Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 8

February 13, 2004

Volume 43, Issue 8

Pages 911–1031

    1. Cover Picture: Multistep Binding of Divalent Cations to Phospholipid Bilayers: A Molecular Dynamics Study (Angew. Chem. Int. Ed. 8/2004) (page 911)

      Rainer A. Böckmann and Helmut Grubmüller

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200490018

      Membrane–cation interactions can greatly affect the properties of biological membranes. In their Communication on page 1021 ff. H. Grubmüller and R. A. Böckmann describe the simulation of the binding of sodium and calcium ions to neutral, zwitterionic lipid membranes. The cover picture shows a snapshot from the molecular dynamics simulation of a membrane with Ca2+ ions.

    2. Saturo Masamune (1928–2003): Natural Products and Small Rings (page 922)

      Koji Nakanishi and Rick L. Danheiser

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200490020

    3. An Introduction to Theoretical Chemistry. By Jack Simons. (pages 923–924)

      B. Christopher Rinderspacher

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200385028

    4. Magnetic Resonance in Chemistry and Medicine. By Ray Freeman. (page 924)

      Gerd Gemmecker

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200385059

    5. Layer-by-Layer Deposition of Polyelectrolytes—A Versatile Tool for the In Vivo Repair of Blood Vessels (pages 926–928)

      Thomas Groth and Andreas Lendlein

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200301708

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      Layer-by-layer adsorption of polygenic polyelectrolytes is a promising method of treatment in which multilayers are formed on the inner arterial wall (see scheme). An advantage of this technique, which has already proved successful in animal models, is that it is very simple to apply, in contrast to in situ polymerization, which requires irradiation with UV light. Furthermore, it is rapid and allows the incorporation of active drugs in the layer.

    6. Rational Synthesis of Covalently Bonded Organic–Inorganic Hybrids (pages 930–935)

      Zhonghua Peng

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200301682

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      A modular building-block strategy is used to rationally synthesize conjugated molecules and polymers containing polyoxometalate (POM) clusters that are covalently linked in a variety of architectures (see picture). The most recent advances in organic–inorganic hybrids that are connected by an imido linkage are highlighted.

    7. The Way into the Bridge: A New Bonding Mode of Tertiary Phosphanes, Arsanes, and Stibanes (pages 938–954)

      Helmut Werner

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200300627

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      Until recently, phosphanes, arsanes, and stibanes were considered to bind to transition-metal centers only in a terminal coordination mode. Replacement of the bridging stibane in complex 1 with tertiary phosphanes leads to the formation of compounds 2 and 3 (see scheme). Other dinuclear analogues, even with bulky phosphanes such as PiPr3 and PPh3, are accessible by an unexpected route.

    8. A CuIICoII Metallacyclophane-Based Metamagnet with a Corrugated Brick-Wall Sheet Architecture (pages 956–958)

      Cynthia L. M. Pereira, Emerson F. Pedroso, Humberto O. Stumpf, Miguel A. Novak, Louis Ricard, Rafael Ruiz-García, Eric Rivière and Yves Journaux

      Article first published online: 27 JAN 2004 | DOI: 10.1002/anie.200352604

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      Magnet brickwork: A two-dimensional molecule-based metamagnet is obtained by the reaction of CoII ions and the tetra-bidentate {Cu2(mpba)2}4− moiety. The CoII ions act as cement between {Cu2(mpba)2} units to form a brick-wall assembly (see picture). The strong CoII anisotropy and weak interplanar interactions lead to a metamagnetic transition and glassy behavior.

    9. Generation of Size-Controlled Pd0 Nanoclusters inside Nanoporous Domains of Gel-Type Resins: Diverse and Convergent Evidence That Supports a Strategy of Template-Controlled Synthesis (pages 959–962)

      Benedetto Corain, Karel Jerabek, Paolo Centomo and Patrizia Canton

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352640

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      Resin molds for clusters: The nanoporous domains of a gel-type microporous functional resin are used as templates for the production of size-controlled Pd0 nanoclusters, the size of which is governed by the largest mesh available (see picture). Inverse steric exclusion chromatography provides the quantitative estimate of resin nanoporosity in its swollen state.

