Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 11

November 1981

Volume 20, Issue 11

Pages 899–990

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 11/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198108991

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 11/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198108992

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Hybrid Orbitals and Their Applications in Structural Chemistry (pages 899–911)

      Prof. Dr. Werner A. Bingel and Prof. Dr. Wolfgang Lüttke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198108993

      All possible cases of symmetry for the s-p hybrid orbitals with which a central atom Z enters into σ bonds with two to four identical or different ligands are treated systematically. The nature of the hybrid orbitals can be used to describe the structural quantities of a molecule, particularly the energetics, charge distribution and, consequently, also reactivity.

    2. Anodic and Cathodic CC-Bond Formation (pages 911–934)

      Prof. Dr. Hans J. Schäfer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109111

      Thumbnail image of graphical abstract

      Electrochemical methods for the formation of C[BOND]C bonds have some advantages over classical chemical methods; thus, e.g., the reactivity of a substrate can be altered merely by electron transfer, which can reduce the number of steps in some syntheses. In principle, a shortening of the reaction times and suppression of passivation of the electrodes are now possible.

    3. Transition Metal Thiometalates: Properties and Significance in Complex and Bioinorganic Chemistry (pages 934–955)

      Prof. Dr. Achim Müller, Dr. Ekkehard Diemann, Dipl.-Chem. Rainer Jostes and Dr. Hartmut Bögge

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109341

      Thumbnail image of graphical abstract

      Brilliantly colored thiometalates having remarkable properties are formed by the electron-deficient transition metals V, Nb, Ta, Mo, W and Re in the highest oxidation states. As complex ligands these anions enable the generation of multimetal complexes. MoSmath image has, moreover, a significance in bioinorganic problems, e.g. the nitrogenase problem and the Cu[BOND]Mo antagonism observed in animals.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Initial Steps in the Degradation of Chlorobenzene Derivatives by Pseudomonas putida (pages 955–956)

      Prof. Dr. Karlheinz Ballschmiter and Charlotte Scholz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109551

      For the first step of the bacterial transformation of chlorobenzene derivatives there are two possibilities: (1) formation of a dioxetane by a dioxygenase attack, (2) formation of an oxirane by a monooxygenase attack. Evidence for a monooxygenase attack is the conversion of 1,2-dichlorobenzene into 2,3-, 3,4- and 2,6-dichlorophenol, as is also the formation of 2,4,6-trichlorophenol from 1,3,5-trichlorobenzene.

    2. Do All Eight Diastereomeric Bacteriochlorophylls Exist in Nature? (pages 956–958)

      Dr. Bernd Scholz and Prof. Dr. Karlheinz Ballschmiter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109561

      Thumbnail image of graphical abstract

      Under optimized separating conditions reversed-phase C18-HPLC gives eight bands each of very different intensity for bacteriochlorophyll ap (R6 = phytyl) and agg (R6 = geranylgeraniol).

    3. A New Cationic Hydrido-Bridged Rhodium(I)-Iridium(III) Complex (pages 958–959)

      Prof. Alberto Albinati, Prof. Dr. Alfredo Musco, Ralph Naegeli and Prof. Dr. Luigi M. Venanzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109581

      Thumbnail image of graphical abstract

      The new complex (1), whose dark green crystals are stable in air, contains a five-coordinate rhodium(I) and a six-coordinate irid-ium(III) with three bridging hydride ligands. (1) can be prepared by reaction of [Rh(di-phos)(MeOH)2][BF4] with mer-[IrH3(PEt3)3] and subsequent precipitation with NaBPh4.

    4. Synthesis of Dithiapropellanes with Annelated Benzene Rings–Precursors for Molecules with the Benzene-Dewar Benzene Structure (pages 960–961)

      Prof. Dr. Klaus Weinges, Dipl.-Chem. Peter Günther, Dipl.-Chem. Wolfgang Kasel, Dipl.-Chem. Georg Hubertus and Petra Güinther

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109601

      Thumbnail image of graphical abstract

      Benzoannelated analogues of l,4-polymethylene-(Dewar)benzene derivatives, e.g. (3) and (4), are obtainable from the dithiapropellanes (1) and (2) (X, Y = S). (2) and (4) are chiral.

    5. Decomposition of the Yellow Form of Thiamine (pages 961–962)

      Dr. Rudolf F. W. Hopmann and Dr. Gian Pietro Brugnoni

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109611

      A novel mechanism is proposed for the alkali-induced transformation of thiamine; it is based on the results of kinetic investigations. The time-dependent UV spectra of alkaline thiamine solutions, whose yellow color rapidly disappears, reveal isosbestic points, thus indicating that no intermediate is formed in significant amounts.

