Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 12

December 1981

Volume 20, Issue 12

Pages 991–1085

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Pyramidal Carbocations (pages 991–1003)

      Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198109913

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      Pyramidal cations are now regarded as the connecting link par excellence between organic and organometallic chemistry. They play a cardinal role in the gas phase chemistry of organic cations. Whereas the prototype (I) previously evaded detection in the condensed phase, the stable ions shown below could be generated and unequivocally characterized in superacid media.

    2. Physical Methods for the Microanalysis of Solids—General Significance, Recent Developments, and Limitations (pages 1004–1013)

      Prof. Dr. Manfred Grasserbauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110041

      Demanding tasks in the characterization of solid systems by physical methods include, inter alia, the direct identification of compounds in solid phases and the quantitative elemental analysis of arerosol particles (e.g. asbestos fibers) in the submicrometer region. Important developments in this area are to be ascribed, in part, to the increase in information content of the analytical signals by application of mathematical methods and to the possibility nowadays of investigating extremely small amounts and concentrations of substances.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Gd5Cl9C2: A Structure with Two Condensed Metal Octahedral and Interstitial C2 Groups (pages 1013–1014)

      Prof. Dr. Arndt Simon, Dr. Eberhard Warkentin and Dr. René Masse

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110131

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      The structure of the gadolinium compound Gd5Cl9C2 is surprising in two respects: On the one hand, a novel cluster consisting of two edge-to-edge coupled metal octahedra is present, on the other, this is the first lanthanoid cluster compound in which the octahedral centers are occupied—namely, by C2-groups.

    2. Diels-Alder Reaction of Cyclopentadiene with Acrylic Acid Derivatives in Heterogeneous Phases (page 1014)

      Dr. habil. Harun Parlar and Rotraud Baumann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110141

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      The ratio of exo-/endo-adducts formed in the reaction of acrylic acid derivatives (1) with cyclopentadiene is hardly influenceable in the homogeneous phase; in contrast, in the heterogeneous phase it strongly depends on the carrier material. For example, when acrylonitrile reacts with cyclopentadiene in a homogeneous phase to give the products in the ratio 3:1, the same reaction on Al2O3 leads to a ratio of almost 1:1.

    3. Electrophilic Addition of a Sulfur, Selenium, and Tellurium Atom as well as of an SO2 Molecule to a Metal-Metal Bond (pages 1014–1016)

      Dr. Werner Hofmann and Prof. Dr. Helmut Werner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110142

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      The cobalt compound (1) reacts with elements of main group 6 and with SO2 to give bridged complexes, e.g. the dinuclear complex (2), which can be protonated or methylated an the sulfur atom.

    4. Polyamide-Catalyzed Dimerization of 2,5-Dihydroxybenzoquinones to 4-Ylidenetetronic acids; a Model for the Biosynthesis of Bovilactone-4,4 (pages 1016–1017)

      Dr. Erhard Jägers and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110161

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      The parent compound (2a) of the fungal pigment bovilactone-4,4 (2b) is formed on heating 2,5-dihydroxybenzoquinone (1a) in the presence of acetylated polyamide-6. The mutual occurrence of (2b) and boviquinone-4 (1b) in the sporophores of Suillus bovinus would suggest that such a reaction could also be of importance in the biosynthesis of (2b)(a, R = H; b, R = geranylgeranyl).

    5. Dimeric N-Chloroiminosulfur Tetrafluoride, a Cyclodiaza-λ6-thiane with Hexacoordinated Sulfur (page 1017)

      Dr. Alfred Waterfeld and Prof. Dr. Rüdiger Mews

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110171

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      The novel four-membered heterocyclc (1) is formed along with Cl2N[BOND]SF5 on reaction of NSF3 with CIF.(1), which is a colorless liquid at room temperature, is the first cyclodiaza-λ6-thiane with hexacoordinated sulfur.

