Angewandte Chemie International Edition in English

Cover image for Vol. 36 Issue 18

October 2, 1997

Volume 36, Issue 18

Pages 1917–2021

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 18/1997)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719151

      Thumbnail image of graphical abstract

      The cover pictur shows the ball-and-stick model of a [{RhBi 7}Br 8] cluster from the structure of one of the first ternary subhalides of bismuth, Bi7 RhBr8. The seven bismuth atoms(blue) surround the central rhodium atom (yellow) forming a regular pentagonal bipyramid. The two apical bismuth atoms are each in an approximate square-planer environment of four bromine atoms. The squares are staggered and thus the {RhBi7} bipyramid is surrounded by a distorted square antiprism of bromine atoms. On closer analysis, this apparently unfavorable atomic arrangement emerges as an exceptional solution to the need to satisfy the electronic requirements of all participating atoms. More about this as yet unique molecular cluster is discussed by M. Ruck on pages 1971 ff. The graphics were generated by M. Ruck and G. Baum with the program POV-Ray.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Cell-Mediated Immunity in Virus Infections (Nobel Lecture) (pages 1926–1936)

      Prof. Peter C. Doherty

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719261

      Being isolated in those pre-fax and pre-e-mail days in Australia was a great advantage, as it allowed time to discuss and to think things through. We had outspoken and informed local critics, the freedom and resources to pursue our own ideas, and were given full credit for our efforts. Those of us who have senior roles in science need to do everything possible to ensure that comparable opportunities and environments remain available to young scientists.” With this provocative exhortation P.C. Doherty ended his Nobel Lecture.

    2. Cellular Immune Recognition and the Biological Role of Major Transplantation Antigens (Nobel Lecture) (pages 1938–1949)

      Dr. Rolf M. Zinkernagel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719381

      In the complex balance between virus and host the T cells and the properties of the virus play an important role. The unexpected discovery of the MHC-restricted T cell recognition (MHC = major histocompatibility complex) prompted many important investigations. Which have led to a detailed understanding on a molecular level of T cell recognition of virus-infected target cells. As a result of these findings the immunological specificity as well as the immunological memory, and above all, pathogenesis of infectionus diseases and of autoimmunity can be better understood.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Inorganic Cauliflower: Functional Main Group Element Dendrimers Constructed from Phosphorus- and Silicon-Based Building Blocks (pages 1951–1955)

      Dr. Dietrich Gudat

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719511

      Thumbnail image of graphical abstract

      The allure of cascade molecules has long since reached main group chemistry. Dendrimers constructed from silicon- and phosphorus-based building blocks (see schematic representation on the right) not only are among the largest cascade molecules ever synthesized, but also offer unique possibilities for binding functional groups at the surface or in the interior. This property may open new perspectives for the design of catalysts and synthetic reagents.

    2. A Chemical Concept for the Treatment of Tay–Sachs Disease (pages 1955–1959)

      Dr. Thomas Kolter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719551

      Thumbnail image of graphical abstract

      Great advances have been made in the treatment of Tay–Sachs disease, one of a group of inherited diseases in which the degradation of sphingolipids is impaired. In the animal model, application of compound 1 was successful in inhibiting the biosynthesis of nondegradable enzyme substrates and in this way reducing the extent of the disease.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Enzyme Models Based on Molecularly Imprinted Polymers with Strong Esterase Activity (pages 1962–1964)

      Prof. Dr. Günter Wulff, Dr. Thomas Gross and Dipl.-Chem. Rainer Schönfeld

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719621

      Thumbnail image of graphical abstract

      Functions similar to those of catalytic antibodies are shown by molecularly imprinted polymers, when the cavities in the polymer not only have the correct form but also contain catalytically active groups. Polymers have now been prepared by imprinting with a transition state analogue of alkaline ester hydrolysis (see picture). These “artificial enzymes” combine strong catalytic activity with typical enzyme properties such as Michaelis—Menten kinetics, competitive inhibition, turnover, and substrate selectivity.