    6. [Ga6Se14]10− : A 1900 pm Long, Hexameric Anion (pages 962–963)

      Dr. Hans-Jörg Deiseroth and Dr. Han Fu-Son

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109621

      Thumbnail image of graphical abstract

      The first ternary compound in the Cs/Ga/Se system, whose structure was investigated on single crystals, is a solid of the composition Cs10Ga6Se14. The pale-yellow, transparent, leaf-shaped crystals contain the anion [Ga6Se14]10− (1), which is composed of six linearly edge-linked GaSe4 tetrahedra.

    7. 1,2,3λ3-Diazaphosphiridines—Synthesis, Molecular Structure and Ring Opening (pages 963–964)

      Prof. Dr. Edgar Niecke, Klaus Schwichtenhövel, Dipl.-Chem. Hans-Günther Schäfer and Prof. Dr. Bernt Krebs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109631

      Thumbnail image of graphical abstract

      Of the three-membered heterocycles with λ3-phosphorus and highly electronegative heteroatoms, l,2,3λ3-diazaphosphiridines (1), R = CHMe2, SiMe3, has now been synthesized. In the ground state of (1) the tert-butyl substi-tuents are trans-oriented. The diazaphosphiridines (1) isomerize in toluene at 100°C within a few minutes to give the ylidic diiminophosphoranes (2).

    8. Structural Properties of Phosphorus Oxides in the Solid Aggregation State (page 965)

      Prof. Dr. Martin Jansen, Dipl.-Chem. Marlen Voss and Dr. Hans-Jörg Deiseroth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109651

      Thumbnail image of graphical abstract

      With the crystal structure of phosphorus(III) oxide P4O6 the structures of all binary phosphorus oxides in the solid state are known. The series P4O6+n (n = 0–4) is suitable for studying the mutual influence of PIII and PV on their bonding properties in practically unchanged environment.

    9. CC Bond Formation Between “Electron-Rich” and “Electron-Deficient” Alkenes (pages 965–966)

      Prof. Dr. Bernd Giese and Dipl.-Ing. Gerhard Kretzschmar

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109652

      Thumbnail image of graphical abstract

      The mild multistep CC bond formation between “electron-rich” and “electron-deficient” alkenes (1) and (2), respectively, can be carried out in good yields as a one-pot reaction. R1 and R2 of (1) can be alkyl-, aryl- and alkoxy groups, while in the case of (2), cyano groups, carboxylic esters, keto-, anhydride, and imide residues are suitable as X, Y and Z.

    10. Steric Effects in the Addition of Alkyl Radicals to Alkenes (page 967)

      Prof. Dr. Bernd Giese and Dipl.-Chem. Stephen Lachhein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109671

      Thumbnail image of graphical abstract

      The influence of steric effects on the addition of alkyl radicals to alkenes important in polymerizations can be investigated by the method of competition kinetics. Cyclohexyl radicals add to α- and β-substituted acrylic acid esters at different rates—a confirmation of the model (1) obtained by calculations for the transition state of this type of reaction.

    11. tBu4P6, a Novel Bicyclic Organophosphane (pages 967–969)

      Prof. Dr. Marianne Baudler, Dipl.-Chem. Yusuf Aktalay, Prof. Dr. Karl-Friedrich Tebbe and Dipl.-Chem. Thomas Heinlein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109672

      Thumbnail image of graphical abstract

      Dehalogenation of a mixture of tert-bu-tyl(dichloro)phosphane and PCl3, with magnesium leads to formation of 2,3,4,6-tetra-tert-butylbicyclo[3.1.0]hexaphosphane, which is stable at room temperature. According to the 31P-NMR spectrum and the X-ray structure analysis the substituents are trans oriented.

    12. Stereoselective Synthesis of β-Glucosides with l, l′-Diacetal Structure (pages 969–970)

      Prof. Dr. Lutz-F. Tietze and Dipl.-Chem. Roland Fischer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109691

      Thumbnail image of graphical abstract

      An example of the use of trimethylsilyl trifluoromethanesulfonate as catalyst is the reaction of β-D-glucopyranoside (1) with acetals (R1 = Me, Ph; R2 = H, CH2Ph, n-C3H7, CH2CH(OMe)2, CH2OMe etc.). It leads highly stereoselectively to the l,l′-diacetals (2) in good yields.

    13. Synthesis of [10-13C]Secologanin (page 970)

      Prof. Dr. Lutz-F. Tietze and Dipl.-Chem. Stephan Henke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109701

      Thumbnail image of graphical abstract

      Secologanin (1) plays a key role in the biogenesis of a series of alkaloids. Compound (1) labeled with 13C at position 10, which should enable identification of non-isolated intermediates, can be prepared from unlabeled (1), inter alia, via OsO4 and Pb(OAc)4-oxidation and a Wittig olefination.

