Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 11

November 1985

Volume 24, Issue 11

Pages 893–1008

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 11/1985)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198508931

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      The cover page shows the crystal structure of the [Ni34Se22(PPh3)10] cluster. The black, dotted circles and hatched circles symbolize the differently bonded nickel atoms; the thirty phenyl groups are omitted. This amazing molecule with 448 valence electrons is obtainable in 30% yield from [NiCl2(PPh3)2] and Se(SiMe3)2 in toluene. It forms black crystals. Further details are reported by D. Fenske et al. on page 993 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Arene Complexes of Univalent Gallium, Indium, and Thallium (pages 893–904)

      Prof. Dr. Hubert Schmidbaur

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198508933

      Arene complexes of main group metals were for a long time a rarity. In the course of systematic studies it has now been possible to synthesize and structurally characterize arene complexes of Ga1, In1, and Tl1. This new type of compound is characterized, inter alia, by a centric (η6-)coordination of the metal to the arene; both mono- and (bent) bis(arene) complexes are known.

    2. Mechanisms of Biological Ion Transport — Carriers, Channels, and Pumps in Artificial Lipid Membranes (pages 905–923)

      Prof. Dr. Peter Läuger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509051

      How do ions migrate through biological membranes, i.e. how do they move at the cellular level? To answer this question, biological transport systems, as a rule proteins, are incorporated into artificial membranes so that their kinetic properties can be studied in detail.

    3. Phosphorus, Arsenic, Antimony, and Bismuth Multiply Bonded Systems with Low Coordination Number — Their Role as Complex Ligands (pages 924–943)

      Prof. Dr. Otto J. Scherer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509241

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      The versatile coordination chemistry of compounds with doubly or triply bonded P, As, Sb or Bi is fascinating. Such species may be coordinated as donor ligands in terminal, side-on, or edge- and/or face-bridging modes to transition metal fragments. An example is the complex 1 (Cp* = C5Me5).

    4. 2,3-Dihydro-1,3-diborole-Metal Complexes with Activated C[BOND]H Bonds: Building Blocks for Multilayered Sandwich Compounds (pages 943–958)

      Prof. Dr. Walter Siebert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509431

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      “Skyscraper molecules” such as “multistoried” 1 — and even semiconducting polymers containing the stacking unit 2 — can be synthesized from substituted 2,3-dihydro-1,3-diboroles (“C3B2”). (For want of space, 1 is illustrated “lying down”.)

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Revised Structure and Absolute Configuration of Chaksine (page 959)

      Prof. Dr. Wolfgang Voelter, Prof. Dr. Werner Winter, Prof. Dr. Viquar Uddin Ahmad and Mohammad Usmanghani

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509591

      Chaksine, a constituent of the seeds of Cassia abuss (var. Chaksa), is an alkaloid containing a 16-membered bislactone ring. In 1958, Wiesner et al. proposed a structure with an eight-membered lactone ring for the alkaloid. Although elemental analyses and NMR data are concordant with both structures, the field desorption mass spectrum suggests a dimeric species, proof for which has finally been provided by an X-ray structre analysis.

    2. Synthesis and Structure of 1,4-Dimethylanthracenemagnesium·3thf and μ-Trichlorodimagnesium·6thf(1+) Anthracenide (pages 960–961)

      Prof. Dr. Borislav Bogdanović, Dipl.-Chem. Nikolaus Janke, Prof. Dr. Carl Krüger, Dr. Richard Mynott, Klaus Schlichte and Dr. Uwe Westeppe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509601

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      An isolated anthracene radical anion is present in the crystalline μ-trichlorodimagnesium·6 thf(1+) anthracenide 2. Compound 2 can be obtained from Mg, anthracene, and MgCl2, or from the Mg-complex 1, anthracene, and MgCl2, in each case in tetrahydrofuran (THF).

