Angewandte Chemie International Edition in English

Cover image for Vol. 17 Issue 11

November 1978

Volume 17, Issue 11

Pages 785–874

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 11/1978)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197807851

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. High-Resolution, Higher-Order UV/VIS Derivative Spectrophotometry (pages 785–799)

      Univ.-Doz. Dr. Gerhard Talsky, Dipl.-Chem. Lothar Mayring and Hans Kreuzer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197807853

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      The evaluation of UV/VIS spectra is frequently facilitated, and sometimes only becomes possible, on consideration of a higher-order derivative (preferably the 3rd, 4th, or 5th derivative) instead of the original spectrum. With aid of a new analog computer, low-noise on-line derivative spectra can now be obtained up to the 7th (or even 9th) order.

    2. Organometallic Syntheses with Diazoalkanes (pages 800–812)

      Priv.-Doz. Dr. Wolfgang A. Herrmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808001

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      Carbene complexes, π-olefin complexes, ketene complexes, organometallic diazoalkanes, complexes with halocyclopentadienyl ligands, and many other compounds are accessible from diazoalkanes, which thus prove to be versatile reagents.

    3. Electrostatics, the Chemical Bond and Molecular Stability (pages 812–819)

      Prof. Dr. Sidney W. Benson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808121

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      The prediction and calculation of chemical reactions is an aim of theoretical chemistry. Electrostatic models based on the virial theorem hold promise of a method for accurate and reliable prediction of ΔHmath image and dipole moments of molecules and radicals.

    4. Polyethylene Fibrids: Preparation and Properties (pages 820–825)

      Dr. Wolfgang Gordon, Dr. Hans Joachim Leugering and Prof. Dr. Harald Cherdron

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808201

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      Polyethylene fibrids are small, highly oriented fibers formed on shear-induced crystallization of polyethylene. They have interesting properties.

    5. Lise Meitner: Her Life and Times—On the Centenary of the Great Scientist's Birth (pages 826–842)

      Prof. Dr. Fritz Krafft

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808261

      Lise Meitner (1878–1968) paved the way for the chemical identification of one of the first fission products of uranium by O. Hahn and F. Strassmann in her joint work with those authors on the “transuranics” (1934–1938); and together with O. R. Frisch she provided the first theoretical interpretation of this experimental result (Ba instead of the expected Ra). Her lot was determined by the times in which she lived, and stands as a warning to us all. Newly discovered documents throw fresh light on some aspects of her life and work.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Unusual Selectivity in the Thermal Rearrangement-Elimination Reaction of a Carbene Complex in Solution and in the Solid State (pages 842–843)

      Dr. Helmut Fischer, Dipl.-Chem. Andreas Motsch and Dr. Willi Kleine

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808421

      Halocarbene complexes such as (1) are potential intermediates in the synthesis of complexes containing M[TRIPLE BOND]C bonds, thus conferring preparative interest upon the mechanism of the thermolysis of (1). On heating in solution (1) gives the carbyne complex (2); heating of the solid affords the isocyanide complex (3) among other products.

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    2. C6H5Sb[Mn(CO)2C5H5]2—The first Compound Containing Trigonal-Planar Coordinated Antimony(I) (pages 843–844)

      Dipl.-Chem. Joachim von Seyerl and Prof. Dr. Gottfried Huttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808431

      Stabilization of phenylstibanediyl (C6H5Sb) is accomplished by coordination to two groups containing transition metals. X-Ray structure analysis shows the SbI atom to have a trigonal-planar environment in compound (1).

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    3. Facile New Synthesis of Chloroarsinidene Complexes (pages 844–845)

      Dipl.-Chem. Joachim von Seyerl, Ute Moering, Adalbert Wagner, Dr. Albin Frank and Prof. Dr. Gottfried Huttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808441

      An extremely facile entry to functionalized chloroarsinidene complexes such as (1) is provided by the reaction shown below. The expected trigonal-planar coordination of the arsenic was confirmed by X-ray studies.

