Angewandte Chemie International Edition in English

Cover image for Vol. 34 Issue 17

September 15, 1995

Volume 34, Issue 17

Pages 1781–1905

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 17/1995)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199517791

      Thumbnail image of graphical abstract

      The cover picture shows a schematic representation of the arrangement in a crystal that resembles a tartan. It is the expected structure for the 1:1 adduct formed between a tetracationic cyclophane and ferrocene (green). The cyclophane was designed to permit recognition both in an external and internal fashion. Indeed, the cyclophane forms sheets and channels in the solid state through external recognition between its constituent components. The cyclophane also complexes substrates such as ferrocene within its cavity as predicted, whilst retaining the ability to form highly structured three-dimensional arrays, in common with the free cyclophane. Stoddart et al. use 1,4-bis(2-bromoethoxy)benzene (red) and bipyridine (blue) as building blocks to assemble the desired tetracationic cyclophane. More about the free cyclophane and its 1:1 ferrocene adduct—examples of “molecular mosaics”—are reported on p. 1862 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Novel Porphyrinoids for Chemistry and Medicine by Biomimetic Syntheses (pages 1795–1811)

      Prof. Dr. Burchard Franck and Dr. Ansgar Nonn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199517951

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      Extremely high intensity pigments with extinction coefficients up to 50 times larger than that of the industrially important pigment indigo are the red 18 π-, the violet 26 π-, and the blue 34 π-porphyrins shown below. For these porphyrins a linear relationship exists between the wavelength of the most intense Soret band and the number of π electrons in the macrocycle. With syntheses based on those in nature, a large number of expanded, bridged, inverted, and N-substituted porphyrin derivatives is accessible with interesting properties for chemical and medicinal applications.

    2. Molecular Imprinting in Cross-Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies (pages 1812–1832)

      Prof. Dr. Günter Wulff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518121

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      Can antibody analogues be synthesized? Is it possible to produce imprints in organic or inorganic polymers which can selectively recognize molecules? To do just this, cross-linked polymers have been prepared in the presence of template molecules T (see top diagram). Removal of the templates then leads to imprinted microcavities with a definite shape and a definite arrangement of binding groups (see bottom diagram). They can be used for chromatographic resolution of enantiomers, as chemosensors, as artificial antibodies, as catalysts, and as enzyme models.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Catalytic Ring-Closing Metathesis: A New, Powerful Technique for Carbon–Carbon Coupling in Organic Synthesis (pages 1833–1836)

      Prof. Dr. Hans-Günther Schmalz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518331

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      A classic reaction in organometallic chemistry has been rediscovered for organic synthesis—olefin metathesis. In this highlight methodological studies and the more recent impressive synthetic applications are described. The total synthesis of fluvirucin B1 aglycon (1) by A. H. Hoveyda is one of the latest impressive achievements.

    2. Distorted Sandwich Compounds: [1]Ferrocenophanes and [2]Ruthenocenophanes (pages 1837–1839)

      Prof. Dr. Max Herberhold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518371

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      The current world record for the largest tilt angle in a [1]ferrocenophane is held by complex 1; no [1]metallocenophanes have been prepared with a bridge smaller than the sulfur atom here (I. Manners et al. Angew. Chem. Int. Ed. Engl.1995, 34, 1506). The greater the ring strain in metallocene derivatives, the more readily they polymerize giving compounds like 3, which is formed from 2 by desulfurization with phosphane. Since the metal atoms in these polymers are arranged in a regular sequence, interesting material properties are anticipated.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Determination of the Bioactive Conformation of the Carbohydrate Ligand in the E-Selectin/Sialyl LewisX Complex (pages 1841–1844)

      Prof. Dr. Thomas Peters, Dipl.-Chem. Karoline Scheffler, Dr. Beat Ernst, Dr. Andreas Katopodis, Dr. John L. Magnani, Wey Tong Wang and Rüdiger Weisemann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518411

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      A mixture of different conformers of the flexible tetrasaccharide sialyl Lewisx is presented in solution to the E-selectin receptor, which binds only one conformation, as shown by NMR spectroscopy. The experimentally determined transfer NOEs can be used to derive proton–proton distance restrictions, which together with the confomer ensemble obtained by Metropolis Monte Carlo simulations, can be used to determine the conformation of sialyl Lewisx in the complexed state.