    10. Selective C[BOND]H Bond Activation by a Supramolecular Host–Guest Assembly (pages 963–966)

      Dennis H. Leung, Dorothea Fiedler, Robert G. Bergman and Kenneth N. Raymond

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352772

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      Interior design: A chiral supramolecular tetrahedral [Ga4L6]12− host (L=bis(bidentate) ligand) is shown to encapsulate a half-sandwich iridium complex. This host–guest assembly reacts with aldehydes through C[BOND]H bond activation, which occurs within the host interior. This activation occurs with high size and shape specificity as well as modest diastereoselectivity (d.r. 55:45–70:30) owing to the well-defined shape of the host cavity.

    11. A Concept for Recyclable Cross-Linked Polymers: Topologically Networked Polyrotaxane Capable of Undergoing Reversible Assembly and Disassembly (pages 966–969)

      Tomoya Oku, Yoshio Furusho and Toshikazu Takata

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353046

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      It's physical: A novel concept for recyclable cross-linked polymers is presented by utilizing mechanical linkages in a polyrotaxane network capable of undergoing reversible assembly and disassembly (see schematic representation).

    12. Self-Assembly in Gold(I) Chemistry: A Double-Stranded Polymer with Interstrand Aurophilic Interactions (pages 969–971)

      Fabian Mohr, Michael C. Jennings and Richard J. Puddephatt

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353127

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      Raising the gold standard: Hybrid organic–inorganic side-by-side double-chain polymers have been prepared in which individual polymer chains are connected through the aurophilic interactions of gold(I) centers (see picture). The use of alternative isomers of the monomeric building blocks leads to the formation of dimeric or trimeric complexes.

    13. Metal–Organic Replica of Fluorite Built with an Eight-Connecting Tetranuclear Cadmium Cluster and a Tetrahedral Four-Connecting Ligand (pages 971–974)

      Hyungphil Chun, Dongwoo Kim, Danil N. Dybtsev and Kimoon Kim

      Article first published online: 27 JAN 2004 | DOI: 10.1002/anie.200353139

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      A non-interpenetrating 3D metal–organic framework, synthesized by a solvothermal reaction of cadmium nitrate and a tetracarboxylate ligand, is the first metal–organic analogue of fluorite (CaF2). In the structure of the title compound, depicted, an eight-connecting tetranuclear cadmium cluster (green sphere) and a tetracarboxylate ligand (brown sphere) play the role of Ca2+ and F ions, respectively, in fluorite.

    14. Laser-Induced Formation of Metal–Peroxide Linkages on the Surface of Lanthanum Sesquioxide under Oxygen (pages 975–977)

      Wei Zheng Weng, Hui Lin Wan, Jian Mei Li and Ze Xing Cao

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200351706

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      Laser irradiation of La2O3 under oxygen at 300–500 °C with the beam of a microprobe Raman spectrometer (λ=325, 514.5, or 632.8 nm) caused the emergence of a peroxide band at ≈840 cm−1 at the expense of the νmath image band at ≈400 cm−1 with clear isosbestic points at 389 and 558 cm−1 (see picture). This photoexcitation process has implications for laser Raman spectroscopic studies on lanthanide oxide catalysts under working conditions.

    15. (C4N2H12)[FeII0.86FeIII1.14(HPO3)1.39(HPO4)0.47(PO4)0.14F3]: A Fluoro–Phosphite–Hydrogenphosphate–Phosphate Iron(II,III) Mixed-Valence Organically Templated Compound (pages 977–980)

      Sergio Fernández-Armas, José L. Mesa, José L. Pizarro, José S. Garitaonandia, María I. Arriortua and Teófilo Rojo

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352219

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      Site insights: The title compound has been synthesized by mild hydrothermal conditions. The iron(II) and iron(III) cations are trapped in two different crystallographic positions, whereas the phosphite and hydrogenphosphate–phosphate oxoanions are disordered in two phosphorus sites (see structure). The compound has antiferromagnetic interactions and the nature of the iron centers is investigated by Mössbauer spectroscopy.

