Angewandte Chemie International Edition in English

Cover image for Vol. 25 Issue 6

June 1986

Volume 25, Issue 6

Pages 487–582

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 6/1986)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198604871

      Thumbnail image of graphical abstract

      The cover shows a computer-graphics-drawn space-filling model of the structure, determined by X-ray diffraction, of the 1 : 1 adduct obtained from the neutral complex trans-[Pt(PMe3)Cl2(NH3)] and dibenzo-[18]crown-6 (Pt yellow, P pink, Cl green, N blue, O red, C black-hatched, H white). The crown ether is anchored in the second coordination sphere of the Pt complex through N[BOND]H ⃛O hydrogen bonds. The ligands in the second coordination sphere of transition-metal complexes can be bound by means of electrostatic forces, hydrogen bonds, charge-transfer interactions, or van der Waals forces. Further details on this phenomenon, which is also important for natural receptor molecules such as cyclodextrins and polyether antibiotics, are reported by J. F. Stoddart et al. on p. 487 ff.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 6/1986)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198604872

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Second-Sphere Coordination–a Novel Rǒle for Molecular Receptors (pages 487–507)

      Dr. Howard M. Colquhoun, Dr. J. Fraser Stoddart and Dr. David J. Williams

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198604873

      Thumbnail image of graphical abstract

      “Supramolecules”—adducts formed between transition-metal complexes and neutral compounds—have long been known; their structures and bonding patterns have been elucidated in recent years by X-ray structure analysis and NMR spectroscopy. 1 is cationic Pt complex in which the [18]crown-6 is bound in the second sphere through hydrogen bonds. Applications of the concept of binding in the second coordination sphere have ben found in such distinct areas as analytical chemistry and the controlled release of medicaments.

    2. The Palladium-Catalyzed Cross-Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)] (pages 508–524)

      Prof. Dr. John K. Stille

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605081

      For the formation of carbon-carbon bonds, the reaction of electrophiles with organotin compounds has proved especially useful. The latter may be prepared by several routes, can bear a variety of functional groups, and, moreover, are not very sensitive to air or moisture. The Pd-catalyzed coupling takes place under mild conditions to afford high yields of product. One example is reaction (a), in which a wide variety of R and R′ groups may be employed.

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    3. Orthophosphates in the Ternary System Al2O3[BOND]P2O5[BOND]H2O (pages 525–534)

      Prof. Dr. Rüdiger Kniep

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605251

      Thumbnail image of graphical abstract

      Aluminum orthophosphates have applications as, for example, ceramic binding agents, anticorrosion agents, and antacids. The wide variety of applications has repeatedly stimulated interest in the structural chemistry of this well-known class of substances. A large number of structures arise from the numerous ways in which the cationic coordination polyhedra of the aluminum ions can be linked with phosphate ions. The picture shows part of the crystal structure of Al(H2PO4)3[BOND]A.

    4. High-Pressure Liquid Chromatography (HPLC) of Proteins [New Analytical Methods (29)] (pages 535–552)

      Dr. Gerhard Seipke, Dr. Hubert Müllner and Dr. Ulrich Grau

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605351

      The current renaissance of protein biochemistry—brought about by the rapid development of gene technology and stimulated by the therapeutic importance of proteins—has given rise to new analytical and preparative separation problems, for which HPLC procedures offer ideal solutions. Accordingly, HPLC has long ceased to be merely a laboratory method: at present, “industrial” systems are being developed for the separation of proteins on a 100-g scale. The scope of application of these methods is exemplified by insulin and interleukin 2.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Reduced Cobalt-meso-Tetraphenylporphyrin Complexes: Synthesis and Structure of [Na(thf)3]2[Co(TPP)] (pages 553–554)

      Stefano Ciurli, Dr. Sandro Gambarotta, Prof. Dr. Carlo Floriani, Dr. Angiola Chiesi-Villa and Dr. Carlo Guastini

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605531

      Not the monoanion but ratehr the dianion, [Co(TPP)]2⊖, of cobalt(II) meso-tetraphenylporphyrin [Co(TPP)] is obtained upon reduction of the latter with two equivalents of sodium metal. It is of particular importance for the exact determination of the experimental conditions under which the monoanion, [Co(TPP)], which is frequently employed as a metal nucleophile, is formed. The structure of the title complex is characterized by a symmetrically arranged threefold contact ion.

