Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 10

October 1984

Volume 23, Issue 10

Pages 747–830

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 10/1984)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407471

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      The title page shows a “Möbius cube”, which should encourage attempts at realizing the virtually impossible. Not impossible, but highly improbable, was the successful synthesis of chiral heteromacrocycles with 1,4-dihydropyridine, amino acid, crown ether, and macrolide part structures via use of cesium ions. Such compounds have a variety of fascinating properties. Further details are reported by R. M. Kellogg in a review article on p. 782.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Gas Chromatographic Separation of Enantiomers on Optically Active Metal-Complex-Free Stationary Phases. New Analytical Methods (24) (pages 747–765)

      Prof. Dr. Volker Schurig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407473

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      The exact determination of enantiomeric compositions and control of the purity of enantiomers in up to 99.9% exemplify what can be accomplished with the method mentioned in the title. A prerequisite is a chiral phase such as 1 for which the substance to be separated shows a chemical affinity.

    2. Photochemistry of Alkyltransition-Metal Complexes (pages 766–782)

      Priv.-Doz. Dr. Helmut G. Alt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407661

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      Alkyltransition metal complexes have proven indispensable, not only in industrial but also in biological processes (coenzyme B12!). In the photochemical dealkylation of thermally stable complexes, highly reactive intermediates are formed which can be trapped and used preparatively.

    3. Chiral Macrocycles as Reagents and Catalysts (pages 782–794)

      Prof. Dr. Richard M. Kellogg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407821

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      The “artificial hydrolases” of type 1 containing at least 17 ring members combine a wealth of structural features of interesting classes of compounds. These chiral macrocycles can, e.g., differentiate between the prochiral sides of carbonyl compounds R1[BOND]CO[BOND]R2 in a predictable way. In a newly developed method for CC coupling they serve as ligands for transition-metal ions.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Conversion of “LiNS(F)OCMe3” into an (Li8)2 Double Cluster (pages 795–796)

      Dr. Wilhelm Isenberg, Prof. Dr. Rüdiger Mews and Prof. George M. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407951

      Nucleophilic substitutions of thiazyl fluoride (N[TRIPLE BOND]SF) should afford access to thiazyl derivatives R[BOND]SN. On reaction of N[TRIPLE BOND]SF with LiOCMe3, the primary product “LiNS(F)OCMe3” could be trapped for the first time as the double cluster 1 and subsequently characterized. A molar ratio of NSF: nucleophile of 1:1 is essential for the formation of 1.

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    2. Asymmetic Microsomal Epoxidation of Simple Prochiral Olefins (pages 796–797)

      Prof. Dr. Volker Schurig and Dipl.-Chem. Dorothee Wistuba

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407961

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      The enantioselectivity of enzymatic epoxidation as a function of the olefin structure was checked for the simplest substrate. Decisive in this connection was the analysis by complexation gas chromatography using an optically active nickel compound.

    3. Easy Rotation about the Exocylic Carbon-Carbon Bond in Lithium α-Aminoenolates: A Comparison (pages 797–798)

      Prof. Dr. Gernot Boche, Ferdinand Bosold and Dipl.-Chem. Robert Eiben

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407971

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      The rotation barriers in the title compounds could be determined by 1H-NMR spectroscopy; ΔG+ in 1 is 17.5 (70°C), in 2 14.0 (25°C), and in 3 < 8 kcal/mol (−106°C). 3, with its cyclic (“aromatic”) 6π-electron system, is energetically preferred over 2 with its acyclic system; in contrast, the 8π- “antiaromaticity” in 1 cannot be of significance energetically.

    4. Iterative Cyclopentane Annulation of α,β-Enones (pages 798–799)

      Dipl.-Chem. Maria Dorsch, Prof. Dr. Volker Jäger and Dipl.-Chem. Wolfgang Spönlein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407981

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      A novel method for the stepwise annulation of cyclopentane rings uses α,β-enones as starting material. α,β-Enones with an annulated five-membered ring are obtained in a few steps and are useful as educts for further reactions.

