Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 9

September 1984

Volume 23, Issue 9

Pages 645–746

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 9/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406451

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      The title page shows a computer graphic, which provides an almost stereo portrayal of a zeolite structure. The lattice encloses cavities and channels in which cations, guest reactants, or product species can be accomodated—and move. The unique structural and reactive properties of zeolites are particularly amenable to illustration by computer (especially color) graphics. A detailed report of this modern approach to chemical crystallography is presented in the article by J. M. Thomas et al. on p. 671.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 9/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406452

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Experimental and Theoretical Nuclear Astrophysics; The Quest for the Origin of the Elements (Nobel Lecture) (pages 645–671)

      Prof. William A. Fowler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406453

      The heavier chemical elements were formed–and are being formed–in stars. Substantiation of this concept necessitated, inter alia, a detailed knowledge of numerous nuclear processes. With his quantitative experimental data, W. A. Fowler (Nobel Prize for Physics 1983) was able to put the theory of formation of the elements in the interior of stars on a firm footing. Supernovae also participate in the nucleosynthesis.

    2. Modelling the Chemistry of Zeolites by Computer Graphics (pages 671–679)

      Dr. Subramaniam Ramdas, Prof. Dr. John M. Thomas, Paul W. Betteridge, Dr. Anthony K. Cheetham and Dr. E. Keith Davies

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406711

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      “Structure-activity relationships” in zeolites are amenable to illustration by computer graphics, especially color graphics. For example, the sites of cations and guest species, as well as the occurrence of various kinds of intergrowths, can all be effectively portrayed in such a manner as to emphasize the shape-selective character of these microporous solids. Dynamic phenomena can also be probed interactively using appropriate potential functions.

    3. On Stars, Their Evolution and Their Stability (Nobel Lecture) (pages 679–689)

      Prof. Dr. Subrahmanyan Chandrasekhar

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406791

      That the fate of stars is determined by their masses, and thus, that not all stars end as white dwarfs, is one of the underlying principles of the work of S. Chandrasekhar (Nobel Prize for Physics 1983). Because of the relativistic increase in mass of the electron there is an upper limit for the mass of white dwarfs: about 1.4 solar masses. Stars with about 2 solar masses form neutron stars as the final state; beyond this limit, black holes are formed.

    4. Organic Polymeric and Non-Polymeric Materials with Large Optical Nonlinearities (pages 690–703)

      Dr. David J. Williams

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198406901

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      Many areas of optoelectronics-e.g. optical communications, laser scanning and control functions, and integrated optics technology-make use of the nonlinear optical properties of organic compounds. These properties depend on the electronic and solid-state structures of the compounds. The importance of these materials has already been compared with that of semiconductors. Examples of this type of compound are the merocyanine dyes 1.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Optional Diastereo- and Enantioselective Synthesis of Vicinal threo- or erythro-Dihydroxy Derivatives (pages 704–705)

      Prof. Dr. Johann Mulzer, Dipl.-Chem. Michael Kappert, Prof. Dr. Gottfried Huttner and Dipl.-Chem. Ibrahim Jibril

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407041

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      A possibility of obtaining the desired diastereomer of compounds containing the 1,2-di-O structural element was realized with the isopropylidene-protected (R)-glyceraldehyde 1a. Compound 1a can be converted >90% threo- or erythro-selectively into the β-alkoxycarboxylates 2/3. For the preparation of 2, the method of choice is the addition of diallylzinc followed by Lemieux cleavage, whereas the best route from 1a to 3 is via the aryl ester 1b and the addition of alkoxide to 1b. 2 and 3 can be converted into the lactones 4 and 5, respectively.

    2. Carbanion-Induced Skeletal-Rearrangements: From the Dibenzo[a,e] cyclooctene to the Indeno[2,1-a]indene Framework (pages 705–706)

      Prof. Dr. Dieter Hellwinkel, Hans-Joachim Hasselbach and Dr. Frank Lämmerzahl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407051

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      A surprising ring contraction to give derivatives 2 and 3 of indeno[2, 1-a]indene is observed in the reaction of 1 with organolithium compounds (R = alkyl, Ph; R1, R2 = H, alkyl, Ph). The expected nucleophilic substitution of 1 has so far only been accomplished in one case: with CuCN, the tetracarbonitrile 1, CN instead of Br, is formed.

