Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 48

November 26, 2012

Volume 51, Issue 48

Pages 11907–12131

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of C[DOUBLE BOND]C, C[DOUBLE BOND]O, and C[DOUBLE BOND]N Bonds (Angew. Chem. Int. Ed. 48/2012) (page 11907)

      Dr. Guoqi Zhang, Dr. Brian L. Scott and Dr. Susan K. Hanson

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208739

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      The substitution of cobalt for precious metals in catalysis is a variation on the ancient alchemical theme of transmuting base metals into precious ones. In their Communication on page 12102 ff., S. K. Hanson et al. describe the cobalt-catalyzed hydrogenation of alkenes, aldehydes, ketones, and imines under mild reaction conditions. The precatalyst is a cationic cobalt(II) alkyl complex. (The artwork is by Josh Smith, Los Alamos National Laboratory.)

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      Inside Cover: An Integrated “Energy Wire” for both Photoelectric Conversion and Energy Storage (Angew. Chem. Int. Ed. 48/2012) (page 11908)

      Tao Chen, Longbin Qiu, Zhibin Yang, Zhenbo Cai, Jing Ren, Houpu Li, Huijuan Lin, Xuemei Sun and Prof. Huisheng Peng

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208673

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      An integrated energy wire simultaneously realizes photoelectric conversion and energy storage in the same device. It is based on aligned carbon nanotube fibers wrapped around a TiO2 nanowire that is several centimeters long. In their Communication on page 11977 ff., H. Peng and co-workers show that after treating one end with a light-sensitive dye and the other with an electrolyte, the resulting integrated energy wire has a high entire photoelectric conversion and storage efficiency of 1.5 %

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      Inside Back Cover: Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+ (Angew. Chem. Int. Ed. 48/2012) (page 12133)

      Dr. Thomas J. Robilotto, Dr. John Bacsa, Prof. Dr. Thomas G. Gray and Prof. Dr. Joseph P. Sadighi

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208587

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      A triangular [L3Au3]+ ion is stabilized by an N-heterocyclic carbene ligand. In their Communication on page 12077 ff., T. G. Gray, J. P. Sadighi, and co-workers present the analogy between [L3Au3]+ and [H3]+. Density functional calculations suggest full valence delocalization among the gold atoms. In the presence of soft Lewis bases, the cluster undergoes two-electron oxidation to form three equivalents of AuI.

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      Back Cover: Nitrogen-Doped Graphene Foams as Metal-Free Counter Electrodes in High-Performance Dye-Sensitized Solar Cells (Angew. Chem. Int. Ed. 48/2012) (page 12134)

      Dr. Yuhua Xue, Dr. Jun Liu, Dr. Hao Chen, Dr. Ruigang Wang, Dr. Dingqiang Li, Dr. Jia Qu and Prof. Liming Dai

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208588

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      High-performance dye-sensitized solar cells with nitrogen-doped graphene foams as the counter electrode are used for the efficient conversion of solar light into electricity. In their Communication on page 12124 ff., J. Qu, L. Dai, et al. show the application of the foam as a metal-free electrocatalyst for the reduction of triiodide, leading to a power conversion efficiency up to 7.07 %.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
  3. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: Enantioselective Oxidation of Aldehydes Catalyzed by Alcohol Dehydrogenase (page 11924)

      Dr. Paul Könst, Dr. Hedda Merkens, Dr. Selin Kara, Svenja Kochius, Dr. Andreas Vogel, Dr. Ralf Zuhse, Dr. Dirk Holtmann, Prof. Dr. Isabel W. C. E. Arends and Dr. Frank Hollmann

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201208486

      This article corrects:

      Enantioselective Oxidation of Aldehydes Catalyzed by Alcohol Dehydrogenase1

      Vol. 51, Issue 39, 9914–9917, Article first published online: 31 AUG 2012

    2. You have free access to this content
  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Shu-Li You (page 11934)

      Article first published online: 17 JUL 2012 | DOI: 10.1002/anie.201204368

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      “I like refereeing because it is the only way to keep scientific publishing working. The biggest problem that scientists face is distractions from outside science. …” This and more about Shu-Li You can be found on page 11934.

