Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 15‐16

September 2, 1994

Volume 33, Issue 15-16

Pages 1525–1674

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 15/16/1994)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415231

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      The cover picture shows schematically the construction of two isostructural, adamantanoid, spacer-free, metallospherands [Fe4L6] (L = dianion of dialkyl 2,5-dialkoxy-carbonyl-3,4-dioxo-l,6-hexanedicarboxylate) formed by self-assembly. An NHmath image ion is encapsulated in its center. One FeII (silver sphere) and three FeIII ions (golden spheres) form a regular tetrahedron, whose six edges are bridged by bis(bidentate) ligands L (charcoal-colored angled rods). The cover picture was produced with the program POV-Ray on a Silicon Graphics Indigo Workstation by Dr. R. Burak. Further details of the synthesis, characterization, and properties of these inclusion compounds are reported by R. W. Saalfrank et al. on p. 1621ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. Molecular Catalysts for Multielectron Redox Reactions of Small Molecules: The “Cofacial Metallodiporphyrin” Approach (pages 1537–1554)

      Prof. James P. Collman, Dr. Paul S. Wagenknecht and Dr. James E. Hutchison

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415371

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      Redox transformations between O2/H2O, N2/NH3, and H+/H2 are extremely important biologically and industrially. Natural enzymes containing one or more transition metals catalyze these transformations. Functional mimics of enzymes can lead to a better understanding of the biological mechanisms of these processes and to the invention of new homogeneous catalysts.

    2. Synthesis and Reactions of Optically Active Cyanohydrins (pages 1555–1564)

      Prof. Dr. Franz Effenberger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415551

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      Immobilized enzymes in organic solvents are used in the enantioselective synthesis of cyanohydrins (3, R1 = alkyl, aryl, heteroaryl; R2 = H, alkyl) from carbonyl compounds (1) and hydrogen cyanide (2). Enzymatic kinetic resolution of rac-3 is also conducted in organic media. Chiral cyanohydrins can thus be prepared in high optical purities and serve as valuable synthetic building blocks owing to the wide range of subsequent conversions.

    3. Ligands as “Compass Needles”: How Orientations of Alkene, Alkyne, and Alkylidene Ligands Reveal π-Bonding Features in Tetrahedral Transition Metal Complexes (pages 1565–1572)

      Prof. Vernon C. Gibson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415651

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      A triad representation and the competition between the π-donor ligands for the available dπ symmetry orbitals on the metal can be used to explain the preferred orientations of alkene, alkyne, and alkylidene ligands in tetrahedral complexes. In complexes such as 1 with two strong π donors (Cp and NR ligand), for example, alkenes point to the weakest π donor (PMe3 ligand). With a few simple rules a qualitative ordering of ligand π-donor bond strengths can be derived and structures can be rationalized or predicted.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. Binary Encoding of Compound Libraries (pages 1573–1575)

      Dr. Peter Eckes

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415731

      The rapid identification of functional molecules that participate in specific supramolecular interactions is a major problem in the screening of compound libraries. The binary encoding developed by Still et al. allows the structure assignment of “active” compounds according to a simple encoding scheme, and is independent of the synthetic chemistry employed. The viability of this concept has already been demonstrated, but the advantages will first be fully realized with libraries of small organic molecules.

    2. New Ionic, Isoelectronic Analogues of CO2 and CS2 (pages 1575–1576)

      Priv.-Doz. Dr. Thomas M. Klapötke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415751

      The linear arrangement of the atoms in CO2 also occurs, in most cases, in its anionic analogues NBN3− and CBN4−, as well as in the ions SNS+, PCS3−, and PBP3− that are analogous to CS2. Many of the findings and structures predicted by quantum chemical calculations have since been confirmed by crystal structure analyses. This should encourage the synthesis of additional isoelectronic analogues.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. Template Effects in New Self-Replicating Molecules (pages 1577–1579)

      M. Morgan Conn, Edward A. Wintner and Prof. Dr. Julius Rebek Jr.

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415771

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      The whole is greater than the sum of its parts-this adage holds for the new replication system composed of 1 and 2, which features a very high affinity between complementary components. In this system all reactions proceed via complexes, which minimizes the effects of background reactions. The autocatalysis displayed by the system is shown to arise solely from template effects. R = [BOND]C6H4[BOND]C6H4[BOND]COOC6F5.