    2. Palladacycles as Structurally Defined Catalysts for the Heck Olefination of Chloro- and Bromoarenes (pages 1844–1848)

      Prof. Dr. Wolfgang A. Herrmann, Dr. Christoph Brossmer, Dr. Karl Öfele, Claus-Peter Reisinger, Thomas Priermeier, Dr. Matthias Beller and Dr. Hartmut Fischer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518441

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      The catalytic C[BOND]C coupling of chloroarenes by both the Heck and the Suzuki reactions has been achieved for the first time with new palladacycles of type 1, in which R can be, for instance, o-tolyl or mesityl. They are an order of magnitude more active than conventional catalysts and, moreover, thermally considerably more robust. But above all, the cleavage of the P[BOND]C bond and the deposition of palladium is not observed. Analogous reactions with bromoarenes can also be catalyzed to advantage with 1. The Heck reaction of haloarenes with vinyl derivatives (e.g., n-butyl acryiate) gives (E)-styrene derivatives in one step. In the Suzuki reaction the haloarenes are converted into biphenyl derivatives with phenylbornic acid, also in one step.

    3. Palladacycles as Efficient Catalysts for Aryl Coupling Reactions (pages 1848–1849)

      Dr. Matthias Beller, Dr. Hartmut Fischer, Prof. Dr. Wolfgang A. Herrmann, Dr. Karl Öfele and Dr. Christoph Brossmer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518481

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      The catalytic C[BOND]C coupling of chloroarenes by both the Heck and the Suzuki reactions has been achieved for the first time with new palladacycles of type 1, in which R can be, for instance, o-tolyl or mesityl. They are an order of magnitude more active than conventional catalysts and, moreover, thermally considerably more robust. But above all, the cleavage of the P[BOND]C bond and the deposition of palladium is not observed. Analogous reactions with bromoarenes can also be catalyzed to advantage with 1. The Heck reaction of haloarenes with vinyl derivatives (e.g., n-butyl acryiate) gives (E)-styrene derivatives in one step. In the Suzuki reaction the haloarenes are converted into biphenyl derivatives with phenylbornic acid, also in one step.

    4. Carbenoid or Lithium Complex of a Carbanion? Synthesis and Structure of (Me3Si)2C[DOUBLE BOND]P(aryl)[DOUBLE BOND]C(Cl)Li(thf)3 and LiCl Elimination To Give the Phosphirene (pages 1849–1852)

      Prof. Dr. Edgar Niecke, Dipl.-Chem. Petra Becker, Dr. Martin Nieger, Priv.-Doz. Dr. Dietmar Stalke and Prof. Dr. Wolfgang W. Schoeller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518491

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      The transition to the carbanion is represented by the structure of the carbenoid 2, which is accessible from 1. The solid-state structures of 1 and 2 have been determined. Compound 2 is converted into the phosphirene 3 by elimination of LiCl.

    5. Ylidediyl Halophosphane Oligomers, (Ph3PCPX)n—A Structurally Diverse Class of Compounds (pages 1853–1856)

      Dipl.-Chem. Hans-Peter Schrödel, Dr. Georg Jochem, Prof. Dr. Alfred Schmidpeter and Prof. Dr. Heinrich Nöth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518531

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      More electron-rich, and displaying a greater diversity of structures and a greater tendency to dissociate than the cyclophosphazanes, the members 1–3 of the new oligomeric family from the Ph3PC/PX combination, isoelectronic to RN/PX, have the longest P[BOND]X bonds yet observed. X = Br, Cl.

    6. Carbene Complex Functionalized Sugars (pages 1856–1858)

      Prof. Dr. Karl Heinz Dötz, Dipl.-Chem. Wolfgang Straub, Dipl.-Chem. Richard Ehlenz, Prof. Dr. Klaus Peseke and Dipl.-Chem. Roland Meisel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518561

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      Stereoselective functionalization of carbohydrates may be possible with sugar–carbene complexes 1, in which the C-1 atom is modified to be a metal-coordinated carbene. This results in an increase both of the electrophilicity of C-1 and the acidity of the adjacent C[BOND]H group. M = Cr, Mo, W, x = 5; M = Fe, x = 4.

