Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 1

January 1980

Volume 19, Issue 1

Pages 1–76

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Reaction Paths on Multidimensional Energy Hypersurfaces (pages 1–13)

      Priv.-Doz. Dr. Klaus Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000013

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      The number-crunching dinosaur—drawn by the author like all the other cartoons in this article—is intended to illustrate one aspect of the calculation of the minimum-energy reaction path: the time requirement. For instance, a point grid approach involving (only!) 1016 calculations at 1 second a time would require 109 years. In contrast, the method of locating saddle points and reaction paths by means of ascending and descending valley points soon gives the desired result.

    2. Chromatographic Resolution of Racemates. New analytical methods (17) (pages 13–24)

      Prof. Dr. Gottfried Blaschke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000131

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      Resolution of racemic mixtures into the enantiomers by conventional methods requires large amounts of material, much time, and great patience. This is where chromatography on synthetic polymers with optically active groups or on natural products such as starch or cellulose can help. Optical purity becomes very important in drugs where the two enantiomers often have extremely different activities.

    3. Determination of Morphological Properties of Swellable Solids by Size Exclusion Chromatography (pages 24–28)

      Prof. Dr. István Halász and Dr. Peter Vogtel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000241

      The pore structure of swellable ion exchangers or adsorbents for catalysis is of great importance in the industrial application of these solids. In general, the pore structure of such polymers depends upon the swelling agent and can therefore only be examined in the swollen state. This has now become possible by means of exclusion chromatography.

    4. A Model of Hydrogen-Bonded Liquids (pages 28–41)

      Prof. Dr. Werner A. P. Luck

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000281

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      A readily appreciated orientation defect model (treatment of H-bonds as a chemical equilibrium) can be used, with due caution, for quantitative estimates and for gaining an understanding of the properties of H-bonded liquids such as alcohols and water. No exact description of this most versatile medium is yet in sight.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of CH2-Bridged [4n + 2]Annulenes by a Building-Block Approach (pages 41–43)

      Prof. Dr. Emanuel Vogel, Dr. Hans M. Deger, Dr. Johannes Sombroek, Dipl.-Chem. Jürgen Palm, Dipl.-Chem Arwed Wagner and Dr. Johann Lex

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000411

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      Homologous series of syn-bridged annulenes are of interest for a deeper understanding of the Hückel rule. Dialdehydes like (3) could be key compounds for syntheses of such annulenes. The synthesis of (3) from the dialdehyde (1) was accomplished in three steps: reaction with (2) to give the diester, reduction to the diol, and oxidation to (3). This three-step sequence is also suitable for synthesis of the two next higher dialdehydes with three and four CH2 groups, respectively.

    2. Generation and Direct Observation of the Xanthenide Anion; a Stable 4n π-System (pages 43–44)

      Prof. Dr. A. G. Anastassiou and Prof. Dr. H. S. Kasmai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000431

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      The stable anion (1) can be regarded as an antiaromatic species; it is generated from xanthene with KNH2 in liquid ammonia. Skeletal rearrangements with ring contraction occurring in non-annelated heterocycles do not take place. The 1H-NMR spectrum of (1) is indicative of a paramagnetic ring current.

    3. Structural Investigations on (η12-[3.3]Paracyclophane)chromium(0) and Its Cation in (η12-[3.3]Paracyclophane)chromium(I) Triiodide (pages 44–45)

      Dr. Reinhard Benn, Dipl.-Chem. Norman E. Blank, Priv.-Doz. Dr. Matthias W. Haenel, Jochen Klein, Dipl.-Chem. Ali R. Koray, Dr. Klaus Weidenhammer and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000441

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      The first crystal structure analysis of a chromium insertion product in a cyclophane has been achieved on the salt (1), whose cation exists exclusively in the chair conformation. In contrast, according to its 1H-NMR spectrum, the corresponding chromium(0) compound is present in the boat conformation (2) and the chair conformation (3) in a ratio of 1:1 in solution at −70°C.

    4. Stable 4-Imino-1,2-oxazetidines from N-Neopentylidene-tert-butylamine N-Oxide and Isocyanides (pages 45–46)

      Priv.-Doz. Dr. Dietrich Moderhack and Dr. Michael Lorke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000451

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      Syntheses of four-membered rings by [3+1]-cycloaddition of isocyanides to 1,3-dipoles with internal octet stabilization are still rare. One example is the reaction of the nitrone (1) which affords the first stable 4-imino-1,2-oxazetidine.