    2. Reciprocal Template Effects in a Replication Cycle (pages 1579–1581)

      Roland J. Pieters, Ivan Huc and Prof. Julius Rebek Jr.

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415791

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      Complementary surfaces and reactive functionalities are the ingredients of a system that mimics the two-step replication process of DNA. Two separate coupling reactions each give a product that is a template for the next reaction.

    3. Synthesis of C-2 Taxol Analogues (pages 1581–1583)

      Prof. Dr. Kyriacos Costa Nicolaou, Elias A. Couladouros, Phillipe G. Nantermet, Joanne Renaud, Rodney Kiplin Guy and Wolfgang Wrasidlo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415811

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      Nucleophilic ring opening of cyclic carbonates 1 leads regioselectively to the less substituted ester 2. Moreover, for molecules with several carbonyl groups the reaction is chemoselective: In a taxol precursor the carbonate group and not one of the three additional carbonyl groups was attacked; the resulting esters were converted into taxol analogues that displayed differing cytotoxicities.

    4. A Water-Soluble Prodrug of Taxol with Self-Assembling Properties (pages 1583–1587)

      Prof. Dr. Kyriacos Costa Nicolaou, Rodney Kiplin Guy, Emmanuel Nicolauo Pitsinos and Wolfgang Wrasidlo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415831

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      Just as effective and not as toxic, taxol derivative 1 displays antitumor activity comparable to that of the parent compound. Since 1 is water soluble, complications that arise in clinical applications of taxol may be avoided.

    5. Trigonal Symmetry as a Host Design Element: Novel Conformation of Dodecakis(3,5-dimethyl-phenylthio)coronene in its 1,4-Dioxane Clathrate (pages 1587–1589)

      Dr. Gary A. Downing, Dr. Christopher S. Frampton, Dr. David D. MacNicol and Dr. Paul R. Mallinson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415871

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      The first versatile coronene-based host is the dodecathioether 1. The structure of the highly crystalline 1,4-dioxane adduct of 1 was elucidated; it revealed that the host molecule has the novel C3-symmetric aabbaabbaabb conformation.

    6. A General Synthetic Strategy for Neutral Phosphorus-Containing Dendrimers (pages 1589–1592)

      Nathalie Launay, Dr. Anne-Marie Caminade, Dr. Roger Lahana and Dr. Jean-Pierre Majoral

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415891

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      Up to fourth-generation neutral phosphorus-containing dendrimers are prepared in good yields in the synthesis outlined here. The only byproducts are NaCl and H2O, and the products contain highly reactive functional groups along the periphery. The first-generation dendrimer is shown on the right.

    7. Ferromagneto-Structural Correlations in [Mn(OC6X3H2)2(bipy)]2 Compounds, X [DOUBLE BOND] Cl, Br (pages 1592–1594)

      Dr. Marcel Wesolek, Dr. Daniel Meyer, Prof. Dr. John A. Osborn, Dr. André De Cian, Prof. Dr. Jean Fischer, Ing. Alain Derory, Dr. Patrick Legoll and Dir. Dr. Marc Drillon

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415921

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      Intra- and intermolecular ferromagnetic interactions characterize the dimeric manganese complexes 1 and 2. This unexpected behavior is attributed to π-π interactions between the phenoxy ligands, to π-π interactions within the chains present in the crystal, and for 2, in addition, to π-π interactions between bromine atoms of neighboring chains. These findings should be useful for the design of molecular magnetic materials.

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    8. Preparation and Preliminary Characterization of a Covalently Pillared Zirconium Phosphate- Diphosphonate with Interlayer Microporosity (pages 1594–1597)

      Prof. Dr. Giulio Alberti, Dr. Fabio Marmottini, Dr. Sonia Murcia-Mascarós and Dr. Riccardo Vivani

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415941

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      The computer-generated structural model on the right clearly shows the interlayer microporosity (Vmicrop. = 0.12cm3g−1) of the covalently pillared γ-zirconium phosphate -diphosphonate. Thus, this type of compound could be of interest as a molecular sieve or for shape-selective catalysis. The pillaring was achieved by a simple topotactic reaction.

