Angewandte Chemie International Edition in English

Cover image for Vol. 26 Issue 3

March 1987

Volume 26, Issue 3

Pages 161–274

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 3/1987)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198701611

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      The cover picture shows a europium (III) cryptate which has extremely interesting photochemical and photophysical properties. The complex absorbs ultraviolet light by the macrocyclic ligand; an excitation of Eu3⊕ by energy transfer from excited states of the ligand thenenables the luminous red Eu3⊕ emission. Further information about these interesting molecular light converters, which could, for example, be used in the development of luminescent materials for biological application is given by J.-M. Lehn et al. On p. 266ff. (Illustration: I. D. Illustration and design, Mannheim (FRG)).

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 3/1987)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198701612

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Electrodes for Potential Measurements in Aqueous Systems at High Temperatures and Pressures (pages 161–169)

      Dr. Leonard W. Niedrach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198701613

      Novel zirconium oxide electrodes are finding application in ever so many fields of research and technology. Thus they are especially suitable as sensors for the measurement of pH values, redox potentials, and corrosion potentials at high temperatures and pressures, as are frequently necessary for the controlling and monitoring of industrial processes; such sensors are also required for research on the thermodynamics of high-temperature aqueous solutions, e.g. in connection with geothermal and hydrothermal reactions.

    2. Neutral and Charged Biradicals, Zwitterions, Funnels in S1, and Proton Translocation: Their Role in Photochemistry, Photophysics, and Vision (pages 170–189)

      Prof. Vlasta Bonačić-Koutecký, Prof. Jaroslav Koutecký and Prof. Josef Michl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198701701

      The structures of photoproducts are decisively determined by geometries corresponding to the local minima on the potential hypersurfaces of electronically excited molecules. Since many of these geometries are associated with a biradicaloid character of the system, qualitative predictions can be made from a simple two-electron two-orbital model. The results so obtained could be confirmed by detailed ab initio calculations with configuration interaction. This information is used as a basis for the discussion of photochemical mechanisms such as the cis-trans isomerization of olefins, the formation of TICT states, and singlet photocycloadditions.

    3. Directed Homogeneous Hydrogenation [New Synthetic Methods (65)] (pages 190–203)

      Dr. John M. Brown

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198701901

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      A polar group in proximity to the double bond to be hydrogenated characterizes the substrates for the title reaction. The hydrogenation proceeds very selectively in the presence of cationic rhodium or iridium catalysts. The configuration of the products is predictable on the basis of a few simple rules.

    4. New Reductive Transformations of Unsaturated Cyclic Hydrocarbons [New Synthetic Methods (66)] (pages 204–217)

      Prof. Dr. Klaus Müllen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702041

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      The title reactions are ideal examples for the combined use of preparative, spectroscopic and bond-theoretical methods. The octalene dianion 1 is methylated at the bridgeheads, i.e. the site of highest charge density; the primary diadduct rearranges into the 1,8-dimethyl[14]annulene 2 and its conformers.

    5. Transcription in Eukaryotes—The Role of Transcription Complexes and Their Components (pages 218–227)

      Dr. Edgar Wingender and Prof. Dr. Klaus H. Seifart

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702181

      That DNA is transcribed into RNA has long been known; the mechanisms responsible for controlling this process at the individual genes of higher cells (eukaryotes), however, are still not completely understood. RNA polymerases apparently require a number of auxiliary factors (transcription factors (TF)) for gene recognition. These factors combine with the enzyme at the gene to form a transcription complex. Particularly well-documented is TF III A, a protein with a novel “finger structure”. It is stabilized by zinc ions, which coordinate two His and two Cys residues. The results contribute quite generally to a better understanding of DNA-protein interactions.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. 1D and 2D NMR Investigations of the Jump Mechanism of CoII Ions in [12]Crown-4 Stacks (pages 228–229)

      Prof. Dr. Franz L. Dickert, Dipl.-Chem. Wolfgang Gmeiner, Dr. Walter Gumbrecht and Dipl.-Chem. Harald Meissner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702281

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      Aggregation of free [12]crown-4 molecules with the Co2⊖-complex 1 of this ligand leads to formation of the stacks illustrated on the right, through which the Co2⊙ ions can move. Dynamic NMR- and 2D-1H-exchange NMR-measurements suggest a jump mechanism, reminiscent of the mechanism of ion transfer through biomembranes.