    16. An Organic–Inorganic Hybrid Electrolyte Derived from Self-Assembly of a Poly(Ethylene Oxide)–Poly(Propylene Oxide)–Poly(Ethylene Oxide) Triblock Copolymer (pages 980–984)

      Hsien-Ming Kao and Chien-Liang Chen

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352243

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      High lithium ionic conductivity is exhibited by an organic–inorganic hybrid electrolyte prepared by self-assembly of a PEO-PPO-PEO triblock copolymer (Pluronic F127; PEO=poly(ethylene oxide), PPO=poly(propylene oxide)), complexed with LiClO4, on a silica framework. The good performance of the hybrid material with an [O]:[Li] ratio of 16:1 is due to its well-ordered mesophase consisting of a hexagonal arrangement of cylinders (see diagram).

    17. Diorganophosphanylphosphinidenes as Complexed Ligands: Synthesis via an Anionic Terminal Phosphide of Niobium (pages 984–988)

      Joshua S. Figueroa and Christopher C. Cummins

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352779

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      Reductive cleavage of a bridging diphosphide complex with sodium amalgam affords the sodium salt of the terminal niobium phosphide anion [PNb(N[Np]Ar)3] (1; Np=neopentyl, Ar=3,5-Me2C6H3), which is best formulated as containing an Nb[BOND]P triple bond. The phosphorus atom of 1 is nucleophilic. Treatment of 1 with ClP(tBu)2 or ClP(Ph)2 provides η2-phosphanylphosphinidene complexes, which are the first examples of such complexed ligands bound to an early-transition-metal fragment.

    18. A 1,3-Lithium Shift of Propargylic/Allenylic Lithium and the Subsequent Transmetalation Coupling Reaction with Aryl Halides (pages 988–990)

      Shengming Ma and Qiwen He

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352924

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      The lithiation reagent and temperature may be the key factors controlling the 1,3-lithium shift of propargylic/allenylic lithium (see scheme). Under the right conditions, 1,1-diarylallenes and 1,3-diarylallenes can be easily and highly selectively synthesized by the lithiation of 1-aryl-1-alkynes and the subsequent transmetalation (1), and Pd-catalyzed coupling with aryl halides (2).

    19. A Unique 3D Alternating Ferro- and Antiferromagnetic Manganese Azide System with Threefold Interpenetrating (10,3) Nets (pages 990–994)

      Cai-Ming Liu, Song Gao, De-Qing Zhang, Yong-Hong Huang, Ren-Gen Xiong, Zhi-Liang Liu, Feng-Chi Jiang and Dao-Ben Zhu

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352780

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      Alternative bridging: Alternating ferro- and antiferromagnetic interactions are mediated by alternating end-on and end-to-end azido bridges, respectively, in a novel manganese azido complex. The compound has an interesting framework of threefold interpenetrating (10,3) nets, one of which is shown in the picture.

    20. Chiral Molecular Recognition by Aluminum Tris(2,6-diphenylphenoxide) in an Asymmetric 1,4-Addition (pages 994–997)

      Hirotsugu Ito, Takashi Nagahara, Kazuaki Ishihara, Susumu Saito and Hisashi Yamamoto

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352809

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      A precomplex of a chiral α,β-unsaturated ester and a bulky aluminum oxide is crucial to setting the diastereoselectivity in the 1,4-addition of a Grignard or organolithium reagent. This approach based on chiral recognition broadens the potential of the strategies relying on stoichiometric reagents.

    21. C74F38: An Exohedral Derivative of a Small-Bandgap Fullerene with D3 Symmetry (pages 997–1000)

      Alexey A. Goryunkov, Vitaliy Y. Markov, Ilya N. Ioffe, Robert D. Bolskar, Michael D. Diener, Igor V. Kuvychko, Steven H. Strauss and Olga V. Boltalina

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352960

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      Experimental support for the IPR-D3h structure of the empty-cage C74 fullerene (IPR=isolated pentagon rule) has been obtained from an exohedral derivative of the small-bandgap fullerene D3-C74F38 (see picture). Selective fluorination is proposed as a general procedure for protecting nonextractable fullerenes and their endohedral derivatives.

