Angewandte Chemie International Edition in English

Cover image for Vol. 28 Issue 12

December 1989

Volume 28, Issue 12

Pages 1601–1793

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 12/1989)

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916011

      Thumbnail image of graphical abstract

      The cover illustration shows the unusual ribbon-like structure of tetraphenylethenedisodium bisdiethyl ether, which in the solid state is shiny, metallic green. The picture centers on the C[BOND]C bond joining the two halves of Ph2C[BOND]CPh2, and it clearly reveals how the two Ph2C units are twisted relative to each other (by 56°). Na atoms (shown in violet) display two types of coordination: those occupying “outer” positions are virtually surrounded by pairs of phenyl rings in what amounts to a “sandwich” arrangement, while the central Na atom is bound to two Et2O molecules and six C atoms from the Ph2C[DOUBLE BOND]CPh2 dianion. These findings represent a new high point in the investigation of organoalkali metal compounds, a field that has recently proven extremely fruitful. More about this ethene dianion (and about the structure of an ethene dication) is reported by H. Bock et al. on page 1685ff (and 1684f, respectively).

      This is the last issue of Angewandte Chemie that will include the special section Advanced Materials. From the very beginning, this section attracted a great deal of attention from both readers and authors. Indeed, we soon found it necessary to move from a bimonthly to a monthly format, and during the current year the amount of space devoted to Advanced Materials has steadily increased. Since June, the scope of the section has been expanded as well, so that it now includes not only Editorial Essays, Reviews, Research News, and Conference Reports, but also Short Communications. The rapidly growing significance of interdisciplinary materials research means that the time has now come to take the next step : starting with the new year, Advanced Materials will become an independent publication, better equipped to serve in integrating the subdisciplines of chemistry, physics, ceramics, and metallurgy which make up today's materials science. This change will permit us to do a more effective job of reporting the latest developments in areas such as polymer and ceramics research, thin films and liquid crystals, sensors and catalysts, superalloys, and superconductors.

      At the same time, Angewandte Chemie will continue to concentrate on its traditional role of transmitting important information derived from all branches of chemistry. In 1989 we received ca. 600 short communications, 356 of which were published; the corresponding numbers only five years ago were 449 and 309. Over the same period, the so-called “Impact Factor” of the journal, a measure of the frequency with which published articles are cited, increased from 4.0 to 5.1, giving Angewandte Chemie a leading position amongst, chemistry journals publishing reports of novel research. The high degree of respect on the part of readers and authors that these numbers reflect is a powerful incentive for us to strive to make the “Angewandte” even more attractive for 1990.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Image Enhancement—Chemical, Digital, Visual (pages 1601–1612)

      Dr. Joachim Lohmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916013

      Thumbnail image of graphical abstract

      The best model for effectively processing digital images, and to some extent also those captured on photographic film, is the biological visual apparatus. Edge effects, which can be a source of improved definition, are achieved within the eye by ensuring that receptor cells transmit activating signals to adjacent ganglion cells, but inhibitory signals to ganglia that are more remote. The result is apparent in the picture to the right : points where white bars intersect represent sites of particularly intense inhibition, and what one actually perceives is a matrix of (nonexistent) gray dots.

    2. Synthesis, Structure and Reactivity of Sulfur-Rich Cyclopentadienyl-Transition Metal Complexes: Sulfur Chemistry from an Organometallic Point of View (pages 1613–1626)

      Dr. Joachim Wachter

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916131

      Elemental sulfur and reactive fragments from cyclopentadienyl transition metal complexes usually interact in predictable ways. In most cases the products are soluble, binuclear complexes with mono-, di-, and polysulfido ligands, and these may in turn serve as useful intermediates. The findings reported here are of considerable interest, because metal-sulfur complexes are important models for metalloproteins and heterogeneous metal sulfide catalysts. The author discusses factors associated with the formation, structure, and reactivity of such binuclear complexes as a function of both the central metal and substituents present on the cyclopentadienyl ligands.

