Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 2

February 1, 1994

Volume 33, Issue 2

Pages 133–241

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1994)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401311

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      The cover picture shows a Fe3+-doped KNbO3 single crystal (formed from the orthorhombic, ferroelectric phase of KNbO3), which can be obtained from a molten K2O solution at 1050 °C, as well a matchstick for comparison (crystal growth: H. Wüest, ETH Zürich; photograph: M. Bischof, ETH Zürich). The crystals, which are yellow because of the doping with Fe3+ ions, can be used for information storage in a purely optical way (holography). Pure KNbO3 crystals are colorless and are applied in nonlinear optical materials to generate green and blue laser light. The critical review by J. Hulliger on p. 143 ff contains valuable information about crystal growth.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Chemistry and Crystal Growth (pages 143–162)

      Prof. Dr. Jürg Hulliger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401431

      Still no crystals!—what chemist has not at some time or other waited desperately for crystals to form from newly synthesized compounds. Although the need for crystals, for example, for X-ray structural analysis and materials science is continually increasing, chemists leave the study of crystallization, crystal growth, and the specific properties of solid materials to physicists. This review is not only a guideline for single-crystal synthesis, but also a plea for the role of crystallization in chemistry to be newly defined.

    2. New Forms and Functions of Tellurium: From Polycations to Metal Halide Tellurides (pages 163–172)

      Prof. Johannes Beck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401631

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      The synthesis of ternary M/tellurium/halogen systems (M = metal), which were hitherto virtually unknown for M = molybdenum and tungsten, has afforded a number of compounds ranging from novel tellurium polycations to halide tellurides with chainlike structures. The diverse structural chemistry is thus determined by the tendency of tellurium to form homonuclear bonds, and by the various types of metaltellurium interactions. MoTe4Br, for example, forms infinite one-dimensional Mo(Te2)2 chains in which Brions are intercalated (shown on the right).

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. The Photochemical Activation of Carbon Dioxide Using a Nickel Complex (pages 173–174)

      Dr. Walter Leitner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401731

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      The radical anion COmath image is formed by photochemical reduction of CO2 mediated by the redox-active Ni3 cluster 1, as shown recently by Kubiak et al. The COmath image radical ion can be trapped with cyclohexene to yield cyclohexanedicarboxylic acid with the formation of two new C[BOND]C bonds. This reaction is an important step towards the use of CO2 as a building block for chemical synthesis in solution.

    2. Enantioselective Transformations and Racemization Studies of Heteroatom Substituted Organolithium Compounds (pages 175–177)

      Dr. Varinder Kumar Aggarwal

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401751

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      Although high enantioselectivity distinguishes the generation and reactions of α-amino- and α-alkoxyorganolithium compounds, alkylthio and alkylseleno derivatives (1, X = S, Se) racemize quite readily. The research groups led by R. W. Hoffmann and H. Reich have recently shown that racemization of Li compounds 1 is a unimolecular process and that the rate-determining step involves rotation about the C[BOND]X bond. These results should form the basis of a strategy for the asymmetric synthesis of sulfides and selenides.

    3. The Sialyl Lewisx Group and its Analogues as Ligands for Selectins: Chemoenzymatic Syntheses and Biological Functions (pages 178–180)

      Priv.-Doz. Dr. Athanassios Giannis

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401781

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      Inhibitors of leukocyte adhesion have potential as antiphlogistics, antithrombotics, and immunosuppressants. The interaction of selectins and their membrane-bound carbohydrate ligands is decisive for the initial phase of adhesion, and the sialyl Lewisx group 1 is a common ligand for all three selectins. Thus the ingenious chemoenzymatic synthesis of 1 and its analogues reported recently by Paulson, Wong, et al. has received much attention.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Proton-Transfer-Dependent Reversible Phase Changes in the 4,4′-Bipyridinium Salt of Squaric Acid (pages 181–183)

      Prof. Dr. Manfred T. Reetz, Dr. Sigurd Höger and Dr. Klaus Harms

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401811

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      A color change from yellow to red is observed on heating the bipyridinium salt of squaric acid (1). This reversible process is based on a proton transfer during the phase change. According to the Bürgi–Dunitz structure-correlation principle, the structure of the anion in solid 1 represents a point on the reaction coordinate of the deprotonation of squaric acid.