    5. Red α-Indium(III) Iodide (pages 799–800)

      Prof Dr. Rüdiger Kniep and Dipl.-Chem. Peter Blees

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198407991

      Indium(III) iodide is dimorphic: As is already well-known, individual domains in yellow β-InI3 transform irreproducibly into red α-InI3 at low temperature. It has now been possible to gain information about the structure of this phase by way of the InI3[BOND]InBr3 system. On cooling a melt, mixed crystals of α-InI3−xBrx (x ≈ 1) could be grown which were suitable for X-ray structure analysis.

    6. Acyl- and Thioacylketenes: Synthesis of 3-Benzoly-4-phenylthiet-2-one (pages 800–802)

      Prof. Dr. Curt Wentrup, Hans-Wilhelm Winter, Gerhard Gross, Klaus-Peter Netsch, Prof. Dr. Gert Kollenz, Dr. Walter Ott and Adolf G. Biedermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408001

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      Insights into the valence tautomerization 1 ⇌ 2 were obtained using dibenzylketene and benzoyl(thiobenzoyl)ketene as examples. The former dimerizes, whereas the latter cyclizes to the thietone, whereby an equilibrium exists in the gas phase. The ketenes were generated by flash pyrolysis from furan and thiophenedione, respectively.

    7. A Novel Ketoketene — Ketoketene Rearrangement (page 802)

      Prof. Dr. Curt Wentrup and Klaus-Peter Netsch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408021

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      The degenerate 1,3-shift of the phenyl group in benzoylketene was demonstated by 13C-labeling. In the flash pyrolysis of Ph13CO[BOND]CH2[BOND]COOMe, benzoylketene is formed in which the labeling is distributed about 1:1 between the ketene and the ketone carbonyl C atoms.

    8. C[DOUBLE BOND]C Stretching Frequencies in Model Compounds of the Protonated Retinal Schiff Base (pages 803–804)

      Timor Baasov and Dr. Mordechai Sheves

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408031

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      Do the changes in ν(C[DOUBLE BOND]C) in visual pigments and bacteriorhodopsin orginate from interaction of the chromophore with charges in the protein moiety? This question was investigated by FT-IR investigations on the model compounds 1–3. That ν(C[DOUBLE BOND]C) in them is significantly higher than in the unprotonated parent compounds suggests that the answer to the question is “yes”.

    9. Vanadium Thiolate Complexes with VS5- and VOS4-Centers: Synthesis and Structure of [VS(SC2H4S)2]2⊖ and Na2[VO(SC2H4S)2]·8MeOH (pages 804–805)

      Dipl.-Chem. Detlef Szeymies, Prof. Dr. Bernt Krebs and Dr. Gerald Henkel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408041

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      The anion [VS(SC2H4S)2]2⊖ is the first five-fold coordinated vanadium complex with complete S-substitution and at the same time the first sulfide-thiolate complex of vanadium (see 1). It was prepared by reduction of VSmath image with 1,2-ethanedithiolate and isolated as the Ph4P salt.

    10. Synthesis of an all-cis-Organocyclotriphosphane (P3-Nortricyclane) and its Pentacarbonylchromium Complex (pages 805–806)

      Prof. Dr. Jochen Ellermann and Alfons A. M. Demuth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408051

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      An unsymmetrical chromium complex 1 is formed by triphosphanotricyclane, which was obtained for the first time from MeC(CH2Br)3 and NaP/KP. The coordination tendency of the ligand is especially interesting, since the analogous (Me3Si)3P7 does not form complexes.

    11. Stabilization of Sulfur Monoxide by Coordination to Transition Metals (pages 806–807)

      Prof. Dr. Wolfdieter A. Schenk, Dipl.-Chem. Johanna Leissner and Dr. Christian Burschka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408061

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      The complexation of SO is one possible way of stabilizing this classical small molecule. Fragmentation of thiirane S-oxide ([RIGHTWARDS ARROW]SO + ethylene) in the coordination sphere of Rh and Ir afforded square-planar complexes containing an angular M[BOND]S[BOND]O moiety.

    12. A Facile Route to 1,4,7-Trithiacyclononane (pages 807–808)

      Prof. Dr. Dieter Sellmann and Dipl.-Chem. Lothar Zapf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408071

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      An increase from 4% to 60% in the yield of 1,4,7-trithiacyclononane is achieved by a new synthetic method. The key step is the “template” alkylation of 1 with 1,2-dibromoethane at the molybdenum(0) center.