    6. Cyanation of Tertiary Alkyl Chlorides: A Novel Method for the Geminal Dialkylation of Ketones (pages 1017–1018)

      Prof. Dr. Manfred T. Reetz and Dipl.-Chem. Ioannis Chatziiosifidis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110172

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      The SnCl4-catalyzed CC-Coupling of tertiary alkyl halides (1) with trimethyl-silyl cyanide (2) is of preparative interest; the resulting nitriles (3) can be modified in a number of ways, e.g. by Grignard reaction or reduction. Since the educts (1) are accessible from ketones, the geminal dialkylation of ketones is thus possible.

    7. First Detection of a π-Coupled 1,5-Diradical via Cycloaddition (pages 1018–1019)

      Prof. Dr. Gerd Kaupp and Inge Zimmermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110181

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      The addition of a π-bond to a five-membered ring σ-bond has been observed for the first time on irradiation of a crystalline film of the cyclopentanone derivative (1). Intermolecular addition of the π-coupled 1,5-diradical formed from (1) to the carbonyl group of a further molecule of (1) leads, aside from other dimers, to the spiroheterocycle (2).

    8. Carbene-Analogous Germylenes (Germandiyls): Singlets or Triplets?–The First Stereospecific Cycloadditions of R2Ge to Conjugated Dienes (pages 1019–1021)

      Dipl.-Chem. Michael Schriewer and Prof. Dr. Wilhelm P. Neumann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110191

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      Dimethylgermylene (1)—unlike the carbene analogue—exists as singlet species in the ground state; this finding is consistent with the results of quantum-mechanical calculations. (1), which can be obtained from benzoannelated 7,7-dimethyl-7-germanorbornadiene, adds stereospecifically to the D,L-diallene (2) to give (3). With meso-(2) the Z,Z/E,E isomeric pair of (3) was obtained.

    9. The Carbon Zip Reaction: A Method for Expanding Carbocycles (page 1021)

      Dr. Yoshihiko Nakashita and Prof. Dr. Manfred Hesse

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110211

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      The zip-reaction developed for ring expansion of N-alkylated lactams is also applicable to carbocycles: The cyclooctane derivative (1) reacts with tetrabutylammonium fluoride with ring expansion to give the cyclo-dodecene derivative (2) an X-ray structure analysis of which has been reported.

    10. Isobenzofulvene (pages 1021–1023)

      Gerhard Gross, Prof. Dr. Curl Wentrup, Prof. Dr. Armin Schweig and Dipl.-Chem. Reinhard Schulz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110212

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      Flash pyrolysis of the acetates (1) or (3) at, 50°C yields the title compound (2), which was characterized by variable temperature photoelectron spectroscopy. When the products of pyrolysis are condensed at −196°C and then allowed to warm, a mixture of C20H16-dimers and acetic acid is obtained.

    11. Intramolecular 1,3-Cl/H Exchange in F3CCCI2N(CH3)2 and Cl3CCCl2N(CH3)2 (pages 1023–1024)

      Dr. Monique Rover-Kevers, Dr. Luc Vertommen, Dr. Fabienne Huys, Dipl.-Ing. Robert Merényi, Dr. Zdenek Janousek and Prof. Dr. Heinz Günther Viehe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110231

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      The CF3- or CCl3-group can be conveniently incorporated into various substrates with the aid of the title compounds, which may be regarded as amide chlorides of trifluoro- and trichloroacetic acid, respectively. Their central CCl2-unit is substituted with an electron-donor and an electron-acceptor; they enable, inter alia, the synthesis of compounds (1)–(4).

    12. Highly Alkylated 1-Oxyallyl Anions from N,N-Dialkylcarbamic Acid Allyl Esters: γ-Hydroxyalkylation (Homoaldol Reaction) (pages 1024–1026)

      Priv.-Doz. Dr. Dieter Hoppe, Dipl.-Chem. Rudolf Hanko, Dipl.-Chem. Alfons Brönneke and Dipl.-Chem. Florian Lichtenberg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110241

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      1-Oxyallyl anions (2) are synthetic equivalents of the aldehyde- and ketone-ho-moenolates(1), which—even if they are highly alkylated—can be generated without problem. They react with carbonyl compounds predominantly in the γ-position to give the hydroxyenol esters (3), which, as protected “homoaldol” derivatives, are preparatively very useful.