    3. Stereochemical Evidence Supporting the Intermediate-Mechanism of Dihalocarbene Addition (pages 706–707)

      Prof. Dr. Eckehard V. Dehmlow and Dipl.-Chem. Roland Kramer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407061

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      That the addition of dibromocarbene to alkenes proceeds via an intermediate (IN) follows from observations on trans-cyclooctene 1. The less reactive dichlorocarbene furnishes the expected trans-adduct 2; dibromocarbene, however, does not add stereospecifically, and isomerizes the unreacted 1 to cis-cyclooctene, cis-1. This affords evidence of involvement of an intermediate—most likely a CT complex.

    4. Novel Tricarbonyl(η4-dihydroacepentalene)iron Complexes and Tricarbonyl(η2-dihydroacepentalene)ferrates(−2) (pages 707–708)

      Dr. Holger Butenschön and Prof. Dr. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407071

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      The first spectroscopically characterized (η2-olefin)ferrates( – 2), 3, are formed on reduction of the novel (η4-diene)iron complexes 2 with sodium. This reaction proceeds via a radical anion; high spin density at the iron is detected by ESR spectroscopy in the case of the reduction product of 2, NR2 = piperidino.

    5. Homocyclobutadienes and Cyclopropenes by Reaction of a Stable Cyclobutadiene with Diazo Compounds (pages 708–710)

      Dipl.-Chem. Uwe-Josef Vogelbacher, Dr. Philipp Eisenbarth and Prof. Dr. Manfred Regitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407081

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      The substituents in the diazoalkane 2 are decisive in determining whether compounds of type 3 or 4 are formed in the reaction with the stable cyclobutadiene 1. Reaction of 1 with diazomethane or diazoethane affords dihydropyrazole derivatives, from which N2 can be cleaved off to yield thermally stable homocyclobutadienes such as 3. With doubly acylated or arylated 2, azines 4 containing cyclopropenyl groups are formed. These reaction proceed via addition of 2 and ring contraction.

    6. Facile Synthesis of Heteroalkenes CF3E[DOUBLE BOND]CF2 (E[DOUBLE BOND]P, As) (pages 710–711)

      Prof. Dr. Joseph Grobe and Dr. Duc Le Van

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407101

      A general entry to E [DOUBLE BOND] C(p-p)π systems might be afforded by the elimination of Me3SnF from stannylated trifluoromethylelement compounds. Thus, the phosphane 1a (E [DOUBLE BOND] P) and the arsane 1b (E [DOUBLE BOND] As) react in the gas phase at 10−3 torr and 300—340oC to give the heteroalkenes 2a and 2b, respectively, in quantitative yield. CF3As [DOUBLE BOND] CF2 is the smallest molecule known so far with As [DOUBLE BOND] C bonding.—Further examples of species thus generated are S [DOUBLE BOND] CF2, Se [DOUBLE BOND] CF2, and Me3SnP [DOUBLE BOND] CF2.

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    7. Facile Synthesis of Highly Reactive Ferracycloalkanes (pages 711–712)

      Prof. Dr. Ekkehard Lindner, Eckard Schauss, Dr. Wolfgang Hiller and Riad Fawzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407111

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      Nucleophilic elimination-cycloaddition is a suitable method for the synthesis of cyclic organoiron compounds. 2a, L [DOUBLE BOND] CO, is extremely volatile. In the case of the more stable 2b, L [DOUBLE BOND] PPh3, enantiomers have been found in the crystal. 3a, L [DOUBLE BOND] CO (already known), and 3b, L [DOUBLE BOND] PPh3, are likewise readily accessible in this way.—Metallacyclopentanes such as 2 occur as highly reactive intermediates in numerous metal-catalyzed reactions.

    8. Novel Host Structures for the Selective Inclusion of Aromatic and Aliphatic Guests in Aqueous Solution (pages 712–714)

      Prof. Dr. Fritz Vögtle and Walter M. Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407121

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      Thirty-membered cyclic hexalactams of the type 1, each with six α-, β-, or γ-pyridylmethyl side-arms, are novel host compounds. In aqueous solution, they can trap both aromatic as well as aliphatic organic neutral molecules. In all the guest molecules investigated, 1 (R [DOUBLE BOND] β-pyridylmethyl) induces the strongest upfield shifts of the 1H-NMR signals. With respect to the desired enzyme model character it is interesting that 1, R = α-pyridylmethyl, solvates salts such as NaMnO4 in CH2Cl2.