    2. Epoxidation of Olefins with Elemental Fluorine in Water/Acetonitrile Mixtures (pages 554–555)

      Prof. Dr. Shlomo Rozen and Michael Brand

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605541

      Not fluorinated compounds but rather epoxides are formed in good yields from alkenes with the reagent F2/MeCN/H2O. Both alkenes with a terminal double bond, which are especially sensitive to oxidation, and enones react smoothly.

    3. [MoR(η3-C3H5)3], R = Alkyl: Alkylmolybdenum Complexes with Agostic C[BOND]H ⇀ Mo Bond (pages 555–556)

      Priv.-Doz. Dr. Reinhard Benn, Sigrid Holle, Dr. Peter W. Jolly, Dr. Richard Mynott and Prof. Dr. Carlos C. Romão

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605551

      A dramatic high-field shift of an 1H-NMR signal characterizes the agostic Mo↼H[BOND]C interaction in the isopropylmolybdenum complex 2. The bright yellow compound is accessible in 65% yield by reaction of the binuclear molybdenum complex 1 with isopropylmagnesium chloride at −78°C in ether.

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    4. Diastereoselective Synthesis of Functionalized Tetrahydrofuran Derivatives from γ-Lactols (pages 556–557)

      Dipl.-Chem. Christiane Brückner, Hiltrud Lorey and Priv.-Doz. Dr. Hans-Ulrich Reissig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605561

      Thumbnail image of graphical abstract

      Very high diastereoselectivity is often characteristic of reaction (a), which allows substituents to be introduced next to the oxygen atom of tetrahydrofuran derivatives. This method might be of use for the synthesis of sugars and antibiotically active natural products having tetrahydrofuran partial structures.

    5. Complex-Induced Fragmentation of As4S4: Stabilization of an As2S3 Ligand (pages 557–558)

      Prof. Dr. Henri Brunner, Dr. Heike Kauermann, Dr. Bernd Nuber, Dr. Joachim Wachter and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605571

      Thumbnail image of graphical abstract

      For the first time it has been possible to stabilize an almost complete AsS cage molecule as a complex ligand. The photochemical reaction of [C5Me5Co(CO)2] with As4S4 affords [(C5Me5)2Co2As2S3] 1, which consists of a “basket” formed by the cobalt, arsenic, and sulfur atoms (homoprismane skeleton).

    6. Heterogeneous Catalysis of Ammonia Synthesis at Room Temperature and Atmospheric Pressure (pages 558–559)

      Prof. Dr. Ken-ichi Aika

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605581

      The dream of many chemists, the nonenzymatic catalytic synthesis of ammonia from N2 and H2 at room temperature and normal pressure, has been achieved with a potassium-containing ruthenium/active carbon system. Even though the activity of the catalyst is small (0.011 mmol NH3 per day and gram of catalyst), this discovery represents a beginning. In comparison, nitrogenase from Klebsiella pneumoniae produces 0.25 mmol NH3 per minute and gram of protein.

    7. Reaction of Phosphonium Ylides with Alkyldichloroboranes (pages 559–560)

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

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605591

      Thumbnail image of graphical abstract

      New, interesting bis-ylides 1, R1[DOUBLE BOND]R4, are formed from Ph3P[DOUBLE BOND]CHR1 and R3BCl2 in a 4 : 1 molar ratio. When the 1 : 1 adduct of these two species is allowed to react with the ylide Ph3P[DOUBLE BOND]CHR4 (3 : 1), on the other hand, the unsymmetrically substituted 1, R1 ≠ R4, is formed. These bis-ylides may be suitable as complex ligands.

    8. 2-Substituted 1,3,2-Dioxaboroles as Synthetic Equivalents for the Glycolaldehyde Anion (pages 560–562)

      Prof. Dr. Günter Wulff and Dipl.-Chem. Achim Hansen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605601

      Thumbnail image of graphical abstract

      The synthesis of unusual sugars through chain extension by two C atoms (for example, L-ribose) may be achieved with the new solid-phase reagent 1, which was obtained from 2-phenyl-1,3,2-dioxaborole, a compound synthesized for the first time. Immobilization suppresses multiple addition.

    9. N-Aryl-O-(diphenylphosphinoyl)hydroxylamines: Electrophilic Amination of Amines to Hydrazines; a Model Reaction for the Carcinogenicity of Aromatic Amines (pages 562–563)

      Prof. Dr. Gernot Boche, Dipl.-Chem. Reinhard H. Sommerlade and Ferdinand Bosold

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605621

      Thumbnail image of graphical abstract

      The phosphinic acid derivatives 1 are stable hydroxylamine esters that react with amines HNR2R3 to give hydrazines 2. They are model compounds for metabolites of carcinogenic aromatic amines in living organisms, which include compounds also formed by electrophilic amination of N-arylhydroxylamine derivatives.

