Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 20

November 2, 1994

Volume 33, Issue 20

Pages 1997–2120

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 20/1994)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199419951

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      The Cover picture shows the structure of the complex cation [Fe(1-methyltetrazole)6]2+, the electron distribution in the low-spin (blue ion) and high-spin (red ion) states, and the corresponding oscillator potentials of the totally symmetric mode of the complex. In spin crossover compounds the energy difference ΔEkBT between the lowest vibrational levels and the much higher density of high-spin states lead to a reversible spin transition well below the decomposition temperature. Also light of different wavelengths switches between the low-spin and the metastable high-spin state at low temperatures. The results of research on the spin crossover phenomenon are summarized by P. Gütlich et al. on p. 2024 ff.

  1. Editorial

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
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      EDITORIAL (pages 1997–2000)

      Peter Gölitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199419971

  2. Reviews

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. The Photochemical Synthesis of Fine Chemicals with Sunlight (pages 2009–2023)

      Dr. Peter Esser, Dipl.-Chem. Bettina Pohlmann and Prof. Dr. Hans-Dieter Scharf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420091

      Preparative photochemistry with sunlight is considered an unusual undertaking, even though photosynthesis forms the basis for the existence of life on earth, That “solar photochemistry” is a technique which could make a contribution to the chemistry of the future is demonstrated by fundamental considerations and the results of solar field experiments. In this context [2 + 2] cycloadditions, Paternò-Büchi reactions, and 1O2 reactions were investigated.

    2. Thermal and Optical Switching of Iron(II) Complexes (pages 2024–2054)

      Prof. Philipp Gütlich, Dr. habil. Andreas Hauser and Dr. habil. Hartmut Spiering

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420241

      The color change dark-red ⇌ colorless accompanies the transition of [Fe(l-propyltetrazole)6](BF4)2 from the low-spin state to the metastable high-spin state. These states in this complex can be interconverted as often as desired by irradiation with light of the appropriate wavelength or by increasing and decreasing the temperature. Such spin transitions change the properties of the material and can be influenced by many factors like pressure, ligand exchange, or isotopic exchange. If the effect could be controlled, these spin crossover complexes could be potential switches in optical information technology.

  3. Highlights

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. Designer Proteins: On the Art of Synthesizing De Novo Metalloproteins (pages 2055–2056)

      Dr. Heinz-Bernhard Kraatz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420551

      Straddling the boundaries between protein chemistry and coordination chemistry, a promising new field of research has developed. The latest work in this area includes the synthesis of metal-binding metalloproteins by M. R. Ghadiri et al. and the introduction of redox-active centers in nonnatural proteins by W. F. DeGrado et al. One can imagine that the concepts behind these syntheses can be extended to, for example, the preparation of metalloproteins that could function as light-harvesting analogues of the photosystem of green plants.

    2. Novel Copper Nitrosyl Complexes: Contributions to the Understanding of Dissimilatory, Copper-Containing Nitrite Reductases (pages 2057–2058)

      Prof. Bruce A. Averill

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420571

      The first functional models for copper nitrite reductases, enzymes that play a central role in the nitrogen cycle, were recently prepared by Tolman et al. Thus, complex 1 in which one nitrite ligand is coordinated through the N atom to the Cu1 center reacts smoothly with two equivalents of acid to give NO, and Cu1 complexes of the type 2 react with NO in a novel disproportionation reaction to give N2O and CuII[BOND]NO2 complexes—in both cases the complexes can mimic certain aspects of the reactivity of copper nitrite reductases. L1 = N,N′,N″-triisopropyl-1,4,7-triazacyclononane, L2 = substituted hydridotris(pyrazolyl)borate.

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  4. Communications

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. A Novel Procedure for the Synthesis of Libraries Containing Small Organic Molecules (pages 2059–2061)

      Dr. Thomas Carell, Edward A. Wintner, Dr. A. Bashir-Hashemi and Julius Rebek Jr.

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420591

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      Accelerated drug searches should be possible through the generation and screening of libraries of smaller organic molecules. The reaction of tetracarboxylic acid tetrachloride 1 with a mixture of 21 amines (predominantly amino acids) in solution yields a complex mixture, which can theoretically contain 97461 compounds. Compound 2, an inhibitor of trypsin-catalyzed amide hydrolysis (K1 = (9 ± 2) × 10−6M), was selected by four-step screening procedure. This result demonstrates the usefulness of libraries of molecules and the screening of these complex mixtures.