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    4. A Substitution with Retention at the Cyclopropane Ring (pages 845–846)

      Dipl.-Chem. Jürgen Schäffler and Prof. Dr. János Rétey

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808451

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      Cobalt-substituted cyclopropanes could be of significance in coenzyme B12-catalyzed rearrangements. Interestingly, a cobaloxime generated in situ reacts only with the exo bromide (2) and not with the endo bromide (1) to give product (3). The retention of configuration observed in this reaction is probably due solely to shielding by the dihydrophenanthrene flank.

    5. Stabilization of a Phosphinic Anhydride R2POPR2 on Gold(I) and Formation of the Trinuclear Complex (R2POAu)3—Production of an Octahedral Structural Unit Ag4Brmath image by Clamping with R2PN(R′)PR2 (pages 846–847)

      Prof. Dr. Hubert Schmidbaur, Aref. A. M. Aly and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808461

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      Tetra-tert-butyldiphosphoxane, a new complex ligand, has now been stabilized for the first time in the gold compound (2). Compound (2) was obtained from ClAuCO and tBu2PCl via the complex (1). There is also something new to report about a related “old” ligand: the 1:2 complex of Ph2P[BOND]NMe[BOND]PPh2 with AgBr contains a clamped Ag4Br2 octahedron.

    6. Pentacyclo[6.4.0.02,5.03,10.04,9]dodeca-6,11-diene, an o,o′:o,p′-Dimer of Benzene (pages 847–848)

      Prof. Dr. Hans-Dieter Martin and Dipl.-Chem. Peter Pföhler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808471

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      The benzene dimer (1) having C2 symmetry and two “isolated” double bonds attracts interest on account of its considerable stability and its suitability as a model for the study of intramolecular interactions.

    7. Existence of a New C6H6 Isomer: Tricyclo[3.1.0.02,6]hex-1(6)-ene (pages 848–850)

      Dipl.-Chem. Ursula Szeimies-Seebach, Dr. Joachim Harnisch, Priv.-Doz. Dr. Günter Szeimies, Prof. Dr. Maurice Van Meerssche, Dr. Gabriel Germain and Dr. Jean-Paul Declerq

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808481

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      “Isobenzvalene”(1), a very highly strained molecule, has now been trapped in the form of the Diels-Alder adduct (2) with anthracene. The structure of (2) is also unusual: C-11 and C-16 are both located outside the tetrahedron formed by their four substituents (“inverted tetrahedron”).

    8. A Stable σ/π-Organometallic Radical of Vanadium: (η5-C5Me4Et)2 V[BOND]C[TRIPLE BOND]C[BOND]C6H2Me3 (pages 850–851)

      Doz. Dr. Frank H. Köhler, Dipl.-Chem. Wolfram Prössdorf, Dr. Ulrich Schubert and Dietmar Neugebauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808501

      The stabilization of vanadocene Cp2VR with a σ-bonded ligand proves possible on complete alkylation of the cyclopentadienyl groups. X-Ray structure analysis of the title compound (1) permitted the first determination of the length of the VIII[BOND]Csp bond (203.2 pm). The paramagnetic 1H-NMR spectrum shows that (1) contains two unpaired electrons.

    9. Optically Active Tricyclo[6.4.0.04,9]dodecane (page 851)

      Dipl.-Chem. Hartmuth Buding and Prof. Dr. Hans Musso

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808511

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      Chiral molecules without measurable optical rotation are rare. In the case of the enantiomers (1a) and (1b), which were synthesized as potential new examples, the prediction of negligible optical rotation proved to be false. The rotations of ca. −30 and +27° could be due to the twisted chair form of the rings.

    10. Template Reactions on Chromium(0): Synthesis of a Functionalized Indene from Pentacarbonyl[methoxy-(phenyl)carbene]chromium and Bis(diethylamino)acetylene (pages 851–852)

      Dr. Karl-Heinz Dötz and Dietmar Neugebauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808512

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      The template action of chromium is held responsible for ring closure of (1) to form the complex (2). The reaction fails to occur with the homologous tungsten compound.

    11. PdTeI and Pd2SeI3 - The First Chalcogenide Halides of a Platinum Metal (pages 852–853)

      Prof. Dr. Gerhard Thiele, Dr. Maria Köhler-Degner, Dipl.-Chem. Kurt Wittmann and Dipl.-Chem. Gerd Zoubek

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808521

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      Pd3+Te2−I, one of the extremely rare “true” palladium(III) compounds, forms brass-yellow crystals characterized, inter alia, by their good electrical conductivity. The bonding can only be described by the band model.