    9. Functionalized, Oligocyclic Large Cavities — A Novel Siderophore (pages 714–715)

      Dipl.-Chem. Wolfgang Kiggen and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407141

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      A fundamentally novel type of complex-ligand is exemplified by the triply bridged hexalactam structure and octahedral donor geometry. The ligand dissolves stainless steel, iron, chromium, and nickel to form colored, stable complex anions of type 1, which are not even decomposed by excess EDTA. 1:1-Stoichiometry has been demonstrated for the iron(III) complex.—Almost 1 g of ligand can be conveniently obtained per charge.

    10. Synthesis and Crystal Structure of [Ph4As]4[Au12S8], a Distorted Cubane-Like Thioaurate(I) (pages 715–716)

      Dipl.-Chem. Gerolf Marbach and Prof. Dr. Joachim Strähle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407151

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      A cube with twelve Au atoms on the sides and eight S atoms at the corners constitutes the structure of the novel thioaurate(I) ion [Au12S8]4⊖. It is obtained quantitatively as the yellow [Ph4As] salt on addition of Ph4AsCl to an aqueous solution of Au2S and Na2S. Very few examples of thioaurates(I) are known.

    11. 2-(Pyridyl)ethyl Esters as Secure yet Readily Removable Polarophilic Carboxy-Protection in Peptide Synthesis (pages 716–717)

      Prof. Dr. Horst Kunz and Dipl.-Chem. Michael Kneip

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407161

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      Pet (pyridyl-ethyl ester) signifies two advantageous novel carboxy-protecting groups for peptide synthesis. 2-(2-Pyridyl)- and 2-(4-pyridyl)ethyl esters of amino acids and peptides are both acid-stable as well as relatively base-stable; thus, they survive the acidolytic cleavage of the Z- and the Boc-protecting group. After methylation to the extremely base-labile pyridinium form (e.g. 1), Pet esters can be mildly cleaved with morpholine.

    12. Novel Synthesis and Molecular Structure of the Pyrene Isomer Dicyclohepta[cd,gh]pentalene (Azuleno[2,1,8-ija]azulene) (pages 717–719)

      Prof. Dr. Emanuel Vogel, Dr. Herbert Wieland, Lutz Schmalstieg and Dr. Johann Lex

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407171

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      The planar structure of the title compound 1 could be confirmed by X-ray structure analysis. The shortness of the central bond (1.35 Å) favors the resonance structure B; that is, 1 can be regarded as a [14]annulene perturbed by the C [DOUBLE BOND] C bridge.—The decisive reaction step is a novel type of Ramberg-Bäcklund analogous rearrangement.

    13. Thermal Deoxygenation of syn-15, 16-Dioxo-1,6 : 8,13-bismethano[14]annulene to the Pyrene Isomer Dicyclohepta[cd,gh]pentalene (Azuleno[2,1,8-ija]azulene) (pages 719–720)

      Prof. Dr. Emanuel Vogel, Dr. Gerd Markowitz, Lutz Schmalstieg, Shô Itô, Rolf Breuckmann and Prof. Dr. Wolfgang R. Roth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407191

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      A unique reaction takes place in the pyrolysis of the diketone 1. The formation of the pyrene isomer 2 (60%) can hardly be explained other than in terms of via a 1,2-dioxetane; thus, this reaction would be the reverse of the oxidative cleavage of electron-rich double bonds with singlet oxygen. In addition, 30% anthracene is obtained by the expected stepwise decomposition of 1 via a norcaradienone derivative.

