Angewandte Chemie International Edition in English

Cover image for Vol. 30 Issue 6

June 1991

Volume 30, Issue 6

Pages 613–722

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 6/1991)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106131

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      The Cover picture shows schematically the possibility of characterizing reactions at high pressure (flange) and high temperatures (red heat) spectroscopically. In the center of the picture are a series NIR spectra which were recorded during the polymerization of ethylene (E) to polyethylene (PE) at 463 K and 2630 bar. In this way the percentage conversion of the polymerization can be monitored directly. More about quantitative absorption spectroscopy in the IR and UV regions at pressures up to 7 kbr and temperatures up to 900 K is reported by M. Buback on p. 641.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 6/1991)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106132

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Chemically Modified Oligonucleotides as Probes and Inhibitors (pages 613–629)

      Dr. Uwe Englisch and Dr. Dieter H. Gauss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106133

      Three possible types of application are, in principle, open to modified oligonucleotides: the detection of complementary sequences, inhibition, and use as enzyme and substratre analogues. Thus, one can check whether and where a messenger RNA or a corresponding gene is present and whether bacterial or viral sequences are present in a tissue or a solution. In addition attempts are being made to inhibit the translation of a mRNA or the transcription and replication of a DNA. Currently of particular interest is the inhibition of protein biosynthesis and the reverse transcription of retroviruses.

    2. Molecular Structures from Density Functional Calculations with Simulated Annealing (pages 630–640)

      Dr. Robert O. Jones

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106301

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      The most stable isomers of atomic clusters frequently have amazing structures—at any rate this is what was disclosed by calculations with the new computational methods reviewed in this article. Thus, in the case of the most stable Al8 cluster, calculations in no way give a compact “spherical” structure, but rather the structure 1. Advantages of these computational methods are that they are free from parameters, that they can also be applied to heavy atoms, and that, because of the molecular dynamics, not only a local but the global minimum is found.

    3. Spectroscopy of Fluid Phases—The Study of Chemical Reactions and Equilibria up to High Pressures (pages 641–653)

      Prof. Dr. Michael Buback

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106411

      Nowadays, changing the rate and selectivity of reactions by increasing the pressure is a well-used principle. However, being able to monitor the course of the reaction by UV and IR spectroscopy in situ—and thus not to have to vary the reaction parameters “blind”—is still no trivial task. The current possibilities of the method and the necessary investment in apparatus and measuring equipment are outlined with examples taken from, inter alia, inorganic complex chemistry and organic synthesis.

    4. The Chemistry of Rose Pigments (pages 654–672)

      Prof. Dr. Conrad Hans Eugster and Dipl.-Chem. Edith Märki-Fischer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106541

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      The color scale of rose blossoms has been successfully fathomed out by the authors of this review by purely scientific methods without robbing the “Queen of Flowers” of her aesthetic. magic appeal. Three structurally different groups of pigments are present in rose blossoms, namely the chlorophylls, the flavonoids inclusive of the anthocyanins, and the carotenoids. The yellow color of roses is determined by the structurally very diverse carotenoids, the red color by anthocyanins. The structural formula of the most important pigment of the red roses is shown on the right.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Metalla-enes and Metalla-ynes—from Small Molecules to Infinite Polymers (pages 673–674)

      Prof. Malcolm H. Chisholm

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106731

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      Inorganic polymers with conjugated multiple bonds and metal atoms in the polymer main chain have recently been the subject of a series of publications. Such materials are of interest, inter alia, because of anticipated nonlinear optical properties. Marder et al. and Lewis et al. have synthesized polymeric alkynerhodium complexes such as 1, while Hopkins et al. have studied the optical properties of the polymeric nitrido complexes 2.

    2. Stable Carbenes—Illusion or Reality? (pages 674–676)

      Prof. Dr. Manfred Regitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106741

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      Some ten years ago a graduate student in chemistry would have failed sadly in his masters examination, had he contended that carbenes could be stored in bottles at room temperature. But precisely this is possible with the compounds 1 and 2, which were recently described by Arduengo et al. and by Bertrand et al. Compound 1 melts only at 240°C, owing to electronic and stereochemical effects. The carbene 2 not only shows carbene reactivity but also reactivity characteristic of phosphaalkynes. R = adamantyl, R′ = iPr2N.