    2. A Solution-Phase Screening Procedure for the Isolation of Active Compounds from a Library of Molecules (pages 2061–2064)

      Dr. Thomas Carell, Edward A. Wintner, Julius Rebek Jr. and Dr. A. J. Sutherland

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420611

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      Accelerated drug searches should be possible through the generation and screening of libraries of smaller organic molecules. The reaction of tetracarboxylic acid tetrachloride 1 with a mixture of 21 amines (predominantly amino acids) in solution yields a complex mixture, which can theoretically contain 97461 compounds. Compound 2, an inhibitor of trypsin-catalyzed amide hydrolysis (K1 = (9 ± 2) × 10−6M), was selected by four-step screening procedure. This result demonstrates the usefulness of libraries of molecules and the screening of these complex mixtures.

    3. Nonclassical Stabilization of Planar Allenes: Low Rotational Barriers for Allene Double Bonds (pages 2064–2067)

      Dipl.-Chem. Dirk Steiner, Dipl.-Chem. Heinz-Jürgen Winkler, Sigrid Wočadlo, Stefan Fau, Prof. Dr. Werner Massa, Prof. Dr. Gernot Frenking and Prof. Dr. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420641

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      π[BOND]π and π[BOND]σ delocalization facilitates rotation about the C[BOND]C double bond adjacent to the boron atoms in 1. After rotation by 90° to the transition states, the negative charge of the highly polarized C[BOND]CB2 bond is stabilized homoaromatically in a homodiboriranide, and the positive charge by hyperconjugation in a 3c[BOND]2e bond. The energy difference between the planar transition state and orthogonal 1 is only 8.6 kcalmol−1.

    4. Synthesis of Sulfonamido-Pseudopeptides: New Chiral Unnatural Oligomers (pages 2067–2069)

      Prof. Dr. Cesare Gennari, Barbara Salom, Dr. Donatella Potenza and Dr. Anthony Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420671

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      Chiral vinylogous aminosulfonic acids 1 can be used to synthesize the title compounds 2 by a straightforward iterative approach. The new chiral unnatural oligomers have defined conformational preferences in chloroform and may have interesting recognition and biological properties.

    5. Localization of Electrons in Intermetallic Phases Containing Aluminum (pages 2069–2073)

      Dipl.-Chem. Ulrich Häussermann, Dipl.-Chem. Steffen Wengert, Dipl.-Chem. Patrick Hofmann, Priv.-Doz. Dr. Andreas Savin, Dr. Ove Jepsen and Prof. Dr. Reinhard Nesper

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420691

      Many forms of chemical bonding are exhibited by Al in intermetallic and Zintl phases. This is revealed by the calculation of the electron localization function for the series Al, CaAl2, SrAl2, BA14, CaAl2Si2, and Si. With this procedure it is possible to distinguish clearly between metallic, covalent multicenter, and homo- and hetero-nuclear single bonding.

    6. Unequivocal Partitioning of Crystal Structures, Exemplified by Intermetallic Phases Containing Aluminum (pages 2073–2076)

      Dipl.-Chem. Ulrich Häussermann, Dipl.-Chem. Steffen Wengert and Prof. Dr. Reinhard Nesper

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420731

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      A space-filling partitioning of the unit cell into atomic and electronic domains is achieved by the method described in this communication. This contributes to a better understanding of the bonding in intermetallic phases. The polyhedra representing the atomic domains of Ca and Al in CaAl2 are shown on the right as example.

    7. Totally Enantioselective Inversion of Configuration of (S)-(+)-Carnitine Derivatives (pages 2076–2078)

      Dipl.-Chem. Ida Bernabei, Dr. Roberto Castagnani, Prof. Dr. Francesco De Angelis, Paolo De Witt Scalfaro, Dr. Fabio Giannessi, Prof. Dr. Domenico Misiti, Dr. Sandra Muck, Dipl.-Chem. Nazareno Scafetta and Dr. Maria Ornella Tinti

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420761

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      Tons of waste (S)-carnitinamide 1 are obtained in the industrial production of the (R) isomer 3, which is a biologically active pharmaceutical product. A method has now been developed to recycle 1 in a five-step reaction sequence with 80% overall yield via β-lactone 2.

