Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 5

May 1984

Volume 23, Issue 5

Pages 329–394

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1984)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403291

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      The cover shows a collage of all formulas and figures chosen by Henry Taube to illustrate his Noble Lecture. The Laureate outlines in retrospect the historical development of his field of research, electron transfer between metal complexes—For more information, see p. 329ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Electron Transfer between Metal Complexes — A Retrospective View (Nobel Lecture) (pages 329–339)

      Prof. Dr. Henry Taube

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403293

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      Redox reactions between metal complexes form the theme of Henry Taube's lifework, for which he was awarded the 1983 Nobel Prize for chemistry. The most interesting examples include self-exchange processes and reactions which proceed via inner-sphere activated complexes such as 1. Of importance in this connection is also the electronic situation in mixed valence complexes such as the “Creutz-Taube ion” 2.

    2. “… to make Chemistry more Applicable and Generally Beneficial”—The Transition in Scientific Perspective in Eighteenth Century Chemistry (pages 339–347)

      Dr. Christoph Meinel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403391

      The concept of “pure” and “applied” chemistry predates the “Angewandte” by more than a century; this differentiation was introduced by the Swedish chemist Wallerius in 1751. Behind this was a new scientific concept of chemistry which emphasized the importance of applying chemistry's accumulated knowledge and its capabilities of providing for the general economic benefit. The reasons behind and causes of the change in scientific perspective associated with this concept point to the social and institutional conditions under which this field has developed into an independent academic discipline.

    3. Liquid Crystals: A Tool for Studies on Chirality (pages 348–362)

      Prof. Dr. Guy Solladié and Richard G. Zimmermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403481

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      The amplification of small optical activities can be achieved with nematic liquid crystals such as are formed, e.g., by MBBA (4-butyl-N-(4-methoxybenzylidene)aniline). Optically active compounds are capable of transforming the parallel array of molecules in the nematic phase into a helical arrangement. Important parameters of these induced-cholesteric phases are the handedness and pitch of the helix.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Isolation of the First Six- and Seven-Membered Selenium-Sulfur Rings and Mechanism of their Conversion into Other-Sized Rings (pages 362–363)

      Prof. Dr. Ralf Steudel and Dipl.-Chem. Eva-Maria Strauss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403621

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      Se2S5, the first cyclic selenium sulfide of type SexSy with x + y = 7, was prepared from titanocene pentasulfide and dichlorodiselane. In solution, Se2S5 forms Se3S5 and SeS5 (the first SexSy species with x + y = 6). A spirocyclic intermediate 1 is proposed for the decomposition reaction.

    2. 15N-15N Coupling Constants and Rotational Barriers of Nitrosamines (pages 363–364)

      Dipl.-Ing. Heinz Bandmann, Peter Heymanns, Carola Siem and Prof. Dr. Paul Rademacher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403631

      The double bond character of the NN bond in secondary nitrosamines can be measured from the15N[BOND]15N coupling constants in 15N-Labeled model compounds: In the examples selected the coupling constants, the degree of π-bonding, and the calculated ΔH* value of the internal rotation are linearly correlated.

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    3. Synthesis of Tetrahydro-3-thienylacetic Acid Esters by Consecutive Photo-Induced Reactions (pages 364–365)

      Elke Anklam and Prof. Dr. Paul Margaretha

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403641

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      The unusual photochemical behavior of 2(5H)-thiophenone 1 manifests itself on irradiation in the presence of alcohols and 2,3-dimethyl-2-butene: The thienylacetates 3 are formed selectively via the crotonates 2. The step 2 [RIGHTWARDS ARROW] 3 is possibly a radical reaction.

    4. Enantioselective Synthesis of β-Substituted Primary Amines; α-Alkylation/Reductive Amination of Aldehydes via SAMP-Hydrazones (pages 365–366)

      Prof. Dr. Dieter Enders and Dipl.-Chem. Heinrich Schubert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403651

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      Either of the desired enantiomers of the β-substituted amines 3 can be prepared in high enantiomeric purity (ee ≥ 95%) from the aldehydes 1. The new, generally applicable synthesis involves α-alkylation, followed by reductive amination via the SAMP-hydrazones 2.

