Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 5

May 1985

Volume 24, Issue 5

Pages 357–438

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503571

      Thumbnail image of graphical abstract

      The title page shows the layer sequence ([001]) of the new intercalation compound (Te2)2(I2): tellurium double layers alternate with planar iodine layers. The perspective drawing gives an idea of the spatial structure of the compound, which was obtained by hydrothermal synthesis from GeTe, Te, and HI. A tellurium modification with a double layer structure was previously unknown. Further details on the preparation, structure, and properties of (Te)2(I2) are reported by R. Kniep et al. on page 393.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 5/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503572

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Radwaste Immobilization by Structural Modification—the Crystallochemical Properties of SYNROC, a Titanate Ceramic (pages 357–365)

      Dr. Timothy J. White, Robert L. Segall and Peter S. Turner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503573

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      For the final storage of radioactive material, a variety of suggestions have been discussed and in part realized. According to the synroc (synthetic rock) concept, a “sodium titanate—sodium zirconate” is combined with (simulated) waste and, after cation exchange, reductively calcined. The crystalline material so obtained is characterized, among other things, by hydrothermal stability.

    2. The Glycine Receptor of Rat Spinal Cord: Exploring the Site of Action of the Plant Alkaloid Strychnine (pages 365–370)

      Prof. Dr. Heinrich Betz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503651

      The transmission of nerve impulses in nerve cell membranes requires the binding of glycine to specific receptors. The glycine receptor from rat spinal cord has been characterized with the help of strychnine, which is able to reversibly block these receptors. The receptor is a large membrane protein consisting of three different subunits.

    3. The 3′-End of tRNA and Its Role in Protein Biosynthesis (pages 371–391)

      Prof. Dr. Stanislav Chládek and Prof. Dr. Mathias Sprinzl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503711

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      The formation of a peptide bond between the 3′-ends of aminoacyl-tRNA and peptidyl-tRNA is catalyzed—according to a new model—by a special region of the 23S RNA. Two strands of the 23S RNA, which are brought into close proximity by folding, are involved both in the binding of the two tRNAs and in the catalysis.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Reactivity of the [Fe22-O)(μ-acetato)2] Unit in Methemerythrin Model Compounds towards Nmath image and NCS (pages 392–393)

      Prof. Dr. Karl Wieghardt, Dipl.-Chem. Klaus Pohl and Dipl.-Chem. D. Ventur

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503921

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      The enzyme deoxyhemerythrin reacts in a completely different manner with Nmath image and NCS than the methemerythrin model compounds containing the partial structure 1, L = N,N′,N″-trimethyl-1,4,7-triazacyclononane. The [Fe22-O)(μ-carboxylato)2] group of the enzyme remains intact, whereas in the model compound the carboxylato bridges and the oxo bridges are replaced.

    2. (Te2)2(I2)—An Unusual Intercalation Compound (pages 393–394)

      Prof. Dr. Rüdiger Kniep and Heinz-Jürgen Beister

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503931

      Tellurium double layers, between which planar layers of iodine molecules are inserted, characterize the new intercalation compound (Te2)2(I2); it contains a tellurium modification that was previously unknown as an independent phase, which is intercalated by elemental iodine. Crystals were obtained by hydrothermal synthesis in concentrated hydrogen iodide.

    3. [Cp2Ti(PMe3)2]—A Versatile Source of Titanocene Derivatives (pages 394–401)

      Lawrence B. Kool, Prof. Dr. Marvin D. Rausch, Priv.-Doz. Dr. Helmut G. Alt, Prof. Dr. Max Herberhold, Prof. Dr. Ulf Thewalt and Brigitte Wolf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198503941

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      The title compound 1 can be viewed as trimethylphosphane-substituted titanocene. 1 provides a readily accessible and simple source of titanocene in solution; the PMe3 ligands can be replaced by a variety of substrates under mild conditions.