    8. Assembly Properties of Bolaamphiphiles from Dimeric Acids (pages 2078–2080)

      Dr. Pilar Bosch, Prof. Dr. José L. Parra and Dr. Alfonso de la Maza

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420781

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      Even at low concentrations bolaamphiphiles synthesized from dimeric acids (for example, cyclohexanebolaamphiphile 1) form multilamellar aggregates. The exact three-dimensional form depends on both the ionic character of the bolaamphiphile polar group and on the counterion.

    9. Photodecomposition of 10-Diazo-2-hexadecyl-anthrone on Graphite Studied by Scanning Tunneling Microscopy (pages 2080–2083)

      Dipl.-Chem. Roland Heinz, Dipl.-Chem. Andreas Stabel, Prof. Dr. Jürgen P. Rabe, Prof. Dr. Gerhard Wegner, Prof. Dr. Frans C. De Schryver, David Corens, Dr. Wim Dehaen and Dr. Carsten Süling

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420801

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      The photochemical conversion of diazoanthrone 1 into anthraquinone 2 in a thin liquid film on graphite was monitored by scanning tunneling microscopy in situ. The structures of the two-dimensional crystals of the starting material and the photoproduct were analyzed.

    10. [Cp2Ti(C[TRIPLE BOND]CtBu)2] as an Alkynyl Transfer Reagent: Synthesis and Characterization of the Asymmetrically Bridged Heterodimetallic Complex [Cp2Ti(C[TRIPLE BOND]CtBu)2Pt(PPh3)]·0.5 THF (pages 2083–2085)

      Dipl.-Chem. Jesús R. Berenguer, Prof. Dr. Juan Forniés, Dr. Elena Lalinde and Dr. Antonio Martín

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420831

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      The coordination in A and B are not the only modes possible when dialkynylbis(cyclopentadienyl)titanium complexes coordinate other metal complex fragments. The reaction of [Cp2Ti(C[TRIPLE BOND]CtBu)2] with [Pt(C2H4)(PPh3)2] affords a dinuclear complex which has structure C in the solid state. Dynamic processes are evident for this complex in solution.

    11. Optically Active Reference Compounds for Environmental Analysis Obtained by Preparative Enantioselective Gas Chromatography (pages 2085–2087)

      Prof. Dr. Wilfried A. König, Dipl.-Chem. Ingo H. Hardt, Dipl.-Chem. Bärbel Gehrcke, Dipl.-Chem. Detlev H. Hochmuth, Priv.-Doz. Dr. Heinrich Hühnerfuss, Dipl.-Chem. Bernd Pfaffenberger and Dr. Gerhard Rimkus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420851

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      A modified cyclodextrin stationary phase was used in the resolution of the enantiomers of the cyclodiene insecticides cis- and trans-chlordane, oxychlordane, heptachlor, and other metabolized xenobiotics on a milligram scale by preparative gas chromatography. Enantiomeric excesses of between 42 and >99% were obtained. The enantiomerically pure (or enriched) compounds can be used in studies into the enantioselective degradation of toxic substances present in the environment.

    12. The Versatility of the Azido Ligand: Linkage of NiII Centers to Form a Chain with One End-to-End and Three End-On Bridges in Alternation (pages 2087–2089)

      Prof. Joan Ribas, Dr. Montserrat Monfort, Dr. Barindra Kumar Ghosh and Prof. Xavier Solans

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420871

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      An average Ni[BOND]N[BOND]Ni angle of only 84° is found in the end-on bridges in complex 1. This small angle possibly explains the antiferromagnetic coupling of the nickel centers in 1. For more than 20 years it has been assumed that end-on coordination should lead to ferromagnetic coupling. The complex occurs as one-dimensional chains in the solid state.

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    13. On the Nature of Zinc Chloride–Aldehyde Interactions (pages 2089–2090)

      Dipl.-Chem. Bodo Müller, Dipl.-Chem. Michael Ruf and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420891

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      The simple aldehyde complexes 1–3 are obtained pure and crystalline under strictly anhydrous conditions. Complexes 2 and 3 are the first fully characterized transition metal halide complexes of aldehydes. Complexes 1–3 should be useful for mechanistic studies on ZnCl2-catalyzed aldehyde reactions.