    2. A Polyoxo–Polyolato Complex of Tantalum (V) with a Double Adamantane-Like [Ta7O12]11+ Core (pages 1964–1966)

      Prof. Dr. Kaspar Hegetschweiler, Dr. Thomas Raber, Dr. Guido J. Reiss, Prof. Dr. Walter Frank, Dr. Michael Wörle, Dr. Antonio Currao, Prof. Dr. Reinhard Nesper and Dr. Thomas Kradolfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719641

      Thumbnail image of graphical abstract

      Only corner-sharing between the seven TaO6 octahedra is observed in the neutral complex [H−11Ta7O12(tdci)6] (tdci = 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol). The structure on the right (only one tdci ligand is illustrated) depicts the Ta7O30 double adamantane core. In contrast to previously described structures of polyoxometalate ions, which have a predominantly edge-shared framework, this compound has an unusually open structure.

    3. Clusters from Vertex- and Face-Sharing Adamantane-Like Units: A New Topology for Multinuclear Complexes (pages 1967–1969)

      Euan K. Brechin, Steven G. Harris, Dr. Simon Parsons and Dr. Richard E. P. Winpenny

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719671

      Thumbnail image of graphical abstract

      Avoidance of a metal–metal bond is a significant factor favoring the formation of the nonanuclear cobalt complex [CO9(chp)18] (framework depicted on the right; chp = 6-chloro-2-pyridonate). The complex is homoleptic, which is unusual for 3d-complexes of pyridonates, and this contrasts with the similar, but heteroleptic, nickel double adamantane frameworks also reported.

    4. Synthesis, Structure, and Oxidation of Donor-Stabilized Gallium(I) Iodide: Ga8I8·6PEt3 (pages 1969–1971)

      Dipl.-Chem. Clemens U. Doriat, Dipl.-Chem. Markus Friesen, Dr. Elke Baum, Dr. Achim Ecker and Prof. Dr. Hansgeorg Schnöckel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719691

      Thumbnail image of graphical abstract

      Merely the illusion of a Ga[BOND]Ga bond is given between the doubly I-bridged atoms of the nearly planar eight-membered ring in Ga8I8 · 6 PEt3 (shown on the right). This finding is remarkable, since the corresponding AlI halides have four-membered Al rings. D = PEt3.

    5. Bi7RhBr8: A Subbromide with Molecular [{RhBi7}Br8] Clusters (pages 1971–1973)

      Dr. Michael Ruck

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719711

      Thumbnail image of graphical abstract

      A unique type of cluster, the [{RhBi7}Br8] molecules, is the building block from which the halogen-rich bismuth subbromide Bi7RhBr8 is constructed. The Bi atoms are arranged as a pentagonal bipyramid around the central Rh atom, and they, in turn, are surrounded by the Br atoms as a square antiprism (shown on the right; Rh = dark gray, Bi = black, Br = pale gray). In contrast to Bi7RhBr8, the metalrich bismuth subiodides known to date are not composed of discrete molecules.

    6. Sc2Te: A Novel Example of Condensed Metal Polyhedra in a Metal-Rich but Relatively Electron-Poor Compound (pages 1974–1976)

      Paul A. Maggard and Professor Dr. John D. Corbett

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719741

      Thumbnail image of graphical abstract

      Condensed double chains of edge-sharing scandium octahedra are contained in Sc2Te. These structural units are augmented by more loosely bound pyramidal and zigzag scandium aggregates. On the right is a projection of these chains together with tellurium (the open circles). The metal array may be viewed as the result of the dissociation of the metal framework in electron-richer chalcogenides.