    3. Novel Polymeric Materials from Monodisperse Copolypeptides by Biotechnological Methods (pages 677–678)

      Prof. Dr. Helmut Ritter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106771

      “The ox can do it better.” This casual, yet time-tested remark by Emil Fischer with reference to the synthesis of peptides has stimulated almost a generation of preparative chemists to take up the challenge. And, “the ox” has recently met with increasing competition through the introduction of modern biotechnological methods. Though these methods have largely been limited to the successful synthesis of active substances in the pharmaceutical and agricultural sectors in recent years, a breakthrough now seems to have been made by D. A. Tirrell et al. in the preparation of new materials. A cyclopeptide with exactly 14 repeat units of an undecapeptide sequence has been prepared which has a glass temperature of 182°C, decomposes above 250°C, and from which homogeneous films can be cast.

    4. C60: From Soot to Superconductors (pages 678–680)

      Prof. Dr. François Diederich and Prof. Robert L. Whetten

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106781

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      Fullerene research will shortly revolutionize chemistry says the author of this highlight. At the spring meeting of the American Chemical and Physical Societies there were already a whole series of lectures devoted to this fascinating new class of compounds. C60 is commercially available and has been oxidized, reduced, hydrogenated, fluorinated, and derivatized in many other ways. Most spectacular of course is that RbxC60 is a superconductor with Tc = 30 K.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. [14]Annulenequinones with Anthraquinone Periphery: “Isopyrenequinone” (pages 681–683)

      Dr. Emanuel Vogel, Dr. Lutz Schmalstieg, Dr. Peter Henk, Dr. Oswald Wilmes, Dr. Johann Lex, Prof. Dr. Rolf Gleiter and Dr. Michael Langer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106811

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      Anthraquinone can cope with the insertion of a C[DOUBLE BOND]C unit into the interior of the molecule! This is demonstrated by the synthesis of the copper-colored pigment “isopyrenequinone” (1), which, according to spectral and structural data, is not a heptafulvalene derivative, but must be regarded as a resonance hybrid with tropylium mesomeric structures. Compound 1 can be reversibly converted into the nonplanar bridged [14]annulenequinone 2.

    2. σ-Homoacenaphthylene and π-Homoacenaphthene (pages 683–686)

      Dr. Roland Arnz, José Walkimar de M. Carneiro, Dr. Wolfgang Klug, Dr. Hans Schmickler, Prof. Dr. Emanuel Vogel, Rolf Breuckmann and Prof. Dr. Frank-Gerrit Klärner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106831

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      “Freezing-in” as norcaradiene valence tautomer is possible in the case of 1,6-methano[10]annulene not only by acceptor substituents on the methylene carbon atom but also by suitable peri-bridges. The prognosis based on force field calculations that 2,10-etheno-1, 6-methano[10]annulene exists as valence tautomer 1, whereas 2,10-ethano-1,6-methano[10]annulene—the product of the diimine reduction of 1—retains the annulene structure, finds impressive experimental confirmation.

    3. Synthesis and Characterization of P-containing ZSM-5 Zeolites (pages 686–687)

      Doz. Dr. Wladimir Reschetilowski, Dipl.-Chem. Brit Meier, Dr. Michael Hunger, Dr. Baldur Unger and Doz. Dr. Klaus-Peter Wendlandt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106861

      The hydrothermal crystallization of a mixture of water glass and aluminum sulfate after addition of phosphoric acid and n-propylamine enables the preparation of ZSM-5 zeolites with variable P content. When the P content is increased the distribution of acid strength of the acidic OH groups is shifted in favor of the weakly acidic Brønsted acidic centers. This is of fundamental importance for the preparation of tailor-made catalysts for proton-catalyzed reactions.