    2. 1,1′-Diarsaferrocene (pages 229–230)

      Prof. Dr. Arthur J. Ashe III, Samir Mahmoud, Prof. Dr. Christoph Elschenbroich and Dipl.-Chem. Martin Wünsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702291

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      A novel, efficient procedure for the synthesis of 1-phenylarsole 1, which can also be extended to 1-phenylphosphole, enabled the preparation of the title compound 2, which forms dark red, air stable crystals. 2 may be electrochemically oxidized as well as reduced and undergoes acid-catalyzed H/D exchange.

    3. Synthesis and Structure of [(C5Me5)2Mo2S4·SO3]: Concerning the Oxidation of Sulfur Ligands in Transition-Metal Complexes (pages 230–231)

      Prof. Dr. Henri Brunner, Dr. Ulrich Klement, Joachim Pfauntsch and Dr. Joachim Wachter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702301

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      The first bidentate thiosulfate ligand was found in the title compound 1. Compound 1 is formed in 17% yield upon oxidation of the SO3-poorer complex in solution with atmospheric oxygen. This reaction could begin with the isomerization of the precursor to complexes with terminal Mo[DOUBLE BOND]S groups.

    4. [2.2](1,4)Benzo[g]chrysenoparacyclophane Dianion: A Novel, Paratropic, Double-Layered Carbanion (pages 232–233)

      Ron Frim, Prof. Dr. Mordecai Rabinovitz, Prof. Dr. Henning Hopf and Dipl.-Chem. Joachim Hucker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702321

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      A novel through-space interaction between a polycyclic charged 4nπ-electron system and a phane like coupled benzene ring could be observed in the title compound 1. This interaction manifests itself in particular in the extreme downfield shifts of the signals of the Hc and Hd protons (M [DOUBLE BOND] Na, Li). The synthesis of the hydrocarbon precursor of 1 was achieved in few steps from commercially available [2.2]paracyclophane.

    5. Synthesis of 2-Deoxy Sugars (pages 233–234)

      Prof. Dr. Bernd Giese, Dipl.-Ing. Kay S. Gröninger, Dipl.-Ing. Tom Witzel, Dr. Hans-Gert Korth and Prof. Dr. Reiner Sustmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702331

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      2-Deoxy sugars are now directly accessible from 1-glycosyl halides: glycosyl radicals generated with Bu3SnH rearrange in accordance with 1 [RIGHTWARDS ARROW] 2 into the 2-deoxy sugars. Glycosyl dihalides afford the corresponding dideoxy sugars. C in 1 and 2 denotes C-1 and C-2, respectively, of a carbohydrate.

    6. Arene Adducts with Weak Interactions: Hexaethylbenzene–bis(tribromoarsane) (pages 234–236)

      Prof. Dr. Hubert Schmidbaur, Dipl.-Chem. Wolfgang Bublak, Dipl.-Chem. Brigitte Huber and Dr. Gerhard Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702341

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      The inverse sandwich complex 1 with η6-coordination of the arene molecule is formed on reaction of AsBr3 and C6Et6, in the molar ratio 2:1. The stability of the adduct is presumably due to an interplay of weak charge transfer and van-der-Waals interactions.

    7. Reaction of Phosphinines with Diazoalkanes: Diphosphachiropteradienes by Intramolecular, Ionic 5s + 5s [6 + 4] Cycloaddition (pages 236–238)

      Prof. Dr. Gottfried Märkl, Dipl.-Chem. Hans J. Beckh, Dr. Klaus K. Mayer, Prof. Dr. Manfred L. Ziegler and Dr. Thomas Zahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702361

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      Phosphinines react with diazaalkanes in a totally different way to the usual PC double-bond systems. In alcohols, 1-alkoxy-1-alkyl-λ5-phosphinines such as 1 are formed. In aprotic solvents, 3 was formed, presumably via 2 as intermediate. 3 was identified by X-ray crystallography. (Chiroptera = an order of eutherian mammals comprising the bats.)