    7. Fluorocarbonate, [FCO2]: Preparation and Structure (pages 1858–1860)

      Dipl.-Chem. Xiongzhi Zhang, Dr. Udo Gross and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518581

      By using “naked” fluoride ions in the form of tetramethylammonium fluoride or hexamethylpiperidinium fluoride, the fluorocarbonate (fluoroformate) [FCO2] can be synthesized. This anion has an extraordinarily weak C[BOND]F bond. It was characterized by 13C solid-state NMR, IR, and Raman spectroscopy, as well as by ab initio calculations.

    8. [Ni3(alkyne)4]—The First Homoleptic Alkyne–Metal Oligomer (Alkyne: 2,5,5-Trimethylhex-3-yn-2-ol) (pages 1860–1861)

      Prof. Dr. Dirk Walther, Dipl.-Chem. Thomas Klettke and Dr. Helmar Görls

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518601

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      Held together by twelve Ni[BOND]C and two Ni[BOND]Ni bonds, and stabilized by intra- and intermolecular hydrogen bonds, the title compound 1 is the first member of the hitherto hypothetical series [Mn(alkyne)n+1] (M = d10 system). Complex 1 contains a bent Ni3 chain (118°) and is stable at room temperature.

    9. Molecular Mosaics Formed by a Square Cyclophane and Its Inclusion Complex with Ferrocene (pages 1862–1865)

      Peter R. Ashton, Christian G. Claessens, Wayne Hayes, Prof. J. Fraser Stoddart, Dr. Stephan Menzer, Dr. Andrew J. P. White and Dr. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518621

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      Highly ordered two-dimensional sheets sustained by π-donor/π-acceptor interactions and the ability to form an inclusion complex with ferrocene with only minimal changes in crystal packing are the outstanding features of the macrocyclic tetracation 1. This cyclophane can be prepared in two steps from bipyridine and the dibromide 2.

    10. Dialkylammonium Ion/Crown Ether Complexes: The Forerunners of a New Family of Interlocked Molecules (pages 1865–1869)

      Peter R. Ashton, Dr. Paul J. Campbell, Dr. Peter T. Glink, Dr. Douglas Philp, Dr. Neil Spencer, Prof. J. Fraser Stoddart, Dr. Ewan J. T. Chrystal, Dr. Stephan Menzer, Dr. David J. Williams and Dr. Peter A. Tasker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518651

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      A simple motif for molecular recognition—the binding of disubstituted ammonium salts, for example dibenzyl- and di-n-butylammonium hexaflurophosphate, with crown ethers like dibenzo[24]crown-8—results in the self-assembly of threaded 1:1 complexes 1. The superstructures of these complexes are stabilized by hydrogen bonds, electrostatic pole–dipole interactions, and dispersive interactions.

    11. Doubly Encircled and Double-Stranded Pseudorotaxanes (pages 1869–1871)

      Peter R. Ashton, Dr. Peter T. Glink, Cesare Schiavo, Prof. J. Fraser Stoddart, Dr. Ewan J. T. Chrystal, Dr. Stephen Menzer, Dr. David J. Williams and Dr. Peter A. Tasker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518691

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      Novel supramolecular architectures formed by self-assembly of three or four charged and neutral species have been prepared and characterized. In both the solution and solid states the two dibenzylammonium ions in the dicationic 1:2 complex 1 are threaded simultaneously through bis-para-phenylene[34]crown-10. This macrocyclic polyether forms a 2:2 complex with α,α′-bis(benzylammonium)-para-xylylene bis(hexafluorophosphate) in the solid state.

    12. (C5Me5)TiF2—A Versatile Building Block for Generating Large Soluble Dimetallic Aggregates (pages 1872–1874)

      Dr. Feng-Quan Liu, Prov.-Doz. Dr. Dietmar Stalke and Prof. Dr. Herbert W. Roesky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518721

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      By wrapping the inorganic core of the cluster with hydrocarbons (Cp* substituents of the Cp*TiF2 building blocks), the very large dimetallic aggregates 1 (core of cluster shown on the right) and 2 can be dissolved in organic solvents. In this way a source of “soluble NaF and CaF2” in common solvents is available for organometallic chemistry. Compounds 1 and 2 are obtained from the reaction of [Cp*TiF3] with Na/Hg and Ca/Hg alloy, respectively. [Cpmath imageTi14Na18F48(thf)6]1[(Cp*TiF2)6CaF2(thf)2] 2