    13. Total Synthesis of Zizyphin A and N-Acetylzizyphin B (pages 1026–1027)

      Prof. Dr. Ulrich Schmidt, Dr. Albrecht Lieberknecht, Dipl.-Chem. Hilmar Bökens and Helmut Griesser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110261

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      The first total synthesis of the title compounds, which number among the ansapeptides, has been achieved via a multistep route; the cardinal step is the cyclization of the pentafluorophenyl ester (1) (Z = benzyloxycarbonyl, R3 = C6F5, R4=H, OH), which proceeds in good yields with Pd/C under dilution conditions.

    14. [3+2]-Cycloadditions of Allyl Cations - Synthesis of Permethylcyclopentene and Other Highly Substituted Cyclopentenes (pages 1027–1029)

      Dipl.-Chem. Herbert Klein and Priv.-Doz. Dr. Herbert Mayr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110271

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      Despite controversial predictions, the cyclization of (3) to (4) can be achieved,because a tertiary carbenium ion is formed. The ZnCl2[BOND]Et2O-catalyzed reaction of 3-methylallyl chlorides (1) with alkenes to give (3) thus opens up a productive entry to highly substituted cyclopentenes.

    15. Dodecamethyl-1λ3,4λ3-diphospha-2,3,5,6,7,8-hexastannabicyclo[2.2.2]octane, a Highly Symmetrical Cage Molecule (pages 1029–1030)

      Prof. Dr. Martin Dräger and Dr. Bernd Mathiasch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110291

      White phosphorus reacts with 1,1,2,2-tetramethyldislannane in the dark at 0°C to give the title compound, which according to an X-ray structure analysis has D3-symmetry. The bicyclo[2.2.2]octane framework with P in the bridgehead position is constructed from three Sn4P2 six-membered rings which share three bonds with each other and adopt a distorted boat conformation.

    16. Direct Diastereoselective Alkylation of Tartaric Acid Through an Enolate (pages 1030–1031)

      Dipl.-Chem. Reto Naef and Prof. Dr. Dieter Seebach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110301

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      The lithium enolates (1) of (R,R)-tartrate acetonides to not decompose with β-elimination; the are stable enough to be alkylated by reactive electrophiles to pentasubstituted trans- and cis-dioxolanes (2) and (3) (80:20), respectively. This reaction provides a route to the synthesis of natural products such as piscidic acid.

    17. Dihydrodioxetobenzodioxins: Synthesis and Chemiluminescence (pages 1031–1032)

      Prof. Dr. Waldemar Adam, Dr. Omar Cueto, Dipl.-Chem. Ernst Schmidt and Dr. Kiyoshige Takayama

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110311

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      The novel “high-energy” dioxetanes (2), prepared by photooxygenation of the 1,4-benzodioxins (1), and isolated chromatographically, decompose with emission of light on heating to give the pyrocatechol derivatives (3) in quantitative yields. The singlet and triplet quantum yields were determined by energy-transfer chemiluminescence.

    18. Donor-Acceptor-Stabilized 1,6-Methano[10]annulene Derivatives (pages 1032–1033)

      Prof. Dr. Richard Neidlein and Dr. Hartmut Zeiner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110321

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      Compound (1), in which the bicyclic quinoid structure is part of a “push-pull system”, is surprisingly stable; the valence isomer with norcaradiene structure could not be isolated. The carbonyl stretching vibration in the IR spectrum (1610 cm−1) and the negative solvatochromism of the longest-wave UV band point to participation of the resonance structure (2).

    19. Potassium Metal Dispersed on Silica: A Versatile Reagent in Organic Chemistry (page 1033)

      Jaacov Levy, Dov Tamarkin, Henry Selig and Prof. Dr. Mordecai Rabinovitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110331

      The title reagent K/SiO2 has a greater reactivity and a different selectivity compared to metallic potassium. It is particularly suitable for dimerizations: benzophenone can be converted with K/SiO2 into benzopinacol in 72% yield; bromo- and iodobenzene afford biphenyl in yields of more than 80%.

