Angewandte Chemie International Edition in English

Cover image for Vol. 31 Issue 12

December 1992

Volume 31, Issue 12

Pages 1541–1693

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 12/1992)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215411

      Thumbnail image of graphical abstract

      The cover picture shows the structure of hexabutadiynylbenzene protected six-fold by tert-butyl groups. Other derivatives have also been prepared, as well as an impure sample of the parent hydrocarbon C30H6. The compound has a 54 π-electron system and might be able to be transformed into the cyclic [6]phenylene, antikekulene, by regioselective, CpCo-catalyzed, threefold co-cyclization with ethyne. This contributin, like Eaton's cubane review last month, shows once more that the chemistry of hydrocarbons has lost none of its appeal. More about hexabutadiynylbenzene and advances en route to the synthesis of tetraethynylmethane is reported by K. C. P. Vollhardt et al. on pages 1643 and 1648.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 12/1992)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215412

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. Emil Fischer's Proof of the Configuration of Sugars: A Centennial Tribute (pages 1541–1556)

      Prof. Dr. Frieder W. Lichtenthaler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215413

      The achievements of chemists from earlier times should not be taken for granted only because their findings are by now common knowledge, or because the development of analytical methods provides formerly almost insurmountable problems with quick and easy answers today. One of the frequently underestimated forefathers is Emil Fischer. His elucidation of the relative configurations of sugars, the derivation of the sugar family tree starting from -LD-glyceraldehyde, and the two-dimensional representation for stereoisomers he introduced, for example, for D- and L-glucose (the Fischer projection), have advanced the development of organic chemistry considerably. A tribute is paid to those works of Fischer that have led to these findings.

    2. Synchrotron X-ray and Neutron Diffraction Studies in Solid-State Chemistry (pages 1557–1570)

      Prof. Anthony Kevin Cheetham and Dr. Angus Paul Wilkinson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215571

      Since the scatterers are different—X-rays are scattered by the electrons of an atom, neutrons by the nuclei—the questions addressed by the two diffraction experiments have been complementary. For example, neighboring elements of the periodic table could be distinguished formerly only by neutron diffraction. Now, however, this is also partly possible with high-energy synchrotron radiation. This review describes recent applications of X-ray and neutron diffraction methods in solid-state chemistry and how the maximal information can be extracted by a combination of techniques.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. Dendrimers, Arborols, and Cascade Molecules: Breakthrough into Generations of New Materials (pages 1571–1576)

      Hans-Bernhard Mekelburger, Prof. Dr. Fritz Vögtle and Dr. Wilfried Jaworek

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215711

      Thumbnail image of graphical abstract

      Compounds with extremely branched molecular structures (for example 1) that are formed in iterative syntheses are penetrating many disciplines of chemistry. Compound 1 has 36 carboxyl groups on its periphery and can be considered a unimolecular micelle. Recently dendrimers have found their way into coordination chemistry through a compound which contains up to 22 metal centers per molecule (see also Balzani et al. Angew. Chem. Int. Ed. Engl.1992, 31, 1493).

    2. The Structure of Water—A Mixture of Cubes and Planar Four-Membered Rings? (pages 1577–1578)

      Prof. Dr. Helmut Bertagnolli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215771

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      From simple thermodynamic considerations, which used only data from ice and the gaseous H2O dimer, Benson and Siebert derived a model for the structure of liquid water. In their opinion, water consists of cubic octamers (picture right), which are linked by hydrogen bonds and can dissociate into cyclic tetramers. The assumption of an isomerization equilibrium between octamers and tetramers can explain the anomalous heat capacity of water and its change with temperature.

