet

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006281

      Thumbnail image of graphical abstract

      Of potential interest as key compound for the synthesis of natural products, especially prostanoids, is the keto enol ether (2). It is accessible in only two steps without time-consuming separations from the catalpol derivative (1) (GAC = tetraacetyl-β-D-glucopyranosyl).

    9. Vitamin B12 and a Vitamin B12 Model Compound as Catalysts of Reductive Removal of β-Haloethyl Protecting Groups from Acids (pages 629–630)

      Prof. Dr. Rolf Scheffold and Dr. Erik Amble

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006291

      The transformation of β-chloroethyl esters (1) into acids (2) under extremely mild conditions, i.e. removal of the protecting group Cl(CH2)2[BOND], can be accomplished with zinc dust/NH4Cl or electrochemically. The catalyst is vitamin B12 or a model compound. Even lactam rings remain intact during the deprotection.

      • equation image
    10. Optically Active Chalcogran (2-Ethyl-1,6-dioxaspiro[4.4]nonane) (pages 630–631)

      Dr. Hartmut Redlich and Dr. Wittko Francke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006301

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      An example of the use of open-chain sugar dithioacetals in the synthesis of natural products is seen in reaction of (1) (from D-glucose) to give (2R,5RS)-chalcogran (2). (2S,5RS)-(2) was also prepared. These compounds were required in order to establish what diastereomeric mixtures serve as alarm pheromones in the bark beetle Pityogenes chalcographus (L.) and a close relative.

    11. 4,5-Benzotricyclo[4.1.0.01,3]hept-4-ene (pages 631–632)

      Dr. Udo H. Brinker and Joachim Streu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006311

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      A novel highly strained hydrocarbon, the tetracyclic compound(1), has been synthesized from o-divinylbenzene. The structure of (1) is secured by spectroscopic data. Compound (1) provides the first opportunity of studying the interaction between the spiropentane unit and the benzene ring.

    12. Reactions of Cycloalkeno-1,2,3-selenadiazoles with Transition Metal Carbonyls (pages 632–633)

      Prof. Dr. Keith H. Pannell, Dr. Armin J. Mayr, Rodney Hoggard and Prof. Dr. Roger C. Pettersen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006321

      Thumbnail image of graphical abstract

      Complexes of a new type, the cage compounds (1), n = 4, 5, 6, are formed at room temperature from annelated selenadiazoles with Fe2(CO)9. On heating, the complexes (1) are transformed into known complexes with two Fe(CO)3 ligands.

    13. Template Polymerization of Rhodium(I) with Rigid Bent Diisocyanide Ligands (pages 633–634)

      Prof. Dr. Avi Efraty, Irene Feinstein, Lorenz Wackerle and Felix Frolow

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006331

      Two-dimensional polymeric networks of the type [Rh(Bridge)math image Cl]n are present in the green polycrystalline material obtained from [Rh(CO)2Cl]2 and bridging ligands such as 1,3-diisocyanobenzene and 4,4′-diisocyanodiphenylmethane. These bidentate ligands cannot form chelates. Information about the structure of the polymers was derived from X-ray powder diagrams.

    14. New C8H10 Isomers: 2-Methylenebicyclo[3.2.0]hept-6-ene and 3-Methylenetricyclo[4.1.0.02,7]heptane—Thermal and Metal-Catalyzed Rearrangements (pages 634–636)

      Priv.-Doz. Dr. Dieter Hasselmann and Dr. Klaus Loosen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006341

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      The highly strained, new xylene isomers (1) and (2) are of interest for mechanistic studies. (1) undergoes thermal isomerization to (3) and (4). In n-heptane solution, (2) forms (1) [which in turn gives a little (3) and (4)], whereas (3) and (4) are formed directly from (2) in the gaseous phase. Formation of (5) is surprising.

    15. 13C-NMR Spectroscopic Studies on [13C]methylated Bituminous Coal (pages 636–637)

      Priv.-Doz. Dr. Matthias W. Haenel, Dr. Richard Mynott, Dr. Klaus Niemann, Ing. grad. Udo-Burckhard Richter and Lother Schanne

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006361

      13C-NMR studies on bituminous coal require preparation of soluble derivatives largely retaining the original structure of the coal. Reductive methylation with solvated electrons/13CH3I satisfies these requirements. The spectrum reveals that the methyl groups are linked mainly to tertiary and quaternary (benzylic) C atoms.—This chemical derivatization with isotopically labeled groups should also be suitable for the study of polymers.