    3. Fundamentals of Silicon Chemistry: Molecular States of Silicon-Containing Compounds (pages 1627–1650)

      Prof. Dr. Hans Bock

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916271

      The much-discussed renaissance of inorganic chemistry is partly a consequence of rapid developments in the field of (organo)silicon chemistry. Spectroscopic methods in particular are being increasingly applied to the study of silicon compounds. The resulting data often include significant amounts of neglected information related to the energy states and their symmetries of the compounds under investigation, as well as clues to the energy-dependent electron distributions. Careful study of such “molecular fingerprints” may ultimately aid the synthetic-minded silicon chemist in developing meaningful guidelines for the interpretation of experimental data and the design of experiments.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. The Thiophene Analogue of Porphyrin: Tetrathiaporphyrin Dication (pages 1651–1655)

      Prof. Dr. Emanuel Vogel, Peter Röhrig, Martin Sicken, Bernd Knipp, Adalbert Herrmann, Michael Pohl, Dr. Hans Schmickler and Dr. Johann Lex

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916511

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      Furfuryl alcohol can be transformed in a simple way into the long-awaited sulfur analog of porphyrin, the tetrathiaporphyrin dication 1, isolated as the perchlorate. The key to the synthesis is a remarkably straightforward sulfur/oxygen exchange in tetraoxaporphyrinogen. As would be expected from the relatively large van der Waals radius of sulfur, the transformation from the tetraoxaporphyrin dication to 1 is accompanied by loss of planarity in the ring system.

    2. A Pyrrolophanediene-Porphycene Redox System (pages 1655–1657)

      Prof. Dr. Emanuel Vogel, Ilona Grigat, Dr. Matthias Köcher and Dr. Jahann Lex

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916551

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      In analogy to the isophlorines discussed by Woodward, N,N′-dihydroporphycenes should be regarded as [4n]annulenes, which explains their extremely facile oxidation to the aromatic porphycenes. Compound 1 is the first example of an N,N′-dihydroporphycene to be synthesized. The phane-like, colorless 1 and the deep violet, planar 2 constitute a redox system.

    3. Optically Active Isoprene(tricarbonyl)iron(0) and Methyltrimethylenemethane(tricarbonyl)iron(0) (pages 1657–1659)

      Dipl.-Chem. Dag Kappes, Prof. Dr. Hans Gerlach, Dipl.-Chem. Peter Zbinden, Prof. Dr. Max Dobler, Prof. Dr. Wilfried A. König, Dipl.-Chem. Ralph Krebber and Dr. Gerhard Wenz

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916571

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      Ionic hydrogenation of (+)-1 has for the first time opened the way to the optically active tricarbonyliron(0) complexes (+)-2 and (−)-3. Their absolute configurations were deduced on the basis of an X-ray structural analysis of (+)-1. Enantiomeric purities (88% and 96% ee) were established by gas chromatographic analysis with a capillary column of perpentylated γ-cyclodextrin. These complexes are of considerable interest in the context of asymmetric syntheses.

    4. Copper(I)-Assisted Formation of an “Organic” Sandwich Structure: Structural Prerequisites for Luminescence of the Dinuclear Complexes [(μ-Bipyrimidine){Cu(PR3)2}2]X2 (pages 1659–1660)

      Dipl.-Chem. Conny Vogler, Dr. Hans-Dieter Hausen, Prof. Dr. Wolfgang Kaim, Dr. Stephan Kohlmann, Prof. Dr. Horst E. A. Kramer and Dr. Jochen Rieker

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916591

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      A phenyl…bpym…phenyl π interaction together with a trapping of BFmath image counterions by solvent molecules, form the basis for the intense solid-state luminescence of 1. This conclusion follows from the fact that with a series of other arylphosphane ligands, with PFmath image or ClOmath image as counterions, or even in solution, luminescence from the metal-to-ligand chargetransfer excited state is either very weak or totally absent.

    5. Ta2Se: A Tantalum-Rich Selenide with a New Layer Structure (pages 1660–1662)

      Dr. Bernd Harbrecht

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916601

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      Only van der Waals forces are responsible for joining the two-dimensional Se-Ta-Ta-Ta-Ta-Se units in crystalline Ta2Se. This selenide, which has the highest tantalum content known, is prepared by reduction of molten TaSe2 with tantalum. Its structure (shown in the picture to the right) is symmetrically related to the body-centered cubic structure of the pure metal.