    7. Direct Solid-Phase Glycosylations of Peptide Templates on a Novel PEG-Based Resin (pages 1976–1978)

      Dr. Axel Schleyer, Prof. Dr. Morten Meldal, Dr. Renil Manat, Prof. Dr. Hans Paulsen and Prof. Dr. Klaus Bock

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719761

      Thumbnail image of graphical abstract

      Glycopeptide libraries in which both the carbohydrate part and the peptide part have been varied can be generated by stereoselctive glycosylation of free hydroxy groups of support-bound peptides with glycosyl trichloroacetimidates. The use of temporary t Bu protecting groups enabled the stereoselctive synthesis of a model library of four glycopeptides (one is depicted on the right) that each have two different glycosyl groups.

    8. Multicomponent Self-Assembly: Preferential Generation of a Rectangular [2 × 3]G Grid by Mixed-Ligand Recognition (pages 1978–1981)

      Dr. Paul N. W. Baxter, Prof. Dr. Jean-Marie Lehn, Boris O. Kneisel and Prof. Dr. Dieter Fenske

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719781

      Thumbnail image of graphical abstract

      A significantly larger variety of ligand combinations is possible for rectangular [m × n] grids (such as the first complex of this type, [2 × 3] grid 1) than for symmetric square [n × n] grids. The product distribution [2 × 3]:[2 × 2]:[3 × 3] for the reaction of tri- and ditopic ligands with AgI ions in a 2:3:6 ration is 90:8:2! The spheres represent the AgI ions.

    9. New Copper Telluride Clusters by Light-Induced Tellurolate–Telluride Conversions (pages 1981–1983)

      Dr. John F. Corrigan and Prof. Dr. Dieter Fenske

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719811

      Thumbnail image of graphical abstract

      Photolytic cleavage of TePh2 from the phosphane- stabilized, hexanuclear cluster 1 results in the mixed telluride–tellurolate cluster 2 in good yields (the structure of the anion in 2 is shown on the right; dark spheres represent Te atoms, hashed spheres Cu atoms, and white spheres P atoms.

      • equation image
    10. Difluorovinylidene, F2C[DOUBLE BOND]C: (pages 1983–1985)

      Dr. Jürgen Breidung, Prof. Dr. Hans Bürger, Dipl.-Chem. Carsten Kötting, Dr. Rodion Kopitzky, Prof. Dr. Wolfram Sander, Dipl.-Chem. Michael Senzlober, Prof. Dr. Walter Thiel and Prof. Dr. Helge Willner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719831

      An alkyne–vinylidene isomerization is also possible with the difluoro compounds 1 and 2! Irradiation of 2 (λ = 193 nm) in an Ar matrix yields 1 exclusively. The IR spectrum agrees with results of novel abinitio calculations, which also suggest that 1—in sharp contrast to the vinylidenes RHC[DOUBLE BOND]C—is protected against isomerization into 2 by a kinetic barrier. Irradiation with light with λ > 230nm converts 1 back into 2. Already at 35–42 K 1 adds CO and N2 to yields F2CCCO and F2CCNN, respectively.

      • equation image
    11. Self-Assembly of Thirty-Six Atom Clusters (Li12S6O6N12) Containing Diazasulfite Anions (pages 1986–1988)

      Justin K. Brask, Prof. Dr. Tristram Chivers, Dr. Masood Parvez and Dr. Gabriele Schatte

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719861

      Thumbnail image of graphical abstract

      Depending on the type of substituent on the nitrogen atom, the two thirtysix atom clusters of main group elements formed on treating RNSO with LiNHtBu adopt different structures (R = t Bu, SiMe3). For instance, the compound depicted on the right can be described as an aggregate of three hexagonal prisms.

    12. A Modular System for the Synthesis of Complex N-Glycans (pages 1989–1992)

      Dr. Carlo Unverzagt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719891

      Thumbnail image of graphical abstract

      Double regioselective glycosylation is the key to the generally applicable strategy by which two triantennary octasaccharides and the tetraantennary nanasaccharide 1 are available. A modular system of oligosaccharides building blocks is the basis of an efficient synthesis of complex N-glycans with the desired number of branches in unexpectedly high yields.