    16. Transition-Metal Complexes of Malonaldehyde and Dithiomalonaldehyde (pages 638–639)

      Dr. Ulrich T. Mueller-Westerhoff and Dr. Arnold Alscher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006381

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      Planar, sterically undemanding Ni, Pd, and Pt complexes of type (1)—useful donor components for CT complexes—have been synthesized from tetraethoxypropane, ethanol, HCl, H2S, and MCl2. The NMR spectra of Pt(ptt)2, (1), M = Pt, X = S, suggest strong electron delocalization.

    17. The Question of Bicycloconjugation in Naphtho-Fused 9-Heterobicyclo[4.2.1]nona-2,4,7-trienes as Examined by 13C-NMR Spectroscopy (pages 639–640)

      Prof. Dr. A. G. Anastassiou, Dr. H. S. Kasmai and R. Badri

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006391

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      Fundamental differences with regard to bicycloconjugation exist between the structurally related systems (1) and (2), X = NH. (1) is bicycloconjugated, whereas (2) is not, entirely in keeping with theoretical predictions.

    18. Permethylated Electron-Excess Metallocenes (pages 640–641)

      Dr. Ulrich Koelle and Dipl.-Chem. Fouad Khouzami

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006401

      Thumbnail image of graphical abstract

      The new compounds permethylcobaltocene and -nickelocene show some surprising reactions which are impossible in the case of the parent compounds. For example, as the first neutral 20-electron complex, permethyl-nick-elocene adds electrophiles R′X to form the novel salts (1), which are stable to air and water.

    19. Conformational Analysis of 1-Phenylethyl Substituents in Metal Complexes and Their Importance for Asymmetric Catalysis (pages 641–642)

      Prof. Dr. Henri Brunner, Dipl.-Chem. Giuseppe Agrifoglio, Prof. Dr. Ivan Bernal and Michael W. Creswick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006411

      Thumbnail image of graphical abstract

      Diastereomeric molybdenum complexes (1A) and (1B) are formed from CpMo(CO)3Cl and the corresponding (S)-amidine. Complexes of type (1) are catalytically active. Knowledge gained in the case of (1A) (X-ray structure analysis) should permit a controlled influence of optically active 1-phenylalkyl substituents on the coordination sites adjacent to the chelate ring in other amidinato complexes.

    20. N-Fluoroiminosulfur Tetrafluoride, F[BOND]N[DOUBLE BOND]SF4 (page 643)

      Prof. Dr. Darryl D. DesMarteau and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006431

      Thumbnail image of graphical abstract

      The simplest fluorinated sulfur(VI) imide has been synthesized starting from Cl2N[BOND]SF5. The molecule of (1) is rigid with the[DOUBLE BOND]N[BOND]F group in an equatorial position. For comparison: CH3[BOND]N[DOUBLE BOND]SF4 and O[DOUBLE BOND]SF4 are mobile, whereas CH2[DOUBLE BOND]SF4 is likewise rigid.

    21. Structure of [(CO)5CrNEt2]BF4, a Key Organometallic Compound; Reaction to Give the Carbene Complex (CO)5CrC(AsPh2)NEt2 (pages 643–644)

      Dr. habil. Ulrich Schubert, Prof. Dr. Ernst Otto Fischer and Dipl.-Chem. Dieter Wittmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006432

      The bond lengths in the carbyne complex [(CO)5CrCNEt2]BF4 suggest considerable participation of the resonance form (B). The complex is a valuable intermediate, for it affords carbene complexes even with weak nucleophiles. A new example of the utility of this approach is provided by the reaction of the intermediate with KAsPh2 to give (CO)5CrC(AsPh2)NEt2.

      • equation image
    22. Molecular and Crystal Structure of β-SeBr (page 645)

      Dr. Detlef Katryniok and Priv.-Doz. Dr. Rüdiger Kniep

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006451

      A contribution to the structural chemistry of compounds of type A2B2 (A = S, Se; B = F, Cl, Br) is provided by the X-ray structure analysis of β-SeBr at −80°C. The BrSeSeBr molecules (Se[BOND]Se = 2.241 Å; dihedral angle 93.58°) are arranged in the crystal in such a manner that some of the Se…Br contacts are significantly closer than the sum of the van der Waals radii.