    3. A Milestone in Genome Sequencing: The Complete DNA Sequence of the Yeast Chromosome III (pages 1578–1582)

      Prof. Dr. Ernst-L. Winnacker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215781

      315357 Base pairs in length, chromosome III of baker's yeast was sequenced by 147 scientists from 35 European laboratories at a cost of approximately DM 10 per base pair. The sequence contains 182 open reading frames coding for proteins more than 100 amino acids long. Until now, the classical genetic map of this chromosome had listed only 34 genes, that is, only 20% of the actual number of genes. If one extrapolates this result to the human genome, the estimated number of our genes must be revised dramatically upwards, to 500 000 or more.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. The First Metal–Metal Silyl Migration in a Heterobimetallic Complex, and the Structure of the Rearrangement Product [(OC)4Fe(μ-PPh2)Pt{Si(OMe)3}(PPh3)](Fe[BOND]Pt) (pages 1583–1585)

      Dr. Pierre Braunstein, Dr. Michael Knorr, Dipl.-Chem. Brigitte Hirle, Dipl.-Chem. Georg Reinhard and Prof. Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215831

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      A Si[BOND]Pt bond is the result of the migration of a silyl ligand from one metal center to another. This rearrangement was proven for the first time for 1 a and 1 b and is highly dependent on the ligands. This is illustrated by the observations that 1 b could be isolated as a solid and in solution rearranges much slower than 1 a and that analogous complexes like 1 c do not isomerize.

    2. Detection of the Tungsten–Carbene–Olefin Intermediates in Catalytic Metathesis Systems Containing High-Valent Metal Centers (pages 1585–1587)

      Dr. Jacky Kress and Prof. Dr. John A. Osborn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215851

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      The catalytic ring-opening polymerization of cycloheptene 2 proceeds through the rearrangement of 3 to give the corresponding metallacyclobutane. Compound 3, which is prepared in situ by addition of 2 to the carbone complex 1 and can be characterized by low-temperature 1H and 13C NMR spectroscopy, is therefore considered a key intermediate for these reactions that are also commercially important. Complexes of this type have up to now been postulated but not detected for catalytic olefin metatheses. R = CH2CMe3.

    3. C[BOND]C Coupling with NO2/Alkyl Substitution at the Vinylic Carbon by Reaction of 2-Aryl-l-nitro-1-alkenes with Dialkylzinc Compounds—A Novel Reaction (pages 1587–1588)

      Prof. Dr. Dieter Seebach, Dipl.-Chem. Harald Schäfer, Dr. Beat Schmidt and Martin Schreiber

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215871

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      No catalyst is needed for the novel vinylic C[BOND]C coupling reaction of 2-aryl-1-nitroalkenes with dialkylzinc compounds [Eq. (a)]. Although NO2 substituents usually activate double bonds for Michael additions, replacement of the NO2 group with an alkyl group provides (E)-1-aryl- and (E) -1-heteroaryl-1-alkenes in yields up to 40%, which can probably still be optimized.

    4. A Homologous Series of Stable Polyenes: Synthesis, Structure, and Redox Behavior (pages 1588–1591)

      Dipl.-Chem. Alfried Kiehl, Anke Eberhardt, Dipl.-Chem. Martin Adam, Dr. habil. Volker Enkelmann and Prof. Dr. Klaus Müllen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215881

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      The Stille coupling of stannyl olefins provides a prolific route to the homologous polyenes 1–3. Their crystallographic and cyclic voltammetric data prove them to be models for polyacetylene compounds.

    5. Chlorins Designed for Photodynamic Tumor Therapy and as Model Systems for Photosynthesis (pages 1592–1594)

      Prof. Dr. Franz-Peter Montforts, Axel Meier, Dr. Gerhard Scheurich, Dipl.-Chem. Gerold Haake and Dr. Jan. W. Bats

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215921

      Thumbnail image of graphical abstract

      Beginning with inexpensive starting materials chlorins can be synthesized in a few steps. A hydroquinone and an estrogen unit are linked to chlorin rac-1 (R = H) by means of a (CH2)3 spacer on the OH group to provide a model for photosynthetic pigments, as well as fluorescence markers and sensitizers for medical applications.

    6. KCeSe4: A New Solid-State Lanthanide Polychalcogenide (pages 1594–1596)

      Anthony C. Sutorik and Prof. Dr. Mercouri G. Kanatzidis

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215941

      Thumbnail image of graphical abstract

      Cerium and molten potassium selenide flux provide access to KCeSe4. The structure of this novel lanthanide polychalcogenide is related to the CuAl2 structure, and Ce and Se form anionic layers with K+ ions in the cavities. Each Ce3+ ion is surrounded by eight Semath image units in a square antiprismatic arrangement (structure shown on the right).

