Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 5

May 1980

Volume 19, Issue 5

Pages 333–410

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Computer Simulation of the Kinetics of Complicated Gas Phase Reactions (pages 333–343)

      Prof. Dr. Klaus H. Ebert, Dr. Hanns J. Ederer and Dipl.-Chem. Gunther Isbarn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003333

      The course of chemical reactions can be simulated with modern digital methods and powerful computers; calculations can be based on a large number of elementary reactions. It is often advisable to use a “reaction model” considering only those elementary reactions which account for the greater part of the conversion. Pyrolysis of alkanes and oxidation of CO are considered as examples.

    2. Cyclodextrin Inclusion Compounds in Research and Industry (pages 344–362)

      Prof. Dr.-Ing. Wolfram Saenger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003441

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      Hydrophobic interactions and enzyme action can be studied with cyclodextrins, their inclusion compounds, and their derivatives. Other applications include micro-encapsulation of sensitive active compounds and aromas, and enhancement of grain harvest yields.

    3. Trimethylphosphane Complexes of Nickel, Cobalt, and Iron—Model Compounds for Homogeneous Catalysis (pages 362–375)

      Prof. Dr. Hans-Friedrich Klein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003621

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      Processes occurring in homogeneous catalysis, e.g. equilibria (1) and (2)/(3) [Su = substrate] can be studied with alkylnickel, -cobalt, and -iron compounds stabilized by PMe3.

    4. Thermal Degradation of Polymers to Polymeric Carbon—An Approach to the Synthesis of New Materials (pages 375–385)

      Prof. Dr. Erich Fitzer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003751

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      Polymeric carbon, produced by thermolysis of synthetic organic polymers, has exceptional properties. Reinforcing fibers made of polymeric carbon care particularly useful for composite materials, and especially for biocompatible all-carbon composites.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Amorphous Silver Silicates, Storage Elements with Low Switching Field Strength (pages 386–387)

      Priv.-Doz. Dr. Martin Jansen and Prof. Dr. Hans Herbert Käs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003861

      Materials for digital information storage are in demand. Amorphous silver silicates, prepared by fusion of Ag2O and SiO2 under ≥ 1800 bar of O2 at 600°C, exhibit bistable switching behavior after a forming process. A given storage state is conserved without any need for a holding current; “silver clusters” are presumably involved.

    2. Three Variants of the [2 + 2]-Cycloaddition of Bicyclopropylidene (pages 387–388)

      Dipl.-Chem. Walter Weber, Dr. Ihsan Erden and Prof. Dr. Armin de Meijere

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003871

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      Bicyclopropylidene(1) has recently become readily accessible, and is a suitable synthon for construction of dispiro compounds. Compound (1) reacts very smoothly with a number of electron-poor double-bond systems. Thus with tetracyanoethylene it forms the products (3), (4), and (5)—presumably via the zwitterion (2). Only two kinds of cycloaddition are accomplished with chlorosulfonyl isocyanate and phenyltriazolinedione.

    3. Aminopyridines (pages 388–389)

      Dr. Werner Jünemann, Dr. Hans-Joachim Opgenorth and Dr. Horst Scheuermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003881

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      An adaptable synthesis of 4,5-unsubstituted pyridines starts from ethyl propiolate (1). The diols (3) can be transformed into dichlorides, which in turn afford diamines. Triamines are accessible from malonic ester and (2), R1 = C6H5SO2, via the triols (4).

    4. Cyclophanes as Diene Components in Diels-Alder Reactions (pages 389–390)

      Aboul Fetouch Murad, Dipl.-Chem. Jürgen Kleinschroth and Prof. Dr. Henning Hopf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003891

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      Cyclohexatriene-type rather than benzene-type behavior is observed for appropriately bridged benzene rings. While non-annelated arenes do not normally undergo addition reactions, (1), (2), and (3) form Diels-Alder adducts with reactive dienophiles. This is impossible for steric reasons in the case of (4) and (5).

    5. “Living Polymers” on Polymerization with Extremely Productive Ziegler Catalysts (pages 390–392)

      Prof. Dr. Hansjörg Sinn, Prof. Dr. Walter Kaminsky, Dr. Hans-Jürgen Vollmer and Dipl.-Chem. Rüdiger Woldt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003901

      At least 10000 polyethylene molecules per zirconium atom can be obtained with a Ziegler catalyst made up of Cp2ZrMe2 and [Al(Me)O]n. Depending upon the conditions, the molecular weight of the polymer lies between 100000 and 200000. All the results available so far are in accord with the following concept: A molecule of organozirconium compound diffuses into an associate of aluminoxanes. H-transfer leads to zirconium hydrides which add ethylene to form alkyl compounds and thus give rise to active sites.