    14. General Entry to Novel Manganese(II) Half-Sandwich Complexes (pages 721–722)

      Prof. Dr. Frank H. Köhler, Dipl.-Chem. Nikolaus Hebendanz, Prof. Dr. Ulf Thewalt, Prof. Dr. Basil Kanellakopulos and Dr. Reinhardt Klenze

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407211

      The chemistry of half-sandwich complexes is of interest, inter alia, because of the high reactivity of these compounds and because of their potential use for the synthesis of novel complexes. From the manganocene 1, the dimeric PEt3 derivatives 3 were synthesized via the THF complexes 2; 3, X [DOUBLE BOND] Cl, is confirmed by X-ray structure analysis. Surprisingly, 2, X [DOUBLE BOND] I, reacts with PMe3 to give the monomeric complex Cp′MnI(PMe3)2. MnII half-sandwich complexes were hitherto unknown (Cp′ [DOUBLE BOND] MeC5H4).

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    15. TMEDA Adducts of CpMnCl and Manganocene (pages 722–723)

      Dr. Jürgen Heck, Priv.-Doz. Dr. Werner Massa and Peter Weinig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407221

      The base-stabilized manganese(II) half-sandwich complex 1, the first unsubstituted cyclopentadienylmanganese(II) halide, was synthesized via the route depicted below. 1 could find wide application as a CpMn transfer agent, e.g. for the synthesis of unsymmetrical sandwich compounds, especially “mixed” manganocenes, which should enable a detailed study of the high-spin—low-spin equilibrium. The thermolysis of 1 leads to Cp2Mn(TMEDA), the first Mn11 compound known to contain a η5- and a η1-ligand (TMEDA [DOUBLE BOND]Me2NCH2CH2NMe2, Cp [DOUBLE BOND] C5H5).

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    16. Stereoselective Nucleophilic Acylation of Benzaldehyde with a Crotonaldehyde-d1 Reagent (pages 723–724)

      Priv.-Doz. Dr. Manfred Braun and Wilhelm Hild

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407231

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      The addition of “umgepolt” carbonyl compounds to aldehydes—one of the most important CC coupling reactions—was studied with the chiral vinyl sulfide 1, X [DOUBLE BOND] Li. 1 (obtainable from (S)-lactic acid) functions as a crotonaldehyde-d1 synthon 2, and on reaction with benzaldehyde yields the unsaturated acyloin 3 stereoselectively.

    17. Synthetic Studies on the Elucidation of the Structure and Configuration of Dolastatin 3 (pages 725–726)

      Prof. Dr. Ulrich Schmidt and Dipl.-Chem. Roland Utz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407251

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      Which structure has dolastatin 3? Certainly not the structure 1 proposed originally! Neither the eight isomers initially synthesized nor the eight stereoisomers newly synthesized with reversed “ring direction” were identical with the natural product obtainable in very small amounts from a marine organism.—Compounds like dolastatin 3 show strong antineoplastic activity in vitro (X [DOUBLE BOND] CONH2).

    18. Unusual Equilibrium between η1- and η2-Isomers of Selenobenzaldehyde Complexes (pages 726–727)

      Priv.-Doz. Dr. Helmut Fischer, Dr. Siegfried Zeuner and Jürgen Riede

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407261

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      Novel complexes with selenobenzaldehyde, which was generated in the ligand sphere of tungsten, are distinguished by an equilibrium between (E)-η1-, (Z)-η1-, and η2-bonded forms. The position of the equilibrium depends on the temperature, the solvent, and the substituents. Examples of such equilibria are very rare. M [DOUBLE BOND] W.

    19. A Novel Entry to 17α-Bromo- and 17α-Iodoethynyl Steroids (pages 727–729)

      Dr. Helmut Hofmeister, Dr. Klaus Annen, Dr. Henry Laurent and Prof. Dr. Rudolf Wiechert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407271

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      The replacement of the H atom in [BOND]C[TRIPLE BOND]CH by Br or I can be accomplished with N-bromo- and N-iodosuccinimide, respectively, in the presence of silver salt catalysts. This method could be used, inter alia, to prepare numerous 17α-bromo- 2 and 17α-iodoethynyl steroids 3. In contrast to older methods, the hydroxy- (and carbonyl-) groups in 1 do not have to be protected.

    20. [2 + 1]-Cycloadditions of Ynamines and Ynediamines to Carbon Monosulfide (page 729)

      Prof. Dr. Adolf Krebs, Andreas Güntner, Lektor fil. lic. Alexander Senning, Ejner K. Moltzen, Prof. Dr. Kenneth J. Klabunde and Michael P. Kramer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407291

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      The first successful cycloadditions of CS led to the cyclopropenethiones 2 and 3. Ynamines 1 and ynediamines were chosen as reaction partners because they are extremely rich in electrons.

