Angewandte Chemie International Edition in English

Cover image for Vol. 17 Issue 6

June 1978

Volume 17, Issue 6

Pages 379–472

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. What Do We Know about the Metal-Metal Bond? (pages 379–392)

      Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197803793

      Thumbnail image of graphical abstract

      Interactions between metal atoms range from very weak to very strong, corresponding in the latter case to a quadruple bond. Metal-metal linked polynuclear complexes show considerable versatility in their ability to act as reservoirs for excess or missing electrons.

    2. Tetrahedral Carbonylcobalt Clusters (pages 392–400)

      Prof. Dr. Günter Schmid

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197803921

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      A simple variable model system such as the heteronuclear clusters (CO)9Co3E(L)n permits systematic study of the geometrical and electronic requirements of various structural types.

    3. The Distribution of Charge in Complex Compounds (pages 400–407)

      Prof. Dr. Joseph Chatt and Dr. G. Jeffery Leigh

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804001

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      The formal and the real charges on metal atoms and ligands in metal complexes show considerable discrepancies: the actual charge rarely exceeds ±0.3e.

    4. Hemoglobin—An Inspiration for Research In Coordination Chemistry (pages 407–423)

      Prof. Dr. Johann Walter Buchler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804071

      Copying, imitation, and modification—that is the threefold invitation extended by hemoglobin to the synthetic chemist. Research reveals the factors responsible for the function of this “honorary enzyme”.

    5. Chemical Ionization—A Mass-Spectrometric Analytical Procedure of Rapidly Increasing Importance (pages 424–439)

      Dr. Wilhelm J. Richter and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804241

      The information content of a mass spectrum is determined in part by the way in which the ions of the substrate are generated in the mass spectrometer. On chemical ionization with species such as CHmath image, fragmentation can be controlled within wide limits.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Thermolysis of endo, exo-Tetracyclo[6.1.0.02,4.05,7]nonane (trans-Tris-σ-homobenzene) (pages 440–441)

      Dr. Werner Spielmann, Dr. Dieter Kaufmann and Prof. Dr. Armin de Meijere

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804401

      Thumbnail image of graphical abstract

      Themal isomerization of trans-tris-σ-homobenzene(1) to (2) (ca. 400°C, flow system) is of interest because related compounds rearrange to different kinds of products. The reaction course is established with 12C-labeled (1). Cyclononatriene is involved as intermediate; cis analogs of (1) give cis,cis,cis-nonatrienes as major product.

    2. Rearrangement of Tris-σ-homobenzenes to 1,4,7-Cyclononatrienes (pages 441–442)

      Dr. Jens Spanget-Larsen and Prof. Dr. Rolf Gleiter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804411

      A better understanding of the rearrangements of tris-σ-homobenzenes was the goal of MINDO/3 calculations of parts of the multidimensional energy surface for the cis- and trans-isomer and for diademane. Cyclononatriene is accordingly expected to be present in addition to trans-tris-σ-homobenzene in equilibrium at elevated temperature.

    3. 15N-NMR Investigation of Solvent Effects on Sulfonamides (pages 442–443)

      Dr. Hans R. Kricheldorf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804421

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      Interpretation of the 15N-NMR spectra of amides is facilitated by a knowledge of solvent effects. Such knowledge permits ready identification of sulfonamide signals alongside those of carboxamides, urethanes, and ureas.

    4. Various Adducts of Isothiocyanates to the λ5-Phosphazene Group of an Azaphosphole (pages 443–444)

      Prof. Dr. Alfred Schmidpeter and Dipl.-Chem. Thomas von Criegern

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804431

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      The new 1,3,2λ5-thiazaphosphetidine ring is present in the bicyclic compound (2), which is formed from the azaphospole (1) and isothiocyanates. Depending upon the substituents and conditions the bicyclic compound (3) and/or a monocyclic phosphonium thiocyanate is formed alongside or instead of (2).