    4. Synthesis of [(η5-C5H5)2Mo(η2-CH2O)]: A Formaldehyde Complex of Molybdenum (page 402)

      Prof. Dr. Gerhard E. Herberich and Dr. Jun Okuda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504021

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      Molybdenocenedihydride 1 can react with paraformaldehyde with practically no side reactions to give the formaldehyde complex 2 and methanol. Formaldehyde organometallic complexes are of interest as model substances for intermediates in the homogeneous reduction of CO.

    5. Synthesis, Dynamic Behavior, and Structure of [Sn{C(PMe2)3}2]—a Homoleptic Tetraphosphanetin(II) Complex with Pseudo Trigonal Bipyramidal Structure (pages 402–404)

      Priv.-Doz. Dr. Hans Heinz Karsch, Dipl.-Chem. Armin Appelt and Dr. Gerhard Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504022

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      The first main-group complex of the tris(dimethylphosphino)methanide ion in which the coordination of the ligands occurs exclusively via the P atoms, compound 1, has been prepared. The two carbanion centers of the ligands are exactly planar coordinated.

    6. On the Aggregation of Lithiated Bicyclobutane Derivatives in Solution (pages 404–405)

      Dr. Arnulf-Dieter Schlüter, Helmut Huber and Prof. Dr. Günter Szeimies

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504041

      Thumbnail image of graphical abstract

      The “1,2-dianion” 1 could be identified by reaction with Me3SiCl and D2O. 1 was shown by 1H- and 13C-NMR spectroscopy to aggregate in solution into a polymeric network—in contrast to the behavior of dimeric monolithiobicyclobutanes.

    7. Chain-Lengthening Difunctionalization of Grignard Compounds by Reaction with Ketenylidenetriphenylphosphorane (pages 405–406)

      Prof. Dr. Hans Jürgen Bestmann, Dipl.-Chem. Martin Schmidt and Dipl.-Chem. Rainer Schobert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504051

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      The α,β-unsaturated ketones of type 4, which are of interest in pheromone chemistry, were prepared, via 3, from the title compounds 1 and 2. The acylyides 3 can be transformed in a variety of ways.

    8. Synthesis and Structure of trans-[MCl([DOUBLE BOND]C[DOUBLE BOND]CHR)(PiPr3)2] (M[DOUBLE BOND]Rh, Ir): The First Square-Planar Vinylidenemetal Complexes (pages 406–408)

      Dr. Francisco Javier García Alonso, Dipl.-Chem. Arthur Höhn, Dipl.-Chem. Justin Wolf, Dipl.-Chem. Heiko Otto and Prof. Dr. Helmut Werner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504061

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      The two-step mechanism for the transformation of an alkyne complex 1 into a vinylidene complex 3 could be confirmed by the isolation of the intermediate 2a having pentacoordinated iridium. The complexes 3 and their Rh analogues are the first square-planar vinylidenemetal complexes (a, R = Ph; b, R = Me; c, R = H, R′ = iPr).

    9. Sequencing of Short Peptides Using FAB Mass Spectrometry—Increased Information via Derivatization (pages 408–409)

      Dipl.-Chem. Dieter Renner and Prof. Dr. Gerhard Spiteller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504081

      Structure-specific cleavage fragments, all of which contain the amino end of the molecule and which were formed by cleavage of the peptide bond, are obtained by fast atom bombardment (FAB) mass spectrometry of N-dansyl substituted small peptides. This derivatization thus allows an unequivocal determination of the amino acid sequence.

      • equation image
    10. Complexes of 1,5-Di(p-tolyl)-1,4-pentaazadien-3-ide, Crystal Structures of [Cu(tolylNNNNNtolyl)]3 and [Ni(tolylNNNNNtolyl)2]2 (pages 409–410)

      Dipl.-Chem. Johannes Beck and Prof. Dr. Joachim Strähle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504091

      Three linearly arranged Cu ions, coordinated by three parallel N5 zig-zag chains in such a way that each metal ion is surrounded by a trigonal planar array of N atoms, are present in the pentaazadienide complex 1. The red crystals of 1 exhibit weak paramagnetism; the Cu[BOND]Cu distances in the chains are the shortest observed so far in copper(I) complexes.