    5. Chromium(II)-catalyzed Electrochemical Dehalogenation of β-Hydroxyhalides—Convenient Entry to Deoxynucleosides (pages 46–47)

      Dipl.-Chem. Josef Wellmann and Priv.-Doz. Dr. Eberhard Steckhan

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000461

      The dehalogenation of β-hydroxyhalides (halohydrins), as is often required in natural product syntheses, can be achieved by electrochemical reduction, especially by “indirect-electrolysis”. Chromium(II) perchlorate in the presence of butanethiol can be used as catalyst. The OH groups must be protected. This method avoids elimination to give the olefin.

      • equation image
    6. Intramolecular Cycloadditions of Carbonyl Ylides (pages 47–48)

      Univ.-Doz. Dr. Wolfgang Eberbach, Dipl.-Chem. Jürgen Brokatzky and Prof. Dr. Hans Fritz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000471

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      Stereoselective syntheses of heterocycles represent an important area of application of intramolecular 1,3-dipolar cycloaddition. With the aid of model compounds (1), n = 1, 2, it is demonstrated that also carbonyl ylides such as (2) and (3) can undergo this type of reaction. Reaction of (3), n = 1, affords (4) while reaction of (2), n = 1, 2, leads to the trans-coupled compounds corresponding to (4).

    7. Stereospecific Syntheses of Cycloheptatriene Trioxides (pages 48–49)

      Prof. Dr. Waldemar Adam NiH Career Awardee, 1975—80 and Dr. Metin Balci

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000481

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      All three cycloheptatriene trioxides(1a–c) have been obtained by permutation of three reaction steps in a directed synthesis from cycloheptatriene. These steps are: oxygenation with singlet oxygen to the endoperoxide, its thermal rearrangement to the syn-dioxide, epoxidation with peroxy acid.

    8. Cyclopropanimines by Photolysis of Pyrazolinimines; Thermal Reaction of an Excited State (pages 49–50)

      Prof. Dr. Helmut Quast, Dipl.-Chem. Andreas Fuss and Dr. Alfred Heublein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000491

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      A novel entry to cyclopropanimines(2) is afforded by the photolysis of the pyrazolinimines (1). The reaction is surprisingly strongly dependent upon temperature, but—as far as is known—hardly dependent upon solvent (benzene, cyclohexane). X in (1) and (2) is [DOUBLE BOND]NCH3, [DOUBLE BOND]NCH2C(CH3)3, and [DOUBLE BOND]N-c-C6H11.

    9. Short-Path Pyrolsis: Silabenzene (pages 51–52)

      Dr. Bahamn Solouki, Dr. Pavel Rosmus, Prof. Dr. Hans Bock and Prof. Dr. Günther Maier

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000511

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      Generation and PE spectroscopic detection of silabenzene(1) have been accomplished with a newly developed short-path pyrolysis set-up coupled with a photoelectron spectrometer. Assignment of the spectrum to (1) is based on SCF calculations.

    10. Silabenzene (pages 52–53)

      Prof. Dr. Günther Maier, Gerhard Mihm and Dr. Hans Peter Reisenauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000521

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      Silabenzene (1) is stable in an argon matrix at 10 K. The long-sought analog of benzene has been prepared by ester pyrolysis and by retro-ene cleavage.

    11. Crystal Structure of 2-Lithio-2-methyl-1,3-dithiane Tetramethylethylenediamine (pages 53–54)

      Dipl.-Chem. René Amstutz, Prof. Dr. Dieter Seebach, Paul Seiler, Dr. Bernd Schweizer and Prof. Dr. Jack D. Dunitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000531

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      Surprising structural features were revealed by an X-ray study of the title compound (1): it crystallizes as dimer and one molecule each of the solvent TMEDA (tetramethylethylenediamine) is coordinated in spirane fashion to a Li atom. The equatorial position of the lithium is thus possibly a result of steric rather than electronic factors.

    12. Preparation of 1-tert-Butyl-3-methyl-2-phenyl-Δ3-1,2-azaboroline and Utilization of Its Anion as a Complex Ligand Analogous to Cyclopentadienyl (pages 54–55)

      Dipl.-Chem. Joachim Schulze and Prof. Dr. Günter Schmid

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000541

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      Relatives of the “everyday” ligand cyclopentadienyl, such as the Δ3-1,2-azaboroline derivative (1), should permit preparation of numerous metal complexes. Complex (2), the first one to contain the anion of (1), resembles its cyclopentadienyl analog very closely.