    21. Surprising Stability of Nucleophilic CrIII-Alkylating and CrIII-Allylating Reagents towards Ethanol and Water (pages 729–730)

      Prof. Dr. Thomas Kauffmann, Renate Abeln and Dorothea Wingbermühle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407292

      The alkylation and allylation of aldehydes in the presence of ethanol or water are possible with chromium(III) reagents such as 1 or 2. In some cases, the addition of ethanol or water even increases the yields. The maximum yield on addition of 1—3 mol of protic solvent per mol of reagent indicates that 1—3 solvent molecules are incorporated into the ligand spheres of 1 or 2 without cleavage of the Cr[BOND]C bond.

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    22. O[DOUBLE BOND]P[BOND]Cl and S[DOUBLE BOND]P[BOND]Cl: Gas-Phase Ionization (pages 731–732)

      Dr. Michael Binnewies, Bahman Solouki, Prof. Dr. Hans Bock, Dipl.-Chem. Ralf Becherer and Prof. Dr. Reinhart Ahlrichs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407311

      The ionization bands of OPCl and SPCl in the PE spectrum cold be assigned by ab initio-SCF calculations. The structural data calculated for the minimum of the total energy differ very little from those of the educts OPCl3 and SPCl3. The influence of the electron pair at the P atom manifests itself, according to the calculations, in the contraction of the OPCl and SPCl angles from 115 to 109o and from 116 to 110o, respectively; the P [DOUBLE BOND] O and P [DOUBLE BOND] S bonds are about 1—2 pm shorter and the P–Cl distances about 6 pm longer than in the educts.

    23. Metal-Catalyzed Carbonylations of Benzyl and Aryl Bromides in the Presence of Aluminum Alkoxides; A Straightforward Ester Synthesis (pages 732–733)

      Prof. Howard Alper, Dr. Shlomo Antebi and Dr. James B. Woell

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407321

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      Ethyl, isopropyl, and sec-butyl esters are obtainable from benzyl or aryl bromides, aluminum alkoxides, and CO in the presence of catalysts. Metal-catalyzed reactions of the readily available and inexpensive aluminum alkoxides were previously unknown. (Cat. in the case of benzyl bromides: [(1,5-hexadiene)RhCl]2; cat. in the case of aryl bromides: Rh-catalyst + [Pd(PPh3)4].)

    24. Reactivity of CH2[BOND]X[BOND]CHmath image (X [DOUBLE BOND] Cl, Br) with Electrophiles and Nucleophiles in the Gas Phase, a Fourier Transform Ion Cyclotron Resonance Investigation (pages 733–734)

      Thomas Weiske, Hans van der Wel, Prof. Dr. Nico M. M. Nibbering and Prof. Dr. Helmut Schwarz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407331

      Nonclassical chloronium radical ions such as 1 are accessible by electron impact ionization from ClCH2–COOMe. According to ab initio calculations, 1 can be described as an ion-dipole complex. The expected well-defined reactions of such a complex have been demonstrated in an FT-ICR experiment.

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    25. Iron Clusters with Coupled Phosphido-Phosphane Bridges (pages 734–735)

      Prof. Dr. David J. Brauer, Dr. Sibbele Hietkamp, Dipl.-Chem. Herbert Sommer and Prof. Dr. Othmar Stelzer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407341

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      Novel μ3-ligands for trinuclear clusters are the phosphido-phosphane groups of formula R(iPr)P[BOND]CH2[BOND]P(iPr), R [DOUBLE BOND] H, iPr. The clusters 1, R [DOUBLE BOND] H, iPr, are formed spontaneously in the reaction of R(iPr)P[BOND]CH2[BOND]P(iPr)H with Fe2(CO)9 in the molar ratio 1:6. According to the X-ray structure analysis, the Fe[BOND]H[BOND]Fe system can be described in terms of 2e3c bonding.