    14. Cyanide–Isocyanide Isomerism in CN-Bridged Organometallic Complexes (pages 2090–2091)

      Nianyong Zhu and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420901

      The inertness of the organometallic building blocks makes it surprisingly easy to prepare the two isomeric forms of CN-bridged heterodinuclear complexes like 1 a and 1 b. Compounds like these should contribute to the understanding of “molecular Prussian Blue”, dppe = 1,2-bis(diphenylphosphano)ethane.

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    15. Calixarene-Based Macrocyclic Nonet (S = 4) Octaradical and its Acyclic Sextet (S = 5/2) Pentaradical Analogue (pages 2091–2093)

      Prof. Andrzej Rajca, Dr. Suchada Rajca and Dr. Raghavakaimal Padmakumar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420911

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      Magnetization and ESR spectroscopic data indicate a high-spin ground state (S = 4) for 1 in frozen solution. A related acyclic pentaradical also has a high-spin ground state (S = 5/2). These compounds may be the first step towards understanding the impact of defects on spin coupling in multi-site molecules.

    16. Synthesis, Structure, and Thermolysis of a Tetracoordinate 1,2λ4-Oxathietane (pages 2094–2095)

      Prof. Dr. Takayuki Kawashima, Fumihiko Ohno and Prof. Dr. Renji Okazaki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420941

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      Oxidative cyclization of 1 with Br2 yields the tetracoordinate 1,2λ4-oxathietane 2. Instead of an olefin, thermolysis of 2 provided benzophenone and the ketone formed by migration of a phenyl group. Traces of 2,2,3-triphenyloxirane were observed, which hints that a 1,2λ4-oxathietane may be an intermediate in the Corey–Chaykovsky reaction.

    17. Synthesis of Deoxy Sialyl Lewisx Analogues, Potential Selectin Antagonists (pages 2096–2098)

      Dr. Wilhelm Stahl, Dipl.-Chem. Ulrich Sprengard, Dr. Gerhard Kretzschmar and Prof. Dr. Horst Kunz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420961

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      An effective new sialylation method is applied for the first time in an efficient synthesis of the sialyl Lewisx derivative 1. This type of compound is expected to contribute to the development of new anti-inflammatory drugs.

    18. [2,3] Sigmatropic Wittig Rearrangement of Chiral Allyloxyacetaldehyde Hydrazones in the Diastereo- and Enantioselective Synthesis of Protected, γ,δ-Unsaturated α-Hydroxyaldehydes and Cyanohydrins (pages 2098–2100)

      Prof. Dr. Dieter Enders, Dipl.-Chem. Dirk Backhaus and Dr. Jan Runsink

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199420981

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      The polyfunctional chiral building blocks 1 (X = CHO, CN) are accessible by [2,3] sigmatropic Wittig rearrangements. They were synthesized in three or four steps (with purification of an intermediate by chromatography), some of which with syn/anti selectivities of >98% syn and enantiomeric excesses of 94–97%. R1 = Me, Et, nPr, iPr; R2 = H, Me.

    19. Wacker Oxidation of 1-Decene to 2-Decanone in the Presence of a Chemically Modified Cyclodextrin System: A Happy Union of Host–Guest Chemistry and Homogeneous Catalysis (pages 2100–2102)

      Dr. Eric Monflier, Dr. Emilie Blouet, Prof. Dr. Yolande Barbaux and Prof. Dr. André Mortreux

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421001

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      Only assisted by molecular recognition and phase transfer is the title reaction efficient. The stability of the complexes of various host cyclodextrins with decene and decanone is mainly determined by the size of the cyclodextrin aperture; the solubility of the cyclodextrins and their complexes in the aqueous and organic phases depends on the chemical modification of the cyclodextrin. With β-cyclodextrin 1 and PdSO4/H9PV6Mo6O40/CuSO4 as the catalytic system, 1-decene is oxidized with O2 to give 2-decanone in 98% yield.