    9. Molecular Recognition of C60 with γ-Cyclodextrin (pages 1597–1599)

      Prof. Dr. Zen-ichi Yoshida, Hideko Takekuma, Prof. Dr. Shin-ichi Takekuma and Prof. Dr. Yoshiharu Matsubara

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415971

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      Charge-transfer interactions stabilize the 1:2 complex between C60 and γ-cyclodextrin (schematic representation shown on the right). Since it is known that C60 derivatives inhibit, for instance, the HIV-1 protease, this result is also important for the understanding of the molecular recognition of C60 by the hydrophobic pocket of the active site of enzymes.

    10. Macropolyhedral Boron-Containing Cluster Chemistry: Isolation and Characterization of the First Macropolyhedral Thiaborane, the arachno-Type [9,9′-S2B17H18] Ion (pages 1599–1601)

      Dr. Tomáš Jelínek, Dr. John D. Kennedy, Dr. Bohumil Štíbr and Dr. Mark Thornton-Pett

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199415991

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      A novel mode of linkage of polyhedral boranes is exhibited in the title anion 1: The structure of 1 derives formally from the fusion, with two common vertices, of an arachno-SB9 and an arachno-SB10 subcluster. Anion 1 is formed by treatment of anti-Bl8H22 with NaH in THF followed by reaction with sulfur; it crystallizes as the PPhmath image salt.

    11. Stereoselective Reactions of Sulfinylated Benzyl Radicals: Effects of Solvents and Lewis Acids (pages 1601–1603)

      Prof. Philippe Renaud, Thierry Bourquard, Michèle Gerster and Dr. Nadira Moufid

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416011

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      The opposite relative configuration to that observed in the deuteration of de-protonated sulfoxides of type 2 results from the radical deuteration of sulfinylated benzyl radicals of type 1 in the presence of bulky Lewis acids (methylaluminum diphenoxide).

    12. Functionalization of Aromatic Azo Compounds by the Cobalt-Catalyzed, Regioselective Double Addition of Tolane: 2,6-Distilbenylazobenzenes and 2,3-Dihydrocinnolines (pages 1603–1605)

      Dipl.-Chem. Günther Halbritter, Dr. Falk Knoch, Dr. Alexander Wolski and Prof. Dr. Horst Kisch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416031

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      The substitution pattern determines whether distilbenylazobenzene compounds 1 or their subsequent products, the dihydrocinnolines 2, are isolated in the cobalt-catalyzed solvent-free reaction of azo compounds with diphenylacetylene. For several derivatives a photochromic equilibrium exists between the two forms.

    13. Synthesis and Structure of the Smallest Cyclic Cumulene; Reaction of 1,3-Diynes with Zirconocene Complexes (pages 1605–1607)

      Prof. Dr. Uwe Rosenthal, Dipl.-Chem. Andreas Ohff, Dr. Wolfgang Baumann, Dr. Rhett Kempe, Dr. Annegret Tillack and Dr. Vladimir V. Burlakov

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416051

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      The unexpected result of the reaction of “Cp2Zr” with di-tert-butadiyne was the formation of 1, the smallest possible cyclic cumulene. Other disubstituted butadiynes reacted with “Cp2M” by cleavage, dimerization, or dinuclear complex formation.

    14. An Antibody-Catalyzed 1,2-Rearrangement of Carbon[BOND]Carbon Bonds (pages 1607–1609)

      Dr. Yuanwei Chen, Prof. Jean-Louis Reymond and Prof. Richard A. Lerner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416071

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      The transition state of the dienone-phenol rearrangement of 1 to 2 is mimicked by hapten 3. An immune response to 3 yielded an antibody (62C7) which was found to catalyze the rearrangement efficiently. It was shown that 62C7 does not act as a simple acid catalyst, but rather selectively stabilizes the charge distribution in the transition state.