    13. Platination Pathways for Reactions of Cisplatin with GG Single-Stranded and Double-Stranded Decanucleotides (pages 1874–1877)

      Dr. Kevin J. Barnham, Prof. Dr. Peter J. Sadler, Dr. Susan J. Berners-Price, Dr. Tom A. Frenkiel and Dr. Urban Frey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518741

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      1H, 15N correlated NMR spectroscopy has proven to be a suitable method to investigate the reaction of the anticancer drug cisplatin cis-[PtCl2(NH3)2] (1) with DNA. All the intermediates in reactions of 1 with complementary model oligonucleotides can be detected with this method; one of these intermediates is shown.

    14. The [Zr6X18H5]3− Ions with X = Cl, Br, and Related Species (pages 1877–1879)

      Dr. Linfeng Chen, Prof. F. Albert Cotton and Dr. William A. Wojtczak

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518771

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      A new class of octahedral zirconium cluster compounds containing only halide and hydride ligands is described. These contain the anions [Zr6X18H4]4− or [Zr6X18H5]3− (shown on the right). The hydrogen atoms are randomly disordered on positions in or very near to the centers of all the triangular faces of the Zr6 octahedron according to X-ray crystallography.

    15. New Tellurometalates of Gallium and Indium: K[K([18]crown-6)]2[GaTe3] · 2CH3CN and [(NEt4)5][In3Te7] · 0.5 Et2O (pages 1879–1880)

      Chang-Woo Park, Robert J. Salm and Prof. James A. Ibers

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518791

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      The tellurometalate ions [GaTe3]3− and [In3Te7]5− have been prepared by chemical reduction of Ga2Te3 and In2 Te3, respectively, by potassium in liquid NH3 in the presence of an encapsulating ligand. The [GaTe3]3− ion is essentially trigonal planar; the [In3Te7]5− ion is cuboidal, where one corner is missing (structure shown on the right). These anions have no counterparts in S or Se chemistry.

    16. A New Quantitative Description of the Distance Dependence of Through-Space 19F, 19F Spin–Spin Coupling (pages 1881–1882)

      Prof. Ludger Ernst and Dr. Kerstin Ibrom

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518811

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      Fine tuning of the nonbonding F[BOND]F distances, by bridge length variation and suitable substituents, in a series of difluorometa- (1) and -paracyclophanes led to a new quantitative description of distance-dependent 19F, 19F through-space spin–spin coupling. This will be useful for structural studies of di- and oligofluorinated compounds in solution.

    17. Double Helical Dinuclear Copper(I) Complexes of Macrocyclic Bis(dithiadiimine) Ligands (pages 1883–1885)

      Prof. Dr. Peter Comba, Dipl.-Chem. Andreas Fath, Dr. Trevor W. Hambley and Dr. David T. Richens

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518831

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      32- and 34-membered macrocyclic Schiff base type ligands with (N2S2)2 donor units are synthesized in a high-yielding [2 + 2] condensation reaction. Coordination of these ligands to copper(I) results in double helical dicopper(I) complexes with a new figure-of-eight loop structure (see diagram on the right).

    18. Pseudo-Spherical Host Molecules: Synthesis, Dimerization, and Nucleation Effects (pages 1885–1887)

      Dr. Carlos Valdés, Dr. Urs P. Spitz, Dr. Stefan W. Kubik and Prof. Julius Rebek Jr.

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518851

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      The guest decides which host is formed! This was the result of studies with the compounds 1 and 2, which form the adducts 1–1, 2–2, or 1–2 in solution, depending on the molecular size of the solvent molecule. R = CO2Et.

    19. Synthesis and Structure of a Free Germacyclopentadienide Ion: [Li([12]crown-4)2][C4Me4GeSi(SiMe3)3] (pages 1887–1890)

      William P. Freeman, Prof. Dr. T. Don Tilley, Frederick P. Arnold, Prof. Dr. Arnold L. Rheingold and Dr. Peter K. Gantzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518871

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      A highly non-aromatic structure is exhibited by the free germacyclopentadienide ion (shown on the right) in the Li([12]crown-4)2 salt. The angle between the C4Ge plane and the Ge[BOND]Si bond is 100.1°. Calculations at the RHF level of theory on (C4H4GeSiH3) accurately reproduce the observed geometrical parameters, and predict that the analogous Si and Sn derivatives would also have highly pyramidalized structures.