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    6. Phthalocyaninatoiron with Pyrazine as a Bidentate Bridging Ligand (pages 392–393)

      Dipl.-Chem. Otto Schneider and Prof. Dr. Michael Hanack

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003921

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      The synthesis and properties of one-dimensional conductors are of topical interest. It has now proved possible to synthesize (1) and a polymer (2), in which PcFe and pyrazine groups alternate. The physical properties of (2) indicate extensive electron delocalization over the pyrazine bridges.

    7. Direct Observation of the Dibenz[b,g]oxocinide Ion; A Non-Aromatic (4n+2) π Species (pages 393–394)

      Prof. Dr. A. G. Anastassiou and Prof. Dr. H. S. Kasmai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003931

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      The bonding in anion(2) could be elucidated by 1H-NMR spectroscopy. Compound (2), whose central ring contains 10π electrons is to be regarded essentially as a conventional system, in which the negative charge is located primarily on the allyl unit. The heterocycle in (2) is presumably bent.

    8. 4-Sulfobenzyl, a New Carboxy Protecting Group (pages 394–396)

      Dr. Arnulf Hubbuch, Roland Bindewald, Dr. Josef Föhles, Dr. Vinod Kumar Naithani and Prof. Dr. Helmut Zahn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003941

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      A solubilizing polar protecting group for peptide syntheses, viz. 4-sulfobenzyl, combines the advantages of the solubilizing sulfo- and the protecting benzyl function. The new protecting group is introduced by means of sodium 4-(bromomethyl)benzenesulfonate (1) into salts of N-protected amino acids and peptides.

    9. Rigid Phenyl-Group Conformation in Complexes (pages 396–397)

      Prof. Dr. Hendirk tom Dieck, Dr. Horst Bruder, Dipl.-Chem. Kurt Hellfeldt, Prof. Dr. Dieter Leibfritz and Dr. Martin Feigel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003961

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      The topic “conformation and catalysis” confers interest on the structure and behavior of the complex (dad)3FeI2. The rigid conformation of the aromatic groups is manifested in the NMR signals of H-6 at δ ≈ 6.1 and H-2 at δ ≈ 4.4 (!). (Three N-substituents have been omitted from the drawing.)

    10. Unusually Bridged Tungsten Complexes with W(ER)2W(ER)3W Skeleton (E[DOUBLE BOND]S or Se; R [DOUBLE BOND] C2H5, n-C4H9, or C6H5) (pages 397–398)

      Dipl.-Chem. Luise R. Krauth-Siegel, Dipl.-Chem. Wolfgang Schulze and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003971

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      Novel “non-cyclic trinuclear clusters”(1)(3) arise alongside other products on reaction of the thiolates Pb(SR)2 or the selenol HSeC6H5 with η7-C7H7W(CO)2I. The unusual molecular structure has been confirmed in (2) by X-ray methods.

    11. OH Clusters with Homodromic Circular Arrangement of Hydrogen Bonds (pages 398–399)

      Prof. Dr. Wolfram Saenger and Dipl.-Phys. Klaus Lindner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003981

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      The decisive influence of the cooperative effect on formation and direction of H bonds has been confirmed by X-ray structure analysis of an OH cluster in α-cyclodextrin hexahydrate. This structure contains two rings of H bonds. Interactions are homodromic (in the same sense) in two of them, and antidromic (opposing) in the other one.

    12. A Very Crowded Molecule: X-Ray Crystallographic Analysis of Bis(2,4,6-tri-tert-butylphenyl)phosphinic Chloride (pages 399–400)

      Dr. Masaaki Yoshifuji, Dipl.-Chem. Ichiro Shima, Prof. Dr. Naoki Inamoto, Dr. Ken Hirotsu and Prof. Dr. Taiichi Higuchi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003991

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      Two benzene rings having a boat shape have been detected in the highly substituted compund (1). Such distortions have previously been found only in the case of bridged benzene rings.