    2. Calicheamicin θmath image: A Rationally Designed Molecule with Extremely Potent and Selective DNA Cleaving Properties and Apoptosis Inducing Activity (pages 183–186)

      Prof. Dr. K. C. Nicolaou, Dr. T. Li, Masahisa Nakada, Conrad W. Hummel, A. Hiatt and W. Wrasidlo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401831

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      The attack of a thiolate ion on the trisulfide unit of natural calicheamicin γmath image (1) activates it to form a diradical, which then attacks DNA. Thioacetate 2 is even more readily activated—under mildly basic conditions caused by OH- ions—and likewise exhibits extremely interesting biological properties.

    3. Structure of an Antineoplastic Platinum Complex with a Bipyridyl–Crown Ether (pages 186–188)

      Dipl.-Chem. Andreas Gund and Priv.-Doz. Dr. Dr. Bernhard K. Keppler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401861

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      Structurally analogous to the known tumor-inhibiting cisplatin (1), the platinum complexes 2(n = 1–3) also have antineoplastic properties. The novel agents 2 are prepared in water from K2PtCl4 and the macrocyclic ligands.

    4. Cooperativity and Transfer of Chirality in Liquid-Crystalline Polymers (pages 188–191)

      Prof. Dr. Günter Wulff, Dr. Harald Schmidt, Dr. Hartmut Witt and Prof. Dr. Rudolf Zentel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401881

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      A special transfer of chirality through space was observed for polymers of type 1, the first liquid-crystalline polyvinyl compounds that derive their chirality and optical activity from the configuration of the main chain. The influence of chiral arrangements at the main chain (by variation of R1) on the chromophores of the mesogenic, achiral side groups, and on the formation of the liquid-crystalline phase may thus be understood separately.

    5. [K([18]crown-6)]+ [Mo44-H) (OCH2tBu)12], the First Alkoxidohydrido Cluster of Molybdenum, Evidence for a Rare, if not the First, Example of a μ4-Hydride (pages 191–193)

      Dr. Theodore A. Budzichowski, Prof. Malcolm H. Chisholm, Dr. John C. Huffman and Prof. Odile Eisenstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401911

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      A Mo4 butterfly cluster in which a hydrido ligand is bonded to all four metal atoms probably occurs in the anion of the title complex. This anion is accessible from [Mo2(OCH2tBu)6] and K[BsBu3H] in the presence of [18]crown-6. As shown schematically below the H-ligand serves to couple two Mo [TRIPLE BOND] Mo units to generate the Mo44-H)-containing anion.

    6. Re2I2(CO)6(Se7), a Coordination Compound of Elemental Selenium with a Transition Metal: A Solution- and Solid-State Study (pages 193–195)

      Dr. Alessia Bacchi, Dr. Walter Baratta, Prof. Dr. Fausto Calderazzo, Dr. Fabio Marchetti and Prof. Dr. Giancarlo Pelizzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401931

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      The cyclo-Se7 ligand is bound to two rhenium(I) centers in the title compound 1 (depicted on the right). It arises in the reaction of [Re2I2(CO)6(thf)2] with freshly sublimed elemental selenium in CS2 and is the first complex that contains a discrete molecule of an allotropic modification of selenium as a ligand. These findings add to the understanding of the mechanism of oxidation of metals and low-valent metal complexes by chalcogens.