    5. Configurational Stability of Vinyllithium Derivatives with 1-Trimethylsilyl and 1-Alkoxy Substituents (pages 366–368)

      Prof. Dr. Rudolf Knorr and Dipl.-Chem. Therese Freifrau von Roman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403661

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      Rate constants and activation parameters for theE/Zisomerization a ⇌ b could be determined by dynamic 1H-NMR spectroscopy. 1-Trimethylsilylvinyllithium isomerizes rapidly, the ethoxy analogue slowly. These findings are of interest in connection with the use of these species for stereospecific syntheses.

    6. Detection of Intramolecular Linkage Isomerization of a (Pseudo)tetrahedral Nickel(II) Bis(chelate) (pages 368–369)

      Prof. Dr. Rudolf Knorr and Dr. Friedrich Ruf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403681

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      The “interchange” between the six almost equivalentN-substituents in the complex 1 leads to an equilibrium of species with two (= 1), one, or no exocyclic tolyl group. The kinetics of this isomerization, which has been studied in detail, begins with the monomolecular rupture of the N5Ni bond.

    7. Strong 1,3-Interaction in 1,2-Dihydroboretes: Homoborirenes (pages 369–370)

      Rolf Wehrmann, Dr. Harmut Klusik and Prof. Dr. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403691

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      The first 1,2-dihydroboretes 1 were prepared via the route shown below. These species are isoelectronic with cyclobutenyl cations. 13C- and 11B-NMR data reveal a strong 1,3-interaction, which—by analogy with homocyclopropenylium ions justifies the formulation homoborirenes (R1 [DOUBLE BOND] R2 [DOUBLE BOND] Me; R1 [DOUBLE BOND] H, R2 = CMe3; R1 [DOUBLE BOND] R2 [DOUBLE BOND] Ph).

    8. 1,2-Dihydroborete: Structure of a Potential Homoaromatic System (pages 370–371)

      Priv.-Doz. Dr. Dieter Cremer, Jürgen Gauss, Prof. Paul von Ragué Schleyer and Dr. Peter H. M. Budzelaar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403701

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      Do homoaromatic neutral molecules actually exist? Quantum mechanical calculations have shown for the 1,2-dihydroborete 2, as for the cyclobutenyl cation 1, that the puckered form a is preferred. The calculated inversion barrier and the electron density indicate a relatively strong 1,3-interaction and potentially homoaromatic character.

    9. Synthesis and Structure of a 1,3-Dihydro-1,3-diborete (pages 371–372)

      Manfred Hildenbrand, Dr. Hans Pritzkow, Dr. Ulrich Zenneck and Prof. Dr. Walter Siebert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403711

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      A non-planar B2C2 skeleton is present in the title compound 2, which was prepared by dehalogenation of the 1,2-diborylethene 1. An X-ray structure analysis showed that the ring CB bonds are quite short that the distance between the ring C-atoms is 1.81 Å (R1 [DOUBLE BOND] Me2N, R2 [DOUBLE BOND] tBu)

    10. 1,3-Dihydro-1,3-diboretes and Their Radical Anions (pages 372–373)

      Rolf Wehrmann, Christine Pues, Dr. Hartmut Klusik and Prof. Dr. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403721

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      The non-planar 1,3-dihydro-1,3-diboretes 3 form planar radical anions. This was deduced from the ESR data. The unpaired electron resides preferentially on the ring C-atoms. The key step in the synthesis of 3 is the ring expansion of 2 (R = neopentyl, SiMe3).

    11. Puckered Structures of 1,3-Dihydro-1,3-diboretes and Bicyclobutane-2,4-dione: Nonplanar Hückel 2π-Electron Aromatic Molecules (pages 374–375)

      Prof. Dr. Paul von Ragué Schleyer, Dr. Peter H. M. Budzelaar, Priv.-Doz. Dr. Dieter Cremer and Dr. Elfi Kraka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403741

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      A non-classical puckered structure is predicted for bicyclobutane-2,4-dione (and derivatives thereof), which, according to quantum mechanical calculational, is best described in terms of formula 3. The reliability of this calculational method is supported by the fact that the structure thus calculated for 2 is in very good agreement with the experimentally determined structure of 1.

    12. Novel Synthesis of an Unsymmetrical Pt(η2-O2) Complex (pages 375–376)

      Dr. Anil B. Goel and Dr. Sarla Goel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403751

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      An η2[BOND]O2 complex 1 of platinum with two different ligands has been prepared for the first time. The novel synthetic strategy involves reaction of hydridobridged LHPtH2PtHL with 2L′ (L=tBu3P, L′=Ph3P). Evolution of hydrogen is presumably accompanied by formation of LL′Pt, which is oxidized in the air to give 1. Reaction of 1 with 2 leads via a novel O[BOND]O cleavage to the five-membered ring compound 3.