  6. News

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
  7. Obituary

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Horst Prinzbach (1931–2012) (pages 11936–11937)

      Wolf-Dieter Fessner

      Article first published online: 5 NOV 2012 | DOI: 10.1002/anie.201208494

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  8. Book Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Characterization of Solid Materials and Heterogeneous Catalysts. From Structure to Surface Reactivity. Edited by Michel Che and Jacques C. Védrine. (pages 11938–11939)

      Robert A. Schoonheydt

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201207390

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      Wiley-VCH, Weinheim, 2012. 2 volume set, 1182 pp., hardcover, € 349.00.—ISBN 978-3527326877

    2. Diffusion in Nanoporous Materials. By Jörg Kärger, Douglas M. Ruthven and Doros N. Theodorou. (pages 11939–11940)

      Hubert Koller

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201208161

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      Wiley-VCH, Weinheim, 2011. 2 Volume set, 872 pp., hardcover, € 349.00.—ISBN 978-3527310241

  9. Highlights

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Supramolecular Materials

      Hard Autonomous Self-Healing Supramolecular Materials—A Contradiction in Terms? (pages 11942–11944)

      Prof. Richard Hoogenboom

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205226

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      Achieving the unachievable: Hard supramolecular materials displaying autonomous self-healing have been considered unachievable because of the mobility required to reconstitute supramolecular interactions after rupture. Now, relatively hard thermoplastic elastomers have been reported that meet these requirements. The picture shows a triblock copolymer containing soft supramolecular “self-healing” domains and hard, structure-giving domains.

    2. Heteroradialenes

      Phospharadialenes—A New Kid in Town (pages 11945–11947)

      Prof. Dr. Henning Hopf

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206101

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      A bright future: The realization that a mixture of squaraine derivatives drastically improve quantum efficiency in the visible and near-IR region of organic solar cells, and the synthesis of the first phospharadialene serve as the focus for a short overview of oxocarbons and related heteroorganic compounds.

  10. Minireview

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
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    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Cyano-Group Sources

      Synthesis of Aromatic Nitriles Using Nonmetallic Cyano-Group Sources (pages 11948–11959)

      Dr. Jinho Kim, Hyun Jin Kim and Prof. Sukbok Chang

      Article first published online: 6 NOV 2012 | DOI: 10.1002/anie.201206168

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      Introducing CN: Recently, a range of nonmetallic organic cyano-group precursors (see scheme) have been developed as attractive alternatives to metal cyanides that have been frequently employed in the catalytic cyanation of aryl halides. This Minireview summarizes the development of organic cyano-group precursors and their application in the cyanation of aryl halides, boronates, boronic acids, arene carboxylic acids, and (hetero)arene C[BOND]H bonds.

  11. Review

    1. Top of page
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    8. Obituary
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    11. Minireview
    12. Review
    13. Communications
    1. Biomineral Polyamorphism

      Calcium Carbonate Polyamorphism and Its Role in Biomineralization: How Many Amorphous Calcium Carbonates Are There? (pages 11960–11970)

      Dr. Julyan H. E. Cartwright, Prof. Antonio G. Checa, Prof. Julian D. Gale, Dr. Denis Gebauer and Dr. C. Ignacio Sainz-Díaz

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201203125

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      Coming in to form: A summary is given of what is known about polyamorphism in calcium carbonate as well as the role of amorphous calcium carbonate in biomineralization. The amorphous forms of calcium carbonate within the physical notion of polyamorphism lead to new insights when it comes to the mechanisms by which polymorphic structures can evolve. This also has implications beyond biomineralization.

  12. Communications

    1. Top of page
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    4. Corrigenda
    5. News
    6. Author Profile
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    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Chiral Circulenoid

      A Chiral Dicationic [8]Circulenoid: Photochemical Origin and Facile Thermal Conversion into a Helicene Congener (pages 11972–11976)

      Lukáš Severa, Milan Ončák, Dr. Dušan Koval, Dr. Radek Pohl, Dr. David Šaman, Dr. Ivana Císařová, Dr. Paul E. Reyes-Gutiérrez, Dr. Petra Sázelová, Dr. Václav Kašička, Dr. Filip Teplý and Dr. Petr Slavíček

      Article first published online: 28 SEP 2012 | DOI: 10.1002/anie.201203562

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      Doubly positive: A circulene-like species has been transformed into its helical counterpart exclusively by the application of heat (see scheme). The synthesis of the chiral dicationic [8]circulenoid is based on a key [6+6] photocycloaddition and requires only five steps and no chromatographic purification.