    4. Synthesis of Heterocycles by Tandem Reactions: Beckmann Rearrangements/Allylsilane Cyclizations (pages 687–688)

      Prof. Dr. Dieter Schinzer and Yunxin Bo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106871

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      The reaction behavior of functionalized oximes such as 1 is decisively influenced by the position of the N-hydroxyl group. Thus the (Z)-isomer reacts in the presence of diisobutylaluminum hydride to give the azepane 2, while the (E)-isomer gives the perhydroquinoline 3. Apparently, during the formation of 2 a Beckmann rearrangement first takes place with ring expansion, whereas in the case of 3 the oxime N atom is inserted directly into the ring that is being formed.

    5. Oxidative Cleavage of Triethylenetetramine (trien) to Yield Diethylenetriamine (dien): Structure of the MnII/MnIII Heptanuclear Complex [Mn7(trien)2(dien)2O4(OAc)8](PF6)4·2H2O (pages 688–689)

      Dr. Rajumati Bhula and Dr. David C. Weatherburn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106881

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      Two [Mn43-O)2] moieties with butterfly structure, which are coupled via a common Mn atom, are present in the cation of the title compound (structure with coordinated N (equation image) and O atoms (equation image) shown below). The complex cation, which contains six MnIII centers and one MnII center, is formed in the reaction of manganese(II) acetate and triethylenetetramine in methanol. During the reaction a part of the tetramine ligand is cleaved oxidatively with formation of diethylenetriamine.

    6. Dichloro(pentamethylcyclopentadienyl)ruthenium—Novel Dichotomy in a Molecular Structure (pages 690–691)

      Prof. Dr. Urich Kölle, Dr. Janusz Kossakowski, Dr. Norbert Klaff, Dr. Lars Wesemann, Dr. Ulli Englert and Prof. Dr. Gerhard E. Herberich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106901

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      Dimers with very different Ru[BOND]Ru bond lengths and Ru[BOND]Cl[BOND]Ru bond angles—deformation isomers—are present in equal parts in crystals of the title compound. Solid-state NMR investigations show that the isomer 1 a with the shorter Ru[BOND]Ru distance (2.93 Å) is diamagnetic, that with the longer distance (3.75 Å, 1 b), on the other hand, paramagnetic. The temperature dependence of the 1H NMR signal in solution is understandable if one assumes that the two isomers rapidly interconvert.

    7. Synthesis and Structure of the Novel Ga3P3 Ring Compound [(2,4,6-Ph3C6H2)GaP(cyclo-C6H11)]3 (pages 691–693)

      Professor Håkon Hope, Doris C. Pestana and Professor Philip P. Power

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106911

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      The central ring system in 1 consists exclusively of three-coordinate heavy main group elements. In contrast to its B[BOND]P analogue the Ga3P3 ring is not planar, i.e. π-π overlap with tem is not favored. Nevertheless, it contains the hitherto shortest Ga[BOND]P bond (mean length 2.3 Å).

    8. One-Step Synthesis of Organolanthanide(II) Complexes from the Metal (pages 693–694)

      Dipl.-Chem. Anja Recknagel and Dr. Frank T. Edelmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106931

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      The ansa-metallocenes 1 and 2 can be obtained in one-pot processes by reductive coupling of 6,6-dimethylfulvene in the presence of samarium and ytterbium powder, respectively. The ready accessibility and high reactivity make these lanthanide(II) complexes attractive starting materials for organometallic syntheses.

    9. β-Alkyl and β-Alkyl-α-Hydroxy Carboxylic Acid Derivatives from Radical or Ionic 1,4 Addition of Dialkylaluminum Chlorides to α,β-Unsaturated N-Acyl Urethanes (pages 694–696)

      Dipl.-Chem. Karola Rück and Prof. Dr. Horst Kunz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106941

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      Et2AlCl reacts with chiral α,β-unsaturated N-acyloxazolidones 1 exclusively ionically, Me2AlCl, on the other hand, exclusively radically with 1,4 addition of the alkyl residue to give β-branched carboxylic acid derivatives. The intermediary aluminum enolates formed from Me2AlCl after methyl transfer can react with triplet oxygen to give α-hydroxy-β-methylcarboxylic acid derivatives.

