Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 5

May 1981

Volume 20, Issue 5

Pages 413–486

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104131

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 5/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104132

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Transition Metal-Nitrogen Multiple Bond (pages 413–426)

      Prof. Dr. Kurt Dehnicke and Prof. Dr. Joachim Strähle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104133

      Thumbnail image of graphical abstract

      An M[TRIPLE BOND]N bond or an M[DOUBLE BOND]N[DOUBLE BOND]M bridge occur in triazido(nitrido)pyridinemolybdenum (1) or Br5Ta[DOUBLE BOND]N[DOUBLE BOND]TaBr5(2), respectively. Numerous examples of compounds with these structural elements are known today.

    2. Photoelectron Spectra and Molecular Properties: Real-Time Gas Analysis in Flow Systems (pages 427–444)

      Prof. Dr. Hans Bock and Dr. Bahman Solouki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104271

      Thumbnail image of graphical abstract

      The PE-spectroscopic analysis and optimization of gas reactions has been well tried and tested on many systems: Using this procedure to study pyrolyses—on a millimol scale and within a few hours—the temperatures of the various decomposition channels can be determined, the major products characterized and, if neccessary, yields improved.

    3. Structure and Bonding in Cyclic Sulfur-Nitrogen Compounds—Molecular Orbital Considerations (pages 444–452)

      Prof. Dr. Rolf Gleiter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104441

      Thumbnail image of graphical abstract

      Classification of the apparently boundless structural multiplicity of SN-rings is possible within the framework of an MO model: The simple Hückel rule can even be applied to this system. The structures of e.g. S4N4, S4Nmath image, S4Nmath image, S4Nmath image, and S5N6 can be explained on the basis of an eight-membered SN-ring with twelve π electrons.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Photochemical Synthesis of Bis(η2-methyl acrylate)tricarbonylruthenium (pages 452–454)

      Dr. Friedrich-Wilhelm Grevels, Dr. Johannes G. A. Reuvers and Prof. Dr. Josef Takats

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104521

      Thumbnail image of graphical abstract

      The first (η2-olefin)2Ru(CO)3 complex, the title compound (1), was obtained by irradiation of Ru3(CO)12 and methyl acrylate. The reaction proceeds via2-olefin)Ru(CO)4. Two fluxional systems of (1)-isomers are present in solution and can be differentiated by the arrangement of the olefin ligands.

    2. Charge-Transfer Interactions between the Ligands of a Ternary ATP-Cu2+-Phenanthroline Complex (pages 460–461)

      Priv.-Doz. Dr. William S. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104601

      The first elucidation of the structure of a metal complex of ATP has been carried out on [Cu(ATP)(phen)]2·7H2O. This complex could be isolated at pH = 2.8. The two independent Cu atoms exhibit highly distorted octahedral coordination: The two N atoms of the phenanthroline and two phosphate O atoms are equatorial ligands, two further phosphate O atoms are axial. Complexes of this type are interesting as models of ternary enzyme-M2+-ATP complexes which participate in enzymatic phosphate transfer.

    3. Insertion of —CN into the Metal-Carbene Carbon Bond: A Route to Methyleneaminocarbene Complexes (pages 461–463)

      Dr. Helmut Fischer and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104611

      Thumbnail image of graphical abstract

      Novel, readily accessible carbene complexes(1)containing the

      carbenestructural moiety are characterized by their mode of formation (attack of the entering molecule at the ligand) and the unusual nπ—pπ bond between Ccarbene and NMe2.

    4. Ligand Mobility in Carbyne Complexes (pages 463–464)

      Dr. Helmut Fischer, Dipl.-Chem. Andreas Motsch, Dr. Ulrich Schubert and Dr. Dietmar Neugebauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104631

      Thumbnail image of graphical abstract

      Unusual reactions of carbyne complexes have been observed with the octahedrally coordinated compounds (1) to (3). Thus reaction of (1) with NR4X (X = halogen) leads, via isomerization, to the neutral complex (2). The complex (2) is similarly obtained in an equilibrium reaction from (3) and PPh3.

    5. Crystal structure of 2-Lithio-2-phenyl-1,3-dithiane-Tetrahydrofuran-Tetramethylethylenediamine (1/1/1); Electron-Density Difference Maps for Lithio-methyl- and Lithio-phenyl-dithiane (pages 465–466)

      Dipl.-Chem. René Amstutz, Prof. Dr. Jack D. Dunitz and Prof. Dr. Dieter Seebach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104651

      Thumbnail image of graphical abstract

      A non-ionic and a contact ion pair LiC bond have been detected in complexed 2-methyl- (1) and 2-phenyl-2-lithio-1,3-dithiane (2), respectively. This was achieved by determination of bond electron densities from the X-ray diffraction data of single crystals of the two compounds.