    6. K4Al2Nb11O20F—The Missing Link in Cluster Condensation (pages 1662–1663)

      Prof. Dr. Arndt Simon, Dr. Jürgen Kohler, Robert Tischtau and Dr. Gordon Miller

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916621

      Thumbnail image of graphical abstract

      Condensation over octahedral corners is the characteristic feature of the Nb11Omath imageOmath imageFmath image clusters 1 found in the title compound. (Atoms designated with the indices “i” and “a” are located at octahedral edges and vertices, respectively.) K4A12Nb11O20.2F0.8 is prepared by pressing KF, A12O3, NbO, and NbO2 (3:1:2:8) into a tablet and then tempering it under argon for 23 days at 880°C.

    7. An Electron-Rich [4]Radialene (pages 1663–1665)

      Dipl.-Chem. Antonio Fronda and Prof. Dr. Gerhard Maas

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916631

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      A new type of bis(diazo) compound, a stable, electron-rich [4] radialene, and an unusual pentacyclic polyketal are the fruits of this investigation. Catalytic decomposition of silane 1 produces the tricyclic compound 2, whose four-membered ring is folded at an angle of 35.0°. Acid hydrolysis of 2 gives the tetra(oxahomo)cubane 3.

    8. Pd Clusters Containing As and PPh3 Ligands: The Structures of [Pd9As6 (PPh3)8], [Pd2(As2)(PPh3)4], and [Pd20As12 (PPh3)12] (pages 1665–1667)

      Prof. Dr. Dieter Fenske, Dipl.-Chem. Holm Fleischer and Dipl.-Chem. Claudia Persau

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916651

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      A Pd20 polyhedron all of whose surfaces are bridged by μ5-As atoms is one distinctive feature of 1, the title compound with the highest Pd content. Compound 1 was obtained upon treatment of [PdCl2(PPh3)2] with As(SiMe3)3. Other products of the reaction were the Pd2 and Pd9 complexes mentioned in the title as well, whereby the Pd9 complex also results from the reaction of [Pd3S2Cl2(PPh3)4] with As(SiMe3)3.

    9. Si-Promoted Norbornyl–Norpinyl Rearrangements (pages 1667–1669)

      Prof. Dr. Wolfgang Kirmse and Dr. Frank Söllenböhmer

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916671

      Thumbnail image of graphical abstract

      Skeletal rearrangement in the direction of increased ring strain is facilitated by the β-Si effect. Thus, an endo-6-trimethylsilyl group causes solvolysis of endo-2 norbornyl brosylate 1 to be shifted in an unusual way: toward migration of C-7, so that the principal products are bicyclo[3.1.1] heptenes (norpinenes) 2 (R [DOUBLE BOND] H : 86% yield; R [DOUBLE BOND] Me3Si: 95% yield).

    10. A “Spacer”-Modified Trisaccharide as Photolabile Ligand for Affinity Labeling of Antigalactan IgA X24 (pages 1669–1670)

      Prof. Cornelis P. J. Glaudemans, Prof. Dr. Jochen Lehmann and Dipl.-Chem. Markus Scheuring

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916691

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      High affinity for the four-center binding site of a monoclonal antibody is a feature of the spacer-modified trisaccharide 1, in which one monosaccharide residue has been replaced by an appropriately long open-chain link. The connecting link is in turn provided with a reactive functional group. Thanks to its affinitylabeling characteristics, compound 1 is capable of “sounding out” the binding site of the title antibody.

    11. AsImath imageAlClmath image, a Salt of the Last Missing Tetrahaloarsonium Ion (pages 1671–1672)

      Dipl.-Chem. Inis Tornieporth-Oetting and Dr. Thomas Klapötke

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916711

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      The Asmath image ion in the salt 1 displays Td symmetry, as shown unambiguously by the low temperature Raman spectrum of the highly unstable compound. Prepared at −95°C according to reaction (a), compound 1 thus completes the series of tetrahaloarsenic(v) cations

    12. Atropdiastereoselective Ring Opening of Bridged, “Axial-Prostereogenic” Biaryls: Directed Synthesis of (+)-Ancistrocladisine (pages 1672–1673)

      Prof. Dr. Gerhard Bringmann and Dipl.-Chem. Helmut Reuscher

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916721

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      Selective twisting of lactone 1 which has a flat, “axial prostereogenic” biaryl unit to the axial stereogenic ester 2 has been accomplished by a ring-opening reaction involving simple O-nucleophiles. This novel principle was the key to an atropisomer-selective synthesis of the lianene alkaloid ancistrocladisine.