    26. Stable Formylmanganese Complexes (pages 735–736)

      Dr. Heinz Berke, Prof. Dr. Gottfried Huttner, Dipl.-Chem. Olaf Scheidsteger and Dr. Gertrud Weiler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407351

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      The first stable neutral formyl complexes of a light transition metal, the title compounds 2 with aryl phosphite ligands, were prepared by reduction of the cations of 1. Formyl complexes have been postulated as intermediates in the homogeneous catalytic hydrogenation of CO (L [DOUBLE BOND] P(OPh)3, L′ [DOUBLE BOND] CO; L [DOUBLE BOND] P(o-OTolyl)3, L′ [DOUBLE BOND] CO; L [DOUBLE BOND] L′ [DOUBLE BOND] P(OPh)3).

    27. Synthesis of Azidobutadienes (pages 736–738)

      Dr. Hanno Priebe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407361

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      The synthesis of the unsaturated azides 1 and 2 by single and double allylrearrangement, respectively, opens up a novel entry to this class of compound. 1 is obtained from CH2[DOUBLE BOND]C[DOUBLE BOND]CH[BOND]CH2Br and NaN3; the postulated unrearranged azide was not detectable. However, such a species was detectable in the synthesis of 2 from BrCH2[BOND]C [TRIPLE BOND] C[BOND]CH2Br and NaN3. 1 and 2 are suitable, in particular, as cycloaddition partners as well as precursors for 2- and 2,3-functionalized dienes, respectively.

    28. Novel Synthesis of Complexes with Metal-Phosphorus Double Bonds (pages 738–739)

      Elisabeth Gross, Klaus Jörg, Dr. Klaus Fiederling, Axel Göttlein, Prof. Dr. Wolfgang Malisch and Dr. Roland Boese

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407381

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      The mild preparation of Mo [DOUBLE BOND] P- and W [DOUBLE BOND] P-compounds has been achieved by base-assisted dehydrohalogenation or deamination of phosphanes: M(X)[BOND]P(Y)[RIGHTWARDS ARROW]M[DOUBLE BOND]P + XY.The compound 2, R [DOUBLE BOND] H, obtained from 1 by this reaction principle, can be converted in a controlled way into metallacycles of the type 3 (X) [DOUBLE BOND] S, CH2, Fe(CO)4.

    29. Synthesis, Structure, and Reactions of Cluster-Stabilized Phosphaalkenes (pages 739–740)

      Dipl.-Chem. Konrad Knoll, Prof. Dr. Gottfried Huttner, Dr. Marek Wasiucionek and Dipl.-Chem. Laszlo Zsolnai

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407391

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      The transformation of a cluster with a μ3-phosphanediyl ligand into the title compound 1, R [DOUBLE BOND] p-H3COC6H4, was achieved by reaction with NaNH2 and CH2I2. In 1, a phosphaalkene RP[DOUBLE BOND]CH2 is stabilized for the first time as a μ32-bridge; it can be reduced in the cluster to a novel type of μ33-phosphino ligand RPCH3.

    30. Facile Synthesis of PhAs[DOUBLE BOND]AsPh Complexes (pages 740–741)

      Prof. Dr. Gottfried Huttner and Dipl.-Chem. Ibrahim Jibril

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407401

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      The dehydrogenation of complexed diphenyldiarsanes 1 to complexes with “arsenobenzene” ligands (with Pd/C or Pt/C) constitutes a suitable route to this otherwise difficultly accessible class of compounds. X-ray structure analyses have been carried out on 2, L [DOUBLE BOND] P(OMe)3 or 2L [DOUBLE BOND] bpy, as well as 2, Cr(CO)4P(OMe)3 instead of PdL2.

    31. Rapid Proton Transfer as Cause of an Unusually Large Neighboring Group Effect (pages 741–742)

      Günter Wulff, Manfred Lauer and Helmut Böhnke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407411

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      An acceleration of the transesterification of arylboronates by a factor of about 109 can be achieved by introduction of nitrogen-containing substituents or moieties into phenylboronic acid esters. Examples are aryl [DOUBLE BOND] o-(dimethylaminomethyl)phenyl, o-(dimethylamino)phenyl, 8-quinolyl. Arylboronic acids thus become available which are suitable, after immobilization, for a very rapid chromatographic separation of diols.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Book Review: Chemie der Räucherung. By L. Toth (page 744)

      Hans-Dieter Belitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407441

  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. You have free access to this content
      Corrigendum (page 746)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198407461

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