    5. (CO)5Cr·SFeCo2(CO)9: An Organometallic Donor-Acceptor Complex (pages 444–445)

      Dipl.-Chem. Felix Richter and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804441

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      The novel tetranuclear complex(1) contains a sulfur atom linked to three kinds of metal atoms. Its structure was confirmed by X-ray methods.

    6. SE Reactions on the Cmath image-Ring: π-Attack (pages 445–446)

      Doz. Dr. Robert Weiss and Dr. Claus Priesner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804451

      Thumbnail image of graphical abstract

      The range of reactions occurring at the highly strained cyclopropenylium system has been extended by two important examples. Thus conditions have now been reported which favor classical electrophilic aromatic substitution (2)[RIGHTWARDS ARROW](1) and the synthetically important halogen/lithium exchange (2)[RIGHTWARDS ARROW](3) in the Cmath image-system.

    7. SE Reactions on the Cmath image-Ring: σ-Attack (pages 446–447)

      Doz. Dr. Robert Weiss, Dr. Claus Priesner and Hilmar Wolf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804461

      Thumbnail image of graphical abstract

      The range of reactions occurring at the highly stained cyclopropenylium system has been extended by two important examples. Thus conditions have now been reported which favor classical electrophilic aromatic substitution (2)[RIGHTWARDS ARROW](1) and the synthetically important halogen/lithium exchange (2)[RIGHTWARDS ARROW](3) in the Cmath image-system.

    8. Structural Elucidation of Diastereoisomeric 1,3,6-Trioxacyclooctane Systems by Simultaneous Relaxation and Double Resonance Experiments (pages 447–449)

      Lektor Lic. techn. Klaus Bock, Dipl.-Chem. Bernd Meyer and Prof. Dr. Joachim Thiem

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804471

      Thumbnail image of graphical abstract

      A novel NMR technique permitted structural elucidation of the two complex sugar derivatives (1) and (2). Surprisingly, they contain an eight-membered ring.

    9. The First Oxostannate(II): K2Sn2O3 (pages 449–450)

      Dipl.-Chem. Rolf Michael Braun and Prof. Dr. Rudolf Hoppe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804491

      A new SnII[BOND]O compound, the first oxostannate(II) of defined structure, has been obtained as brownish-yellow single crystals. X-Ray structure analysis reveals a complicated perovskite variant (Sn1O3Sn2 double layers) in which half of the anions are missing in a regular manner.

    10. α-Amino Acids as Nucleophilic Acyl Equivalents: Synthesis of Ketones and Aldehydes by Means of Oxazolin-5-ones (pages 450–451)

      Dipl.-Chem. Rainald Lohmar and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804501

      Thumbnail image of graphical abstract

      A new ketone synthesis is shown below. The reaction can also be applied to oxazolinones bearing a (substituted) allyl group on C-4 (R1 or R3) which are thus transformed into allyl ketones.

    11. Ce4O4S3: A Mixed-Valence Cerium Oxide Sulfide (pages 451–452)

      Dr. Winfried Wichelhaus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804511

      The first oxide sulfide of rate earth metals to contain M3+ and M4+ ions is Cemath imageCemath imageO4S3. The compound is a semiconductor and has M3+ and M4+ in two crystallographically distinct positions.

    12. Toonacilin and 6-Acetoxytoonacilin, Two Novel B-seco-Tetranortriterpenoids with Antifeeding Activity (pages 452–453)

      Prof. Dr. Wolfgang Kraus, Dipl.-Chem. Wolf Grimminger and Dr. Gisela Sawitzki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804521

      Thumbnail image of graphical abstract

      Natural plant protecting agents are toonacilin (1), R [DOUBLE BOND] H, and its 6-acetoxy derivatives whose structure has now been elucidated. They occur in the bark of a Toona ciliata species; extracts exert a powerful antifeeding effect on the Mexican bean beetle.