    13. Synthesis and Structure of a 1H-Diphosphirene (pages 1673–1674)

      Prof. Dr. Edgar Niecke, Dipl.-Chem. Rainer Streubel, Dr. Martin Nieger and Dr. Dietmar Stalke

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916731

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      Synthesis of the first 1H-diphosphirene 3 proved straightforward via treatment of the functionalized aminophosphane 1 with the phosphaalkyne 2. X-ray structural analysis of the orange crystals (m.p. −10°C) of 3 clearly suggests the presence of a four-electron, three-center

      bond.

    14. First Isolation of Allenyl Azides (pages 1675–1676)

      Dr. Klaus Banert and Manfred Hagedorn

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916751

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      Until now, allenylazides 2 have been “overlooked”. They form from the propargylazides 1 (e.g., by azide migration), but rapidly react further to give five-membered heterocycles. The intermediates 2 can be isolated by preparative gas chromatography. R [DOUBLE BOND] H, CH2OMe, CH2Cl, CH2OH.

    15. Indications of Cesium in a Higher Oxidation State (pages 1676–1678)

      Dr. Klaus Moock and Prof. Dr. Konrad Seppelt

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916761

      The notion that alkali metals might exhibit oxidation states higher than + I predates concrete evidence for the existence of noble gas compounds with oxidation states up to + VIII, but until now no such species has been positively identified. Cyclovoltammetry and polarography provide evidence for the first time of an electrochemical oxidation of [Cs(Crypt. 2.2.2)]PFmath image, which suggests the presence of higher-valent cesium, specifically CsIII.

    16. Iron-Mediated Diastereoselective Spiroannelation to the Spiro[1,2,3,4-tetrahydroquinoline-4,1′-cyclohexane] System and a Novel Rearrangement to 2,3-Dihydroindole Derivatives (pages 1678–1679)

      Dr. Hans-Joachim Knölker, Dr. Rolaid Boese and Dipl.-Chem. Konrad Hartmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916781

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      Attack anti to the Fe(CO)3 group during spiroannelation (a) causes the aryl ring to be transformed into a cyclohexadiene unit. Demetallation of 1 gives either the free spiroheterocycle or a 2,3-dihydroindole derivative. The spiroheterocyclic framework of 1 is an important component of several natural products.

    17. Double-Stranded Molecules: A [6] Beltene Derivative and the Corresponding Open-Chain Polymer (pages 1680–1682)

      Dipl.-Chem. Adeiheid Godt, Dr. Volker Enkelmann and Dr. Arnulf-Dieter Schlüter

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916801

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      Simple heating of a dime/dienophile precursor can provide either gram-quantities of the [6] beltene derivative 1 or a ribbon-like polymer. Compound 1 is stereochemically uniform, and in the crystalline state it takes the form of flattened, double-stranded rings. The morphology of the ribbon polymer (with a polymerization degree of 24–330!) resembles a “two-dimensional coil.” R [DOUBLE BOND] [BOND](CH2)6[BOND].

    18. TlSPh and TIStBu, Thallium(I) Thiolates with Novel Cagelike Structural Units: [Tl5(SPh)6][Tl7(SPh)6] and [Tl8(StBu)8] (pages 1682–1683)

      Prof. Dr. Bernt Krebs and Dipl.-Chem. Andreas Brömmelhaus

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916821

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      40 years after the first syntheses of thallium(I) thiolates it has finally become possible to isolate crystalline material and to characterize it structurally. Direct reaction of Tl2CO3 with NaSPh and NaStBu in weakly polar solvents gives the corresponding yellow and yellow-orange crystalline thallium(I) thiolates. The polymeric T1SPh consists of [Tl5(SPh)6]1 and [Tl7(SPh)6] cages.

    19. Tetrakis(dimethylamino)ethylene Dication: Two CC Singly Bonded and Almost Perpendicularly Twisted ((H3C)2N)2C Carbenium Ions (pages 1684–1685)

      Prof. Dr. Hans Bock, Dipl.-Chem. Klaus Ruppert, Dr. Kurt Merzweiler, Prof. Dr. Dieter Fenske and Dr. Helmut Goesmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916841

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      Coulomb repulsion between the delocalized positive charges in the two halves of the molecule 12⊕ results in a lengthening of the central C[BOND]C bond compared to that in 1 (152 vs. 136 pm), twisting of the two CN2 planes by up to 76° (for the dichloride), and a charging of the “alkyl shells.” Results of MNDO calculations and X-ray structure analyses are in good agreement with each other. X[DOUBLE BOND]Cl, Br.