    7. Mutual Catalysis of Neutral and Anionic Cobalt Carbonyls in Their CO Scrambling Reactions (pages 1596–1599)

      Prof. Dr. Giuseppe Fachinetti and Dr. Tiziana Funaioli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215961

      Redox-condensation equilibria, probably with the participation of [Co3(CO)10] as intermediate, and not ion pairing as previously postulated, explain the acceleration of the CO scrambling in [Co(CO)4] by alkali metal counterions. The studies described here show that neutral carbonyl complexes catalyze the CO scrambling for anionic metal carbonyls and vice versa, and that the catalysis is less effective in the presence of free CO. The latter is in agreement with [Co3(CO)10] as the intermediate. These results are important mainly because neutral and anionic metal carbonyls frequently exist together as a result of side reactions.

    8. C60 and C70 in a Basket? – Investigations of Mono- and Multilayers from Azacrown Compounds and Fullerenes (pages 1599–1602)

      Dipl.-Chem. Joehem Effing, Ulrich Jonas, Dr. Ludovic Jullien, Dipl.-Chem. Thomas Plesnivy, Prof. Dr. Helmut Ringsdorf, Prof. Dr. Francois Diederich, Dr. Carlo Thilgen and David Weinstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199215991

      Thumbnail image of graphical abstract

      For films of C60 or C70 and azacrown compounds with long side chains, the question immediately arises whether the fullerene molecules are positioned in, between, or on the baskets (see AC). Surface pressure-area diagrams, UV/VIS spectroscopic data, and the preliminary results of atomic force microscopy measurements are consistent with model A.

    9. The Isomers of the Acetylene Derivatives C2Li4: Transferable Structural Units in Hyperlithiated Compounds (pages 1602–1603)

      Dr. Andrea E. Dorigo, Dr. Nicolaas J. R. van Eikema Hommes, Prof. Dr. Paul von Ragué Schleyer and Prof. Dr. Karsten Krogh-Jespersen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216021

      Thumbnail image of graphical abstract

      C2Li4 is an acetylene and not an ethylene derivative, despite its stoichiometry. All the isomers correspond to minima on the potential energy surface of C2Li4. Ab initio calculations established the occurrence of Limath image, Limath image, and Limath image units, characteristic for per- and hyperlithiated molecules, and showed that structure 1 lies at the global energy minimum.

    10. 1-Borabutadiene(cyclopentadienyl)cobalt Complexes (pages 1603–1605)

      Dipl.-Chem. Gernot Gabbert, Dipl.-Chem. Wolfgang Weinmann, Dr. Hans Pritzkow and Prof. Dr. Walter Siebert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216031

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      The reaction of methylene-1,2-diborolane 1 a and its 3-isomer 1 b with [(C5H5)Co(C2H4)2] leads to the formation of the complexes 2 a,b, in which the previously unknown 4-boryl-1-borabutadienes 3 are stabilized as ligands. The borabutadienes 3 a,b are formed by the migration of two hydrogen atoms in 1 a,b to the exo CH2 group and into the B[BOND]B bond, which is opened with the formation of a complexed B[DOUBLE BOND]C bond. 2a, 3a: R1 = H, R3 = Me; 2b, 3b: R1 = Me, R3 = H; R2 = NiPr.

    11. [(π-Me5C5)2SiH]+—A Novel Silyl Cation (pages 1605–1607)

      Prof. Dr. Peter Jutzi and Dr. Ernst-August Bunte

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216051

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      The existence of cations of the type R3Si+ in solution or in the solid state is still controversial. In the novel silyl cation in 2 the π ligands greatly help in stabilizing the cationic center. Compound 2 was obtained from decamethylsilicocene and catechol via the aryloxysilane 1 and was characterized unequivocally by 1H, 13C, and 29Si NMR spectroscopy, molecular weight determination, and conductance measurements.