    20. [Fe3S(S2C10H12)3]2−: The First Synthetic Trinuclear Iron-Sulfur Cluster Compound (pages 1033–1034)

      Dr. Gerald Henkel, Dipl.-Chem. Wolfgang Tremel and Prof. Dr. Bernt Krebs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110332

      In the first model for trinuclear iron-sulfur centers in recently discovered proteins—namely, the central FeS7 moiety in [(C2H5)4N][Fe3S7C30H36]·CH3OH—the Fe atoms from a completely bonded triangle and are each surrounded by a tetrahedron of S atoms which is somewhat distorted from idealized symmetry and consists of an inorganic S atom above the center of the metal triangle and three mercapto S atoms, two of which form slightly asymmetric bridges to neighboring Fe atoms.

    21. tert-Butylimino- tert-butylphosphane: An Inorganic Carbene Analogue (pages 1034–1036)

      Prof. Dr. Edgar Niecke, Dr. Reinhold Rüger and Priv.-Doz. Dr. Wolfgang W. Schoeller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110341

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      The title compound, which contains a highly polar π-bonding system, has been synthesized via two routes, and must therefore by described by the two resonance structures (la) and (1b). Above 0°C, (1) dimerizes with [2 + 2]-cycloaddition to give the 1,2λ3,3λ5-azadiphosphoridine (2).

    22. gem-Bis(halooxy) Compounds from cis- and trans-Tetrfluordioxotellurium(VI) Acid, (HO)2TeF4 (pages 1036–1037)

      Dipl.-Chem. Brigitte Pötter, Dr. Dieter Lentz, Dr. Hans Pritzkow and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110361

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      The title compounds are stable up to 100°C and are soluble without decomposition in water. They can be obtained by melting HO-TeF5 and Te(OH)6t together. Separation or the isomers was achieved via the trimethylsilyl ester: cis-(Me3SiO)2TeF4 is liquid, the trans-derivative is solid; an X-ray structure analysis has been carried out on it.

    23. CH3[BOND]SFmath imageSbFmath image, a “Sulfuranonium” Salt (page 1037)

      Dipl.-Chem. Gert Kleemann and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110371

      Methyl- and ethylsulfur pentafluoride readily react at low temperatures with AsF5 or SbF5. An NMR spectroscopic investigation of the system H3C[BOND]SbF5/SbF5, in SO2 showed that primarily the title compound is formed at −70°C; it rapidly decomposes on heating. H3C[BOND]SFmath imageSbFmath image and H5C2[BOND]SFmath imageSbFmath image could find use as strong alkylating agents.

      • equation image
    24. Monoalkylboranes from Alkylidene(triphenyl)phosphoranes and Borane; Combination of Ylide Reactions and Hydroboration (pages 1038–1039)

      Prof. Dr. Hans Jüirgen Bestmann, Dipl.-Chem. Kurt Sühs and Dipl.-Chem. Thomas Röder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110381

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      A simple entry to the preparatively useful monoalkylboranes(3) is provided by the reaction of BH3. THF with phosphorus ylides. When the boranes (3) are liberated from (2) by treatment with methyl or benzyl iodide in the presence of an olefin, a hydroboration takes place to give “mixed” trialkylboranes, which, e.g. can be converted into tertiary alcohols.

    25. Alcoholate Clusters (“Aggregates”) and Their Role in Alkyne-Forming Elimination Reactions (pages 1039–1041)

      Prof. Dr. Manfred Schtosser and Dipl.-Chem. Tran Dinh An

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110391

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      The decisive step in the elimination of HCl from the (Z)- or (E)-chlorohept-enyne (1) with potassium tert-butyl alcoholate involves participation of dimeric, trimeric or—more rarely—tetrameric alcoholate aggregates; the dehydro-chlorination could proceed according to a “conveyor mechanism”, as indicated for the (Z)-compound in anti-(3).