    8. MNDOC Calculations of the Potential Surfaces for Photochemical α-Cleavage (pages 238–240)

      Dipl.-Chem. Manfred Reinsch, Dr. Udo Höweler and Prof. Dr. Martin Klessinger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702381

      A combination of a semiempirical MO calculation and a limited configuration interaction calculation has been used successfully for the prediction of photoproducts as a function of the excited state of the reactant. As example, the α-cleavage of formaldehyde was investigated. The potential hypersurfaces of the S0 Sa and Ta states for planar formaldehyde were calculated as functions of the C[BOND]H1 distance and of the H2CO angle.

    9. Photoisomerization of Bis(bipyridyl)rhodium(III) Complexes; Synthesis of trans-[Rh(bpy)2YCl]n⊕, Y[DOUBLE BOND]Cl, H2O (pages 240–241)

      Dipl.-Chem. Gerd Krüger, Dipl.-Chem. Stefan Wieland and Priv.-Doz. Dr. Rudi van Eldik

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702401

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      The transformation of cis- into trans-bis(bipyridyl) complex 1 on a preparative scale was achieved by 313 nm-irradiation at room temperature. At the same time the ligands X and/or Y are exchanged. Square-pyramidal species are possibly involved as intermediates.

    10. A New Photosynthesis-like System for the Light-induced Reduction of Water to Molecular Hydrogen (pages 241–243)

      Dr. Wolfgang Schuhmann, Dr. Hans-Peter Josel and Priv.-Doz. Dr. Harun Parlar

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702411

      Two zinc porphyrinate-modified Pt electrodes form the essential part of a very promising solar energy conversion system in which ultimately water is reduced to hydrogen. The Na2 salt of ethylenediaminetetraacetic acid (H4 EDTA) is employed as sacrificial electron donor; methyl viologen (MV2⊕) functions as electron transfer agent and platinized TiO2 as reduction catalyst. Decisive is that the anode is coated with an n-semiconducting porphyrinate (zinc 5-(4-pyridyl)-10,15,20-tritolylporphyrinate) and the cathode with a p-semiconducting porphyrinate (zinc 5,10,15,20-tetra(4-pyridyl)porphyrinate). Currently, the yields of H2 still lie in the μmol range.

    11. Synthesis of the Four-Membered Metallacycle [Cp2Ti(AsPh)3] via the in situ Reduction of [Cp2 TiCl2] (pages 244–245)

      Paul Mercando, Anthony-Joseph DiMaio and Prof. Arnold L. Rheingold

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702441

      The title compound 1 contains an almost planar TiAs3 ring: the three phenyl rings are arranged alternately “upwards” and “downwards”. The two cyclopentadienyl rings are not equivalent at room temperature in solution. 1 is the first cyclic titanium derivative containing elements of the 5th group as ring members which has been characterized by X-ray structure analysis.

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    12. Cooperative Effects in the Phase Transformation of Triethylcyclotriboroxane (pages 245–247)

      Dr. Roland Boese, Dipl.-Chem. Michael Polk and Dipl.-Ing. Dieter Bläser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702451

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      Intermolecular B…O interactions and repulsive intermolecular H…H interactions are the cause of the reversible phase transformation of 1. The ethyl groups and the ring in one third of the molecules rotate with preservation of the single crystal such that an eclipsed stacking becomes a partially staggered stacking.

    13. Kinetic 15N-CPMAS-NMR Study of a Double Proton Transfer in a Crystalline Malonaldehyde Diimine Derivative (pages 247–248)

      Priv.-Doz. Dr. Hans-Heinrich Limbach, Dipl.-Chem. Bernd Wehrle, Herbert Zimmermann, Ray D. Kendrick and Dr. Costantino S. Yannoni

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702471

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      Solid state effects gave rise to an energy difference of about 4 kJ mol−1 between the tautomers 1 and 2. This could be deduced from dynamic 15N-NMR spectra, which were recorded under the conditions of cross-polarization and of sample rotation about the magic angle.