    3. Nickel(0)-Catalyzed Synthesis of Sorbanilide from 1,3-Pentadiene and Phenyl Isocyanate (pages 961–962)

      Prof. Dr. Heinz Hoberg and Dr. Elisa Hernandez

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509611

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      The preparation of the title compound 2 from 1,3-pentadiene and phenyl isocyanate constitutes the first metal-induced synthesis of a conjugated dienecarboxylic acid derivative. The reaction proceeds via CC coupling to give 1, from which the anilide 2 is immediately formed.

    4. Reactivity of Bis(η6-benzene)chromium(0) toward Sulfur Dioxide: Formation and Structure of [(η6-C6H6)2Cr]2S4O10, a Salt Containing the Anion [S2O6·2SO2]2⊖ (pages 967–968)

      Prof. Dr. Christoph Elschenbroich, Rolf Gondrum and Priv.-Doz. Dr. Werner Massa

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509671

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      An adduct of two SO2 molecules and one dithionate ion, namely the anion of the title compound 1 (see below, right-hand side), can be obtained from bis(η6-benzene)chromium and SO2 in acetonitrile. The SO2 molecules are coupled to the dithionate ion via unusually long S(SO2)-O(S2O6) bonds (243 pm).

    5. β-(ET)2AuI2: An Organic Volume Superconductor with Tc = 3.2 K at Ambient Pressure (pages 968–969)

      Prof. Dr. Eberhard Amberger, Dipl.-Chem. Helmut Fuchs and Dr. Kurt Polborn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509681

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      Competition is hard! Concomitantly with an American author, a Munich research group have set a new superconductor record: The hitherto highest critical temperature has been achieved with β-(ET)2AuI2, without pressure, without additional doping, and without tempering. In the compound prepared by electrocrystallization the ET radical cations form stacks with novel spatial arrangement.

    6. (i-C3H7SGaI2)2, the First “Butterfly” Molecule with Tetracoordinated Gallium (pages 970–971)

      Dr. Gerhard Georg Hoffmann and Dr. Christian Burschka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509701

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      The gallane I2Ga-S[BOND]iPr, which can be obtained from diiodo(methylthio)gallane and 2-propanethiol, is present as dimer in the solid state and as trimer in solution. In the crystalline state the GaSGaS four-membered ring is folded at an angle of 143.3°.

    7. A Dithioester as Allylic-Type 4e Ligand (pages 971–972)

      Prof. Dr. Wolfdieter A. Schenk, Dipl.-Chem. Doris Rüb and Dr. Christian Burschka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509711

      Novel complexes with methyl dithioacetate as η3-ligand have been synthesized from nitrile complexes and characterized, inter alia, by X-ray structure analysis of 1. The S[BOND]C[BOND]S group of the ligand is exactly planar and is bound in an allyl-like fashion to the metal. Electrophilic attack at the “thione” sulfur leads to dinuclear complexes or η2-dithiocarbenium derivatives.

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    8. New Bicyclic Ketones and the Stereochemistry of Their Reaction with Carbanions (pages 972–973)

      Dipl.-Chem. Petra Baierweck, Dipl.-Chem. Detlef Hoell and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509721

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      Alkylation of the “Ketone dianion” 1 of 2-indanone with difunctional electrophiles can lead to cyclization with C,C-([RIGHTWARDS ARROW] 2) or C,O-alkylation ([RIGHTWARDS ARROW] 3 and/or double bond isomers), as well as to spiroannelation ([RIGHTWARDS ARROW] 4); the reaction can be controlled and thus opens up a simple entry to bicyclic ketones such as 2. Their reaction with organometallic compounds proceeds diastereoselectively.

    9. Extensions of the Tricyclooctanone Concept. A General Principle for the Synthesis of Linearly and Angularly Annelated Triquinanes (pages 973–975)

      Priv.-Doz. Dr. Martin Demuth and Werner Hinsken

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509731

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      Oxadi-π-methane rearrangements are the key steps of a synthesis of the title compounds of type 1 and 2. Triquinane is of special interest as a skeletal unit of natural products, e.g. hirsutene and 5-oxosilphiperfol-6-ene.