    12. Bridged Aza[10]annulenes—10π-Analogues of Pyridine (pages 853–855)

      Dr. Maria Schäfer-Ridder, Dipl.-Chem. Arwed Wagner, Dipl.-Chem. Michael Schwamborn, Dipl.-Chem. Helmut Schreiner, Dipl.-Chem. Eveline Devrout and Prof. Dr. Emanuel Vogel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808531

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      The two aza derivatives of 1,6-methano[10]annulene are of interest as potential heteroaromatic systems. (1) has been obtained in a multistep synthesis by Vogel et al.; the 10-methoxy (2) and 10-ethoxy derivatives of the isomer have also been prepared.

    13. 10-Ethoxy-3,8-methanoaza[10]annulene, a 10π-Electron Analogue of Pyridine (pages 855–856)

      Hans-Jürgen Gölz, Dr. Joseph M. Muchowski and Michael L. Maddox

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808551

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      The two aza derivatives of 1,6-methano[10]annulene are of interest as potential heteroaromatic systems. (1) has been obtained in a multistep synthesis by Vogel et al.; the 10-methoxy (2) and 10-ethoxy derivatives of the isomer have also been prepared.

    14. Wrapping of Noncyclic Donor Molecule around the Sodium Cation (pages 856–857)

      Dr. Jean Grandjean, Prof. Dr. Pierre Laszlo, Prof. Dr. Fritz Vögtle and Dipl.-Chem. Heinz Sieger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808561

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      The recognition of K and Na by (membrane bound) ligands is one of the fundamental processes occurring in the living cell. The “noncyclic crown ether” (1) is an excellent model substance; the thermodynamic parameters for the formation of complexes between (1) and Na were determined by 23Na-NMR spectroscopy.

    15. Ion-Selective Crown Ether Dyes (pages 857–859)

      Dipl.-Chem. J. Peter Dix and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808571

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      Cation-selective color changes can be accomplished in dyes in which a heteroatom of the chromophore participates as a donor center in complex formation by a crown ether. The greatest effect (Δλ ≈ 120nm) is observed with the combination (1), M = Ba2⊕ (2I as counterion).

    16. Carbonylation of Transition-Metal Carbyne Complexes, a New Method for the Synthesis of Metal-Substituted Ketenes (page 859)

      Dr. Fritz R. Reissl, Dipl.-Chem. Wolfgang Uedelhoven and Dipl.-Chem. Karl Eberl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808591

      Surprising reactions of carbon monoxide with transition metal complexes have been observed with compounds (1) and (2). The carbyne complex (1) takes up CO at normal pressure and −30°C to form the metalated ketene (2) which itself is deoxygenated by CO at +60°C and under 60atm pressure to form the metalated acetylene (3) (L = P(CH3)3).

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    17. Deoxygenation—A Novel Reaction Path of Transition Metal-Substituted Ketenes (page 860)

      Dr. Fritz R. Kreissl, Dipl.-Chem. Karl Eberl and Dipl.-Chem. Wolfgang Uedelhoven

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808601

      Surprising reactions of carbon monoxide with transition metal complexes have been observed with compounds (1) and (2). The carbyne complex (1) takes up CO at normal pressure and −30°C to form the metalated ketene (2) which itself is deoxygenated by CO at +60°C and under 60atm pressure to form the metalated acetylene (3) (L = P(CH3)3).

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    18. Oxygen Evolution from Water via Redox Catalysis (pages 860–861)

      Dr. John Kiwi and Prof. Dr. Michael Grätzel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808602

      The decomposition of water by sunlight is a fascinating concept in view of today's energy debate. Evolution of O2 according to the equation (1) or (2) could be a first step in this direction. Suitable redox catalysts are PtO2 and IrO2. Ce3+ and Ru(bpy)math image can be photochemically reoxidized with evolution of H2.

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    19. Methyl-1,6-dioxaspiro[4.5]decanes as Odors of Para-vespula vulgaris (L.) (page 862)

      Dr. Wittko Francke, Dipl.-Chem. Gerd Hindorf and Dipl.-Chem. Wolfgang Reith

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808621

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      The chemical language of the common wasp is starting to be deciphered. It protects itself from attack by fellow wasps by means of the volatile dioxaspirodecanes (1) and (2).