    14. A Novel Route to Azaalkenylidene-Metal Complexes (pages 248–250)

      Prof. Dr. Helmut Werner, Wolfgang Knaup and Dipl.-Chem. Michael Dziallas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702481

      The oxime complexes 1 have structures analogous to imine complexes. Such oxime complexes have proven suitable as educts for the synthesis of azaalkenylidene complexes 2 of d-electronrich transition metals. The cleavage of water from 1 with formal hydridic hydrogen and an N-bonded OH-group to give 2 proceeds remarkably smoothly [CRR′ = cyclohexylidene or CMe2; {Os} = (C6H6)(PMetBu2)Os].

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    15. Synthesis and Crystal Structure of the Homoleptic Thioether Ruthenium Complex [Ru(1,4,7-trithiacyclononane)2](BPh4)2·2Me2 SO (pages 250–251)

      Michael N. Bell, Dr. Alexander J. Blake, Dr. Martin Schröder, Dipl.-Chem. Heinz-Joseph Küppers and Prof. Dr. Karl Wiegltardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702501

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      The oxidation state two of ruthenium is markedly stabilized by the octahedral coordination with sulfur atoms in 1: the complex is electrochemically inactive-between −2.2 and + 1.3V. The two macrocycles form cavities on each side of the metal, each of which entrap a solvent molecule.

    16. Tetranuclear Mixed-Valence Manganese Complexes with Reduced TCNE or TCNQ as η4 Bridging Ligands (pages 251–253)

      Dipl.-Chem. Renate Gross and Priv.-Doz. Dr. Wolfgang Kaim

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702511

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      Metal[RIGHTWARDS ARROW]ligand electron transfer during the coordination of [Mn]-fragments to the common π-acceptors tetracyanoethylene (TCNE) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) leads to 1 and 2, respectively, the first tetranuclear complexes of this kind. The stable compounds are to be considered as mixed valence complexes, and accordingly have unusual spectroscopic properties (R[DOUBLE BOND]Hor CH3).

    17. Two Different Intercalate Structures in the Intercalation Compounds of Graphite with Perfluorobutanesulfonic Acid (pages 253–255)

      Dr. Bernd Ruisinger and Prof. Dr. Hanns-Peter Boehm

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702531

      Two types of layers which differ in the arrangement of the acid anions and acid molecules and which also have different thicknesses were found on electro–chemical intercalation of perfluorobutanesulfonic acid in graphite. Such a phenomenon, which occurs in the first and second stage of the graphite salt, has never been observed in other graphite compounds. It is of interest, inter alia, in connection with the packing of alkyl chains in crystalline polymers, especially poly (tetrafluoroethylene), and with respect to the investigation of phase transformations in quasi two-dimensional molecular assemblages.

    18. Synthesis and Structure of [(PPh3)2N][Fe3Mn(CO)124-O)]: A Butterfly Oxo Cluster (pages 255–256)

      Dr. Cynthia K. Schauer and Prof. Duward F. Shriver

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702551

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      The first fourfold coordinated “naked” oxygen atom is, aside from the low oxidation state of the four metal atoms, the special feature of the cluster ion 1 of the title compound. Surprisingly, the μ4-O atom of 1 is protonated only with difficulty by Brønsted acids.

    19. The Diradical 2,3,5,6-Tetramethylene-1,4-cyclohexanediyl (“1,2,4,5-Tetramethylenebenzene”) (pages 256–258)

      Prof. Dr. Wolfgang R. Roth, Dipl.-Chem. Reinhard Longer, Dr. Martin Bartmann, Dipl.-Chem. Birgitt Stevermann, Prof. Dr. Günther Maier, Dr. Hans Peter Reisenauer, Prof. Dr. Rainer Sustmann and Dipl.-Chem. Wolfgang Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702561

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      Contrary to theoretical predictions the title compound 1 has a triplet ground state, as is conformed by its ESR and UV/VIS spectra. 1 can be formed in two ways, as outlined below.