    13. Synthesis and Properties of the First Organosilyl-Gallium Compounds (pages 55–56)

      Priv.-Doz. Dr. Lutz Rösch and Dr. Heinrich Neumann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000551

      Tris(trimethyl)silyl compounds of all GroupIIIB metals are known now that the synthesis of Ga(SiMe3)3 has been accomplished. The tetrahydrofuran adduct (1) initially obtained can be freed from solvent by sublimation in a high vacuum. Ga(SiMe3)3 resembles the indium derivative more closely than the (associating) aluminum derivative.

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    14. Stabilization of Diborane(4) Derivatives by tert-Butyl Groups: The First Tetraalkyldiborane(4) (pages 56–57)

      Dipl.-Chem. Werner Biffar, Prof. Dr. Heinrich Nöth and Hans Pommerening

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000561

      Thumbnail image of graphical abstract

      Boron compounds of type (alkyl)2B—B(alkyl)2, which have been sought for more than 40 years, have been independently synthesized by two research teams almost simultaneously and by the same pathway. Stepwise replacement of the methoxy groups of (1) by alkyl groups gave the tetraalkyldiboranes (4), (5) (R[DOUBLE BOND]Me), and (6) (R=tBuCh2). Tetra-tert-butyldiborane could not be prepared, while the silylborane (7), R[DOUBLE BOND]SiMe3, could.

    15. Persistent Tetraalkyldiboranes(4) (pages 57–58)

      Dipl.-Chem. Kaspar Schlüter and Prof. Dr. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000571

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      Boron compounds of type (alkyl)2B—B(alkyl)2, which have been sought for more than 40 years, have been independently synthesized by two research teams almost simultaneously and by the same pathway. Stepwise replacement of the methoxy groups of (1) by alkyl groups gave the tetraalkyldiboranes (4), (5) (R[DOUBLE BOND]Me), and (6) (R=tBuCh2). Tetra-tert-butyldiborane could not be prepared, while the silylborane (7), R[DOUBLE BOND]SiMe3, could.

    16. Tetrakis(trimethylsilyl)borate and Other Trimethylsilylborates (pages 58–59)

      Dipl.-Chem. Werner Biffar and Prof. Dr. Heinrich Nöth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000581

      Formation of silylborates appears to be the rule and that of silylboranes the (sterically determined) exception: attempts to synthesize B(SiMe3)3 from LiSiMe3 and B(OMe)3 in hexane yielded tetrakis(trimethylsilyl)borate. Accordingly, LiSiMe3 forms the strongly nucleophilic anion SiMemath image in hexane.—Li[B(tBu)4] is unknown.

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    17. The First Optically Active Cluster: Resolution of Enantiomers and Absolute Configuration of SFeCoMoCp(CO)8 (page 65)

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000651

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      Clusters with inherent optical activity were hitherto unknown. It has now proved possible to resolve the chiral cluster (1) into the enantiomers (1a) and (1b) via diastereomers with the phosphane (R)-PMePrPh. The ready accessibility of the three metal atoms in the thermally and configuratively stable enantiomeric clusters suggests the possibility of optical induction, e.g. in catalyses.

    18. Tetrathiafulvalenoparacyclophanes (pages 66–67)

      Prof. Dr. Heinz A. Staab, Dr. Joachim Ippen, Chu Tao-pen, Claus Krieger and Barbara Starker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000661

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      In the “metallic” conducting 1:1 complex of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), donor and acceptor molecules form separate stacks in the crystal. In order to enforce other TTF/TCNQ arrangements by altering the molecular architecture the phane-like bridged TTF-paracyclophanes (1), n = 3, and (2) were first synthesized. To do this a novel reaction sequence had to be developed which also facilitated synthesis of the tetrathiafulvalenophanes (3)/(4) (and the corresponding [2.2]-derivatives). (3)/(4) and TCNQ form a 1:4 complex having a conductivity of σ = 5 × 10−3 to 10−2 [Ω cm]−1 (single crystal, long axis, 300 K).