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    11. (Z)-3,7-Bis(phenylsulfonyl)pentacyclo[5.1.0.02,4.03,5.06,8]octane, an Octabisvalene Derivative (pages 411–412)

      Dr. Christoph Rücker and Prof. Dr. Horst Prinzbach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504111

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      Octabisvalene, (CH)8, which still unknown, is the third saturated and highly strained valence isomer of cyclooctatetrane. The first crystalline derivative 1, X = SO2C6H5, has been synthesized from cis-benzenetrioxide. 1 is stable up to ca. 200°C.

    12. Photochemically Initiated, Electron-Transfer-Catalyzed Diels-Alder Reactions of Electron-Rich Dienophiles (pages 412–414)

      Dr. Jiri Mlcoch and Prof. Dr. Eberhard Steckhan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504121

      Photochemically excited triphenylpyrylium tetrafluoroborate catalyzes Diels-Alder reactions that proceed via an electron-transfer chain mechanism. By means of a “redox umploung”, an electron-rich alkene (En) is transformed into the radical cation, which functions as an appropriate electron-poor dienophile (Sens = triphenylpyrylium).

      • equation image
    13. [{1,3,5-(CH3)3H3C6}6Tl4][GaBr4]4 — Synthesis and Structure of a Mixed Mono- and Bis(arene)thallium Complex (pages 414–415)

      Prof. Dr. Hubert Schmidbaur, Dipl.-Chem. Wolfgang Bublak, Jürgen Riede and Dr. Gerhard Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504141

      A tetrameric Tl4[GaBr4]4 skeletal framework, whose Tl ions are alternately coordinated by one or two mesitylene molecules, is present in the title compound. It is formed from Tl[GaBr4] and mesitylene and is the first complex containing both mono- and bis(arene)thallium units to be characterized by X-ray analysis.

    14. A Novel Type of Cyclotriphosphane Complex: Synthesis and Structure of [Ni2(μ-P3iPr3)2(CO)4] (pages 415–416)

      Prof. Dr. Marianne Baudler, Dr. Franz Salzer, Dr. Josef Hahn and Dr. Eberhard Därr

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504151

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      A P6Ni2 tricyclic framework is present in the novel complex 1 in which, for the first time, P3 rings are joined as four-electron ligands to carbonylmetal fragments to form a P4M2 ring. In addition to 1, the “anti” isomer can also be isolated on reaction of (PiPr)3 and Ni(CO)4.

    15. 9-Fluorenylidene-2,2,6,6-tetramethylpiperidinoborane: an Allene Isoester with Two-Coordinated Boron and B[DOUBLE BOND]C Double Bond (pages 416–417)

      Dipl.-Chem. Bernhard Glaser and Prof. Dr. Heinrich Nöth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504161

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      In the 1-aza-2-boraallene 1, the bulky substitutents are responsible for the kinetic stability of the N[DOUBLE BOND]B[DOUBLE BOND]C system. Structural proof is provided by, among other things, its reaction with azides to give azaboriranes.

    16. Cyanogen as a Bridging Ligand—Preparation and Crystal Structure of Polymeric [Ag{(CN)2}2]n[AsF6]n with an Undulating Square Cationic Network (pages 417–418)

      Prof. Dr. Herbert W. Roesky, Dr. Hartmut Hofmann, Jürgen Schimkowiak, Dr. Peter G. Jones, Karen Meyer-Bäse and Prof. George M. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504171

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      Of interest for metal-catalyzed reactions of cyanogen is the structure of complexes containing this pseudohalogen. In the cation 1, the title compound is present in a polymeric network in which each silver atom is surrounded by a square-planar array of nitrogen atoms.