    13. α-D-Glucuronides of 1-(N-Alkyl-N-nitrosoamino)alkyl Alcohols (pages 400–401)

      Horst Braun and Priv.-Doz. Dr. Manfred Wiessler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004001

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      In order to elucidate the fate of nitrosoamines in the body, the title compounds (3) have been synthesized from the compounds (1) and (2). Xenobiotics are known to be hydroxylated in the organism and, bound to glucuronic acids, excreted. However, compounds such as (3) may also be transport forms.

    14. A Cubane-Type Sn4N3O Cage (pages 401–402)

      Prof. Dr. Michael Veith and Dipl.-Chem. Holger Lange

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004011

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      The heterocubane derivative(2), R = tBu, generated by partial hydrolysis of the “open cage” (1) is one of the few examples of cubanes having a skeleton made up of three elements. Structural proof is provided, inter alia, by the “isosteric character” of the AlMe3 adduct with the (SN-tBu)4 cage.

    15. Synthesis of Organotrimetal Polymers Using Trimetal Vapor-Fluid Matrix Techniques (pages 402–404)

      Dr. Colin G. Francis, Helmut X. Huber and Prof. Dr. Geoffrey A. Ozin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004021

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      The linkage of three kinds of metal atoms (Cr, V, Ti) in the same liquid polymer and the generation of the CrV species have now been accomplished in poly(methylphenylsiloxane) at ca. −20°C (detection by UV/VIS spectroscopy). The nature of the bond is shown here and on the front cover of this journal.

    16. Distribution of Terminal and Bridging CO-Groups in an Anionic Carbonylmetal Cluster as a Result of Ion-Pair Formation. Crystal and Molecular Structure of LiCo3(CO)10 · i-Pr2O (pages 404–405)

      Dipl.-Chem. Hans-Norbert Adams, Dr. Giuseppe Fachinetti and Prof. Dr. Joachim Strähle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004041

      Drastic structural changes in an anionic carbonylmetal cluster can be evoked by slight changes in the acid/base properties of the system. In the crystalline title compound (X-ray structure analysis) edge-bridging CO groups are present in the cluster units. In contrast, the IR spectrum recorded in ether indicates an equilibrium between (a few) clusters of this kind and (mainly) clusters having terminal CO groups.

    17. Triple-Decker Sandwich Complexes of 4d and 5d Metals with cyclo-Triphosphorus as μ,η3-Ligand: Structural and Magnetic Properties (pages 405–406)

      Dr. Claudio Bianchini, Dr. Massimo Di Vaira, Dr. Andrea Meli and Prof. Dr. Luigi Sacconi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004051

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      Cationic triple-decker complexes triphos-M1-cyclo-P3-M2-triphos, in which M1 and 4d- and 5d-metals, differ in their magnetic properties from the known complexes of 3d metals (in some cases considerably). Deviation in the complex with M1 = Rh, M2 = Ni is attributed to the fact that the P3 group is not “centered”.

    18. Calcium Isotope Separation on an Exchange Resin Having Cryptand Anchor Groups (pages 406–407)

      Prof. Dr. Klaus G. Heumann and Dr. Hans-Peter Schiefer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004061

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      Record calcium isotope separations are accomplished with an ion exchange resin containing the cryptands (1). The results suggest the feasibility of chemical pre-enrichment of heavy Ca isotopes on an industrially interesting scale.

    19. Acetaldehyde as Main Product of the Oxidation of Ethylene Oxide on a Silver Catalyst (pages 407–408)

      Dr. Günther Prauser, Dr. Guillermo Fischer and Prof. Dr. Kurt Dialer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004071

      False conclusions about the relevance of a process in heterogeneously catalyzed reactions can be drawn if this process is examined in isolation. Thus ethylene is oxidized on an unmodified Ag catalyst to ethylene oxide which can undergo “after-combustion” to CO2 and H2O. In contrast, when examined in isolation under the same conditions, ethylene oxide isomerizes to acetaldehyde. Ethylene appears to block the catalyst sites necessary for this reaction.

    20. New Aspects of the Reaction of Difluorosulfur Imides with Fluorine (pages 408–409)

      Dr. Ingo Stahl, Priv.-Doz. Dr. Rüdiger Mews and Prof. Dr. Oskar Glemser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198004081

      A good entry to the highly reactive fluorine compound(2) is provided by reaction of (1) with fluorine in Pyrex vessels with UV irradiation. In metal autoclaves, (3), (4), and other products are obtained (R = C2F5) without irradiation.

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  3. Book Reviews

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