    19. [2.2]- and [3.3]Tetrathiafulvalenophanes (pages 67–69)

      Dr. Joachim Ippen, Chu Tao-pen, Barbara Starker, Dieter Schweitzer and Prof.-Dr. Heinz A. Staab

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000671

      Thumbnail image of graphical abstract

      In the “metallic” conducting 1:1 complex of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), donor and acceptor molecules form separate stacks in the crystal. In order to enforce other TTF/TCNQ arrangements by altering the molecular architecture the phane-like bridged TTF-paracyclophanes (1), n = 3, and (2) were first synthesized. To do this a novel reaction sequence had to be developed which also facilitated synthesis of the tetrathiafulvalenophanes (3)/(4) (and the corresponding [2.2]-derivatives). (3)/(4) and TCNQ form a 1:4 complex having a conductivity of σ = 5 × 10−3 to 10−2 [Ω cm]−1 (single crystal, long axis, 300 K).

    20. 6-Fulveneselone (pages 69–70)

      Dipl.-Chem. Reinhard Schulz and Prof. Dr. Armin Schweig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000691

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      Highly reactive fulveneselone(2) has been generated from benzoselenadiazole (1) by vacuum flash thermolysis and characterized by PE spectroscopy. The dark red species (2) reacts with explosive violence to give a brown polymer at as low a temperature as 77 K.

    21. μ-Alkylthio- and μ-Arylthio-μ-chlorodicarbonylbis (tri-tert-butylphosphane)dirhodium: Dinuclear Rhodium Complexes with Different Bridging Ligands (pages 70–71)

      Prof. Dr. Herbert Schumann, Dipl.-Chem. Guy Cielusek and Priv.-Doz. Dr. Joachim Pickardt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000701

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      Hydrogenations, decarboxylations, and isomerizations are catalyzed by the dirhodium complexes of type (3), the first stable compounds having a Cl and an SR bridge. The structure of (3), R=tBu, has been elucidated by crystal structure analysis.

    22. Synthesis and Reactions of Diorganophosphinite Complexes of Gold (pages 71–72)

      Prof. Dr. Hubert Schmidbaur and Aref A. M. Aly (M. A.)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000711

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      The donor properties of the phosphorus atom are only slightly poorer in phosphinite ions [R2PO] than in phosphanes R3P; the oxygen atom can also be coordinated. The phosphane-gold(1) phosphinite (1)2 which is stable to air, moisture, and heating up to 350°C, and the salt-like compounds (2), R[DOUBLE BOND]Me, Ph, represent new examples of this type.

    23. Activation and Sulfur-Atom Transfer Reaction of Cluster-Bonded Smath image-Bridge Ligands: Synthesis of the New Cluster [Momath imageS4(CN)9]5− from [Momath imageS(S2)6]2− and CN (pages 72–73)

      Prof. Dr. Achim Müller and Dipl.-Chem. Uta Reinsch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000721

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      Activated ligands of clusters are of topical interest in bioinorganic chemistry of in catalytic reactions. The reaction type shown below could be verified for the first time for the title compounds. The resulting highly symmetrical cluster anion (1) has been characterized by X-ray structure analysis.

    24. Nucleophilic Elimination-Cycloaddition of α,ω-Alkanediyl Bis(triflates), a Novel Method for the Synthesis of Metallacycles with Reactive Metal-Carbon σ Bonds (pages 73–74)

      Prof. Dr. Ekkehard Lindner and Dipl.-Chem. Hans-Jürgen Eberle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000731

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      Stable heterocycles (1) with Mn[BOND]C σ-bond—of significance for catalytic reactions—have been synthesized by reaction of manganese-containing dianions and alkylenebis(triflates) (Z[DOUBLE BOND]OSO2CF3). Insertion of CO into the M—C bond of a metallacycloalkane has now be accomplished for the first time with (1), X[DOUBLE BOND]CH2CH2.

    25. Lithium Nitride Halides—New Solid Electrolytes with High Li+ Ion Conductivity (pages 74–75)

      Dipl.-Chem. Peter Hartwig, Dr. Werner Weppner, Dr. Winfried Wichelhaus and Prof. Dr. Albrecht Rabenau

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198000741

      Solid ionic conductors are a treasure trove for modern technology. Among the lithium nitride halides which have now been thoroughly studied, the thermally stable Li1.8N0.4Cl0.6 can be utilized as thin low-resistance layers, e.g. in printed circuits. Transfer experiments and EMF measurements confirmed that the electrolytic current flow is due to Li+ ions.

  3. Book Reviews

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

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