    15. Oxidation of Metal-Coordinated Thioethers with Dimethyldioxirane—A New Stereoselective Synthesis of Chiral Sulfoxides (pages 1609–1611)

      Prof. Dr. Wolfdieter A. Schenk, Dipl.-Chem. Jürgen Frisch, Prof. Dr. Waldemar Adam and Dr. Frank Prechtl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416091

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      A novel variant of the asymmetric oxidation of prochiral thioethers yields chiral sulfoxides with selectivities of up to 98% de. The thioether is first coordinated to an enantiomerically pure auxiliary and then oxidized in the coordination sphere with dimethyldioxirane [Eq. (a)]. Smooth decomplexation is achieved with Nal.

    16. Acid-Catalyzed Olefination of Benzaldehyde (pages 1611–1612)

      Drs. Henk-Peter van Schaik, Dr. Robert-Jan Vijn and Prof. Dr. Friedrich Bickelhaupt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416111

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      Not only mechanistically interesting but also preparatively attractive-for example, because of inexpensive starting materials-the olefmation of aldehydes such as 1 catalyzed by Lewis acids is described here for the first time. This surprising one-pot reaction leads to styrene 2.

    17. Lewis Acid Promoted [2 + 2] Cycloaddition of Allylsilanes and Unsaturated Esters: A Novel Method for Cyclobutane Construction (pages 1612–1615)

      Prof. Dr. Hans-Joachim Knölker, Gerhard Baum and Dipl.-Chem. Regina Graf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416121

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      A third mode of reactivity for allylsilanes in their reactions with α,β-unsaturated carbonyl compounds has been found in addition to the Sakurai reaction and the [3 + 2] cycloaddition. Silylmethyl-cyclobutanes are formed regioselectively via a siliranium ion intermediate (1). The reaction with methyl propynoate provides bicyclo[2.2.0]hexanes in a one-pot conversion.

    18. The Formation and an Unusual Dimerization of 2-Mesityl-1,1-bis(trimethylsilyl)silene (pages 1615–1618)

      Dipl.-Chem. Clemens Krempner, Dr. Helmut Reinke and Prof. Dr. Hartmut Oehme

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416151

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      A formal role as monoene and also as diene by utilizing the mesityl substituent is possible for the unstable silene 1. In the absence of scavengers, 1 dimerizes in an unusual [2 + 4] reaction to form 2 as soon as it is prepared from (Me3Si)3Si[BOND]C(OH)Mes.

    19. An Efficient Access to Organocerium(IV) Complexes: Synthesis and Structure of Bis[1,3,6-tris(trimethylsilyl)cyclooctatetraene]cerium(IV) (pages 1618–1621)

      Dr. Ulrike Kilimann, Dr. Regine Herbst-Irmer, Priv.-Doz. Dr. Dietmar Stalke and Priv.-Doz. Dr. Frank T. Edelmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416181

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      Extremely soluble, briefly air-stable, and thermally more robust than expected are CeIV complexes such as 1 containing the Me3Si-substituted cycloocta-tetraene dianion as ligands. The metal atom in these complexes is sterically well shielded by an organic shell. The way is now free to investigate the reactivity of this class of compounds.

    20. Mixed-Valence, Tetranuclear Iron Chelate Complexes as Endoreceptors: Charge Compensation Through Inclusion of Cations (pages 1621–1623)

      Prof. Dr. Rolf W. Saalfrank, Dr. Roman Burak, Dipl.-Chem. Alexandra Breit, Priv.-Doz. Dr. Dietmar Stalke, Dr. Regine Herbst-Irmer, Prof. Dr. Jörg Daub, Dipl.-Chem. Michael Porsch, Dr. Eckhard Bill, Dipl.-Phys. Markus Müther and Prof. Dr. Alfred X. Trautwein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416211

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      In a simple one-pot reaction the host-guest compounds 1 (white spheres FeIII; black = FeII; gray = NHmath image; angled rods = 2: R = Me, Et) are accessible in gram quantities by self-assembly. They are the only fully characterized redox isomers whose cyclic voltammograms display four quasi-reversible waves and whose mixed-valent character has been established by Mössbauer spectra. The endohedral complexation of one NHmath image ion in 1 has been confirmed by X-ray crystallography.