    13. Phosphorus(V) Nitride Imide HP4N7: Synthesis from a Molecular Precursor and Structure Determination with Synchrotron Powder diffraction (pages 1992–1994)

      Dr. Stefan Horstmann, Mag. Elisabeth Irran and Prof. Dr. Wolfgang Schnick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719921

      Thumbnail image of graphical abstract

      Starting from a diphosphazene as a molecular precursor, single-phase HP4N7 could be synthesized for the first time. The structure was determined from power-diffraction investigation with synchrotron radiation. A section of the crystal structure is shown on the right.

    14. Trimethylplatinum Triflate: A Versatile Building Block in Coordination Chemistry (pages 1994–1995)

      Dipl.-Chem. Sabine Schlecht, Priv.-Doz. Dr. Jörg Magull, Prof. Dr. Dieter Fenske and Prof. Dr. Kurt Dehnicke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719941

      Thumbnail image of graphical abstract

      Depending on the donor strength of the base, tri-, di-, or mononuclear complexes are formed on reaction of the tetranuclear complex [{Me3Pt(O3SCF3)}4] (structure depicted on the right) with Lewis bases. These complexes of different nuclearity offer a rich synthetic potential because of their precisely tunable properties.

    15. Polycyclic Aromatic Hydrocarbons in the Nanometer Range (pages 1996–1998)

      Dr. Benedikt Schlicke, Prof. Dr. A.-Dieter Schlüter, Dipl.-Chem. Petra Hauser and Prof. Dr. Jügen Heinze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719961

      Thumbnail image of graphical abstract

      The exceptionally long (4.5 nm) monodisperse polycyclic aromatic hydrocarbon 1 contains 29 condensed five-and six-membered rings. Since the dodecyl chains make this extended, flat (tabular) molecule unusually soluble in common organic solvents, it can be readily characterized. Compound 1 can be reduced to the octaanion within a relatively small potential range, and the tetraction that forms on oxidation is stable for several seconds.

    16. Efficient Synthesis of Ganglioside GM2 for Use in Cancer Vaccines (pages 1998–2001)

      Julio C. Castro-Palomino, Dr. Gerd Ritter, Sheila R. Fortunato, Stefan Reinhardt, Dr. Lloyd J. Old and Prof. Dr. Richard R. Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199719981

      Thumbnail image of graphical abstract

      A target antigen for cancer immunotherapy, ganglioside GM2, is expressed on the cell surface of several human cancer types. An efficient chemical synthesis can now make available ample amounts of a structurally well-defined synthetic GM2, free of biological contaminants. This greatly facilitates the systematic construction of safe and efficient GM2 cancer vaccines.

    17. Effects of Environment on Intramolecular Electron Transfer in Mixed-valence 1′,1‴-Dinaphthylmethyl(biferrocenium) Triiodide: Structural and 57Fe Mössbauer Characteristics (pages 2002–2004)

      Prof. Ten-Yuan Dong, Xiao-Qian Lai, Zhi-Wei Lin and Dr. Kuan-Jiuh Lin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720021

      Thumbnail image of graphical abstract

      Extreme sensitivity to change in the lattice is observed for electron-transfer rates in the FeII/FeIII title compound, as shown by Mössbauer spectroscopic investigations of the two crystallographic phases in which the compound can be isolated. The structure of the cation and anion in the monoclinic phase P21/n is shown on the right.

    18. [Ru(Ph)(CO)(PtBu2Me)2]+: A Unique 14-Electron Ru11 Complex with Two Agostic Interactions (pages 2004–2006)

      Dejian Huang, William E. Streib, Prof. Odile Eisenstein and Prof. Kenneth G. Caulton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720041

      Thumbnail image of graphical abstract

      A nonplanar arrangement of four ligands is intrinsic to the title compound is solution and in the crystal. There is no interaction between the Ru center and the Counterion [3,5-(CF3)2 C6H3]4B. Density functional theory calculations of the model complex [Ru(Ph)(CO)(PH3)2]+ provided the structure shown on the right, which shows no ortho-CH … Ru interaction.