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    17. Gas-Phase Reactions of Organic Compounds on Raney Nickel (pages 418–419)

      Prof. Dr. Hans Bock and Dipl.-Chem. Hans Peter Wolf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504181

      The comparison of catalyzed and uncatalyzed thermal gas-phase reactions of model organic compounds showed that reactions in the presence of Raney nickel proceed at appreciably lower temperature with remarkable selectivity. For example, 2-propanol is dehydrogenated to acetone on quartz wool only at 970 K, whereas on Raney nickel it is fifty percent converted already at room temperature and 10−2 mbar.

    18. The First Arsirane (pages 419–420)

      Prof. Dr. Rolf Appel, Thomas Gaitzsch and Dr. Falk Knoch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504191

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      The instability of the arsorane 3, X = As, R = Ph, was exploited to prepare the first arsacyclopropane 4. The colorless crystals of 4 form from 3 within 12 h at room temperature. 3 was obtained from the arsane 1 and the lithium methanide 2.

    19. Tricarbonyl(1,3-diphosphaallyl)cobalt, a Phosphorus Analogue of (η3-Allyl)tricarbonylcobalt (pages 420–421)

      Prof. Dr. Rolf Appel, Winfried Schuhn and Dr. Falk Knoch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504201

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      The first η31,3-diphosphaallyl complex 3 could be obtained from the methylenephosphane 1 and sodium tetracarbonylcobaltate 2. In 3, whose structure has been elucidated by an X-ray structure analysis, the PC distances are identical and lie between those of a PC single and a PC double bond (R = 2,4,6-tri-tert-butylphenyl).

    20. Laser Photolysis of the Bisazoalkane 7-syn,7′-anti-Bis-2,3-diazabicyclo[2.2.1]hept-2-ene (pages 421–422)

      Prof. Dr. Waldemar Adam, Dr. Klaus Hannemann, Eva-Maria Peters, Dr. Karl Peters, Prof. Dr. Hans Georg von Schnering and Prof. Dr. R. Marshall Wilson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504211

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      The tetraradical 1 is not an intermediate in the photolysis of the title compound 2. On the contrary, successive elimination of N2 takes place to give four isomeric monoazoalkanes and three bi-5,5′-bicyclo[2.1.0]pentanes.

    21. Synthesis, Structure, and Reactivity of η3-1-Azaallylmolybdenum Complexes (pages 422–424)

      Dr. Michael Green, Richard J. Mercer, Dr. Carolyn E. Morton and Dr. A. Guy Orpen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504221

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      Azirines and [Mo2(CO)4(η-C5H5)2] are the starting materials for the title compounds 1. These compounds can be alkylated on nitrogen, and a novel 1,3 hydrogen shift provides a route to azavinylidene complexes.

    22. Cluster Expansion with Cp(CO)Rh Fragments (pages 424–425)

      Dipl.-Chem. Darjusch Mani and Prof. Dr. Heinrich Vahrenkamp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504241

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      A ligand containing a RuP triple bond is one way to view the central PhPRu(CO)3 molecular portion of the tetranuclear cluster 1. As in alkynes, this group can bridge the Co2(CO)6 unit and function as a ligand that is bound side-on with respect to the Cp(CO)Rh unit.

    23. Photosignal II as an Indicator for Damage to Forests - EPR Spectroscopic Investigation of Spruce Needles (pages 425–426)

      Prof. Dr. Hartmut B. Stegmann, Dipl.-Ing. (F. H.) Hans J. Ruff and Prof. Dr. Klaus Scheffler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504251

      Following the exposure of spruce needles to SO2 and NOx, it is possible to detect changes in the electron transport chain of the photosynthetic apparatus by EPR spectroscopy and to clearly distinguish between the needles of healthy and of damaged trees.