    20. Catalytic Carbon-Carbon Bond Formation with Carbene Intermediates (pages 862–863)

      Dr. Gisela Henrici-Olivé and Prof. Dr. Salvador Olivé

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808622

      The transformation of methylamine into acetonitrile is catalyzed, e. g. by Moon SiO2. On admixture of hydrogen (H2:CH3NH2 = 12:1) 20–30% of the methylamine are converted into the C2 product. The reaction proceeds via an intermediate of the type H2C[DOUBLE BOND]M.

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    21. Heteronuclear Cobalt Clusters by Metal Exchange (pages 863–864)

      Dipl.-Chem. Harald Beurich and Prof. Dr. Heinrich Vahrenkamp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808631

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      The directed modification of cobalt-containing clusters is possible by exchange of Co for other metals. This generalizable synthetic strategy involves attachment of an AsMe2[BOND]M(CO)3Cp chain to Co and thermal decomposition of the product with release of an oligomer having the approximate composition [(CO)3Co[BOND]AsMe2]x(1); M = Cr, Mo, W.

    22. An Entry to Chiral Clusters (pages 864–865)

      Dipl.-Chem. Felix Richter and Prof. Dr. Heinrich Vahrenkamp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808641

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      Four different atoms at the corners of a tetrahedron are to be found in the cluster (1) (M = Cr, Mo, W). The chiral molecules were prepared from the corresponding FeCo2 cluster by metal exchange. Their chirality can be demonstrated by 1H-NMR spectroscopy of the PPhMe2 derivatives of (1).

    23. Systematic Formation of Metal Complexes Containing Isocyanide Bridging Ligands: [η5-C5H5Fe(CNC6H5)(μ-CNC6H5)]2 (pages 866–867)

      Dr. Wolf Peter Fehlhammer, Dipl.-Chem. Andreas Mayr and Dipl.-Chem. Götz Christian

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808661

      Stable complexes with isocyanide bridges can be synthesized on joint application of the two strategies “isocyanide bridge formation” and “isocyanide transfer.” This promising method, proceeding under especially mild conditions, permitted the synthesis of the dimer (1).

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    24. 1,2,3-Tri-tert-butylphosphirane Oxide and Its Thermal Decomposition into (Z)-2,2,5,5-Tetramethyl-3-hexene and tert-Butylphosphinidene Oxide (pages 867–868)

      Prof. Dr. Helmut Quast and Dipl.-Chem. Manfred Heuschmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808671

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      The first phosphirane oxide(1) has now been obtained by elimination of HCl from the corresponding open-chain compound. On warming, compound (1) decomposes to the alkene (2) and the phosphinidene oxide (3), which could be trapped with a o-benzoquinone derivative.

    25. Paramagnetic Triple-Decker Sandwich Complexes (pages 868–869)

      Prof. Dr. Walter Siebert, Joseph Edwin M. Sc. and Dipl.-Chem. Manfred Bochmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808681

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      The new air-stable complexes(1), (2), and (3)—the first paramagnetic compounds of this kind—contain 31, 32, and 33 valence electrons. So far, only diamagnetic triple-decker complexes having 30 or 34 valence electrons were known. (The central ring in (1)(3) bears one methyl and four ethyl substituents.)

    26. Diorganodichlorophosphonium Hydrogen Dichlorides, a Novel Class of Compounds Containing [ClHCl] Ions (pages 869–870)

      Prof. Dr. Wilhelm Kuchen, Prof. Dr. Dietrich Mootz, Dipl.-Chem. Helnrich Somberg, Dr. Hartmut Wunderlich and Dipl.-Chem. Hans-Georg Wussow

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808691

      Stable salts of the dichlorohydrogenate ion are formed in the reaction shown below if R and/or R′ are p-methoxyphenyl groups. X-Ray structure analysis of (1), R′ = CH3, showed the two Cl[BOND]H bonds in the anion to be of different lengths. The only other known example, [Me4N]+[ClHCl], exhibits a similar asymmetry.

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  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (pages 870–871)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197808701

  4. Book Reviews

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

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