    20. Soluble Organic Derivatives of Aluminosilicates with AI2Si2O4 and AI4Si2O6 Frameworks (pages 2103–2104)

      Dipl.-Chem. Mavis L. Montero, Dr. Isabel Usón and Prof. Dr. Herbert W. Roesky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421031

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      A ring or a cage containing metal and oxygen atoms is formed in the reaction of RSi(OH)3 with HA1-iBu2, depending on the molar ratio used. The structural parameters of the cage compound 1 are very similar to those of the mineral gismondine. Compound 1 is soluble in organic solvents and may suitable for the synthesis of aluminosilicates, in particular zeolites, because of its good leaving groups. R = (2,6-iPr2C6H3)N(SiMe3).

    21. NiO/CaO-Catalyzed Formation of Syngas by Coupled Exothermic Oxidative Conversion and Endothermic CO2 and Steam Reforming of Methane (pages 2104–2106)

      Dr. Vasant R. Choudhary, Amarjeet M. Rajput and Dr. Bathula Prabhakar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421041

      An energy efficient and safe conversion of methane to syngas is possible by carrying out the exothermic oxidation of methane and the endothermic reaction of methane with steam and CO2 simultaneously with the same NiO/CaO catalyst. By coupling the two reactions and manipulating the relative concentrations of CH4, O2, CO2, and steam in the feed, the overall methane-to-syngas conversion can be made mildly exothermic, thermoneutral, or mildly endothermic. The H2/CO ratio of the product can be varied from roughly 1.5 to 2.5.

    22. Purely Organic Mixed-Valence Molecules with Nanometric Dimensions Showing Long-Range Electron Transfer. Synthesis, and Optical and EPR Studies of a Radical Anion Derived from a Bis(triarylmethyl)Diradical (pages 2106–2109)

      Dr. Jacques Bonvoisin, Dr. Jean-Pierre Launay, Dr. Concepció Rovira and Dr. Jaume Veciana

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421061

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      Both optical and thermal electron transfer were examined in detail in radical anion 1, which was generated electrochemically from the analogous stable diradical. Optical electron transfer is induced at λ = 1400 nm. The results are discussed in the context of the Hush-Marcus theory.

    23. Polynuclear Lanthanide Complexes: Formation of a Selenium-Centered Sm6 Complex, [{(C5Me5)Sm}6Se11] (pages 2110–2111)

      Prof. William J. Evans, Dr. Gerd W. Rabe, Dr. Mohammad A. Ansari and Dr. Joseph W. Ziller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421101

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      The central Se atom is surrounded by six (C5Me5)Sm units in a distorted octahedral arrangement in the title compounds (structure shown on the right). Four pairs of (Se2)2− units, the central Se atom, and two further Se atoms connect the six (C5Me5)Sm units. The complex contains a linear (Se3)4− moiety, which is isoelectronic with the (I3) ion.

    24. Monomeric Tris(imino)metaphosphates (pages 2111–2113)

      Prof. Dr. Edgar Niecke, Dr. Matthias Frost, Dr. Martin Nieger, Dr. Volker von der Gönna, Dr. Alexander Ruban and Prof. Dr. Wolfgang W. Schoeller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421111

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      Nitrogen analogues of monomeric POmath image can be obtained as Li+ salts. Depending on the substituents at the nitrogen atoms, the anion is either coordinated to Li as in 1 or separated from the cation as in 2. The anion in2 has a propellerlike structure. Ar = 2,4,6-tri-tert-butyrphenyl, D = donor solvent.

    25. Intramolecular Photocyclization of ω, ω-Diphenyl-(ω−1)-alken-1-ols by an Exciplex Quenching Mechanism (pages 2113–2115)

      Dr. Kazuhiko Mizuno, Dr. Toshiyuki Tamai, Toshinori Nishiyama, Kyoko Tani, Mayumi Sawasaki and Prof. Dr. Yoshio Otsuji

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199421131

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      In the 9,10-anthracenedicarbonitrile-sensitized irradiation of the title compounds 1a–f in benzene, the photocyclization of 1b–d leads efficiently to products 2b–d with five-, six-, and seven-membered rings, respectively (A = 9,10-anthracenedicarbonitrile). This cyclization is also possible with 3-substituted derivatives of 1c. The reaction proceeds via an exciplex of the sensitizer A and alkene 1.

  5. Book Reviews

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews

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