    13. Synthesis of the all-L-Configurated Cyclohexadepsipeptide cyclo-[L-Val-L-Lac]3 by the Peoc/Acid Chloride Method (pages 808–809)

      Prof. Dr. Horst Kunz and Dipl.-Chem. Hans-Georg Lerchen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408081

      The cyclization of linear depsipeptides is known to be especially difficult when only building blocks having the same configuration are present or when the amino acid residues are not N-methylated. Ring closure to give 1 was accomplished with the acid chlorides of Peoc-protected depsipeptides, despite simultaneous occurrence of both complicating factors.

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    14. Unusual Conversion of an Alkynetungsten Complex into a Tungstenacyclopropane Compound by Nitrosyl Chloride (pages 809–810)

      Priv.-Doz. Dr. Helmut Guido Alt, Dipl.-Chem. Heidi Ingrid Hayen, Dr. Heinz-Peter Klein and Prof. Dr. Ulf Thewalt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408091

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      Novel complexes such as 1a, b containing a WC2 ring are accessible by reaction of the corresponding acetylene complex CpW(CO)(C2H2)(COMe) with ClNO. Further diastereomers are not formed. 1a, b cannot be prepared by photoinduced reaction of CpW(CO)2NO with olefins.

    15. Spherical Host Molecules for the Complexation of Aromatic Hydrocarbons in Aqueous Solution (pages 810–812)

      Dr. François Diederich and Klaus Dick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408101

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      A three-dimensional cavity is contained in the novel host molecules, in which three moieties 1, R′ = Et, are coupled via two branched bridges. The host with N(CH2[BOND])2(CO[BOND]) bridges forms 1 : 1 complexes with arenes in aqueous solution. Arenes are complexed much more weakly by the host with N(CH2[BOND])3 bridges.

    16. Arsanediyl (Arsinidene) and Diarsene Complexes by Metal-Induced Degradation of Monoarsane (pages 812–814)

      Prof. Dr. Wolfgang A. Herrmann, Basile Koumbouris, Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408121

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      Managanese complexes with [BOND]AsH[BOND] and

      as bridging ligands could be synthesized from the labile tetrahydrofuran(thf)-complex (C5Me5)Mn(CO)2 (thf) and AsH3. The AsH-complex of 1 with functionalizable bridge is, in turn, an educt for interesting novel complexes.

    17. (PMe3)3MS7(M = Ru, Os): The First Polysulfido Metal Complexes with a Tridentate S2math image Ligand (pages 814–815)

      Josef Gotzig, Prof. Dr. Arnold L. Rheingold and Prof. Dr. Helmut Werner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408141

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      An Ms7 bicycle has been surprisingly obtained from the Ru- and Os-complexes 1. Reaction of 1 with S8 leads to formation of the MS6 species 2. On attempting to grow single crystals of 2, it was converted into the MS7-analogue 3 (X-ray structure analysis).

    18. Diazaboracyclopropane (pages 815–816)

      Prof. Dr. Uwe Klingebiel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408151

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      A compound containing a BN2 ring was prepared as outlined below. Its structure was elucidated, inter alia, by 1H-, 11B-, 13C-, 14N-, and 29Si-NMR spectroscopy and by a cryoscopic determination of Mr.

    19. P4-Degradation with and without Disproportionation (pages 816–817)

      Prof. Dr. Alfred Schmidpeter, Dipl.-Chem. Günther Burget, Prof. Dr. Hans Georg von Schnering and Dr. Dieter Weber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408161

      The cleavage of P4 by diphenyl or diethyl phosphinite OPRmath image proceeds with or without disproprotionation, depending upon the molar ratio. With 0.9 OPRmath image, P4 also gives the OP(R2)PP(R2)O ions 1 and Pmath image; with 2.4 OPRmath image, 1 is likewise formed, but along with Pmath image. With a molar ratio of 1 :4, on the other hand, P4 is degraded without disproportionation. The two P2-halves are stabilized as the OP(R2)PPP(R2)O2⊖ ion.