    10. Spontaneous Intramolecular Ring Opening of the Cyclopropyl Group at a Metal-Metal Double Bond (pages 563–565)

      Prof. Dr. Wolfgang A. Herrmann, Dr. Eberhardt Herdtweck and Dr. Cornelia Weber

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605631

      Thumbnail image of graphical abstract

      Thermally stable dimetallacyclopentanes 1, R[DOUBLE BOND]CH3 and cyclo-C3H5, are obtained by the intramolecular addition of a cyclopropyl group to an electrophilic Rh[DOUBLE BOND]Rh bond (A [RIGHTWARDS ARROW] B, M[DOUBLE BOND]Rh); crucial for the stability of the complex 1, which forms deep red, lustrous crystals, is the incorporation of the dimetallacyclopentane into a polycyclic framework.

    11. Direct Aminolysis of Unactivated Esters at High-Pressure (pages 565–566)

      Prof. Dr. Kiyoshi Matsumoto, Shiro Hashimoto and Prof. Dr. Shinichi Otani

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605651

      The preparation of amides 3 from nonactivated esters 1 and secondary amines 2 has been achieved at 8 kbar and approximately 45°C. This reaction cannot be carried out at normal pressure without a catalyst; even the reaction with primary amines (uncatalyzed, normal pressure) requires temperatures above 200°C.

      • equation image
    12. Red, Transparent Alkali Metal Silicides with Si4 Tetrahedrons (pages 566–567)

      Prof. Dr. Hans Georg von Schnering, Dipl.-Chem. Martin Schwarz and Dr. Reinhard Nesper

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605661

      Thumbnail image of graphical abstract

      K3LiSi4 and K7Li(Si4)2 are not only the first lithium silicides with Si4 tetrahedrons, but also the first red, transparent metal silicides. In K3LiSi4, Li and Si from infinite, one-dimensional chains; in K7Li(Si4)2, bowlshaped Li(Si4)2 units are present (see picture). The coordination of the K atoms is complicated.

    13. A Stable 1,2,4-Thiadiphosphole (“2,4-Diphosphathiophene”) (page 567)

      Prof. Dr. Rolf Appel and Rainer Moors

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605671

      Thumbnail image of graphical abstract

      The new C2P2S heterocycle 1 with a P[DOUBLE BOND]C[BOND]P[DOUBLE BOND]C sequence was obtained from CS2, LiP(SiMe3)2, and Me3SiCl. The structure of the yellow, distillable liquid was determined by 31P-, 13C-, and 29Si-NMR spectroscopy and by mass spectrometry.

    14. Anionic Host Molecules with Bicyclic Carbon Skeletons—Synthesis and Guest Inclusion in Aqueous Solution (pages 567–569)

      Dipl.-Chem. Thomas Merz, Dr. Herbert Wirtz and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605672

      Thumbnail image of graphical abstract

      The inclusion of neutral, organic guest molecules, e.g., benzene, in host compounds in aqueous solution has been achieved with the new cavity compound 1, R[DOUBLE BOND]COmath imageNa, and the analogue with

      C[BOND]CH3 instead of the two central benzene rings. The 1H-NMR signals of entrapped benzene molecules are strongly shifted to high field.

    15. [Cu36I56]20⊖—a Novel Polyanion in the Compound (pyH)2[Cu3I5] (pages 569–570)

      Prof. Dr. Hans Hartl and Prof. Dr. Joachim Fuchs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605691

      The largest discrete iodocuprate(I) ion observed so far has been identified in the compound (pyH)2[Cu3I5]. 36 CuI tetrahedra are linked through common edges to form a highly symmetrical polyanion [Cu36I56]20⊖ with the extremely rare symmetry 432 ([DOUBLE BOND]O).

    16. Transition-Metal Clusters as Catalysts of Unconventional Reactions: Reductive C[BOND]N Coupling of Alkyl Isocyanates (pages 570–571)

      Priv.-Doz. Dr. Georg Süss-Fink and Dipl.-Chem. Gerhard Herrmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605701

      Thumbnail image of graphical abstract

      Transition-metal clusters offer promise for use as catalysts with unusual properties. An example is the reductive C[BOND]N coupling of alkyl isocyanates 1 (R[DOUBLE BOND]Me, Et, nPr) to form N-formylureas 2 (R = alkyl), which is catalyzed by the tetranuclear cluster anion [H3Ru4(CO)12].