    26. Base-Promoted 1,4-Elimination Reactions: On the Origin of an Eventual syn-Stereoselectivity (pages 1041–1042)

      Prof. Dr. Manfred Schlosser, Dr. Claudio Tarchini, Dipl.-Chem. Tran Dinh An, Dr. Renzo Ruzziconi and Dr. Paul J. Bauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110411

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      A “conveyor” or a concerted, E1cb-like mechanism is involved in the 1,4-elimination of HCl from E-(1) and Z-(1). The particular mechanism depends on the solvent: In polar solvents the concerted process is effective, in non-polar solvents the “conveyor” process. Due to the larger distance between the reaction centers in polar solvents alkyne-forming 1,4-eliminations are less stereoselective than analogous 1,2-elimininations.

    27. Molecular Structures of Tri- O-acetyl-D-glucal and Ethyl-4, 6-di- O-acetyl-2, 3-dideoxy-α-D-erythro-2-hexenopyranoside (pages 1042–1043)

      Prof. Dr. Wolfgang Voelter, Dipl.-Chem. Wolfram Fuchs, Dr. John J. Stezowski and Petra Schott-Kollat

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110421

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      The mechanism of the well-known reaction (1)[RIGHTWARDS ARROW](2) in the series of unsaturated pyranosides has been clarified by X-ray structure analyses on (1) and (2). The rearrangement proceeds stereospecifically and predominantly in one plane.

    28. Heterogeneous Hydrogenation of Organic Halogen Compounds by Carrier-Supported Organotin Hydrides (pages 1043–1044)

      Prof. Dr. Herbert Schumann and Dipl.-Chem. Bernd Pachaly

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110431

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      Organotin hydrides supported on inorganic carriers such as Al2O3 or SiO2 exhibit high stability and regenerability. Such reagents, which are effective reducing agents, have now been prepared for the first time. With the Al2O3-supported tin hydride reagent (1), it is possible to reduce 1,1-dichloro-2,2-di-phenylcyclopropane quantitatively to 1,1-diphenylcyclopropane.

    29. Di- tert-butylthia- and -selenadiphosphirane (pages 1044–1045)

      Prof. Dr. Marianne Baudler, Dr. Horst Suchomel, Gabriele Fürstenberg and Dipl.-Chem. Ulrike Schings

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110441

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      The title compounds (1) and (2), which are astonishingly stable towards heat and polar solvents, are best obtained by [2+2]-cyclocondensation of dichlor-odiphosphane with stannyl compounds. (1) and (2) are, respectively, pale and bright yellow, viscous, evil-smelling liquids, which are stable for weeks at −30°C in the absence of air and light.

    30. A Ternary Crown Ether “Supercomplex”: X-Ray Structure Analysis of the 1:1:1 Adduct of Dibenzo-[18]-Crown-6, Potassium Iodide, and Thiourea (pages 1045–1046)

      Dipl.-Chem. Rolf Hilgenfeld and Prof. Dr. Wolfram Saenger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110451

      For the formation of ternary “super complexes” the character of the participating anions is of decisive importance. In the polymeric 1:1:1 complexes of dibenzo-18-crown-6, potassium iodide, and thiourea, K+ is situated in the center of the crown ether cavity and is additionally coordinated by I; thiourea forms polymeric chains linked by H-bridges. Only readily polarizable ions such as I are capable of functioning as connecting links between crown ether complexes and thiourea chain.

    31. A New Route to 6a-Carbacyclins–Synthesis of a Stable, Biologically Potent Prostacyclin Analogue (pages 1046–1048)

      Dr. Werner Skuballa and Prof. Dr. Helmut Vorbrüggen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110461

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      6a-Carbacyclin (1) (X = CH2, R = CH(CH3)CH2C[TRIPLE BOND]CCH3), a potent vasodilator and inhibitor of blood-platelet aggregation, exhibits the same activity-profile and comparable efficacy as prostacyclin, but, in contrast to prostycyclin, is much more stable. It was prepared from the commercially available Corey lactone (2) (R1 = H) via the bicyclo[3.3.0]octane derivative (3).