    12. Distortional Isomerism in Oxomolybdenum Systems; the Evidence Re-evaluated (pages 1607–1609)

      Alan P. Bashall, Dr. S. W. Annie Bligh, Dr. Andrew J. Edwards, Prof. Mary McPartlin, Dr. Vernon C. Gibson and Oliver B. Robinson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216071

      Two blue forms of the oxomolybdenum complex [Mo(O)Cl2(PMe2Ph)3] exist, and not one blue and one green or even only one blue form! The molecules of the two blue forms can be characterized and are deformation isomers in which the phosphane ligands are clearly differently oriented, and the Mo[DOUBLE BOND]O bonds have different lengths, which lead to stretching frequencies differing by about 12 cm−1 in the IR spectra of the solids. The lack of change in the IR spectrum for the isomer absorbing at ṽ = 943 cm−1 on cocrystallization with [MoCl3(PMe2Ph)3] suggests that a crystal packing effect cannot explain the presence of two forms.

    13. Determination of the HN–Hα Coupling Constant in Large Isotopically Enriched Proteins (pages 1609–1611)

      Dr. Stephan Seip, Dipl.-Chem. Jochen Balbach and Prof. Dr. Horst Kessler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216091

      The 3Jmath image coupling constants of very large proteins can be determined independent of the width of the signal in the NMR experiments described here. Both pulse sequences correlating 15N with 13Cα and HN were used to determine 3Jmath image in the P13 domain of mannose permease. This coupling constant provides information on the range of values for the angle φ, which is important in molecular dynamics calculations.

    14. Butatrienes by Desulfurization of Cyclic Trithiocarbonates (pages 1611–1613)

      Dr. Rainer Herges and Dipl.-Chem. Christoph Hoock

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216111

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      A novel synthesis of cumulenes by addition of potassium trithiocarbonate to 1,4-difunctionalized 2-butynes 1 and subsequent desulfurization of the cyclic trithiocarbonate 2 affords substituted butatrienes 3 in good yields and under mild conditions.

    15. Rate Constants for the Attack of Carbenium Ions at Arenes—A Link between the Chemistry of Aliphatic and Aromatic π Systems (pages 1613–1615)

      Prof. Dr. Herbert Mayr, Dr. Jörg Bartl and Dr. Gisela Hagen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216131

      The mechanism of the Friedel-Crafts reaction is one of the most thoroughly studied, yet the absolute rate constants for the key step—the attack of the carbenium ion at arene—have only now been determined for the arylcarbenium ion. Since rate constants for reactions of these carbenium ions with alkenes and complexes of main group elements with the allyl group are already known, a direct comparison between the nucleophilicity or aromatic and aliphatic π systems is now possible.

    16. Spectroscopic Characterization of Two Types of Tetraarylporphyrin Cation Radicals (pages 1615–1617)

      Dr. Zeev Gross and Claudia Barzilay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216151

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      Further insight into the interaction between the paramagnetic metal centers and porphyrin radical cations is derived from the ESR, UV/VIS, and IR spectroscopic characterization of the salts 5–8. These studies indicate that the electronic structures of 7 and 8 differ significantly from those of 5 and 6. R represents the same substituent as at the other two meso positions.

    17. DNA Recognition by Hybrid Oligoether–Oligodeoxynucleotide Macrocycles (pages 1617–1619)

      Squire Rumney IV and Prof. Dr. Eric T. Kool

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216171

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      Exceptionally resistant to nucleases, the 1:1 adducts of single-stranded oligonucleotides and cyclic oligoether–oligonucleotide hybrid compounds form triple-helical structures. The picture on the right shows schematically the binding in these systems.

    18. One-Step Synthesis of a Fourfold Functionalized Catenane (pages 1619–1622)

      Prof. Dr. Fritz Vögtle, Dipl.-Chem. Stephan Meier and Dipl.-Chem. Ralf Hoss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216191

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      One of the simplest catenane syntheses is the reaction described here providing tetra-methoxycatenane 1 (R = OCH3). This catenane is conformationally less flexible than its known, unsubstituted analogue (R = H): in the 1H NMR spectrum of 1 the two signals arising from the OCH3 groups indicate a fixed conformation with inner and outer methoxy groups.

    19. The First Self-Assembled Dinuclear Triple-Helical Lanthanide Complex: Synthesis and Structure (pages 1622–1624)

      Dr. Claude Piguet, Dr. Alan F. Williams and Dr. Gérald Bernardinelli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216221

      Thumbnail image of graphical abstract

      Eighteen europium–nitrogen bonds are formed when a specially designed bis(terdentate) nitrogen-containing ligand L1 reacts with europium(III) perchlorate. In the resulting triple-helical dinuclear cation [Eu2Lmath image]6+1, the metals are coordinated to nine nitrogen atoms each, forming a slightly distorted tricapped trigonal prism (see schematic representation on the right; the open circles are the coordinating N atoms of L1, solid circles the europium(III) ions).