    13. Silver-Catalyzed Formation of Crown Ethers; Synthesis and Structure of [Ag([12]crown-4)2][AsF6] (page 376)

      Dr. Peter G. Jones, Thomas Gries, Hansjörg Grützmacher, Prof. Dr. Herbert W. Roesky, Jürgen Schimkowiak and Prof. George M. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403761

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      An isolable silver sandwich complex containing crown ethers is formed on reaction of AgAsF6 with ethylene oxide in liquid SO2. The Ag atom has the coordination number 8. Only very few examples of complexes of AgI with oxygen-containing ligands are known.

    14. Reactions of the Cyanometal Acids H4M(CN)6 (M[DOUBLE BOND]Fe, Ru, Os), H2Pt(CN)4, and HAu(CN)2 with Epoxides: β-Hydroxyalkyl Isocyanide- and Oxazolidine-2-ylide-Metal Complexes (pages 377–378)

      Prof. Dr. Wolfgang Beck, Dipl.-Chem. Wolfgang Weigand, Dr. Ulrich Nagel and Dr. Matthias Schaal

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403771

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      The behavior of metal-stabilized isocyanic acids (“cyanometal acids”) towards electrophiles has been investigated, using the title compounds as examples. In heterogeneous reactions (in CHCl3) metal complexes of type 1 or 2 (with cyclized ligand) are formed.

    15. [Cu5I7]2⊖ — An Isopolyanion with Cyclic Face-to-Face Linking of CuI4 Tetrahedra (pages 378–379)

      Prof. Dr. Hans Hartl and Dipl.-Chem. Farbod Mahdjour-Hassan-Abadi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403781

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      A pentagonal-bipyramidal structure distinguishes the anion in [Pr4N]2[Cu5I7]. The complex itself is formed along with other compounds on reaction of [Pr4N]I with I2 and Cu powder. The anion deviates only slightly from C5h symmetry.

    16. As4tBu2 — The First Bicyclo[1.1.0]tetraarsane (pages 379–380)

      Prof. Dr. Marianne Baudler and Stefan Wietfeldt-Haltenhoff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403791

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      Two annelated three-membered arsenic rings form the central skeletal unit of the title compound 1. Since the NMR findings indicate that the tert-butyl groups are equivalent, the sterically more favorable exo-exo isomer must be present.

    17. Synthesis of N-(Arylmethylene)dehydroalanine Esters (pages 380–381)

      Prof. Dr. Günter Wulff and Dipl.-Chem. Helmut Böhnke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403801

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      A novel synthetic equivalent of the synthon CH2[BOND]CH(NH2)COOH is now accessible with the first preparation of the N-(arylmethylene) dehydroalanine ester 2. The reaction proceeds via the urethane 1, which can readily be obtained from the methyl ester of serine (R [DOUBLE BOND] C6H5, 4-C6H5[BOND]C6H4).

    18. Stepwise Hydrogenation of Benzonitrile on a Ru3-Cluster (page 381)

      Dipl.-Chem. Wolfgang Bernhardt and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403811

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      Two products of the reduction of PhCN on Ru3(CO)12 with H2 at atmospheric pressure have been isolated and characterized: the Ph[BOND]CH[DOUBLE BOND]NH[BOND] and Ph[BOND]CH2[BOND]NH2-complexes 1 and 2, respectively. This reaction demonstrates the validity of the concept of using clusters as models for catalyst surfaces.

    19. Dialkylboryl-Substituted Triphenylphosphonium Ylides (pages 381–382)

      Prof. Dr. Hans-Jürgen Bestmann and Dipl.-Chem. Thomas Arenz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403812

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      Transylidation of R1HC[BOND]PPh with Rmath imageBCl in the molar ratio 2 : 1 furnished the novel crystalline ylides 1, which can also be described in terms of a mesomeric formulation 1b with B[DOUBLE BOND]C bonding. Hitherto, transylidations have been carried out only with halides of the 4th—7th main group elements.

    20. A Binuclear Molybdenum Complex with Two μ-Hydrazido(3−) N-Ligands (pages 382–383)

      Prof. Dr. Rainer Mattes and Dipl.-Chem. Heinz Scholand

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403821

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      The versatility of alkyldithiocarbazates H2N[BOND]NH[BOND]C(S)[BOND]SR as ligands is manifested in the title compound: the triply deprotonated NNC(S)SEt functions concomitantly as N,N-bridging and N,S-chelating ligand.