    20. [Li(tmeda)]3P7—A Solvated Ion Complex of Trilithium Heptaphosphide (pages 817–818)

      Dr. Wolfgang Hönle, Prof. Dr. Hans Georg von Schnering, Prof. Dr. Alfred Schmidpeter and Dipl.-Chem. Günther Burget

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408171

      A nice example for the stepwise transition from the polymeric solid to a solution in which solvated and separated ions predominate is provided by the Li3P7 system. In solvent-free Li3P7, all the P atoms participate in the coordination of the Li atoms, and the Li atoms always belong to several P7 groups, whereas in [Li(tmeda)]3P7 the Li atoms are only coordinated by the twofold bonded P atoms of one P7-group and by the solvent. The title complex can be regarded as a model for the species in solution. In this case the Li atoms would be of significance for the valence fluctuation in Pmath image.

    21. Novel Double-Layered Annulenes—Models for the Investigation of Successive Electron Transfers (pages 818–820)

      Dr. Wolfgang Irmen, Dr. Walter Huber, Dr. Johann Lex and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408181

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      The coupling of two 14π-perimeter systems by internal bridges is realized in the compounds 1. The layer separation is controlled by the length of the bridge. In the radical anions 1⊙⊖, n = 3, the spin density is delocalized over both annulene moieties, whereas in 1⊙⊖, n = 8, it is localized within one π-system. 1⊙⊖, n = 4, represents an intermediate case.

    22. [(CO)3PPh3FeCNiPr2], a Novel Stable Carbyneiron Complex Cation (pages 820–821)

      Prof. Dr. Ernst Otto Fischer, Dipl.-Chem. Johannes Schneider and Dr. Dietmar Neugebauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408201

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      A cation with Fe[TRIPLE BOND]C bonding is contained in the isolable carbyne complex 2, which was prepared from the carbene complex 1 and BCl3 and characterized by X-ray structure analysis. 1, with PPh3 replaced by CO, does not react in an analogous fashion with BCl3.

    23. Macrobicyclic Polyethers as V-Shaped Hosts for cis-Diammine-Transition Metal Complexes (pages 821–823)

      David R. Alston, Alexandra M. Z. Slawin, Dr. J. Fraser Stoddart and Dr. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408211

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      Ligands of type 1 with three polyether chains between two benzene rings were specifically designed to coordinate cis-diammine complexes such as [Rh(cod)(NH3)2][PF6]. 1, X [DOUBLE BOND] OCH2CH2O, O-o-C6H4[BOND]O, etc. does, in fact, form 1:1 adducts with the Rh-complex, both in solution are mainly held together by H bridges.

    24. Crown Ether Complexes of Phosphonium Salts — The X-Ray Structure Analysis of [(Ph3PMe)2·[18]Crown-6][PF6]2 (pages 824–825)

      Billy L. Allwood, Dr. Howard M. Colquhoun, Dr. John Crosby, David A. Pears, Dr. J. Fraser Stoddart and Dr. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408241

      A higly symmetric cation consisting of two phosphonium ions and a crown ether molecule is obtained in crystalline 1. In 1 the direction PMe…Me′[BOND]P′ coincides with the symmetry axis; the 18C6 host is oriented at right angles to this. All methyl H atoms are bound by discrete H bridges at individual O atoms. These H bridges are in each case directed towards the “rear side” of the crown ether ring.

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    25. An Extraordinary Structure and Topomerization Mechanism for “Diboramethylenecyclopropane” (pages 825–826)

      Dr. Peter H. M. Budzelaar, Prof. Dr. Paul von Rangué Schleyer and Prof. Dr. Karsten Krogh-Jespersen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408251

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      A three-center π bond and a BC double bond are contained in the C2B2H4 isomer 1, according to theoretical investigations. 1 is the parent compound of 2, the first species with B [DOUBLE BOND] C bonding. The intermediates proposed for the topomerization could explain a few reactions of 2.

    26. 1,3-Diboretanes (pages 826–827)

      Rolf Wehrmann, Dr. Hartmut Klusik and Prof. Dr. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198408261

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      The synthesis of the previously only theoretically treated title compound was accomplished using as starting material the heterocycle 2 mentioned in th previous communication. It reacts, e.g., with bis(trimethylsilyl)acetylene to give 1.

  3. Book Reviews

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