    20. Mössbauer Spectroscopy and Electronic Structure Calculations of the Nitridoferrates(III): Li3[FeN2] and Ba3[FeN3] (pages 1624–1626)

      Dipl.-Chem. Nils Jansen, Dr. Hartmut Spiering, Prof. Dr. Philipp Gütlich, Prof. Dr. Peter C. Schmidt, Dr. Volker Eyert, Dipl.-Ing. Dagmar Stahl, Prof. Dr. Rüdiger Kniep and Prof. Dr. Jürgen Kübler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216241

      An unusually negative isomer shift δ is found in the Mössbauer spectrum of the nitridoferrate(III), Ba3[FeN3]. A quantitative analysis of the δ values and the quadrupole splittings for Ba3[FeN3], Li3[FeN2], and a number of other iron compounds by band structure calculations gave a remarkably good linear correlation between δ and the calculated valence electron density. The weakest nuclear shielding by the valence electrons was found for the 3s electrons in Ba3[FeN3], which explains the δ value of −0.55(2) mms−1 relative to α-Fe.

    21. Stereoselective Nucleophilic Addition Reactions of Reactive Pseudopeptides (pages 1626–1629)

      Prof. Dr. Manfred T. Reetz, Dr. Jürgen Kanand, Dipl.-Chem. Nils Griebenow and Dr. Klaus Harms

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216261

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      D,L-Pseudopeptides of type 1 undergo 1,4-additions with tBu2CuLi/Me3SiCl with high stereoselectivity, whereas reactions of the corresponding L,L diastereomers are substantially less diastereoselective. The L,L,L and D,L,L analogues also react with different stereoselectivities. Strict chelation control plays a role in the Grignard-like reaction of L,L peptide aldehydes like 2 with (CH3)2CuLi.

    22. A New Type of Mn–O Cluster with a Mn4 Chain Unit—Relevance to the Photosynthetic Oxygen Evolving Center (pages 1629–1631)

      Christian Philouze, Dr. Geneviève Blondin, Dr. Stéphane Ménage, Dr. Nathalie Auger, Dr. Jean-Jacques Girerd, Daniel Vigner, Monique Lance and Dr. Martine Nierlich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216291

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      Two Mn2(μ-O)2 units linked by another two oxo bridges make up the cluster core of 1 (see structure on the right; two bipyridine ligands have been omitted from both Mn1 and Mn4). The Mn[BOND]Mn distances and magnetic properties of 1 indicate that this cluster may be a model of the reaction center for oxygen evolution in plants. The question whether the Mn4 unit has a chainlike arrangement or a cubane structure in the naturally occurring enzyme is nevertheless still unanswered.

    23. Salting Out Selective Extraction—A Novel Method for the Optical Resolution of Chiral Sulfinylcarboxylic Acids and Its Application for the Convenient Determination of Optical Purity (pages 1631–1633)

      Dr. József Rábai

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216311

      When fractional recrystallization fails to separate diastereomeric salts, the enantiomers may still be resolved by the selective extraction of the diastereomeric salts. Racemic sulfinylcarboxylic acids were treated with cinchona bark alkaloids and NaOH (or KHCO3). Repeated extractions led to high enantiomeric excesses.

    24. Gas-Phase Reactions of M+ and [CpM]+ (M = Fe, Co, Ni) with 1,3,5-Trisilacyclohexane: First Evidence for the Formation of 1,3,5-Trisilabenzene (pages 1633–1634)

      Dr. Asgeir Bjarnason and Prof. Dr. Ingvar Arnason

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216331

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      Preferential elimination of HD in the gasphase reactions of [CpM]+, M = Fe, Co, Ni, with deuterated trisilacyclohexane 1 points to the formation of trisilabenzene, previously unknown, as a ligand. The results of collision experiments also support the formation of 2 (deuterated) in these reactions.