    13. Ring Contraction in the Reaction of Cationic C5H5Mo(CO)2 Chelate Complexes with Methyllithium (pages 453–454)

      Prof. Dr. Henri Brunner, Heinrich Schwägerl, Dr. Joachim Wachter, Dr. George M. Reisner and Prof. Dr. Ivan Bernal

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804531

      Thumbnail image of graphical abstract

      The five-membered chelate ring in cation(1) surprisingly contracts to a three-membered ring on reaction with CH3Li, yielding the complexes

    14. [Fe2(NO)6]2+, A Binary Nitrosyliron Cation (pages 454–455)

      Prof. Dr. Max Herberhold and Dipl.-Chem. Reinhard Klein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804541

      Thumbnail image of graphical abstract

      The first binary cationic nitrosylmetal complex(1) is stable as the PF6 salt below −20°C. Formation of the salt from iron powder and NO+PFmath image in nitromethane is remarkable.

    15. γ-Sultenes and 1,3-Oxazolidinethiones by 1,3-Dipolar Cycloaddition of Thioketene S-Oxides to Azomethines (pages 455–456)

      Prof. Dr. Ernst Schaumann, Dipl.-Chem. Jörn Ehlers and Dr. Ulrich Behrens

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804551

      Thumbnail image of graphical abstract

      The novel 1,2,4-oxathiazolidine system(4) was surprisingly obtained from the thioketene (1) and the azomethine (2). Compound (1) reacts as a 1,3-dipole.

    16. σ-Dicarbonylcyclopentadienyliron Derivatives of Cyclopropenes and Cyclopropenylium Salts (pages 456–457)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Ekkehard Bartmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804561

      Thumbnail image of graphical abstract

      A potential equivalent of a cyclopropenyl anion is seen in the cyclopropene derivative (3), R1 = Ph, R2 = H, bearing an organometallic substituent. Its reaction with electrophiles gives almost exclusively the cyclopropenylium salts (4) ([Fe] = [Fe(C5H5)(CO)2]).

    17. Coordinatively Unsaturated Transition Metal-Substituted Cyclopropenylium Systems (pages 457–458)

      Doz. Dr. Robert Weiss and Dr. Claus Priesner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804571

      Thumbnail image of graphical abstract

      A 14-electron system and hence possibly a novel catalyst has been found in the Pd-substituted, coordinatively unsaturated cyclopropenylium salt (1) (and its CF3SOmath image analog). 14-electron systems play an important role in homogeneous catalysis.

    18. Double Deprotonation of 3-Nitropropene and 4-Nitro-1-butene: Derivatives of Their Dianions as Novel Reagents for CC-Linkage (pages 458–459)

      Prof. Dr. Dieter Seebach, Dr. Rainer Henning and Dipl.-Chem. Friedrich Lehr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804581

      Thumbnail image of graphical abstract

      Doubly deprotonated 4-nitro-1-butene(1) is a crotonaldehyde enolate equivalent (2), which preferentially affords γ-substituted products (3), rather than the α-substituted compounds (4) formed from normal dienolates, on treatment with electrophiles. Compounds (3) can be transformed into α,β-unsaturated aldehydes by Nef reaction.

    19. Cathodic Acylation of Aryl Olefins (page 460)

      Dipl.-Chem. Rainer Engels and Prof. Dr. Hans J. Schäfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804601

      Thumbnail image of graphical abstract

      Electrochemical acylation, especially formylation, has now been accomplished with aryl olefins. The products from the initially generated radical anions or dianions and the electrophilic solvent are subsequently hydrolyzed.

    20. Synthesis of Donor-substituted Sulfonium Salts (pages 460–461)

      Dr. Hans-Ulrich Wagner and Dipl.-Chem. Aviv Judelbaum

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804602

      Thumbnail image of graphical abstract

      Stable sulfonium salts of type (2), R2 = OR or NR2, have been synthesized by alkylation of the sulfinic acid derivatives (1). Yields are practically quantitative.