    10. Direct Assignment of Absolute Configuration of Chiral Alkyl Gluconamides by Wettability Measurements (pages 696–698)

      Jinn-Lung Wang, Prof. Dr. Meir Lahav and Prof. Dr. Leslie Leiserowitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106961

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      The contact angle of a crystal face affords information about the absolute configuration of the molecules forming the crystal. This could be demonstrated with the alkylgluconamides 1, which crystallize with the molecules arranged in layers. The angle of contact at the face consisting of the chain-end alkyls is 75–87°, while at the oppositely disposed face consisting of the CH2OH groups it is 44–56°C.

    11. Tetraethynylethene (pages 698–700)

      Yves Rubin, Carolyn B. Knobler and Prof. François Diederich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199106981

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      The first C10H4 hydrocarbon, the title compound, and a few of its derivatives have been synthesized by simple reactions from bis(trimethylsilyl)-1,4-pentadiyn-3-one. Compound 1 can be isolated in the form of colorless leaflets that are extremely sensitive to polymerization. Because of its cross-conjugated π-electron system, 1 is of interest as a precursor for novel polymers. The tetrakis(trimethylsilyl) derivative could be characterized by X-ray structure analysis.

    12. Mononuclear Silylvinylidene Rhodium Complexes from Silylalkynes: The SiMe3 Migration as an Alternative to the [1,2]-H Shift (pages 700–702)

      Dipl.-Chem. Dirk Schneider and Prof. Dr. Helmut Werner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107001

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      Vinylidene complexes can be prepared in the coordination sphere of rhodium with silylalkynes, RC[TRIPLE BOND]CSiMe3 whereas such complexes were hitherto accessible only with 1-alkynes, RC[TRIPLE BOND]CH. The synthesis proceeds via a [1,2]-SiMe3 migration along the alkyne C[BOND]C bond, which is just as facile as [1,2]-H shifts. The corresponding alkyne complexes formed as intermediates can also be isolated.

    13. Furfural as a Marker of DNA Cleavage by Hydroxylation at the 5′ Carbon of Deoxyribose (pages 702–704)

      Dr. Geneviève Pratviel, Marguerite Pitié, Prof. Dr. Jean Bernadou and Dr. Bernard Meunier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107021

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      Depending upon the type of DNA substrate, a manganoporphyrin/KHSO5 system as artificial nuclease preferably attacks at the C1′ or C5′ atom of the deoxyribose moiety, whereby subsequent heating of the reaction mixtures leads to release of 5-methylene-2-furanone (5-MF) and furfural (FUR). The ratio 5-MF/FUR directly reflects the relative reactivities of the cleaving reagent with respect to C1′ and C5′. A possible reaction for the formation of FUR is outlined below.

      = terminal phosphate residue, B = nucleobase.

    14. The Structure of “Organic Permanganate” (pages 704–705)

      Prof. Maree L. Burgess, Donald C. Craig and Michael J. Gallagher

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107041

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      Not a diphenylketene dimer, as has long been presumed, but the p-quinodimethane derivative 1 is formed (inter alia) upon pyrolysis of benzilic acid. In contrast to the related orange-yellow 2 (“Thiele's hydrocarbon”), 1 is deep black-red; this can be attributed to expansion of the conjugated system by the condensed furanone ring.

    15. Synthesis of β,γ-Unsaturated D-α-Amino Acids from L-Cysteine (pages 705–707)

      Dr. Rudolf O. Duthaler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107051

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      D-α-Amino acids 2 are accessible in high optical purity by acid hydrolysis of the 5-thiazolidinone 1. Compounds of the type 1 can be prepared in a few reaction steps from L-cysteine; during the conversion of 1 into 2 unsaturated residues R remain intact. Boc = tert-butoxycarbonyl.