    20. Tetraphenylethylenedisodium: The Band Structure of the CC Singly Bonded, Twisted (C6H5)2C Carbanions (pages 1685–1688)

      Prof. Dr. Hans Bock, Dipl.-Chem. Klaus Ruppert and Prof. Dr. Dieter Fenske

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916851

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      “The preparative exploration of ever more shallow potential troughs” is facilitating the synthesis of supramolecular complexes with increasing “storybook” character. Reduction of Ph2C [DOUBLE BOND] CPh2 under argon using a sodium mirror and diethyl ether results in green crystals with metallic luster and a novel band structure. A single C2Ph4 segment is shown on the right, the view being one that clearly reveals the rotation of one half of the molecule relative to the other.

    21. TII-TII Interactions in the Molecular State—an MO Analysis (pages 1688–1690)

      Dr. Christoph Janiak and Prof. Roald Hoffmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916881

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      Theoretical considerations indicate TlI-TlI bonding with a Tl-Tl distance of 363 pm, as observed in 1. Calculations on H[BOND]Tl … Tl[BOND]H show that the ligand-metal metal-ligand angle is the determining factor with respect to s-p hybridization, and thus for the extent of bonding in this subshell, which is formally closed through an s2-s2 interaction. The trans disposition found in 1 end H[BOND]Tl…Tl[BOND]H is related to the bending in simple molecules such as NH3 and H2O, as well as in R2SnSnR2 systems.

    22. Inter- and Intramolecular Photochemical C[BOND]H Activation in Matrices and in Solution with (η6-Arene)(carbonyl)osmium Complexes (pages 1690–1692)

      Andrew McCamley, Dr. Robin N. Perutz, Dipl.-Chem. Stefan Stahl and Prof. Dr. Helmut Werner

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916901

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      Oxidative addition of CH4—i.e., intermolecular C-H activation—as well as intrramolecular C-H activation have been achieved photochemically with arene(carbonyl)osmium complexes. Compounds 1 and 2 lead to 3 through elimination of CO or H2 in a CH4 matrix, while 4 isomerizes in a matrix as well as in toluene solution to give 5; R[DOUBLE BOND]Me.

    23. Encapsulation of Polypyrrole Chains in Zeolite Channels (pages 1692–1694)

      Prof. Dr. Thomas Bein and Patricia Enzel

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916921

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      Isolated “molecular wires” are produced in the channels of zeolites by polymerizing pyrrole with embedded FeIII or CuII ions, according to spectroscopic, stoichiometric, and kinetic investigations. The doped zeolites (zeolite Y and mordenite) display no “bulk” conductivity, but they should be useful for studying the properties of isolated polypyrrole chains.

    24. Monohapto versus Dihapto CO2 Coordination in Bis(amine)Ni0 Complexes: A CAS-SCF Study (pages 1694–1695)

      Dr. Alain Dedieu and Florent Ingold

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916941

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      ηI-O-coordinated CO2 is thought to characterize the intermediate in Ni0-catalyzed coupling of CO2 with unsaturated compounds such as ethylene. This is the conclusion derived from a sophisticated ab initio calculation on [Ni(NH3)2(CO2)], on the basis of which the η1-O structure A is only 1.3 kcal mol−1 higher in energy than the ground state structure B despite considerable diradical character.

    25. Phosphaalkenes from Monochlorophosphanes and Alkylidenetriphenylphosphoranes (pages 1695–1697)

      Prof. Dr. Gottfried Märkl and Dipl.-Chem. Walter Bauer

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916951

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      Mono- and disubstituted, nonstabilized methylenetriphenylphosphoranes 1 can be converted by transylidation with the monochlorophosphane 2 into the kinetically more stable phosphaalkenes 4. Probable intermediates in every case are the betaines 3. Aryl [DOUBLE BOND] 2,4,6-tri-tert-butylphenyl.