    21. Effects of 35Cl/37Cl, 13C Residual Dipolar Coupling on the Variable-Temperature 13C CP/MAS NMR Spectra of Solid, Chlorinated Sodium Acetates (pages 1624–1625)

      Sergio H. Alarcón, Prof. Alejandro C. Olivieri, Stephen A. Carss and Prof. Robin K. Harris

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416241

      Agreement between theory and practice: Solid-state NMR studies on organic compounds with CH2Cl, CHCl2, and CCl3 groups show that residual dipolar coupling between 35Cl/37Cl and 13C nuclei influences the splitting of the signals depending on the magnetic field strength B. When molecular motions are slow enough to prevent self-decoupling, signals for C nuclei affected by a single Cl nucleus appear as symmetric doublets at B0 >5 T and as asymmetric triplets at lower fields.

    22. Dissolution of Cholesterol in Water by a Synthetic Receptor (pages 1625–1628)

      Blake R. Peterson and Prof. Dr. François Diederich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416251

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      A new therapeutic approach to treating atherosclerosis? The chiral, D2-symmetrical cyclophane 1 is a selective receptor for cholesterol in water and dissolves the insoluble solid steroid efficiently through inclusion complexation. The cavity of 1 with dimensions of 9 x 13 x 11 Å has the ideal shape and hydrophobic surface for encapsulating steroids.

    23. 61,61-Bis(trimethylsilylbutadiynyl)-1,2-dihydro-1,2-methanofullerene[60]: Crystal Structure at 100 K and Electrochemical Conversion to a Conducting Polymer (pages 1628–1632)

      Dr. Harry L. Anderson, Corinne Boudon, Prof. Dr. François Diederich, Jean-Paul Gisselbrecht, Prof. Maurice Gross and Paul Seiler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416281

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      The presence of a transannular bond at a methano-bridged 6–6 ring junction in C60 was confirmed conclusively with an accurate crystal structure of the title compound 1, thus putting an end to a heated debate. The length of the 6–6 bond is 1.574(3) Å.

    24. An Unusual Route to Potential Platinum Antitumor Compounds: Synthesis, Reactivity, and Spectroscopic Properties of the PtIV Complex fac-[PtCl3(NH3)2L]Cl (pages 1632–1634)

      Dr. Ulrich Bierbach and Prof. Dr. Jan Reedijk

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416321

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      Oxidative addition to the antitumor agent cisplatin yields the PtIV complex 1, in which 1,1,3,3-te-tramethylthiourea is coordinated to platinum. The structure was determined primarily by impressive high-resolution 1H and 195Pt NMR experiments and by analysis of the IR spectrum.

    25. Monomer–Dimer Equilibria in Homo- and Heterodinuclear Cationic Alkylzirconium Complexes and Their Role in Polymerization Catalysis (pages 1634–1637)

      Dr. Manfred Bochmann and Simon J. Lancaster

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416341

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      The reactive cationic 14-electron complex 2 is stabilized by formation of methyl-bridged binuclear complexes of type 1 and 3. The compounds are highly active catalysts for the polymerization of ethylene and propylene. As expected for the dissociation equilibrium shown, neutral alkyl metal compounds in excess act as inhibitors; thus, the activity of 3 decreases significantly with increasing AlMe3 concentration.

    26. The First Decaisopropylmetallocene: One-Pot Synthesis of [Rh(C5iPr5)2]PF6 from [Rh(C5Me5)2]PF6 by Formation of 20 Carbon–Carbon Bonds (pages 1637–1639)

      Dr. Dirk Buchholz and Prof. Didier Astruc

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416371

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      Only with a second-row transition metal as the central atom can decamethylmetallocenes [M(C5Me5)2]+ be fully permethylated to give decaisopropylmetallocenes 1. The corresponding rhodium complex, M = Rh, was isolated in 55% yield; in the analogous reaction of the cobalt sandwich complex, a maximum of 14 methyl groups were introduced.