    7. Spectroscopic and Reactivity Studies of a Copper-Containing Metallacrown (pages 195–197)

      Dr. Alexander J. Blake, Dr. Robert O. Gould, Craig M. Grant, Paul E. Y. Milne, Dr. David Reed and Dr. Richard E. P. Winpenny

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401951

      Cumath image and Cu3Mg-containing complexes form when the metallacrown 1 is treated with lead or magnesium nitrate, respectively. In the first reaction the sodium ion in the cavity formed by the six copper atoms of the macrocyclic host is replaced by a copper ion, which suggests the destruction of the structure of the macrocycle. In the replacement of the sodium ion by a magnesium ion in the second reaction the macrocycle is cut in half. According to the NMR spectrum of the metallacycle 1, its structure in the solid state is retained in solution. MeLH = 2-hydroxy-6-methylpyridine.

      • equation image
    8. New Titanium–Boron Complexes with a Planar Tetracoordinate Carbon or a Planar Tricoordinate Phosphorus Center (pages 197–198)

      Prof. Dr. Paul Binger, Dipl.-Chem. Frank Sandmeyer, Prof. Dr. Carl Krüger, Jörg Kuhnigk, Dr. Richard Goddard and Prof. Dr. Gerhard Erker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401971

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      A novel coordination geometry of phosphorus is achieved in a simple way by the reaction of the (η2-tert-butylphosphaalkyne)titanocene 1 with tetraethyldiborane [Eq. (a)]. The resulting dinuclear complex 2 contains a planar tricoordinate phosphorus atom whose lone pair of electrons is not involved in bonding.

    9. [P4(Cp*Al)6]: A Compound with an Unusual P4Al6 Cage Structure (pages 199–200)

      Dipl.-Chem. Carsten Dohmeier, Prof. Dr. Hansgeorg Schnöckel, Priv. Doz. Dr. Christian Robl, Dipl.-Chem. Uwe Schneider and Prof. Dr. Reinhart Ahlrichs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401991

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      Two face-sharing Al4P4 cubes, which lack two P atoms at the corners—this is the (idealized) framework of the title compound in the crystal. According to calculations, the isomer with adamantane structure is less stable by 30 to 80 kJ mol−1. As a result of quantum mechanical calculations on the model [P4(CpAl)6], [P4(Cp*Al)6] can be characterized as an electron-deficient compound that is stabilized by considerable ionic bonding contributions.

    10. (Iminoboryl)borates [(tBuN[TRIPLE BOND]B)BtBu2R] from the Azadiboriridine NB2tBu3 (R = Me, Bu) (pages 201–202)

      Ellen Eversheim, Dr. Ulli Englert, Priv.-Doz. Dr. Roland Boese and Prof. Dr. Peter Paetzold

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402011

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      A two-coordinate and a four-coordinate boron atom are bound together in the borates 2 (R = Me, Bu) obtained according to Equation (a). The anions may be considered adducts of BtBu2R and tBuN [TRIPLE BOND] B- (isoelectronic with the isonitrile tBuN [TRIPLE BOND] C). The azadiboriridine of type 1, containing an N-mesityl instead of a tert-butyl group, has a B–B bond with considerable double-bond character and reacts with LiR analogously to 1. tmeda = N,N,N′,N′-tetramethylethylenediamine.

    11. 5-Pentamethylcyclopentadienyl)iron Complexes with η5-2,3,5-Tricarbahexaboranyl and η5-2,3-Dihydro-1,3-diborolyl Ligands (pages 203–204)

      Prof. Dr. Walter Siebert, Dr. Ralph Hettrich and Dr. Hans Pritzkow

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402031

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      The extreme folding of the heterocycle and the Me groups on the C5 ring stabilize complex 1 to such an extent that an additional C5Me5Fe fragment cannot be stacked to give a triple-decker complex. The green, air-sensitive compound is the first structurally characterized iron sandwich complex with 16 valence electrons.

    12. Photoisomerization of Highly Alkylated Butadienes (pages 204–205)

      Prof. Dr. Henning Hopf, Dr. Helmut Lipka and Prof. Dr. Marit Traetteberg

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402041

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      Bicyclobutane formation and a 1,5 H shift, and not photocyclization to the cyclobutene derivative, predominate on the irradiation of highly alkylated nonplanar 1,3-dienes 1. Bicyclobutanes 2 are also formed from dienes with two central tBu groups, whereas the corresponding iPr-substituted compounds afford almost exclusively 3. For dienes with an iPr and a tBu group, the two pathways are almost equally likely to occur.