    25. A 1 : 1 Adduct of 2-Aminobenzothiazole and a Urea Derivative, and Its Spatial Arrangement (pages 1634–1636)

      Matthew G. Davidson, Avelino Martin, Dr. Paul R. Raithby, Dr. Ronald Snaith, Dr. David R. Armstrong and Dr. Dietmar Stalke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216341

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      A central tunnel catches the eye in the symmetric arrangement of the adduct (1 · 2)2 of 2-aminobenzothiazole 1, an analogue of a DNA base, and 1,3-dimethyl-2-oxohexahy-dropyrimidine (2) (on the right a view down the b axis). The adduct is dimeric; two molecules of 1 form a base pair, and each molecule of 1 is also bound to one molecule of 2. The halves of the dimer are linked by hydrogen bonds, but each dimer is discrete.

    26. Corannulene Tetraanion: A Novel Species with Concentric Anionic Rings (pages 1636–1637)

      Art Ayalon, Prof. Dr. Mordecai Rabinovitz, Pei-Chao Cheng and Prof. Dr. Lawrence T. Scott

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216361

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      Described as an annulene-within-an-annulene, the tetraanion 2 of corannulene (1) was prepared by reducing 1 with lithium at −78 °C and then investigated by NMR spectroscopy. Compounds with concentric aromatic rings have long been sought.

    27. Towards Artificial Ion Channels: Transport of Alkali Metal Ions across Liposomal Membranes by “Bouquet” Molecules (pages 1637–1640)

      Dr. Marko J. Pregel, Dr. Ludovic Jullien and Prof. Jean-Marie Lehn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216371

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      If “bouquet” molecules with a central crown ether or cyclodextrin unit and poly(oxyethylene) or polymethylene arms are built into the membranes of liposomes (as shown in the diagram), Na+ and Li+ ions can be transported across the membrane. All the results are consistent with a channel transport mechanism.

    28. Optimization of the Production and Separation of Fullerenes (pages 1640–1642)

      Dipl.-Chem. Andreas Mittelbach, Dr. Wolfgang Hönle, Prof. Dr. Hans Georg von Schnering, Dr. Jürgen Carlsen, Dr. Rolf Janiak and Prof. Dr. Helmut Quast

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216401

      Mixtures of C60 and C70 containing up to 50% C70 are obtained from the production of fullerenes with a DC furnace with high currents (400 A). In addition, two chromatographic methods using silica gel and reversed-phase silica gel are introduced for the separations of 400 and 300 mg, respectively, of mixed fullerenes per hour. Larger amounts of fullerenes can thus be purified on standard chromatographic supports.

    29. The First Stibepine: Synthesis and Structure of Sb-Chlorobenzo[d]stibepine (pages 1642–1643)

      Prof. Dr. Arthur J. Ashe III, Lukas Goossen, Dr. Jeff W. Kampf and Dr. Hisatoshi Konishi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216421

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      The benzostibepine 1 is unexpectedly more stable than the analogous arsenic compound. It is formed from dibutylbenzostannepine and SbCl3 at 0 °C. The crystal structure investigation reveals a boatlike conformation of the seven-membered ring and markedly alternating C[BOND]C bond lengths, which precludes π conjugation. The Me and Bu derivatives can also be prepared from 1.

    30. The First Hexabutadiynylbenzenes: Synthesis and Structures (pages 1643–1645)

      Dr. James R. Green, Dr. Joachim Mittendorf, Debra L. Mohler, Prof. Dr. K. Peter C. Vollhardt and Priv.-Doz. Dr. Roland Boese

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216431

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      An important intermediate en route to antikekulene is the C30H6 hydrocarbon 1 d. A precursor for this intermediate is l a, which can be protodesilylated; but in contrast to 1 a–1 c, 1 d cannot yet be obtained in pure state. An X-ray crystal structure of 1 c confirms the high symmetry of the compound.

    31. New Layered Iron-Lanthanum-Oxide-Sulfide and -Selenide Phases: Fe2La2O3E2(E = S,Se) (pages 1645–1647)

      Prof. James M. Mayer, Dr. Lynn F. Schneemeyer, Dr. Theo Siegrist, Joseph V. Waszczak and Dr. Bruce Van Dover

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216451

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      A two-dimensional network of face-sharing FeO2E4 octahedrons (E = S, Se) interspersed with double layers of square E4O4 antiprisms, in whose centers lanthanum atoms are situated, is one description of the layers in the unusual structure of the Fe2La2O3E2 phases (see structure for E = Se on the right). Both the oxidesulfide and the oxideselenide are semiconductors with interesting magnetic properties.