    26. Anion Coordination and Cl[BOND]H…Cl Bridges in the Low-melting Poly(Hydrogen Chloride) Me3N · 5HCl (pages 1697–1698)

      Prof. Dr. Dietrich Mootz and Dr. Jörg Hocken

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916971

      Thumbnail image of graphical abstract

      [Me3NH] and [Cl(HCl)4] ions are characteristic of the structure of the poly(hydrogen chloride) Me3N 5 HCI, which melts at −54°C. Moreover, the cation and complex anion form an ion pair (structure shown on the right) involving an N[BOND]H … Cl bridge, resulting in distorted trigonal-bipyramidal coordination for the Cl ion.

    27. A Chiral AgI-Coordination Polymer with a Polydentate Chiral Ligand; Crystal Structure of the 1:1 Complex of CF3SO3Ag and N-[N-(5-Methylthenylidene)-L-methionyl]histamine (pages 1698–1700)

      Johan F. Modder, Prof. Dr. Gerard van Koten, Prof. Dr. Kees Vrieze and Dr. Anthony L. Spek

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198916981

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      A clearer understanding of the structure of the Cu[BOND]N2S2 chromophores from blue copper proteins may emerge from the complex obtained by reaction of CF3SO3Ag with a chiral, potential N,N′S,S′ donor system. Instead of the expected mononuclear complex, the product proved to be a coordination polymer in which each ligand molecule is bound to three Ag atoms (as in the fragment illustrated on the right). The twist in this coordination polymer, which forms a single stereoisomer containing a Δ-helix, apparently is due to only one stereogenic center in the ligand.

    28. Generation, Stereochemistry, and Molecular Dynamics of a 1,3-Bis(phosphonio)propenide Cation (pages 1700–1701)

      Prof. Dr. Hubert Schmidbaur, Dipl.-Chem. Christos Paschalidis, Dipl.-Chem. Oliver Steigelmann and Dr. habil. Gerhard Müller

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917001

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      A useful model for the free allyl anion is the methyldiphosphoniopropenide 3, which is readily prepared from the diphosphinoethene 1 via the dication 2. According to NMR and X-ray structural analyses, 3 has the E/Z configuration. Temperature-dependent NMR studies indicate a rotational barrier of 20.5 kcal mol−1 for the allyl anion fragment.

    29. LiCaN and Li4SrN2, Derivatives of the Fluorite and Lithium Nitride Structures (pages 1702–1703)

      Dr. Gerhard Cordier, Dipl.-Chem. Axel Gudat, Prof. Dr. Rüdiger Kniep and Prof. Dr. Albrecht Rabenau

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917021

      Thumbnail image of graphical abstract

      The list of known ternary nitrides of lithium has been extended by two through the investigation of LiCaN and Li4SrN2. In the case of LiCaN, infinitely long math image[LiN3/3] bands are joined through common nitrogen atoms with CaN4 tetrahedra to give a structural unit that can be derived directly from the fluorite structure: “Li[4]Ca[4]N[8][RIGHTWARDS ARROW] Li[3]Ca[4]N[1] (see illustration).

    30. Chirality and Isomerism in Binuclear Iron Complexes with Sulfur Ligands: [Fe(CO)(μ-“S4”)]2, a Model Complex for Oxidoreductases (pages 1703–1705)

      Prof. Dr. Dieter Sellmann, Dipl.-Chem. Robert Weiss and Dr. Falk Knoch

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917031

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      Metal atoms at the active centers of oxidoreductases must be chirotopic. In the course of a search for model complexes for nitrogenases and hydrogenases, a new type of chiral complex was discovered, represented by the complex 1. It was obtained by coupling two homochiral [Fe(CO)(“S4”)] fragments, and it contains Fe centers that are capable of binding σ-π ligands. This complex may thus be regarded as one segment of a metalloprotein structure. (“S4”)2⊖ = 2,2′-(ethylenedithio)dibenzene thiolate.