    14. Alkylation of Amino Acids without Loss of Optical Activity: α- and β-Alkylation of an Aspartic Acid Derivative (page 971)

      Prof. Dr. Dieter Seebach and Dipl. sc. nat. Daniel Wasmuth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109711

      Thumbnail image of graphical abstract

      The α-alkylation of β-heterosubstituted carbonyl compounds leads to a surprising result in the case of L-(+)-N-formylaspartic acid di-tert-butyl ester: A mixture of the β- and α-substituted aspartic acid derivatives (1) and (2) (ca. 7:2) is obtained. The erythro-isomers of (1) are formed stereospecifically, while, interestingly, an enantiomer of (2) is formed in excess; R[DOUBLE BOND]CH3, C2H5, CH2CH[DOUBLE BOND]CH2, CH2C6H5.

    15. Novel Five-Membered C2BNSi-Rings (page 972)

      Prof. Dr. Roland Köster and Chem.-Ing. Günter Seidel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109721

      Thumbnail image of graphical abstract

      Δ3-1,2,5-Azasilaborolines (1)-novel complex ligands for transition metals-could be synthesized by a previously unknown ring-closure reaction: The most important step is the intramolecular aminolysis of an amino-borate(R = CH3, Si(CH3)3).

    16. Simple Metal-Catalyzed Synthesis of Functionalized Pyrimidines from Dicyanogen and 1,3-Dicarbonyl Compounds (pages 972–973)

      Prof. Dr. Benedetto Corain, Dr. Marino Basato and Prof. Dr. Hans-Friedrich Klein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109722

      Thumbnail image of graphical abstract

      Highly functionalized pyrimidines (1) can be prepared from dicyanogen and 1,3-dicarbonyl compounds (R1 = COCH3, COC6H5, CO2C2H5) under mild conditions in a Ni(acac)2− or Cu(acac)2-catalyzed one-pot reaction.

    17. A New Onium Salt: Synthesis and Characterization of the Difluorophosphonium Ion, PH2 Fmath image (pages 973–974)

      Prof. Dr. Herbert W. Roesky, Dipl.-Chem. Karl-Liudwig Weber and Jürgen Schimkowiak

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109731

      Unlike salts of NH2Fmath image, which decompose explosively at room temperature, PH2Fmath image AsFmath image( 1) is surprisingly stable. The fine crystalline, colorless (1) can be stored for several days at room temperature in polyethylene vessels; it decomposes with loss of HF and formation of red phosphorus, only on warming.

      • equation image
    18. Synthesis and Structure of a Non-Polymeric Molecule Containing Eleven Alternating Sulfur- and Nitrogen-Atoms (pages 974–975)

      Michael Witt, Prof. Dr. Herbert W. Roesky, Dr. Mathias Noltemeyer, Dr. William Clegg, Martin Schmidt and Prof. Dr. George M. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109741

      Thumbnail image of graphical abstract

      In compound (2), which formally stands between (SN)x and the sulfur imides, the average SN bond length is 1.602 Å and is thus similar to that in (SN)x(1.611 Å). (2) is formed as orange needles from the blood-red (1) in acetoni-trile by cleavage of S4N4 and sulfur.

    19. Synthesis of Dithiophosphinato Complexes with Bis(diorganothiophilosphoryl)disulfanes: Mo3S7-Cluster Dithiophosphinates (pages 975–976)

      Dr. Helmut Keck, Dr. Wilhelm Kuclhen, Dipl.-Chem. Jürgen Mathow, cand. rer. nat. Beate Meyer, Prof. Dr. Dietrich Mootz and Hartmut Wunderlich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109751

      Molybdenum-sulfur clusters are of topical interest as model substances in bio-inorganic chemistry. The readily soluble Mo3S7-cluster chelates (1) and (2) have been synthesized for the first time from Mo(CO)6 and R2P(S)–S2–P(S)R2, R= Et or nPr. An X-ray structure analysis of (1), a 1 :1 electrolyte, has been carried out. Further functionalization via suitable sub-stituents R would seem to be possible.

      • equation image
    20. Trimethylsilylated Cyclopentadienones (pages 976–977)

      Prof. Dr. Günther Maier, Dipl.-Chem. Hans Werner Lage and Dr. Hans Peter Reisenauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109761

      Thumbnail image of graphical abstract

      Not a tetrahedrane derivative but the butatriene.derivative (2) is formed on irradiation of tetrakis(trimethylsilyl)cyclopentadienone (1). During the synthesis of (1), trimethylsilylated cyclopentadienones are obtained as stable intermediates, which are of interest as synthetic building blocks.