    6. Ca3AlAs3—An Intermetallic Analogue of the Chain Silicates (page 466)

      Dr. Gerhard Cordier and Prof. Dr. Herbert Schäfer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104661

      Chains of AlAs4 tetrahedra have been detected in the intermetallic compound Ca3AlAs3. Hence, it could be shown for the first time that such groups of chains also occur in Zintl phases—and not only in silicates and polyphosphates.

    7. Macrotricyclic Quaternary Ammonium Salts: Enzyme-Analogous Activity (pages 466–468)

      Dr. Franz P. Schmidtchen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104662

      Thumbnail image of graphical abstract

      Reactions in presence of the low molecular weight, modifiable enzyme models(1)and(2) lead in some cases to surprising results. Thus, (1) inhibits the reaction of fluorodini-trobenzene with Nmath image, whereas (2) accelerates this reaction, as well as that of methyl iodide with Nmath image and the decomposition of erythro-(3).

      • equation image
    8. Tetracyclo[4.1.0.02,4.03,5]heptanes from 7,8-Diazatetracyclo[4.3.0.02,4.03,5]non-7-enes (pages 468–469)

      Prof. Dr. Manfred Christl and Dipl.-Chem. Erich Brunn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104681

      Thumbnail image of graphical abstract

      For a systematic study of the tetracyclic cycloheptatriene isomer(3), R = H, and its 7-methyl- and 7-aryl-derivatives, the reaction scheme outlined below has proven especially useful.

    9. Chemiluminescence of Tricarbonyl(chloro)(1,10-phenanthroline)rhenium(I) during the Catalytic Decomposition of Tetralinyl Hydroperoxide (pages 469–470)

      Prof. Dr. Arnd Vogler and Dr. Horst Kunkely

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104691

      Thumbnail image of graphical abstract

      What does the catalytic decomposition of hydroperoxides involve? On addition of the complex [Re(Phen)(CO)3Cl], (1) rapidly decomposes in boiling tetralin to (2) and water with emission of bright light. The spectrum of this chemiluminescence is identical with that of the photoluminescence of the pure complex. From this result and from intensity/concentration relationships it can be concluded that the Schuster mechanism of catalysis is involved.

    10. Nitrogen Dioxide and the Isoelectronic COOH Group as 5-Electron Donors in Carbonylmetal Complexes; Preparation and Characterization of the First “Metallacarboxylic Acid” (pages 470–471)

      Dipl.-Chem. Barbara K. Balbach, Dr. Frantisek Helus, Dipl.-Chem. Franz Oberdorfer and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104701

      No ReRe bonds, but NO2 and COOH as 5-electron donors characterize the novel trinuclear complexes (1) and (2). They are formed along with other complexes in the photolysis of Re2(CO)10 in the presence of NO and cyclo-octatetraene. The complexes (1) and (2) contain a Re(CO)4[BOND]C(O)[BOND]Re(CO)4[BOND]N[BOND]O[BOND] and [BOND]C[BOND]O[BOND] ring, respectively, with an Re(CO5)[BOND]O-group on the N or C atom.

      • equation image
    11. Preparation of η7-C7H7Mo(CO)2EO2CH3 (E = S, Se, Te); the First Insertion of TEO2 into a Metal-Carbon Bond (pages 471–472)

      Dipl.-Chem. Winfried Dell and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104711

      Thumbnail image of graphical abstract

      The isolation of “insertable” TeO2 from the crystal has been achieved for the first time in a metal evaporator. Reaction of (1) with the TeO2, after condensation at −196 °C in an ether matrix, yielded the insertion product (4) after 8 weeks at −78 °C.

    12. A Triple-Decked Sandwich Complex of Rhodium with 1,4-Diborabenzene as Bridging Ligand (pages 472–473)

      Prof. Dr. Gerhard E. Herberich, Dr. Bernd Hessner, Prof. Dr. Gottfried Huttner and Dipl.-Chem. Laszlo Zsolnai

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104721

      Thumbnail image of graphical abstract

      The first sandwich complex with a six-membered bridging ligand, namely the cation (1), was obtained from the corresponding mono-nuclear sandwich complex in CF3COOH. The 30-valence electron complex (1) is at the same time the first triple-decked complex containing a heavy transition metal. It has a hexagonal-pyramidal structure previously not observed in 8-cornered closo-polyhedra.