    24. Synthesis of a Novel Stable Carbanion: 1,1,2-Tricyano-2-(3,4-dicyano-5-imino-2,5-dihydro-1H-pyrrol-2-ylidene)ethanide by Reduction of Tetracyanoethylene with Tris(2,2′-bipyridine)titanium (pages 426–427)

      Dr. Giulia Dessy, Dr. Vincenzo Fares, Dr. Alberto Flamini and Dr. Anna Maria Giuliani

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504261

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      The mechanism of reduction of tetracyanoethylene (TCNE) to the anionic dihydropyrrole derivative 1 with tris(2,2′-bipyridine)titanium has been elucidated. 1 is formed via condensation of two TCNE molecules. The X-ray structure analysis was carried out on a Ph4As salt of 1. ◯ = N, • = C.

    25. Transformation of [{(CO)5W}3Sn] into [{(CO)5W}3Te2], a Compound Containing Unusually Bonded Ditellurium (page 428)

      Dipl.-Chem. Olaf Scheidsteger, Prof. Dr. Gottfried Huttner, Prof. Dr. Kurt Dehnicke and Dr. Jürgen Pebler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504281

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      Compound 1 can be viewed as a stannanediyl complex according to Mössbauer investigations. It is converted with H2Te into 2, in which a Te[DOUBLE BOND]Te unit is stabilized by side-on and end-on coordination to W(CO)5 groups.

    26. Walk Rearrangement in the 1,2,3,4-Tetra-tert-butylhydroxycyclobutenylium Ion (pages 429–430)

      Prof. Dr. Günther Maier, Dipl.-Chem. Rolf Emrich and Dr. Hans-Otto Kalinowski

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504291

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      Contrary to the predictions of the Woodward-Hoffmann rules, the walk rearrangement (1) proceeds with inversion at the migrating C atom. The cause is an unusually strongly pronounced secondary orbital interaction.

    27. d6-Metal Complexes of 4,4′-Bipyrimidine, an Ambident Ligand with High π-Acceptor Ability (pages 430–431)

      Dipl.-Chem. Sylvia Ernst and Priv.-Doz. Dr. Wolfgang Kaim

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504301

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      The highest π-acidity of all bidiazines, which have the possibility of forming α-diimine chelates (14), is not exhibited by 2,2′-bipyrazine 3 but rather by the 4,4′-bipyrimidine 2, which has not been used up to now in complex chemistry. This result was obtained from a theoretical analysis as well as an investigation of the corresponding d6 metal complexes.

    28. Synthesis and Structure of New Potassium-Gold-Tellurium Polyanions: [KAu9Te7]4⊖, [K2Au4Te4(en)4]2⊖, and [K2Au4Te4(dmf)2(CH3OH)2]2⊖ (pages 432–433)

      Dr. Robert C. Haushalter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504321

      By extraction of tertiary K[BOND]Au[BOND]Te alloys, the salts 13, which contain new KAuTe polyanions, could be obtained. The anion of 1 can be roughly described as a derivative of an [M12X8]4⊖ cube; in 2 and 3, planar [Au4Te4]4⊖ rings are present, the sides of which are capped by K.

      • equation image
    29. Synthesis and Structure of New Hg[BOND]Te Polyanions: [Hg4Te12]4⊖, a Cluster Containing Te2⊖, Temath image, and Temath image Ligands and [Hg2Te5]2⊖, a New One-Dimensional Inorganic Polymer (pages 433–435)

      Dr. Robert C. Haushalter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198504331

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      The first polynuclear mercury-tellurium anions [Hg4Temath image] and [Hg2Te5]2⊖ could be obtained by extraction of K[BOND]Hg[BOND]Te alloys with ethylenediamine. The structures are related; an Hg2Te3 ring with two exocyclic Hg-bonded tellurium atoms is contained in both anions. [Hg4Te12]4⊖ is formally a dimer of the repeat unit of the polymeric math image[Hg2Te5]2⊖1 with two additional Te toms per dimer.

  3. Book Reviews

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

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