    31. Directed Synthesis of Trinuclear Hydrocarbon-Bridged Complexes such as [(OC)5ReCH2CH2Os(CO)4CH2CH2Re(CO)5] (pages 1705–1706)

      Prof. Dr. Wolfgang Beck, Dipl.-Chem. Burkhard Niemer and Dipl.-Chem. Barbara Wagner

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917051

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      Nucleophilic addition of carbonyl metallates to coordinated, unsaturated hydrocarbons in cationic complexes can be used for the directed synthesis of various hydrocarbon-bridged complexes. Application of this established principle to [Os(CO)4]2⊖ has now permitted the synthesis of OsRe2, OSMn2, and OsMo2 complexes such as 1 and 2. Trinuclear complexes of this type are of interest as precursors to heterogeneous bimetallic catalysts.

    32. Stereoselective Synthesis of γ-Aminocarboxylates (pages 1706–1709)

      Prof. Dr. Manfred T. Reetz and Dipl.-Chem. Dirk Röhrig

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917061

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      1,3-Allyl strain may explain the high diastereoselectivity observed in the conversion of optically active α-amino acids 1 into the homochiral γ-amino acid esters 3. The esters 2, accessible via the α-N,N dibenzylaminoaldehydes, are intermediates in this synthesis, and subsequent cuprate addition leads stereoselectively to the products 3.

    33. Oxoiron Porphyrin Species with High-Valent Iron: Formation by Solvent-Dependent Protonation of a Peroxoiron(III) Porphyrinate Derivative (pages 1709–1711)

      Dr. Dominique Mandon, Prof. Dr. Raymond Weiss, Dipl.-Phys. Michaela Franke, Dr. Eckard Bill and Prof. Dr. Alfred X. Trautwein

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917091

      Thumbnail image of graphical abstract

      Activation of O2 by cytochrome P-450 monooxygenase is generally thought to proceed by way of a peroxoiron(III) porphyrinate species that is then transformed into an oxoiron(IV) porphyrinate radical cation. Such a radical cation, the “picket fence” model compound 1, has now been isolated for the first time from the peroxoiron(III) species by treatment with HBF4 · Et2O.

    34. Bicycloprop-2-enyl (C6H6) (pages 1711–1712)

      Prof. Dr. Wilbur E. Billups and Michael M. Haley

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917111

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      The only valence isomer of benzene not previously prepared has now been synthesized by reaction in vacuo of the β-halosilane 1 with tetra-n-butylammonium fluoride. The elusive bicycloprop-2-enyl 2 was characterized by NMR spectroscopy. 2 can also be trapped as a Diels-Alder adduct. In the presence of Ag it rearranges to Dewar benzene.

    35. [4 + 2]-Cycloadditions with 1,4-Bis(N,N-dimethylamino)-1,3-dienes: Stereochemical Studies and Observation of Radical Ions (pages 1713–1715)

      Prof. Dr. Refiner Sustmann, Dr. Karin Lücking, Dr. Gebhard Kopp and Dipl.-Chem. Michael Rese

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917131

      Thumbnail image of graphical abstract

      Electron transfer as a mechanistic alternative in [4 + 2] cycloadditions has been examined in the case of the electron-rich dienes 13 reacting with a series of dienophiles of increasing acceptor strength. ESR spectroscopy permits the phenomenon actually to be observed with dienophiles having reduction potentials ≥ −0.5 V (vs. SCE; oxidation potential of the dienes ca. −0.3 V). In the absence of electron transfer, reaction of 1 or 2 with E,Z-isomeric dienophiles is stereospecific; otherwise it is a multistep process, and thus not stereospecific.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Book Review: The Technical Writer's Handbook. By Matt Young (page 1717)

      David I. Loewus

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917171

  4. Editorial Essay

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. The Nature of Materials Science Publishing (page 1721)

      Dr. Peter Gregory

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917211

      Editorial Essay: The best way to present results, opinion, news and information to the widest possible audience is the subject under discussion. As, in this issue, Advanced Materials and Angewandte Chemie appear together for the last time, it is appropriate to comment on the approaches taken by leading journals both in materials science and in other areas.

  5. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Structural Characterization of Non-Oxide Chalcogenide Glasses using Solid State NMR (pages 1723–1732)

      Prof. Hellmut Eckert

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917231

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      Review: Non-oxide chalcogenide glasses have wide ranging applications in infrared optics and semiconductor technology. Quantitative solid state NMR techniques have recently offered unique insights into the structural organization of these systems (see figure). The principles governing glass formation in these systems and the NMR techniques used to investigate them are described.