    20. Dinuclear Complexes of Gold(I) Containing Bridging Cyclometalated Arylphosphane or Arylarsane Ligands (pages 258–260)

      Dr. Martin A. Bennett, Dr. Suresh K. Bhargava, K. David Griffiths, Dr. Glen B. Robertson, Dr. Wasantha A. Wickramasinghe and Dr. Anthony C. Willis

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702581

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      Gold–gold distances similar to those in the metal (2.88 Å) are found in several dinuclear gold(I) complexes. The title compounds 1 make no exception: the Au…Au distance in 1a (2.86 Å) suggests a marked bond interaction between the metal atoms. 1a is obtained on reaction of [o-LiC6H4PPh2] with [AuBr(PEt)3]; 1bd can be prepared analogously.

    21. Coupling of Cyclometalated Phenylphosphanes in Dinuclear Gold(II)-Complexes (pages 260–261)

      Dr. Martin A. Bennett, Dr. Suresh K. Bhargava, K. David Griffiths and Dr. Glen B. Robertson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702601

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      CC-linkage of two o-phenylene ligands was observed in the isomerization of the dinuclear gold(II) complex 1, X = I or Br, to 2. An unusual feature of this rearrangement is that the product remains fixed via the P-donor atoms in the coordination sphere of the metal atoms.—1 is obtained from 1a (see previous communication).

    22. Chemistry of Pyrrocorphins: Biomimetic Regioselectivity of C-Methylation at the Ligand Periphery of Magnesium(II) Uropyrrocorphinate(Type I)-octanitriles (pages 261–264)

      Dipl.-Chem. ETH Christian Leumann, Dipl. Sc. Nat. ETH Thomas Früh, Dr. Michael Göbel and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702611

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      The position with the acetonitrile side chain is preferentially methylated if the ligands 1 are complexed with Mg2+ and allowed to react with CH3I. The regioselectivity of the reaction l [RIGHTWARDS ARROW] 2 is reminiscent of that of the enzymatic C-methylations in the biosynthesis of vitamin B12. (Only one configurational isomer is depicted in each case.)

    23. Structure of Triphenylarsane Diiodide, [Ph3As · I2], a Compound Formed in the Thermal Decomposition of [Mn(OAsPh3 )3I2 (SO2)2] (pages 264–265)

      Prof. Dr. Charles A. McAuliffe, Dr. Brian Beagley, Dr. George A. Gott, Anthony G. Mackie, Philomena P. MacRory and Dr. Robin G. Pritchard

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702641

      The reduction of Ph3AsO by SO2 presumably takes place in the ligand sphere of a manganese(II) complex. Reddish-violet crystals of the title compound [PhAs · I2], a typical iodine transfer complex are formed upon thermolysis of [Mn(OAsPh3)3I2(SO2)2] in a vacuum. The As–I–I unit is slightly bent and the I–I bond is relatively long (3.005(1) Å).

    24. Energy Transfer Luminescence of Europium(III) and Terbium(III) Cryptates of Macrobicyclic Polypyridine Ligands (pages 266–267)

      Béatrice Alpha, Prof. Dr. Jean-Marie Lehn and Dr. Gérard Mathis

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702661

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      The Eu3⊕- and Tb3⊕-cryptates of the ligands 1–3 can function as molecular light converters. The complexes give characteristic 1H-NMR spectra, and the Eu3⊕-cryptate can be electrochemically reversibly reduced (−535 mV vs SCE).

    25. Diastereoselective Diels–Alder Reaction on Carbohydrate Matrices (pages 267–269)

      Prof. Dr. Horst Kunz, Dipl.-Chem. Bernd Müller and Dirk Schanzenbach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702671

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      A complex or carbohydrate-bound acrylate and chlorotitanate determines the configuration of the Diels–Alder product of acrylate and cyclopentadiene. That (R)-2 and (S)-2 are formed in the ratio 93 : 7 can be rationalized in terms of the structure 1 for this complex.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Chemistry of Hydrocarbon Combustion. By D. J. Hucknall (pages 269–270)

      Klaus-Heinrich Homann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702691

    2. Book Review: Organische Chemie. By S. Hauptmann (pages 271–272)

      Henning Hopf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702712

    3. Book Review: Carbocation Chemistry. By P. Vogel (page 274)

      Herbert Mayr

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198702741