    20. C4Smath image: A Bridging Bis(dithiolato) Ligand for the Preparation of Semiconducting Inorganic Polymers (pages 1890–1892)

      Dr. Lisa F. Szczepura, Collin P. Galloway, Dr. Yifan Zheng, Dr. Pengdi Han, Dr. Scott R. Wilson, Prof. Thomas B. Rauchfuss and Prof. Arnold L. Rheingold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518901

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      Planar and highly polarizable, the dianionic thiocarbon 1 reacts with metal salts to give inorganic polymers like [Cu2C4S6] and [NiC4S6] with semiconductor properties. The Ni coordination polymer forms a one-dimensional ribbonlike strand of edgesharing square-planar complexes such as 2.

    21. Synthesis of New Sworski-Type Dehydroannulenes: 3,4-Benz-1,2,5,6,8,9,12,13-octadehydro[14]-annulenes (pages 1892–1894)

      Dr. Yoshiyuki Kuwatani and Prof. Dr. Ikuo Ueda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518921

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      An intramolecular pinacol coupling and subsequent reduction were the key steps in the construction of the 14-membered ring of dione 1. Depending on the substituent R, the new dehydroannulenes 2 (R = H, Ph, tBuC6H4, OSiMe2tBu) can be prepared by different methods. These compounds display considerable aromaticity despite only nominal stability.

    22. A Gold(I) [2]Catene (pages 1894–1895)

      Prof. D. Michael P. Mingos, John Yau, Dr. Stephan Menzer and Dr. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518941

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      Two interlocking Au6 rings, whose individual metal atoms are linked through ethynyl ligands, are present in the title compound [{Au(C [TRIPLE BOND] CtBu)}6]2. This novel homoleptic organometallic [2]catenane spontaneously self-assembles in the reaction of [Au(NH3)2]BF4 with tBuC [TRIPLE BOND] CH. Weak Au[BOND]Au interactions may contribute to the self-assembly of the structure. The bonding in one ring is shown schematically on the right.

    23. Novel Networks of Unusually Coordinated Silver(I) Cations: The Wafer-Like Structure of [Ag(pyz)2][Ag2(pyz)5](PF6)3·2G and the Simple Cubic Frame of [Ag(pyz)3](SbF6) (pages 1895–1898)

      Dr. Lucia Carlucci, Prof. Gianfranco Ciani, Dr. Davide M. Proserpio and Prof. Angelo Sironi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518951

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      The silver salts AgPF6 and AgSbF6 react with pyrazine to give unprecedented networks of two- and three-dimensional cubic units. The PFmath image derivative has a layered structure, whereas the SbFmath image derivative (shown schematically on the right) contains a simple cubic frame of the α-polonium type.

    24. A One-Step Synthesis of Squalene from Farnesol under Prebiotic Conditions (pages 1898–1900)

      Dr. Gérard Teller, Prof. Dr. Yoichi Nakatani, Prof. Dr. Guy Ourisson, Dr. Martin Keller, Dipl.-Biol. Doris Hafenbradl and Prof. Dr. Karl O. Stetter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199518981

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      Together, hydrogen sulfide and iron(III) sulfide mediate the reductive coupling of farnesol giving squalene (1), albeit in low yield. This finding is interesting, because the reducing system H2S/FeS plays a central role in the theory of the “pyrite-driven” prebiotic world, and squalene is present in all organisms.

    25. Radical Cation [4 + 2] Cycloadditions with 2-Vinylindoles (pages 1900–1901)

      Dipl.-Chem. Christoph F. Gürtler, Prof. Dr. Siegfried Blechert and Prof. Dr. Eberhard Steckhan

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199519001

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      Electron transfer induction enables [4 + 2] cycloadditions of 2-vinylindoles 1 with electronically similar dienophiles such as 2. The reaction of 1 and 2 furnishes the alkaloid skeleton 3 with highly stereoselectivity. SET = single electron transfer.

  4. Book Reviews

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

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