    21. Enantioselective Synthesis of ( R)-α-Vinylamino Acids (pages 977–978)

      Prof. Dr. Ulrich Schöllkopf and Dipl.-Chem. Ulrich Groth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109771

      Thumbnail image of graphical abstract

      Important enzyme inhibitors such as α-vinylamino acids (2) can be prepared in highly optically pure form in a few steps from the heterocycle cyclo(L-Val-Gly)(1) by the bislactim ether method.

    22. CC-Coupling and Reversible γ-H Abstraction in the Tantalum Complex Cl(η5-Cp)(η3-C9H7)Ta(CHCMe3) (pages 978–980)

      Dr. Anton W. Gal and Harry van der Heijden

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109781

      Thumbnail image of graphical abstract

      The potential of organotantalum compounds for CC-coupling and H-shift reactions has been demonstrated by a newly discovered type of reaction: A CC-coupling between the η3-indenyl and the neopentylidene ligands in (1) leads, even at room temperature, to an intermediate, from which the novel tantala-bicycloheptene derivative (2) is formed by a γ,α H-shift reaction. (2) reacts with ethylene to give the tantalanorbornane (3).

    23. Palladation of sp3 -Carbon Atoms: Preparation of N-PalladiomethyIthioamides (pages 980–981)

      Dr. Yoshinao Tamaru, Masahiro Kagotani and Prof. Dr. Zen-ichi Yoshida

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109801

      Thumbnail image of graphical abstract

      N,N-Dialkylthioamides can be regioselectively metalated with PdCl2; thus, reaction of (2) with PdCl2 in CH3OH leads to the orthometalated compound (1), while in HMPA the product of palladation contains a CH2 group adjacent to the nitrogen atom.

    24. Addition of Aryl Isocyanides to 1,4-Quinones: Synthesis of Novel Deep-Blue Dyes (pages 982–983)

      Dr. Walter Ott and Dr. Victor Formacek

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109821

      Thumbnail image of graphical abstract

      1,4-Benzoquinone reacts with 4-substituted aryl isocyanides to give the adducts (1)–(3), whose longest wavelength absorption maximum lies at ca. 600 nm. The structure of the symmetric compounds (2) and (3) could be determined by 13C-NMR spectroscopy.

    25. Rearrangement of Bridged Diazene N-Oxides: Selective Cleavage of the C[BOND]NO Bond (pages 983–984)

      Dr. Henrik Olsen and Prof. Jean F. M. Oth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109831

      Thumbnail image of graphical abstract

      A surprisingly selective thermal isomerization has been observed in the case of the bicycles (1): At 130°C, only the C[BOND]NO and not the C[BOND]N bond is opened. There is ample evidence for the participation of a diradical of type (2) (R, R′= Me and/or Ph).

    26. Valence Isomerization of a cis-Diazene-/Isodiazene- N-Oxide: Thermolysis of 7,8-Diazabicyclo[4.2.2]deca-2,4,7-triene N-Oxide (pages 984–985)

      Dr. Henrik Olsen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109841

      Thumbnail image of graphical abstract

      The first example of the title reaction is the rearrangement (1)[RIGHTWARDS ARROW](2), which most likely proceeds via the diradical (3).

    27. Chemical Applications of NMR Isotope Effects: Ring Inversion and Conformational Equilibrium in [2H1]Cyclohexane (pages 985–986)

      Dipl.-Chem. Rafet Aydin and Prof. Dr. Harold Günther

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109851

      Thumbnail image of graphical abstract

      The large and easily measurable 1H/2H isotope effect on the chemical shift of the 13C nucleus has been exploited in the investigation of the ring inversion (1a)⇌(1b). At equilibrium, (1a) predominates.

    28. Cleavage of Water by Visible-Light Irradiation of Colloidal CdS Solutions; Inhibition of Photocorrosion by RuO2 (pages 987–988)

      Kuppuswamy Kalyanasundaram, Enrico Borgarello, Dung Duonghong and Michael Grätzel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198109871

      The conversion of light into chemical fuels in photochemical devices equipped with semiconductor electrodes (e.g. of n-CdS) is associated with a serious problem: “holes” produced in the valence band of the semidonductor upon irradiation migrate to the surface where photocorrosion occurs. In mi-croheterogenous CdS systems this is remedied by a thin layer of RuO2. A CdS sol prepared in the presence of maleic anhydride/styrene copolymer has now been loaded with RuO2 and Pt; these CdS microelectrodes are surprisingly active catalysts for cleavage of H2O and H2S.

  3. Book Reviews

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

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