    16. Facile N[BOND]H Cleavage of Ammonia (pages 707–709)

      Dr. Robert Koelliker and Dr. David Milstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107071

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      The dinuclear Ir complex 1 already reacts with excess NH3 at − 50°C to give not only mono– and dicationic complexes but also 2, the first amido-olefin complex. An N[BOND]H activation under such exceptionally mild conditions is of interest for the catalytic functionalization of olefins with NH3.

    17. Methylene Phosphonium Ions (pages 709–710)

      Dr. Hansjörg Grützmacher and Dr. Hans Pritzkow

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107091

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      Despite steric shielding of the P[DOUBLE BOND]C bond, the methylenephosphonium ions 1 and 2 react with 2,3-dimethylbutadiene in an ene reaction and a [2 + 4]cyclo-addition reaction, respectively, to give 3 and 4 (counterion in all cases AlClmath image). This reaction behavior is understandable from the pronounced electron-deficient character of the alkyl-substituted P atoms. Compounds 1 and 2 are formed in high yields from the corresponding P-chloro-substituted phosphorus ylides by chloride abstraction.

    18. Effects of Perturbed Symmetry: Low-Melting Stable Mesogens Based on ortho-Palladated Imines (pages 711–712)

      Maria Jesús Baena, Prof. Dr. Pablo Espinet, Dr. Maria Blanca Ros and Prof. Dr. José Luis Serrano

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107111

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      Melting points and clearing temperatures of metal-containing liquid crystals can be reduced drastically if the symmetry of the ligand sphere is lowered. This is achieved in case of the dinuclear metallomesogen 1 by replacement of PdC12-azomethine by acetyl acetonate with formation of the mononuclear complex 2. The temperature range in which the mesophase exists is thereby reduced by around 100 K to 80–130°C—an exceptionally important aspect with regard to processibility.

    19. Chemoenzymatic Syntheses of ω-Ureido D-Amino Acids (pages 712–714)

      Dr. Karlheinz Drauz, Dr. Matthias Kottenhahn, Dr. Kyriakos Makryaleas, Dr. Herbert Klenk and Dr. Michael Bernd

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107121

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      D-Amino acids can be prepared chemoenzymatically in very high yields with high enantioselectivity by cleavage of the corresponding hydantoins with Agrobacterium radiobacter bacterial culture. Hydantoins with highly functionalized side chains are also accepted. The synthetic concept is discussed taking D-citrulline (1) as example.

    20. 2,3,6,7-Tetramethoxythianthrene Dication: An “Aromatic” π System “Gives Up the Ghost” (pages 714–716)

      Prof. Dr. Hans Bock, Dipl.-Chem. Andreas Rauschenbach, Dipl.-Chem. Klaus Ruppert and Dr. Zdenek Havlas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107141

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      The structure of the dication of tetra-methoxythianthrene (1) can be described as two nine-membered cyanine units coupled by C[BOND]C single bonds. This shows that the tendency for a cyanine-like structure perturbation is very great, since 12⊕ still contains two electrons too many for real cyanine subsystems and could alternatively have exhibited aromatic character as heteroanthracene.

    21. Nickel-catalyzed Cyclotrimerization of Malononitrile: The Dicyanomethanide-bridged, Anionic NiII Complex [{Ni(C5F5)2(μ-NCCHCN)}2]2⊖ (pages 716–718)

      Prof. Gregorio López, Dr. Gregorio Sánchez, Dr. Gabriel Garciá, Dr. José Ruiz, Joaquín García, Prof. M. Martínez-Ripoll, Dr. A. Vegas and Juan A. Hermoso

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107161

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      A remarkable twelve-membered heterocycle is present in the title complex anion 1. It is formed in the reaction of the NBu4 salt of the corresponding hydroxo-bridged anion with malonitrile in the molecular ratio 1:2. Catalytic amounts of the Ni compound, on the other hand, effect a cyclotrimerization of the malonitrile, leading to a highly functionalized pyridine derivative.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Book Review: Analytical NMR. Edited by L. D. Field and S. Sternhell (page 721)

      Herbert Kogler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199107211