    13. Stable Metal-Phthalocyanines as Poison-Resistant Catalysts in Homogeneous Catalysis: Reduction of Organic Compounds with NaBH4 (pages 473–475)

      Dr. Heiner Eckert and Yvonne Kiesel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104731

      The metal phthalocyanines MPc (M = VO, Mn, Fe, Co, Pd) related to vitamin B12 are stable reduction catalysts having advantageous properties and also potential industrial applications. These compounds are soluble (MPc) during the reduction (with NaBH4) and insoluble (MPc) under non-reducing conditions. They enable selective reductions and are not, or rarely, poisoned by SH, CN, or I.

      • equation image
    14. P,P,P′,P′-Tetraphenylethylenediphosphane-dichlorogermanediyl: A Fluxional Phosphorus Ylide (page 475)

      Prof. Dr. Wolf-Walther du Mont, Dr. Gero Rudolph and Dipl.-Chem. Norbert Bruncks

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104751

      Thumbnail image of graphical abstract

      An interesting borderline case between chelate complex and conventional ylide is the diphosphane-germanediyl (1). R = C6H5. It is the first fluxional ylide in which the “carbene-analogous” GeCl2 moiety is still mobile in solution, even at −80 °C (31P{1H}-NMR).

    15. [(−)-diop]RhCl—Catalyzed Asymmetric Addition of Bromotrichloromethane to Styrene (pages 475–476)

      Prof. Dr. Shinji Murai, Ryoji Sugise and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104752

      Thumbnail image of graphical abstract

      The catalytic preparation of a chiral alkyl bromide in which the chirality center is formed by asymmetric addition of Br[BOND]CCl3 to a C[DOUBLE BOND]C double bond was achieved in the presence of the chiral catalyst [(−)-diop]RhCl. This is the first example of an asymmetric catalytic reaction involving coupling of a C-halogen bond.

    16. Introduction of an Optically Active Ligand into Transition Metal Complexes with Five Independent Ligands (pages 476–477)

      Dr. Ernesto Colomer, Prof. Dr. Robert J. P. Corriu and Dr. Ing. André Vioux

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104761

      Thumbnail image of graphical abstract

      A Mo-compound containing five different ligands which does not isomerize below 100 °C has been prepared by reaction of the salt (1) with benzyl bromide. In (2), M = Mo, R = benzyl, the CH2 protons are magnetically non-equivalent. Complexes such as (2) are of interest as potential educts for other stable chiral transition metal compounds.

    17. Cleavage of Silicon- and Germanium-Cobalt Bonds: Change of Stereochemistry with Different Ligands (pages 478–479)

      Dr. Geneviève Cerveau, Dr. Ernesto Colomer and Prof. Dr. Robert J. P. Corriu

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104781

      Thumbnail image of graphical abstract

      In order gain more knowledge about Co[BOND]Si and Co[BOND]Ge bonding the optically active complexes (S)-(1) (M [BOND] Si or Ge and L [BOND] CO, P(OPh)3, PPh3) and (S)-(2) (M [BOND] Ge, L [BOND] nBuC(OEt), containing these bonds have been synthesized and cleaved. The compounds (S)-(1) react with 60–91% inversion and compounds (S)-(2) with 55% retention.

    18. “Isolated” Olefinic Double Bonds as 2π-Components in [8 + 2]-Cycloadditions (pages 481–483)

      Dipl.-Chem. Martin Riediker and Dr. Walter Graf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104811

      Thumbnail image of graphical abstract

      Diels-Alder reactions with inverse electron demand open up many interesting possibilities. Thus the heterocyclic 8π electron system (1) reacts with cyclo-hexene to give the tricycles (2), which form pyridyl-substituted aldehydes or ketones on deprotonation with ring opening.

    19. MoIV in Aqueous Solutions: The Trinuclear Cluster [MoIVO4F9]5−, the First Species Isolated from Mineral Acid Solution (pages 483–484)

      Prof. Dr. Achim Müller, Andreas Ruck, Mechthild Dartmann and Dipl.-Chem. Uta Reinsch-Vogell

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104831

      Thumbnail image of graphical abstract

      What species are present in acid, aqueous, MoIV-containing solutions? This long discussed question has now been answered in one case: In the presence of HF and NH4F the species (NH4)5[Mo3O4F9]·NH4F·H2O could be isolated.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Statistical Mechanics of the Liquid Surface. By C. A. Croxton (pages 484–486)

      Helmut Bertagnolli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198104842

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