    23. Phatolysis of Water Catalyzed by Transition Metal Dithiolenes (pages 645–646)

      Dr. Rainer Henning, Wilhelm Schlamann and Priv.-Doz. Dr. Horst Kisch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006452

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      As potential catalysts for the photochemical cleavage of water, attention has been focused on compounds of type (1), especially (1a), n = 2, M = Ni, R = Ph, z = 0. Irradiation (λ ≥ 290 nm) of (1) in neutral THF/H2O solution does indeed produce H2, part of it coming from the THF.

    24. Cyclic Water Cleavage by Visible Light: Drastic Improvement of Yield of H2 and O2 with Bifunctional Redox Catalysts (pages 646–648)

      Dr. John Kiwi, Enrico Borgarello, Prof. Dr. Ezio Pelizzetti, Dr. Mario Visca and Prof. Dr. Michael Grätzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006461

      A further step on the road to utilization of solar energy by cleavage of water is made possible by a new catalyst which promotes both H2-and O2-formation in the (known) Ru(bpy)math image/methylviologen system. The catalyst consists of RuO2 (0.1%) in (Nb-doped) n-TiO2 charged with finely divided Pt. The rate of generation of H2 remains constant even after irradiation for 4 d with visible light.

    25. Photochemistry of Sulfonamides and Sulfonylureas: A Contribution to the Problem of Light-Induced Dermatoses (pages 648–650)

      Dr. Bernd Weiss, Prof. Dr. Heinz Dürr and Prof. Dr. Hermann Josef Haas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006481

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      Photochemical studies on model sulfonamides and antidiabetics(1) led to the conclusion that that appearance of light-induced dermatoses on administration of tolbutamide (1a) could be due to the reaction of radicals (and SO2) with the cell components; furthermore, (1a) might attack the cell protein as hapten.

    26. Cyclotri(phosphazene) Complexes with P-Coordinated PdX2 and PtX2 (pages 650–651)

      Prof. Dr. Alfred Schmidpeter, Dr. Klaus Blanck, Prof. Dr. Heinz Hess and Dr. Heinz Riffel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006501

      Thumbnail image of graphical abstract

      The first cyclotriphosphazenes with P-coordinated metal (2) are formed on treatment of (1) with PdCl2 or K2PtCl4via a 1,2-H shift. X-ray structure analysis was performed in the case of (2), M = Pd, X = Cl. In the other metalated cyclotriphosphazenes the metal (Li, Cu1) is N-coordinated.

    27. Synthesis of the First Methylidyne-Rhodium Cluster by Proton-Induced H2/CH4-Elimination from a μ-Methylene Complex (pages 651–653)

      Prof. Dr. Wolfgang A. Herrmann, Dipl.-Chem. Johann Plank, Dipl.-Chem. Ernst Guggolz and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006511

      The transformation of a μ-methylene-dirhodium complex into a μ3-methylidyne-trirhodium complex (X-ray structure analysis) has been accomplished in reaction (1) [RIGHTWARDS ARROW] (3). The first step is protonation of (1) to form the (isolable) μ-hydrido complex (2).

      • equation image
    28. A Novel SN-Ligand: Structure of PtCl(S4N3) (pages 653–654)

      Dr. Helmut Endres and Dipl.-Chem. Elisabeth Galantai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006531

      S4Nmath image, a new tridentate ligand with alternating S and N atoms has been obtained from S4N4. The reaction of S4N4 with cis-tCl2(NCPh)2 leads to deep purple PtCl(S4N3) in which the terminal S atoms and the central N atom of the ligand are coordinated to the Pt atom.

    29. MoSmath image and MoOSmath image as Structurally Versatile and Biochemically Interesting Ligands in Crystalline Multinuclear Cu- and Fe-Complexes (pages 654–655)

      Prof. Dr. Achim Müller, Dr. Hartmut Bögge, Dipl.-Chem. Heinz-Gerhard Tölle, Dipl.-Chem. Rainer Jostes, Uwe Schimanski and Mechtild Dartmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198006541

      Thumbnail image of graphical abstract

      The biochemical antagonism between Cu and Mo (as thiomolybdate) and Fe and Cu prompted the synthesis of multinuclear complexes of these metals. The observations made suggest direct interactions between Fe, Cu, and Mo (MoSmath image) in biological processes.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews

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