    2. Wire Devices

      An Integrated “Energy Wire” for both Photoelectric Conversion and Energy Storage (pages 11977–11980)

      Tao Chen, Longbin Qiu, Zhibin Yang, Zhenbo Cai, Jing Ren, Houpu Li, Huijuan Lin, Xuemei Sun and Prof. Huisheng Peng

      Article first published online: 29 OCT 2012 | DOI: 10.1002/anie.201207023

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      Light my wire: Aligned carbon nanotube (CNT) fibers are wrapped around a TiO2 nanowire that is several centimeters long. Treating the ends of the nanotube wire with a light-sensitive dye and an electrolyte, creates photoelectric-conversion and energy-storage regions in the same device (see scheme). The “wire” shows a high overall photoelectric conversion and storage efficiency of 1.5 %.

    3. Chiral Resolution

      Pasteurian Segregation on a Surface Imaged In Situ at the Molecular Level (pages 11981–11985)

      Dr. Hong Xu, Wojciech J. Saletra, Dr. Patrizia Iavicoli, Dr. Bernard Van Averbeke, Elke Ghijsens, Dr. Kunal S. Mali, Prof. Albertus P. H. J. Schenning, Dr. David Beljonne, Prof. Roberto Lazzaroni, Prof. David B. Amabilino and Prof. Steven De Feyter

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201202081

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      A good sort: A racemate is observed to segregate in situ upon diastereoselective adsorption on an achiral surface by surface-mediated complex formation in a liquid (see picture; yellow: enantiopure resolving agents, ovals: the enantiomers of the racemate to be resolved).

    4. Heterogeneous Catalysis

      Hard X-ray Nanotomography of Catalytic Solids at Work (pages 11986–11990)

      Dr. Ines D. Gonzalez-Jimenez, Korneel Cats, Dr. Thomas Davidian, Dr. Matthijs Ruitenbeek, Dr. Florian Meirer, Dr. Yijin Liu, Dr. Johanna Nelson, Prof. Dr. Joy C. Andrews, Prof. Dr. Piero Pianetta, Prof. Dr. Frank M. F. de Groot and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201204930

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      A closer look at catalysis: In situ hard X-ray nanotomography has been developed (see picture) as a method to investigate an individual iron-based Fischer–Tropsch-to-Olefins (FTO) catalyst particle at elevated temperatures and pressures. 3D and 2D maps of 30 nm resolution could be obtained and show heterogeneities in the pore structure and chemical composition of the catalyst particle of about 20 μm.

    5. Non-Equilibrium Processes

      Belousov–Zhabotinsky Reaction in Protic Ionic Liquids (pages 11991–11994)

      Dr. Takeshi Ueki, Prof. Dr. Masayoshi Watanabe and Prof. Dr. Ryo Yoshida

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201205061

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      The Belousov–Zhabotinsky (BZ) reaction using hydrated protic ionic liquid (PIL) as reaction medium is reported. For the first time it is found that the BZ oscillation reaction occurred in certain hydrated PILs without adding strong acid such as HNO3 (see red oscillation profile). Furthermore, a stable and long-lasting self-oscillation can be realized when the component concentrations of the BZ medium are optimized.

    6. Nanostructures

      Template Assembly of Spin Crossover One-Dimensional Nanowires (pages 11995–11999)

      Dr. Paulo N. Martinho, Dr. Tibebe Lemma, Brendan Gildea, Dr. Gennaro Picardi, Dr. Helge Müller-Bunz, Prof. Robert J. Forster, Prof. Tia E. Keyes, Prof. Gareth Redmond and Dr. Grace G. Morgan

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205122

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      Wired for action: An alumina-based template method produces nanowires of an alkylated mononuclear spin-crossover FeIII complex. The wires can be isolated by dissolving the template in acid without decomposition of the product, and have a narrow distribution of diameter widths in the range of 80–100 nm. Electronic characterization of a single wire is possible by using Raman spectroscopy coupled to AFM (see picture).

    7. Synthetic Methods

      Structure-Selective Catalytic Alkylation of DNA and RNA (pages 12000–12004)

      Kiril Tishinov, Kristina Schmidt, Priv.-Doz. Daniel Häussinger and Prof. Dr. Dennis G. Gillingham

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201205201

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      Nuc 'em: A variety of nucleic acids can be catalytically alkylated with rhodium-carbenoids generated from diazo compounds in aqueous buffer through an N[BOND]H insertion process (see scheme; MES=2-(N-morpholino)ethanesulfonic acid). The method specifically targets unpaired bases such as those present in single strands, turn regions, and overhangs while leaving double-stranded sequences untouched.