    13. Fullerene Dications as Initiators for Gas-Phase “Ball-and-Chain” Polymerization of Ethylene Oxide; Termination by Cyclization (pages 206–207)

      Jinru Wang, Dr. Gholamreza Javahery, Dr. Simon Petrie, Prof. Dr. Alan C. Hopkinson and Prof. Dr. Diethard K. Bohme

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402061

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      Cmath image reacts sequentially in the gas phase with five molecules of ethylene oxide to form adducts like 1; in contrast Cmath image is unreactive. A mechanism is proposed in which the course of the reaction is determined by Coulombic repulsion between two positive charges.

    14. [(Ph3PAu)6(dppeAu2)(AuCl)4Pd], an Icosahedral Au12 Cluster with a Central Pd Atom (pages 207–209)

      Dipl.-Chem. Martin Laupp and Prof. Dr. Joachim Strähle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402071

      Photolysis of the azido complexes [Ph3PAuN3] and [(dppe)Pd(N3)2] or [(Ph3P)2Pd(N3)2] in the presence of [Ph3PAuCl] affords the new heterodimetal clusters 1 and 2, in which the twelve gold atoms form an icosahedron around a central Pd atom. These first icosahedral Au12 clusters containing a heteroatom in their center are isoelectronic with the Au13 cluster [(PhMe2PAu)10(AuCl)2Au]3+.

      • equation image
    15. Synthesis of Dihydroxyacetone Phosphate (and Isosteric Analogues) by Enzymatic Oxidation; Sugars from Glycerol (pages 209–212)

      Prof. Dr. Wolf-Dieter Fessner and Dipl.-Chem. Gudrun Sinerius

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402091

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      The combination of enzymes glycerol phosphate oxidase and catalase allows the efficient preparative oxidation of glycerol phosphate 1 (X = O) with elemental oxygen which yields dihydroxyacetone phosphate 2 (X = O). Phosphate 2 can be added to various aldehydes in a one-flask, enzyme-catalyzed reaction to furnish 3 (X = O). Isosteric analogues of glycerol phosphate 1 (X = CH2, NH, S) can be converted into the corresponding adducts 3.

    16. Neutral Gold(I) Fluoride Does Indeed Exist (pages 212–214)

      Dr. Detlef Schröder, Dr. Jan Hrušák, Dr. Inis C. Tornieporth-Oetting, Priv.-Doz. Dr. Thomas M. Klapötke and Prof. Dr. Helmut Schwarz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402121

      AuF+ and AuF- can be neutralized in the gas phase. Neutralization-reionization mass spectrometry thus provides proof of the existence of neutral AuF, which was predicted by theory. The upper and lower limits for the bond dissociation energy could also be deduced: 68 kcal mol−1 < BDE < 85 kcal mol−1. The AuF ions are generated by electron impact ionization from AuF3.

    17. “Head-to-Tail” Linkage in Double Calix[4]arenes (pages 214–216)

      Dipl.-Chem. Wojciech Wa̧sikiewicz, Dr. Gabriel Rokicki, Dr. Jȩdrzej Kiełkiewicz and Dr. Volker Böhmer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402141

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      The two linked units have the same orientation in the double calix[4]arene 1; thus, for example, their dipole moments do not cancel. Until now the only compounds known of this type were linked “head-to-head” or tail-to-tail. Compound 1 can, in principle, stack and can therefore be considered as the first oligocalix[4]arene.

    18. Inversely Coordinating Silanide Ions in an Oligomeric Sodium Alcoholate (pages 216–217)

      Dr. Hans Pritzkow, Dipl.-Chem. Thomas Lobreyer, Prof. Dr. Wolfgang Sundermeyer, Dr. Nicolaas J. R. van Eikema Hommes and Prof. Paul von Ragué Schleyer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402161

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      The H atoms and not the Si atom of the SiH3 groups coordinate to two of the eight Na atoms in [Na8(OC2H4OC2H4OCH3)6-(SiH3)2]. Shown here is the novel Na8O6 polyhedron containing the two SiH3 groups. The surfaces of the Na8 cube are capped by oxygen atoms. Ab initio calculations on a suitable model showed that the inverted coordination mode is indeed energetically more favorable.