    10. Preparation and Structure of a Diphosphorus Compound with Positive Charges on the Two Directly Bonded Phosphorus Atoms (pages 975–976)

      Priv.-Doz. Dr. Dietmar Schomburg, Dipl.-Chem. Gerhard Bettermann, Priv.-Doz. Dr. Ludger Ernst and Prof. Dr. Reinhard Schmutzler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509751

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      No significant deviation from the usual P[BOND]P. bond lengths is observed in the diphosphorus compound 1 in which two phosphonium centers are directly adjacent. Presumably the positive charge is delocalized on the P and the N atoms.

    11. Photoreaction of Thiones with Bromoketene Acetals (pages 976–977)

      Dr. Pieter H. J. Ooms and Dr. Willy Hartmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509761

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      Acrylic esters 3 instead of the expected thietanes are formed in the reaction of the n,π*-excited aromatic thiones 1 with the bromoketene acetals 2. In contrast adamantanethione reacts with 2 to give the 1,3-dithiolanes 4. In both cases, thiocarbonyl ylides are probably formed as intermediates.

    12. 3-Aminoidoles, Imidazolidines, and Oxazolidines from Isocyanides and Carbene Complexes by Metal-Induced [4+2]- and [3+2]-Cycloadditions (pages 978–979)

      Prof. Dr. Rudolf Aumann, Dipl.-Chem. Eberhard Kuckert and Ing. Chem. Heinrich Heinen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509781

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      the azaalene complexes 1 (M = Cr, Mo, W) are especially useful building blocks in the synthesis of heterocycles. They undergo [3 + 2]-cycloadditions with aldehydes, isocyanates or carbodiimides to give carbene complexes such as 2, from which the carbonylmetal fragment can be oxidatively cleaved such that the corresponding five-membered ring heterocycles are formed. For example, the hydantoin 3 can be obtained in high yields from the isocyanate adduct 2 (X = NR″, Y = O).

    13. Isocyanomethylenetriphenylphosphorane (pages 979–980)

      Dipl.-Chem. Gerhard Zinner and Prof. Dr. Wolf Peter Fehlhammer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509791

      The novel compound 2 combines the structural elements of α-metalated isocyanides and Wittig reagents. Like its “storable form” 1 it is extraordinarily reactive. For example, metal-coordinated 2 undergoes [3 + 2]-cycloadditions with heteroallenes, nitriles, acetylenes, and olefins to give metal-C bonded five-membered heterocycles.

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    14. [μ-N2H2{Ru(PPh3)dttd}2], the First Diazene Complex with Sulfur-Coordinated Transition Metal Centers (dttd = 2,3,8,9-Dibenzo-1,4,7,10- tetrathiadecane(2 –)) (pages 981–982)

      Prof. Dr. Dieter Sellmann, Dr. Elmar Böhlen, Dipl.-Chem. Michael Waeber, Prof. Dr. Gottfried Huttner and Dr. Laslo Zsolnai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509811

      The complex 2, in which trans-N2H2 bridges two ruthenium centers, could, as illustrated below, be obtained from the hydrazine complex 1. 2 forms blackish-green crystals with 2 CH2Cl2. Complexed diazene, such as is present in 2, is probably the key compound in the reduction of N2 at the iron and/or molybdenum centers of nitrogenases.

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    15. Donor-Acceptor Substituted Anions and Cations in the Cyclopentadienyl System (pages 982–984)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Thomas Gessner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509821

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      A cyclopentadienyl anion 1–formally aromatic–and a cyclopentadienyl cation 3–formally antiaromatic–can be generated from the donor-acceptor substituted cyclopentadiene 2. 1 and 3 (as K- and BFmath image-salt, respectively) are similarly stable and are of interest, inter alia, with regard to the synthesis of dyes and organic metals (via novel fulvenes and fulvalenes).