    27. Octahydro-1,2,3:4,5,6-dimethenopentalene-2-carbonitrile, the First Derivative of a Yet-Unknown (CH)10 Hydrocarbon (pages 1639–1641)

      Prof. Dr. Manfred Christl, Dipl.-Chem. Michael Türk, Eva-Maria Peters, Dr. Karl Peters and Prof. Dr. Hans Georg von Schnering

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416391

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      Two proximate bicyclobutane units are contained in the new hexacycle 3. Their arrangement facilitates a transannular reaction in the radical addition of thiophenol to give the cage compound 4. Starting from benzvalene (1), the route to 3 comprises only five steps: the first (1 [RIGHTWARDS ARROW] 2) is a Pauson-Khand reaction.

    28. The Use of Heterometallic Bridging Moieties To Generate Tractable Lanthanide Complexes of Small Ligands (pages 1641–1644)

      Prof. William J. Evans, Dr. Reiner Anwander, Prof. Robert J. Doedens and Dr. Joseph W. Ziller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416411

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      Hexane-soluble derivatives of neodymium amide Nd-(NMe2)3 such as 1 or the unsolvated heterometallic peralkyl compound 2 form in the reaction of MMe3 (M = Al, Ga) with 3. This provides a route to soluble lanthanide complexes with small ligands.

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    29. A Liquid-Crystalline Polymer Network Built by Molecular Self-Assembly through Intermolecular Hydrogen Bonding (pages 1644–1645)

      Dr. Takashi Kato, Hideyuki Kihara, Dr. Uday Kumar, Prof. Toshiyuki Uryu and Prof. Jean M. J. Fréchet

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416441

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      Liquid-Crystalline behavior over a wide temperature range and reversible phase transitions are observed for the polymer network 1, which is held together by hydrogen bonds between benzoic acid and pyridyl units

    30. Ladder Polymers and Oligomers Based on Hemiporphyrazine (pages 1646–1648)

      Dipl.-Chem. Michael Rack and Prof. Dr. Michael Hanack

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416461

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      Ladder oligomers of various lengths containing metallomacrocycles as structural elements (shown on the right) have been synthesized in a controlled fashion for the first time. The oligomers posses three, five, or seven nickel atoms, the polymer at least nine.

    31. Biosynthetic Investigations on Pyridazomycin (pages 1648–1651)

      Dr. Heike Bockholt, Prof. Dr. John M. Beale and Priv.-Doz. Dr. Jürgen Rohr

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416481

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      An unexpected amino acid metabolism is used by a subspecies of the soil bacterium Streptomyces violaceoniger to produce the antifungal antibiotic pyridazomycin 1-C1. Feeding studies with isotopically labeled precursors indicate that 1 is constructed from ornithine, glycine, and probably oxaloacetate.

    32. Preparation and Structure of C76(S8)6: A First Step in the Crystallographic Investigation of Higher Fullerenes (pages 1651–1654)

      Rudi H. Michel, Prof. Manfred M. Kappes, Dr. Peter Adelmann and Dr. Georg Roth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416511

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      A sandwich-like structure, in which planes of closely packed C76 molecules are interleaved with layers of S8 rings, is formed by the fullerene-sulfur adduct. C76(S8)6 (shown on the right). The structure of this compound has been studied by single-crystal X-ray diffraction. The results are consistent with a chiral C76 molecule with D2 symmetry.

    33. Synthesis of an Azathymidine and Its Incorporation into Oligonucleotides (pages 1654–1657)

      Dr. Karl-Heinz Altmann, Dr. Susan M. Freier, Dr. Uwe Pieles and Dr. Tammo Winkler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416541

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      Increased stability towards enzymatic degradation is observed for oligonucleotides if they contain the thymidine analogue 1. Its binding ability for complementary RNA is not decreased significantly, which makes 1 interesting as a building block for antisense oligonucleotides. Compound 1 can be prepared in a nineteen-step synthesis starting from D-serine.