    22. Reactivity-Based One-Pot Synthesis of Oligomannoses: Defining Antigens Recognized by 2G12, a Broadly Neutralizing Anti-HIV-1 Antibody (pages 1000–1003)

      Hing-Ken Lee, Christopher N. Scanlan, Cheng-Yuan Huang, Aileen Y. Chang, Daniel A. Calarese, Raymond A. Dwek, Pauline M. Rudd, Dennis R. Burton, Ian. A. Wilson and Chi-Huey Wong

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353105

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      An HIV-1 vaccine may eventually be developed from oligomannoses synthesized by a reactivity-based one-pot self-condensation strategy. The compounds were tested for their ability to inhibit the binding of gp120 to the broadly neutralizing HIV-1 antibody 2G12. New epitope mimics (see structure for example) were identified that inhibit this binding as well as, or better than the natural epitope Man9GlcNAc2 (Man=mannose, Glc=glucose).

    23. Denitrogenation of Transportation Fuels by Zeolites at Ambient Temperature and Pressure (pages 1004–1006)

      Arturo J. Hernández-Maldonado and Ralph T. Yang

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353162

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      Cleaner fuels: Preferential adsorption of organonitrogen compounds from commercial diesel can be achieved by using a Faujasite zeolite in which Cu ions occupy the 6-ring windows sites. The key to this denitrogenation process is π complexation with the CuI ion, as illustrated for pyrrole.

    24. A Biomimetic Pathway for Hydrogen Evolution from a Model of the Iron Hydrogenase Active Site (pages 1006–1009)

      Sascha Ott, Mikael Kritikos, Björn Åkermark, Licheng Sun and Reiner Lomoth

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353190

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      Good potential: A biomimetic model of the iron hydrogenase active site functions as a catalyst for electrochemical proton reduction at relatively moderate negative potentials. The catalytic cycle (see scheme) involves the protonation of the azadithiolate nitrogen atom as its initial step. This system may eventually be used to achieve light-activated hydrogen evolution.

    25. Enantiodivergence in the Reactions of a Highly Enantiomerically Enriched Silyllithium Compound with Benzyl Halides: Control of Inversion and Retention by Selection of Halide (pages 1011–1014)

      Carsten Strohmann, Martin Bindl, Verena C. Fraaß and Jan Hörnig

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200352700

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      Inversion of the configuration at the silicon center is observed for the reaction of benzyl bromide with the highly enantiomerically enriched silyllithium compound 2. In contrast, retention of configuration occurs at the silicon center with benzyl chloride, which suggests two different reaction mechanisms.

    26. A Modular Assembly of Chiral Oxazolinylcarbene–Rhodium Complexes: Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones (pages 1014–1017)

      Lutz H. Gade, Vincent César and Stéphane Bellemin-Laponnaz

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200353133

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      A novel class of chiral bidentate ligands with a carbene and an oxazoline moiety is obtained by the coupling of N-arylimidazoles and a 2-bromooxazoline derivative. The rhodium complex 1 catalyzes the hydrosilylation of aryl alkyl ketones and otherwise problematic dialkyl ketones in high yields and good enantioselectivities (up to 95 % ee).

    27. Nucleophilic Catalysis of the Iodine–Zinc Exchange Reaction: Preparation of Highly Functionalized Diaryl Zinc Compounds (pages 1017–1021)

      Florian F. Kneisel, Maximilian Dochnahl and Paul Knochel

      Article first published online: 27 JAN 2004 | DOI: 10.1002/anie.200353316

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      Sensitive functional groups are tolerated in an iodine–zinc exchange reaction catalyzed by Li(acac). Aryl and heteroaryl diorganozinc compounds with keto, aldehyde, or isothiocyanate substituents can be prepared by this method (see example in scheme; acac=acetylacetone, NMP=1-methyl-2-pyrrolidinone). Such zinc reagents serve as substrates for a wide variety of coupling reactions.

    28. Multistep Binding of Divalent Cations to Phospholipid Bilayers: A Molecular Dynamics Study (pages 1021–1024)

      Rainer A. Böckmann and Helmut Grubmüller

      Article first published online: 4 DEC 2003 | DOI: 10.1002/anie.200352784

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      Step by step: The sequential coordination of calcium ions (yellow) to four lipid carbonyl oxygen atoms in neutral zwitterionic phospholipid bilayers has been studied by molecular dynamics simulations.

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      Preview: Angew. Chem. Int. Ed. 8/2004 (page 1031)

      Article first published online: 11 FEB 2004 | DOI: 10.1002/anie.200490017

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