    21. Exhaustive Oxidative Decarbonylation of Metal Carbonyls by Light and Oxygen: The Example of (η5-C5Me5)ReO3 (pages 383–385)

      Prof. Dr. Wolfgang A. Herrmann, Dr. Ricardo Serrano and Prof. Dr. Hans Bock

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403831

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      The trioxorhenium complex 3—lemon yellow, air-stable, crystalline—is surprisingly formed on photolysis of the tricarbonylrhenium complex 1 in THF. In complete absence of oxygen the initial product is 2, which (unlike analogous manganese complexes) is oxidized by air to 3.

    22. Dextran-Linked N6-(2-Isopentenyl)adenosine—A Polymer-Bound Antimetabolite with a Predetermined Cleavage Position (pages 385–386)

      Dr. Helmut Rosemeyer and Prof. Dr. Frank Seela

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403851

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      The cleavage of a covalently bonded active substance from a polymeric carrier is rarely a resolvable task with sensitive active components. The modified nucleoside in 1, linked via a special “spacer” with dextran, exhibits high antitumor activity. The S[BOND]S bond can be opened reductively even with dithiothreitol.

    23. Bis(1,3,5-trimethylbenzene)indium(I) Tetrabromoindate(III), the First Arene Complex of Indium (pages 386–388)

      Jan Ebenhöch, Dr. Gerhard Müller, Jürgen Riede and Prof. Dr. Hubert Schmidbaur

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403861

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      Arene complexes of main group elements are still a rarity. In[InBr4] reacts directly with 1,3,5-trimethylbenzene to give the crystalline 1 : 2-compound 1. The central atom is additionally bonded to three coplanar bromine atoms; an overall one-dimensional coordination polymer is formed.

    24. Bonding Attitudes in Crystalline SeF4 and TeF4 (pages 388–389)

      Prof. Dr. Rüdiger Kniep, Dr. Lutz Korte, Dipl.-Chem. Rainer Kryschi and Dr. Wolfgang Poll

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403881

      Solid SeF4 is monomeric, and not—like solid TeF4—polymeric. The differences in the bonding can be ascribed to the respective degrees of hybridization of the chalcogens and can be described in terms of sp3d (SeF4, pseudo trigonal bipyramidal) and sp3d2 states (TeF4, pseudo-octahedral).

    25. Mixed Crystals Containing the Diamagnetic Complex [Mo2(SO2)(S2)(CN)8]4⊖ and the Paramagnetic Complex [Mo2(SO2)(S2)(CN)8]5⊖ (pages 389–390)

      Prof. Dr. Achim Müller, Dr. Werner Eltzner, Dr. Rainer Jostes, Dr. Hartmut Bögge, Dr. Ekkehard Diemann, Jürgen Schimanski and Prof. Dr. Heiko Lueken

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403891

      Blackish violet crystals of the mixed valence Mo compound 1 were obtained on oxidation of [(MoIII)22-S)2(CN)8]6⊖. The MoIII/IV species in 1 belongs to the rare paramagnetic binuclear complexes of the heavy transition metals; the MoIV species is diamagnetic. Although the structures of the two complex anions differ only slightly, markedly different Mo[BOND]Mo distances of 279.0 and 268.4 pm, respectively, are observed.

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    26. All-cis-[5.5.5.5]fenestrane (pages 390–391)

      Marcel Luyten and Prof. Dr. Reinhart Keese

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403901

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      Unusual bonding behavior at the central C atom is observed in fenestranes such as, e.g., compound 2, which was obtained for the first time by one-step reductive decarboxylation of the lactone 1.

    27. [Mo43-S)4(μ-S2CNEt2)2(S2CNEt2)4], a Compound Containing a Cubane-Like Mo4S4 Cluster (pages 391–392)

      Prof. Dr. Thomas C. W. Mak, Dr. Khalid S. Jasim and Prof. Dr. Chung Chieh

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198403911

      An Mo4 tetrahedron as part of a readily distorted Mo4S4 cube is observed in the title compound (black crystals). In this complex, molybdenum is coordinated only by sulfur. Four of the six dithiocarbamate ligands are each bound to an Mo atom; the two remaining ligands each bridge an Mo[BOND]Mo bond.

  3. Book Reviews

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

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