    32. A Phenoxy-Bridged Homodinuclear Zn Complex with an Unusual Coordination Sphere; Model Compound for the Active Site of Phospholipase C (pages 1647–1648)

      Dipl.-Chem. Stefan Uhlenbrock and Prof. Dr. Bernt Krebs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216471

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      The imitation of not only the structure but also the function of the active site of the metalloenzyme phospholipase C seems to have been achieved with complex 1 (Ow = OH2). The two Zn atoms in 1 are bridged by a phenoxy and a carboxylate group. In addition, one Zn atom binds an H2O molecule, which is important for the catalytic process.

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    33. Tetraalkynylmethanes: Synthesis of Diethynyl-dipropargyl- and Tetrapropargylmethane (pages 1648–1651)

      Dr. Uwe Bunz, Prof. Dr. K. Peter C. Vollhardt and Jennifer S. Ho

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216481

      Thumbnail image of graphical abstract

      In a few steps the novel monomers 1 and 2, can be synthesized. Despite four C[BOND]C triple bonds that lie close together, neither 1 nor 2 are air- and moisture-sensitive. The hydrocarbon 2 was characterized by X-ray crystal analysis.

    34. Diastereoselective Three-Center Michael Addition of β-Ketoesters to Prostereogenic α,β-Unsaturated Carbonyl Compounds Catalyzed by K2CO3 or Cs2CO3 (pages 1651–1653)

      Nicole Ouvrard, Dr. Jean Rodriguez and Prof. Dr. Maurice Santelli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216511

      Thumbnail image of graphical abstract

      The stereocontrolled construction of three contiguous quaternary and tertiary carbon atoms is possible by the title reaction [Eq. (a)]. The diastereoselectivity can be reversed by the addition of crown ethers or other cryptands. R1 = Me, tBu, Bz; R2 = H, Me.

    35. meta-Phenylene Units as Conjugation Barriers in Phenylenevinylene Chains (pages 1653–1655)

      Heike Gregorius, Dr. Martin Baumgarten, Ronald Renter, Prof. Dr. Klaus Müllen and Prof. Dr. Nikolai Tyutyulkov

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216531

      Thumbnail image of graphical abstract

      Independent of the chain length are the optical and redox chemical properties of the oligomers 1, because the formally continuous π conjugation in them is interrupted by the meta-phenylene units. This is valid for neutral as well as for ionic systems. The charge localization on a stilbene unit causes extremely long wavelength “intervalence” bands in the UV/VIS spectra of the radical ions of these compounds.

    36. Structure of the Lowest Temperature Phase of the Solid Benzene–Hexafluorobenzene Adduct (pages 1655–1657)

      Dr. Jeffrey Huw Williams, Dr. Jeremy Karl Cockcroft and Dr. Andrew Nicholas Fitch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216551

      Thumbnail image of graphical abstract

      Similarities with a number of liquid-crystal systems are revealed by the structural characterization of the low-temperature phases II—IV of the solid adduct from benzene and hexafluorobenzene (right). As the temperature is raised, increased rotation leads to a reduction in the interactions between neighboring columns of alternating C6H6 and C6F6 molecules. These results could only be obtained by using a combination of powder diffraction techniques with neutrons and synchrotron radiation.

  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. You have free access to this content
      Corrigenda (page 1657)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216571

  5. Index of Review Articles and Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. REVIEW ARTICLES AND HIGHLIGHTS (pages 1661–1662)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216611

  6. Author Index

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. Author Index [Angew. Chem. Znt. Ed. Engl. 1992, 31] (pages 1663–1669)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216631

  7. Index of Authors and Reviewers of Books

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index
    1. INDEX OF AUTHORS AND REVIEWERS OF BOOKS (page 1670)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199216701

  8. Subject Index

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Index of Review Articles and Highlights
    7. Author Index
    8. Index of Authors and Reviewers of Books
    9. Subject Index

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