    32. 18,19-Didehydrocorrinoids—Possible Intermediates in the Biosynthesis of Vitamin B12 (pages 1048–1049)

      Dr. Bernd Dresow, Dr. Ludger Ernst, Dr. Lutz Grotjahn and Dr. Volker B. Koppenhagen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110481

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      A common biosynthetic precursor of metal-free and cobalt-containing corrinoids could be the 18,19-didehydrocobyrinic acid c-am-de (1) in its cobalt-free form; the structure of (1) was determined, in particular, by 1H-and 13C-NMR spectroscopic investigation of its hexamethyl ester.

    33. Novel Reactions of Phosphorus Ylides with Carbonyl(cyclopentadienyl)metal Complexes: Preparative Access to μ-Alkylidene Complexes and Unexpected Acylations (pages 1049–1051)

      Dipl.-Chem. Richard Korswagen, Reinhold Alt, Dieter Speth and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110491

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      5-CpFe(CO)2]2 undergoes a previously unknown type of reaction with phoshorus ylides Ph3P[DOUBLE BOND]CHR (R[DOUBLE BOND]H, Me, iPr) to give the cis- and trans-alkyli-ene complexes (1) and (2) and a small amount of the organometal-substituted ylide (3), Surprisingly, analogous manganese complexes react with methylenephosphorane with ortho-acylation of one of the P-phenyl groups.

    34. Second Sphere Coordination of Cationic Platinum Complexes by Crown Ethers— The X-Ray Crystal Structure of [Pt(bpy)(NH3)2. Dibenzo[30]crown-10]2+[PF6]math imagexH2O (x≈0.6) (pages 1051–1053)

      Dr. Howard M. Colquhoun, Dr. J. Fraser Stoddart, Dr. David J. Williams, John B. Wolstenholme and Ryszard Zarzycki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110511

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      Hydrogen bonding and charge-transfer interactions stabilize the crystalline 1:1 adduct of [Pt(bpy)(NH3)2]2+[PF6] and dlbenzo-30-crown-10. An X-ray structure analysis showed that the crown ether envelopes the dication; this coordination in the second sphere, which-as UV and 1H-NMR data show—also exists in solution, is to a great extent made possible by interactions between the two benzene rings of the host molecule and a pyridine ring of the guest complex.

    35. Does a Molecule have the Same Conformation in the Crystalline State and in Solution? Comparison of NMR Results for the Solid State and Solution with those of the X-ray Structural Determination (pages 1053–1055)

      Prof. Dr. Horst Kessler, Dr. Gottfried Zimmermann, Dr. Hans Förster, Dr. Jürgen Engel, Dr. Gerhard Oepen and Dr. William S. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110531

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      The comparison of structures in the solid state and in solution by one method—NMR spectroscopy — enabled unequivocal demonstration of structural changes on dissolution of a solid compound. Thus,e.g., in the crystal the vinylogous amide (R = C6H11) investigated is E-configurated at the CC double bond; in solution a Z-form is most stable.

    36. Ring-Opening Reactions of 2-Lithio-1,3-dithiane and 2-Lithio-1,3,5-trithiane with Carbene Complexes of Chromium and Tungsten (pages 1055–1056)

      Prof. Dr. Helgard G. Raubenheimer, Prof. Dr. Ernst Otto Fischer, Priv.-Doz. Dr. Ulrich Schubert, Prov.-Doz. Dr. Carl Krüger and Dr. Yi-Hung Tsay

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110551

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      Alkoxycarbene complexes such as (1) (M = Cr, R′ = CH3) react with 2-lithio-1,3,5-trithiane (2) (X = S) already at −60°C, whereby formation of the phenyl(thiocarbene) complexes (3) and (4) is favored. The first step of the synthesis is most likely the formation of a 2:1 adduct, which contains both a metal-ylide carbon bond as well as a metal-alkyl carbon bond.

    37. Crown Ether-Assisted Change of Regioselectivity in the Reductive Cleavage of Allylsulfonamides (pages 1057–1058)

      Dr. Alexander M. Moiseenkov, Dipl.-Chem. Evgeni V. Polunin and Prof. Dr. Alexei V. Semenovsky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110571

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      In order to use the hydroxysulfonamide (1) for the C5-homologation of isoprenoids it was necessary to regioselectively reduce allylsulfonamides such as (2). If classical methods are used for this purpose a ca. 1:9 mixture of nerol (3) and isogeraniol (4) is formed; in contrast, (2) reacts with Na/NH3 in the presence of dibenzo-[18]crown-6 to give almost exclusively (3).