    19. Syntheses of Cyclopentanols by a Silicon-Induced Cascade Reaction (pages 217–218)

      Michael-Ralph Fischer, Dr. Andreas Kirschning, Dipl.-Chem. Tycho Michel and Prof. Dr. Ernst Schaumann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402171

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      Through the rare [4 + 1] construction strategy, the cyclopentanols 1 are accessible by a sequence of epoxide ring opening, silyl migration, and tosylate substitution. Optically active and annelated cyclopentanols can also be prepared by this route.

    20. New Porphyrinoid Macrocycles Containing Pyridine (pages 219–220)

      Kurt Berlin and Prof. Dr. Eberhard Breitmaier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402191

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      Pyriporphyrins like the isolable porphyrin analogue 1 react unexpectedly upon oxidation. Depending on the reaction conditions either a ketone (C = O instead of CH2) or a dimer is formed. A conjugated [18]annulene derivative is, however, not obtained.

    21. Chiroporphyrins: An Approach to Asymmetric Catalysts with Stereocenters Near the Plane of the Porphyrin Ring (pages 220–223)

      Dipl.-Chem. Marc Veyrat, Olivier Maury, Frédéric Faverjon, Dr. Diana E. Over, Dr. René Ramasseul, Dr. Jean-Claude Marchon, Dr. Ilona Turowska-Tyrk and Prof. W. Robert Scheidt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402201

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      Readily available chiral aldehydes and pyrrole provide porphyrins like 1 in a single step. Mn-Cl derivatives of such compounds are effective catalysts for the enantioselective epoxidation of nonfunctionalized olefins. The design of chiral porphyrin ligands should receive new impetus, since in the synthesis of 1, the D2-symmetric isomer is formed preferentially, and time-consuming resolution is not necessary.

    22. Coexistence of Mobile and Localized Electrons in Bis(ethylene)dithiotetrathiafulvalene (BEDT-TTF) Radical Salts with Paramagnetic Polyoxometalates: Synthesis and Physical Properties of (BEDT-TTF)8[CoW12O40]· 5.5 H2O (pages 223–226)

      Dr. Carlos J. Gómez-García, Dr. Lahcène Ouahab, Carlos Gimenez-Saiz, Dr. Smaïl Triki, Prof. Dr. Eugenio Coronado and Dr. Pierre Delhaès

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402231

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      Alternating layers of radicals of the π-electron donor 1 and of polyoxonions [CoW12O40]6− (2, polyhedral representation) are contained in the title compound. Thus, organic charge carriers and inorganic electron-acceptor components lie next to each other. Since the polyoxometalates can accommodate different metal ions at specific sites, such anions are attractive precursors for the preparation of radical cation salts with new electrical and magnetic properties.

    23. Amides as a New Type of Backbone Modification in Oligonucleotides (pages 226–229)

      Dr. Alain De Mesmaeker, Dr. Adrian Waldner, Dr. Jacques Lebreton, Dr. Pascale Hoffmann, Dr. Valérie Fritsch, Dr. Romain M. Wolf and Dr. Susan M. Freier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402261

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      No decrease in the affinity for the complementary RNA target is observed when the natural phosphodiester linkages in oligonucleotides are replaced with amide units. This was found in investigations of oligonucleotides containing one or more modified components 1. In addition these oligonucleotides are roughly ten times more resistant towards 3′-exonucleases.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Book Review: Crown Compounds: Toward Future Applications. Edited by S. R. Cooper (page 235)

      David N. Reinhoudt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402351

  5. New Books

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. New Books (Angew. Chem. Int. Ed. Engl. 2/1994) (page 241)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199402411