    21. Cyclooctenynes (pages 461–462)

      Dipl.-Chem. Hermann Petersen, Dipl.-Chem. Heinz Kolshorn and Prof. Dr. Herbert Meier

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804611

      Thumbnail image of graphical abstract

      Highly reactive 1-cycloocten-3-yne(2), which is moderately stable at room temperature, has been synthesized by thermolysis of the selenadiazole (1). Quantum mechanical calculations show (2) to be of even higher energy than the two isomeric cyclooctenynes.

    22. Unusual Reaction of Nickelocene with Bis(diphenylphosphino)maleic Anhydride (pages 462–463)

      Dr. Walter Bensmann and Priv.-Doz. Dr. Dieter Fenske

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804621

      Thumbnail image of graphical abstract

      The first insertion of cyclopentadiene into a P[BOND]C bond has been observed in the reaction of nickelocene with doubly Ph2P-substituted maleic anhydride. The product (X-ray analysis) belongs to a class of compounds having unusual bonding properties.

    23. Reductive Elimination Reactions of Cationic Acylcobalt Complexes: Transformation of a CoIII[BOND]COR Bond into a CoI[BOND]CO Bond (pages 464–465)

      Prof. Dr. Helmut Werner and Dipl.-Chem. Werner Hofmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804641

      Thumbnail image of graphical abstract

      An acyl group with umpolung of reactivity is present in the organocobalt compounds(1), as shown by their resistance to acids and ready reaction with bases. Compound (1), R[DOUBLE BOND]CH3, quantitatively forms the CoI compound (2) with NaH; compounds (1) bearing other substituents R give products of types (2) and (3).

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    24. Dienylketenimines—An Entry to Linearly Conjugated Cyclohexadienimines (pages 465–466)

      Dipl.-Chem. Heinz H. Eckhardt and Prof. Dr. Hartwig Perst

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804651

      Thumbnail image of graphical abstract

      The new cyclo/seco system(1)(2) is accessible from the amide corresponding to (2) by removal of water. Product (1) is isolated and regenerates (2) on UV irradiation. For instance, (2), R1 = CH3, R2 = i-C3H7, can be kept for several days in THF at room temperature.

    25. Novel Coordination of (Benzoylmethylene)triphenylphosphorane in a Nickel Oligomerization Catalyst (pages 466–467)

      Prof. Dr. Wilhelm Keim, Dr. Frank H. Kowaldt, Dr. Richard Goddard and Dr. Carl Krüger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804661

      Thumbnail image of graphical abstract

      The first defined complex for oligo- and polymerization of ethylene which requires no co-catalyst is the crystalline nickel complex (1). Its structure was established by X-ray analysis. Dissolved in toluene, compound (1) reacts with ethylene (50 bar) at 50°C giving almost exclusively linear α-olefins; linear polyethylene is formed under a different set of conditions.

    26. N-Terminal Cyclization of Peptides with N,N′-Carbonyldiimidazole or N,N′-Thiocarbonyldiimidazole (pages 467–468)

      Dr. Franz Esser and Dr. Otto Roos

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804671

      Thumbnail image of graphical abstract

      Partial conformational fixation of peptides by extremely mild N-terminal cyclization facilitates studies of structure-activity relations in peptide hormones and identification of the first two amino acids in a sequence.

    27. 3d-Orbital Participation in Sulfur Diimides (pages 468–469)

      Dipl.-Ing. Richard Bartetzko and Prof. Dr. Rolf Gleiter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804681

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      An electron decet is often invoked to explain unusual properties of sulfur compounds. The PE and electronic spectra of (1) and (2) have now been compared. They are almost superposable, suggesting analogus distributions of valence electrons. Tetravalent sulfur does not appear to be present.

  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (page 470)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197804701

  4. Book Reviews

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

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