    38. The Dihydrocorphinol [RIGHTWARDS ARROW] Corrin Ring Contraction: A Potentially Biomimetic Mode of Formation of the Corrin Structure (pages 1058–1060)

      Dr. Vittorio Rasetti, Dipl. Ing. Chem. ETH Kurt Hilpert, Dipl. Naturwiss. ETH Alexander Fässler, Dr. Andreas Pfaltz and Prof. Dr. Albert Eschenmoser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110581

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      The structural types 20-corphinol (1), 1,19-secocorrin (2) and 19-acetyl-l-methylcorrin (3) are kinetically readily interconvertible; a secocorrin diradical of the type (4) assumes the role of a “transit structure”.

    39. Stabilization of Diphosphorus Tetrabromide as the Bis(pentacarbonylchromium) Complex (page 1060)

      Dipl.-Chem. Axel Hinke, Prof. Dr. Wilhelm Kuchen and Dipl.-Chem. Jürgen Kutter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110601

      The hitherto unknown P2Br4 has been stabilized as ligand for the first time, namely in the bis(pentacarbonylchromium) Complex(1). (1) is formed, inter alia, on reaction of (CO)5Cr. THF with PBr3, and of (2) with HBr. Evidence of the formation of free P2Br4 was also obtained.

      • equation image
    40. (Ph4P)2[CuCN(MoS4)] and (Me4N)2(CuCN)2MoS4: Thiomolybdate Ligands on the Cu Atoms of a CuCN Molecule and a zigzag-CuCN Chain (pages 1060–1061)

      Prof. Dr. Achim Müller, Mechtild Dartmann, Christian Römer, Dr. William Clegg and Prof. George M. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110602

      Thumbnail image of graphical abstract

      MoSmath image also coordinates neutral Cu compounds: It adds, e.g., to the “CuCN molecule” to give a complex with a dinuclear anion, in which a linear Mo…Cu…CN array is present with Mo in a tetrahedral and Cu in an almost trigonal planar environment. An infinitely long CuCN chain is analogously directly coordinated.

    41. Determination of the Structure of New Tetrathiomolybdato Complexes of FeII, CuI and AgI by the Resonance Raman Effect: Textbook Examples for its Application in Coordination Chemistry (pages 1061–1063)

      Prof. Dr. Achim Müller, Anne-Marie Dommröse, Dipl.-Chem. Wolfram Jaegermann, Erich Krickemeyer and Dr. Sabyasachi Sarkar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110611

      Precursors with a high Fe content, such as (1), are especially suitable for the construction of the MoFe cofactor of nitrogenase. Reaction of AgNO3, (NH4)2MoS4 and PPh3 affords the symmetrical trinuclear complex (2). The structures of (1) and (2) and related compounds were determined by the Resonance-Raman-Effect method; the influence of the nearest and next nearest neighbors on the vibrations of the ligand chromophore is investigated.

      • equation image
    42. Hydroformylation of Alkylidyne(nonacarbonyl)tricobalt Clusters: Model Reaction for the Direct Conversion of Synthesis Gas into C1- and C2-Oxygenated Compounds (pages 1063–1064)

      Dr. Giuseppe Fachinetti, Dr. Raffaello Lazzaroni and Dr. Sergio Pucci

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110631

      Thumbnail image of graphical abstract

      The occurrence of the hydroxymethylidyne cluster (1) as intermediate in the carbonylco-balt-catalyzed hydrogenation of CO explains The formation of methanol and of C2-alconols. That (I) actually is an intermediate in this reaction is demonstrated by the results of the reaction of the alkylidyne complexes (2)(4) with CO/H2 at high temperatures and pressures in the presence of Co2(CO)8.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
  4. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Author Index (pages 1067–1070)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110671

  5. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Subject Index (pages 1071–1085)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198110711

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