    16. Dimethylamino-Pyrazoles and Pyrazolylium Salts (pages 984–985)

      Prof. Dr. Rudolf Gompper, Dr. Rainer Guggenberger and Dr. Rolf Zentgraf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509841

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      The cation in the pyrazolylium salt 1 can be regarded as a novel stable ring system with 4π electrons and thus–formally–as antiaromatic. It was prepared from the corresponding 1-unsubstituted pyrazole by oxidation with NOBFmath image.

    17. A Novel Route to Pentamethylcyclopentadienyllutetium Alkoxides and Thiolates (pages 985–986)

      Prof. Dr. Herbert Schumann, Dr. Ilse Albrecht and Dr. Ekkehard Hahn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509851

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      A folded Lu(μ-S)2Li four-membered ring is present in the complex 1, in which a hard metal of the lanthanoid series is complexed by a ligand that is bound via the soft element sulfur to the metal. The synthesis of 1 was accomplished by reaction of the (μ-CH3)2-analogue with tBuSH.

    18. The Structure of the Lichen Macrolide (+)-Aspicilin (pages 987–988)

      Prof. Dr. Gerhard Quinkert, Dipl.-Chem. Nana Heim, Dr. Jan W. Bats, Dipl.-Chem. Hartmut Oschkinat and Prof. Dr. Horst Kessler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509871

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      4R,5S,6R,17S–That the title compound 1 has this absolute configuration was established by a combination of several methods: single crystal X-ray structure analysis of 1, NOESY NMR spectroscopy of a derivative, and synthesis of a key degradation product and its enantiomer.

    19. Reaction of Phenylcarbene with Oxygen (pages 988–989)

      Dr. Wolfram Sander

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509881

      The thermal generation of oxygen atoms is very useful in organic chemistry. This reaction has now been observed in the oxidation of phenylcarbene with O2. Carbonyl oxide, frequently postulated as an intermediate, decomposes very rapidly, even at 8 K; this has been demonstrated in an IR spectroscopic investigation of the title compound in an argon matrix at low temperatures.

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    20. Chelation-Controlled Stereoselective Synthesis of Cyanohydrins (pages 989–991)

      Prof. Dr. Manfred T. Reetz, Dipl.-Chem. Kurt Kesseler and Dipl.-Chem. Alfred Jung

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509891

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      Tertiary and secondary alkoxycyanohydrins such as 1 and 2 can be synthesized in high diasteromeric purity. Alkoxyacyl cyanides are allowed to react with allylsilanes or alkoxyaldehydes with silyl cyanides, namely in the presence of chelating reagents such as TiCl4, SnCl4, or Znl2.

    21. As12tBu8—a Tricyclo[,6]dodecaarsane (pages 991–992)

      Prof. Dr. Marianne Baudler and Dr. Stefan Wietfeldt-Haltenhoff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509911

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      The first organoarsane containing twelve As atoms, the title compound 1, has been prepared from tBuAsCl2, AsCl3 and Mg as a bright yellow, light-sensitive solid. The skeletal structure of 1 was elucidated by 1H-NMR and mass spectroscopy. Upon warming in solution, 1 disproportionates into other tert-butylcycloarsanes.

    22. Decamethyl-7-thiahexasilanorbornane (CH3)10Si6S (pages 992–993)

      Prof. Dr. Wiesław Wojnowski, Mgr. Bogusław Dręczewski, Dr. Aleksander Herman, Dr. Karl Peters, Eva-Maria Peters and Prof. Dr. Hans Georg von Schnering

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509921

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      The first thiasilane derived from a polysilane, the title compound 1, is readily accessible from 1,4-dichlorodecamethylhexasilacyclohexane and H2S with elimination of HCl.