    2. Polysilanes—A New Look at Some Old Materials (pages 1733–1740)

      Dr. Robert D. Miller

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917331

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      Review: Polysilanes are radiation sensitive polymers with unusual electronic properties and thermochromic behavior. Renewed interest in these materials has stemmed from their applications as ceramic precursors, in microlithography (see figure) and in nonlinear optics etc. These new applications are reviewed, the historical background traced and future trends assessed.

  6. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. 15N CPMAS NMR Study of the Structure of Polyaniline (pages 1741–1743)

      Dr. Bernd Wehrle, Prof. Hans-Heinrich Limbach, Dr. John Mortensen and Prof. Jürgen Heinze

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917411

      Communication: The structure and properties of polyaniline are investigated using 15N cross polarization magic angle spinning (CPMAS) solid state NMR spectroscopy. The high resolution spectra obtained demonstrate the potential of the method for studying the structures of other nitrogen containing heterocyclic polymers.

    2. 15N CPMAS NMR Study of the Structure and Reactions of Phthalocyaninatopolysiloxane and its Precursors in the Solid State (pages 1743–1745)

      Dr. Bernd Wehrle, Prof. Hans-Heinrich Limbach, Dr. Tilman Zipplies and Prof. Michael Hanack

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917431

      Thumbnail image of graphical abstract

      Communication: The high conductivities of the iodine-doped title compound (see figure) and its germanium analogue have attracted considerable interest. Structural analysis by X-ray crystallography has not been possible, and solid state 13C NMR has yielded complex spectra which are often difficult to assign. 15N CPMAS NMR spectroscopy of 15N enriched samples provides a powerful tool for the study of the structure and reactivity of these species.

    3. A New Route to Highly Conducting Polyenes (pages 1745–1746)

      Prof. Henning Hopf, Cand.-Chem. Olaf Kretschmer and Dr. Herbert Naarmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917451

      Communication: Polymeric films synthesized by the simple heat treatment of allene (propadiene) and several terminal alkynes exhibit a 109 fold increase in electrical conductivity when doped with iodine. The new synthetic method obviates the need for catalysts and the washing process needed to remove impurities from the polymer.

  7. Research News

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Glass-Ceramics in the Scheme of Inorganic Materials (pages 1746–1749)

      Graham Partridge

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917461

      Research News: Inorganic Materials I. Glasses, ceramics, and glass-ceramics are examined in the first article of a regular series by Graham Partridge of GEC ALSTHOM. Their definitions, and their mechanical, electrical and thermal properties are summarized and the scene set for future articles.

  8. Conference Report

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Powder Metallurgy (PM'89)in San Diego (pages 1750–1753)

      Rainhard Laag

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917501

      Conference Reports:Rainhard Laag reports on the Powder Metallurgy '89 meeting, Hugh Byrne gives us a taste of macromolecular physics in Poland and Peter Bachmann describes a recent meeting on surface modification technology held in Switzerland.

    2. Macromolecular Physics in Lodz (pages 1753–1755)

      Prof. Hugh J. Byrne

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917531

      Conference Reports:Rainhard Laag reports on the Powder Metallurgy '89 meeting, Hugh Byrne gives us a taste of macromolecular physics in Poland and Peter Bachmann describes a recent meeting on surface modification technology held in Switzerland.

    3. Surface Modification Technology in Neuchâtel (pages 1755–1757)

      Dr. Peter K. Bachmann

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917551

      Conference Reports:Rainhard Laag reports on the Powder Metallurgy '89 meeting, Hugh Byrne gives us a taste of macromolecular physics in Poland and Peter Bachmann describes a recent meeting on surface modification technology held in Switzerland.

  9. Corrigenda

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. You have free access to this content
      Erratum (page 1757)

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917571

  10. Materials Forum

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Materials Forum (pages 1758–1759)

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917581

  11. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
  12. Conference Calendar

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Conference Calendar (pages 1765–1766)

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917651

  13. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
  14. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Editorial Essay
    6. Reviews
    7. Communications
    8. Research News
    9. Conference Report
    10. Corrigenda
    11. Materials Forum
    12. Book Reviews
    13. Conference Calendar
    14. Author Index
    15. Subject Index
    1. Subject Index (pages 1775–1793)

      Version of Record online: 30 DEC 2003 | DOI: 10.1002/anie.198917751

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