    34. Active Surface Carbon—A Reactive Intermediate in the Production of Synthesis Gas from Methane and Carbon Dioxide (pages 1657–1660)

      Dipl.-Chem. Michael F. Mark and Prof. Dr. Wilhelm F. Maier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416571

      Pulse chemisorption studies reveal that a subsequent reaction is part of the mechanism of the formation of synthesis gas from CH4 and CO2, known since 1928. In the first step CH4 is decomposed on a Rh/A12O3 catalyst into reactive surface carbon CS and H2; in the second step C8 reacts with CO2 to give CO, but it is still not clear whether this step is also catalyzed by Rh.

    35. Carboxylatoiron(II) Aggregates: A Novel Femath image Complex with Threefold Symmetry (pages 1660–1662)

      Dr. Stéphane Ménage, Dr. Hiroshi Fujii, Dr. Michael P. Hendrich and Prof. Lawrence Que Jr.

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416601

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      One monodentate and two bidentate carboxylato ligands link the central FeII ion in the cation of 1 (shown on the right) with each of the three neighboring FeII ions. This arrangement results in a complex with threefold symmetry and weak ferromagnetic interactions between the iron centers. Such aggregates may be important in the initial stages of ferritin core formation in the absence of dioxygen. Hbpg = N,N-bis(2-pyridylmethyl)glycine.

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    36. Molecular Golf Balls: Vesicles from Bowl-Shaped Host Molecules (pages 1662–1663)

      Dipl.-Chem. Albertus P. H. J. Schenning, Bas de Bruin, Dr. Martinus C. Feiters and Prof. Dr. Roeland J. M. Nolte

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416621

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      Vesicles with concave binding sites on the surface form when the bowlshaped amphiphile 1 is dispersed in water. The dimples on the outer surface of these molecular “golf balls” strongly bind guest molecules (association constant Ka = 4 × 105M−1).

    37. Synthesis and Structure of [Ni(SO2)6](AsF6)2 and [Fe(SO2)4(FAsF5)2] (pages 1663–1665)

      Enno Lork, Jan Petersen and Prof. Dr. Rüdiger Mews

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416631

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      Six η1-O-coordinated SO2 ligands are present in the pinwheel-shaped cation of complex 1. This mode of coordination was considered unusual. The synthesis was achieved by oxidation of Ni powder with AsF5 in liquid SO2. An analogous reaction with iron yielded m-[Fe(SO2)4(FAsF5)2].

      • equation image
    38. Three-Dimensional Interpenetrating Double and Triple Framework Structures in [Cd(bpy)2{Ag(CN)2}2] and [Cd(pyrz){Ag2(CN)3}{Ag(CN)2}] (pages 1665–1666)

      Takayoshi Soma, Dr. Hidetaka Yuge and Prof. Dr. Toschitake Iwamoto

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416651

      Thumbnail image of graphical abstract

      No bonding interactions exist between the three interpenetrating framework structures in 1, and all of the two-dimensional networks are constructed by coordinate linkages-these two principles describe the structure of 1 (shown schematically on the right). Compound 1 was prepared from K2[Cd(CN)4], Ag-NO3, and pyrazine at pH 10.

      • equation image
    39. Octaplane: A Saturated Hydrocarbon with a Remarkably Low Ionization Energy Leading to a Cation with a Planar Tetracoordinate Carbon Atom (pages 1667–1668)

      Jennifer E. Lyons, Danne R. Rasmussen, Dr. Mark P. McGrath, Dr Ross H. Nobes and Prof. Leo Radom

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416671

      Thumbnail image of graphical abstract

      A planar tetracoordinate carbon atom in a singly-charged saturated hydrocarbon is found for the first time. Ab initio calculations at the HF/6-31G* level predict a planar geometry for the central five-carbon moiety in the octaplane radical cation (1•+). The ionization energy of octaplane (5 eV) is found to be remarkably low for a saturated hydrocarbon; indeed, it is comparable to that of the alkali metals lithium and sodium.

  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. You have free access to this content
      Corrigenda (page 1668)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416681

  5. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. Book Review: Neural Networks for Chemists. An Introduction. By J. Zupan and J. Gasteiger (page 1671)

      Gisbert Schneider and Paul Wrede

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416711

  6. New Books

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    7. New Books
    1. New Books (Angew. Chem. Int. Ed. Engl. 15/16/1994) (page 1674)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199416741

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