    23. New Co and Ni Clusters with Se and PPh3 as Ligands: [Co43-Se)4(PPh3)4], [Co63-Se)8(PPh3)6], [Co94-Se)33-Se)8(PPh3)6], and [Ni345-Se)24-Se)20(PPh3)10] (pages 993–995)

      Prof. Dr. Dieter Fenske, Dipl.-Chem. Johannes Ohmer and Dipl.-Chem. Johannes Hachgenei

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509931

      Four novel clusters of Co or Ni, Se, and PPh3 have been obtained in good yields from [MCl2(PPh3)2] and Se(SiMe3)2 in toluene. In all four clusters, whose structures have been elucidated, the actual core is surrounded by a sheath of phenyl groups. The empirical formulas are given in the title; the structure of the nickel complex is to be seen on the cover page of this issue. The four complexes are 60e, 98e, 137e, and 448e species, respectively.–The longer known analogous reaction with S(SiMe3)2 gave other types of products.

    24. Enantioselective Hydrosilylation of Prochiral 3,4-Dihydro-2H-pyrrole Derivatives (pages 995–996)

      Dipl.-Chem. Richard Becker, Prof. Dr. Henri Brunner, Siavosh Mahboobi and Prof. Dr. Wolfgang Wiegrebe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509951

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      The asymmetric synthesis of pyrrolidines can be accomplished with moderate ee values by Rh-catalyzed hydrosilylation of dihydropyrroles such as 1. After acylating work-up of the silylamines 2 initially formed (≤64%), trifluoroacetamides 3 can be isolated in yields of between 80 and 90%.

    25. Stereo- and Enantioselective Synthesis of Both cis-Chrysanthemic Acid Methyl Esters in High Optical Purity (pages 996–998)

      Dr. Michel Franck-Neumann, Dr. Madjid Sedrati, Dr. Jean-Paul Vigneron and Vincente Bloy

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509961

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      The insecticidal activity of pyrethroids depends strongly upon their configuration. A novel synthesis of the highly active title compounds 1 and ent-1 does not require separation of racemates or diastereomers nor microbiological or enzymatic reactions.

    26. Hydroboration and Hydrozirconation of tert-Butylimino-2,2,6,6-tetramethylpiperidinoborane (pages 998–999)

      Dr. Detlef Männig, Prof. Dr. Heinrich Nöth, Dipl.-Chem. Manfred Schwartz, Dr. Siegfried Weber and Dipl.-Chem. Ulrich Wietelmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509981

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      A novel bond system, reminiscent of a μ-H-metallaborane, is contained in the hydrozirconation product 2 of the title compound 1. The structure of 2 could be elucidated by an X-ray structure analysis (X = Cl).

    27. Synthesis and Structure of a Diaza-λ2-phosphanylia-λ5-stannatacyclobutane (pages 999–1001)

      Manuela Bürklin, Dipl.-Chem. Elisabeth Hanecker, Prof. Dr. Heinrich Nöth and Dr. Wolfgang Storch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198509991

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      A planar four-membered ring is formed by the zwitterion 2, which can be prepared from the amine 1 and PCl3. The possibility of replacing Cl by alkyl or aryl groups underscores the remarkable stability of the system.

    28. Novel Polymerization of α-Olefins with the Catalyst System Nickel/Aminobis(imino)phosphorane (pages 1001–1003)

      Dipl.-Chem. Volker Michael Möhring and Priv.-Doz. Dr. Gerhard Fink

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198510011

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      A new type of linking of α-olefins upon polymerization has been achieved by catalysis with nickel(0) complexes and [X2N[BOND]P([DOUBLE BOND]NX)2], X = Me3Si. 2,ω-linking leads to polymers with methyl branches at well-defined intervals; products of type 1 are obtained from linear α-olefins.

    29. The Synthesis of Porphyrins Doubly Linked to Quinones by Hydrocarbon Chains (pages 1003–1004)

      Brian Morgan and Prof. David Dolphin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198510031

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      The title compounds 1 (n = 5, 6) are model compounds for light-induced charge separation in photosynthesis. In their synthesis from pyrrole and benzene derivatives the porphyrin ring was closed only in the last step. The synthetic route should also enable the synthesis of analogues with even shorter bridging chains.

  3. Book Reviews

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