    17. Bis(η6-arsabenzene)chromium(0) (pages 571–572)

      Prof. Dr. Christoph Elschenbroich, Dipl.-Chem. Jörg Kroker, Priv.-Doz. Dr. Werner Massa, Dipl.-Chem. Martin Wünsch and Prof. Dr. Arthur J. Ashe III

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605711

      Thumbnail image of graphical abstract

      The first sandwich complex of an unsubstitued neutral heteroarene, the title compound 1, is formed by metal atom-ligand cocondensation. The electrochemical oxidation of 1 is completely reversible, whereas the reduction is only partially reversible. Both potentials are anodically shifted compared with those of free arsabenzene.

    18. Dihydropyrazolopyridine and Bis(dihydroindolizine)—Novel Mono- and Bifunctional Photochromic Systems (pages 572–574)

      Prof. Dr. Heinz Dürr, Dipl.-Chem. Charles Schommer and Dipl.-Chem. Thomas Münzmay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605721

      Thumbnail image of graphical abstract

      A reversible 1,5-electrocyclization is the basis of the photochemistry of the systems 1 and 3. The corresponding betaines 2 and 4, which were also precursors in the syntheses of 1 and 3, respectively, are intense deep red to violet (E[DOUBLE BOND]CO2Me).

    19. A Polyfunctional Dititanacyclobutane (pages 574–575)

      Prof. Dr. Hubert Schmidbaur, Dipl.-Chem. Reinhard Pichl and Dr. Gerhard Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605741

      Thumbnail image of graphical abstract

      The replacement of both methylene H atoms of a methylenephosphorane by transition—metal atoms has been achieved by reaction of TiCl4 with the phosphorus ylide (Et2N)3P[DOUBLE BOND]CH2. Violet crystals of the dititanium cyclobutane 1 are formed in over 70% yield; 1 is expected to exhibit interesting chemical properties. The markedly short Ti-C distances are characteristic of the centrosymmetric molecular structure.

    20. Methylene-Bridged Dinuclear Gold(III) Complexes with Terminal and Bridging Ylide Ligands (pages 575–577)

      Prof. Dr. Hubert Schmidbaur and Dipl.-Chem. Christoph Hartmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605751

      Thumbnail image of graphical abstract

      Two exclusively C-bonded gold atoms are present in the complex cation of 1, which, except for the bonds to the CH2 bridge, only contains onium-stabilized Au-C bonds. The salt 1 may be converted reversibly into the corresponding ylide without isomerization of the ligands.

    21. Secondary Deuterium Kinetic Isotope Effects in Enantioselective Hydroborations with (+)-Diisopinocampheylborane (pages 577–578)

      Dr. Brian E. Mann, Dr. Peter W. Cutts, Dr. James McKenna, Dr. Jean M. McKenna and Dr. Catriona M. Spencer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605771

      Thumbnail image of graphical abstract

      Not the substituents in the vinyl position but rather those in the allyl position are crucial for the enantioselectivity of the hydroboration of alkenes with (+)-diisopinocampheylborane. This was shown from measurements of the isotope effect on deuterated alkenes such as 1 and 2.

    22. A Novel Entry to Dendralene Systems (pages 578–579)

      Dr. Thomas Loerzer, Ralf Gerke and Prof. Dr. Wolfgang Lüttke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605781

      Thumbnail image of graphical abstract

      Sterically rigid dendralenes such as 2 are appreciably better suited for the study of bonding properties than the strongly twisted parent compounds. 2 has now been synthesized from 1 via the enol phosphate and its subsequent reduction. UV spectroscopic findings indicate the existence of a significantly weaker π-delocalization than in linear polyenes.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Reductions in Organic Chemistry. By M. Hudlicky (pages 579–580)

      Franz-Peter Montforts

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605791

    2. Book Review: Handbuch der Gaschromatographie. Edited by E. Leibnitz and G. Struppe (page 580)

      Wilfried A. König

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605801

    3. Book Review: Macrolide Antibiotics. Chemistry, Biology and Practice. Edited by S. Ōmura (pages 580–581)

      Walter Keller-Schierlein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605802

    4. Book Review: Common Fragrance and Flavor Materials. By K. Bauer and D. Garbe (page 582)

      Günther Ohloff

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198605821