    19. Solution Structures of a Pair of Stable Hexaaminecobalt (III/II) Conformers (pages 2006–2008)

      Prof. Dr. Peter Comba and Dr. Achim F. Sickmüller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720061

      Thumbnail image of graphical abstract

      The structure of the exciting blue form of a new hexaaminecobalt(III) cage compound (Lewis structure shown on the right) was not known, while that of the more usual yellow conformer was determined experimentally. A combination of molecular-mechanics calculations and the simulation of spectroscopic and electrochemical properties can be used to determine the structure, and to interpret the unprecedentedly low ligand field and high redox potential.

    20. Ln3Au2Al9 (Ln [DOUBLE BOND] Dy, Tb): Heteronuclear versus Homonuclear Bonding in Intermetallic Phases (pages 2008–2010)

      Karen J. Nordell and Prof. Dr. Gordon J. Miller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720081

      Thumbnail image of graphical abstract

      A variant of the BaAl4 structure, the α-La3Al11 structural type is observed upon crystallization of the new ternary intermetallic phase Ln3Au2Al9 (Ln = Dy and Tb). Calculations of the electronic structure were used to investigate the characteristics of Au and Al atoms within the framework. The gray atoms in the picture of the structure prefer heteronuclear Au[BOND]Al contacts over homonuclear Al[BOND]Al and Au[BOND]Au contacts.

    21. [NH4]3[Ir(S4)(S6)2]: A Reevaluation of Hofmann and Höchtlen's Report of [NH4]3[Ir(S5)3] from 1904 (pages 2010–2011)

      Thomas E. Albrecht-Schmitt and Prof. James A. Ibers

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720101

      Thumbnail image of graphical abstract

      Not 15, but 16 sulfur atoms are found in [NH4]3[Ir(S4)(S6)2], which was first reported as “[NH4]3[IrS15]” in 1904. This was determined by comparing the results of the crystal structure analysis (structure shown on the right) with the optical goniometric data reported in the original work. [NH4]3[Ir(S4)(S6)2] spontaneously resolves upon crystallization. Therefore, these enantiomeric crystals were available a decade before Werner first separated optically active inorganic complexes.

    22. NADH-Dependent Halogenases Are More Likely To Be Involved in Halometaolite Biosynthesis Than Haloperoxidases (pages 2012–2013)

      Dipl.-Chem. Kathrin Hohaus, Dipl.-Chem. Annett Altmann, Dr. Wassily Burd, Dipl.-Ing. (FH) Ilona Fischer, Dr. Philip E. Hammer, Dr. Dwight S. Hill, Dr. James M. Ligon and Prof. Dr. Karl-Heinz van Pée

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720121

      Thumbnail image of graphical abstract

      NADH instead of hydroged peroxide is required by two newly identified, substrate-specific and regioselective halogenases. Both were isolated from a pyrrolnitrin-producing Pseudomonas fluorescens strain. One enzyme catalyzes the chlorination of L-tryptophan to 7-chloro-L-tryptophan (1).

    23. Boratabenzene Zirconium(II) Complexes: An Unusual Annulation with Ethynes (pages 2014–2016)

      Prof. Dr. Arthur J. Ashe III, Dr. Saleem Al-Ahmad and Dr. Jeff W. Kampf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720141

      Thumbnail image of graphical abstract

      The folding of the boratanaphthalene ring over the metal in 2 ensures that all ten non-hydrogen atoms are with in bonding distance to Zr. This complex with the novel boratanaphthalene ligand was furnished in an unprecedented ring annulations reaction of ethyne with the boratabenzene ligand 1.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Book Review: Color Atlas of Biochemistry. By J. Koolman and K.-H. Röhm (pages 2019–2020)

      Paul Wentworth Jr. and Kim D. Janda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199720191