    8. 3D Chemical Imaging

      3D Chemical Image using TOF-SIMS Revealing the Biopolymer Component Spatial and Lateral Distributions in Biomass (pages 12005–12008)

      Seokwon Jung, Dr. Marcus Foston, Dr. Udaya C. Kalluri, Dr. Gerald A. Tuskan and Prof. Dr. Arthur J. Ragauskas

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201205243

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      Show me inside: 3D time-of-flight secondary-ion mass spectrometry (TOF-SIMS) with a dual-beam mode allows the detection of the characteristic biopolymers from surface to subsurface in plant cell walls. Lateral and vertical distribution of major components can thereby be mapped to understand the structural architecture of plant cell walls at under sub-micrometer scales (see picture: green=cellulose, red=lignin).

    9. Molecular Switches

      Bistability Loss as a Key Feature in Azobenzene (Non-)Switching on Metal Surfaces (pages 12009–12011)

      Reinhard J. Maurer and Prof. Dr. Karsten Reuter

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201205718

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      Flip the switch on metals: Coinage metal adsorbed azobenzene is investigated as a prototypical molecular switch. Switching capabilities are not just lost owing to excited-state quenching, but also because of changes in the ground-state energetics (see graph; black=gas phase, gray=Ag(111), yellow=Au(111)). Electron-demanding coadsorbates are suggested as a strategy to regain the switching function.

    10. Charge-Transfer Interactions

      A Photoswitchable and Photoluminescent Organic Semiconductor Based On Cation–π and Carboxylate–Pyridinium Interactions: A Supramolecular Approach (pages 12012–12015)

      Sandipan Roy, Dr. Suvra Prakash Mondal, Prof. Samit K. Ray and Prof. Kumar Biradha

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201205822

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      More than the sum of the parts: The property of a supramolecular material can differ significantly from those of the constituent materials. Two organic components, which are nonconductive, nonphotochromic, and nonluminescent, were shown to self-assemble by cation–π, π–π, and carboxylate–pyridinium interactions. An organic semiconductor is thus produced with significant charge mobility and photochromic and photoluminescence properties.

    11. Magnetic Nanoparticles

      Changing the Enzyme Reaction Rate in Magnetic Nanosuspensions by a Non-Heating Magnetic Field (pages 12016–12019)

      Prof. Dr. Natalia L. Klyachko, Dr. Marina Sokolsky-Papkov, Nikorn Pothayee, Maria V. Efremova, Dr. Dmitry A. Gulin, Nipon Pothayee, Artem A. Kuznetsov, Dr. Alexander G. Majouga, Prof. Judy S. Riffle, Prof. Dr. Yuri I. Golovin and Prof. Dr. Alexander V. Kabanov

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205905

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      Deactivation and structural deformation of enzymes immobilized on magnetic nanoparticles (MNPs) are observed after exposure to magnetic fields. These changes are due to realignment of MNPs in response to the AC magnetic field, which leads to stresses in MNP-linked polymer chains. Such stresses translated to an enzyme molecule immobilized on a MNP aggregate induce deformations and irreversible (or long lasting) conformational changes.

    12. Virus Binding

      You have full text access to this OnlineOpen article
      Norovirus GII.4 Virus-like Particles Recognize Galactosylceramides in Domains of Planar Supported Lipid Bilayers (pages 12020–12024)

      Marta Bally, Gustaf E. Rydell, Raphael Zahn, Waqas Nasir, Christian Eggeling, Michael E. Breimer, Lennart Svensson, Fredrik Höök and Göran Larson

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201205972

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      A sticky situation: Domain-dependent recognition of the glycosphingolipid galactosylceramide by norovirus-like particles (see picture; red/yellow) is shown using supported lipid bilayers (purple) as model membranes. Optimal ligand presentation is found to promote strong binding to GalCer. This presentation can be found at the edges of the glycosphingolipid-enriched domains (green) and binding is repressed in the absence of these domains.

    13. Photosystem II Structure

      Rationalizing the 1.9 Å Crystal Structure of Photosystem II—A Remarkable Jahn–Teller Balancing Act Induced by a Single Proton Transfer (pages 12025–12028)

      Phillip Gatt, Dr. Simon Petrie, Prof. Rob Stranger and Prof. Ron J. Pace

      Article first published online: 26 OCT 2012 | DOI: 10.1002/anie.201206316

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      Balancing act: DFT calculations show that the structures of the water-oxidizing complex in the two most recent single crystal XRD studies of photosystem II at 2.9 Å and 1.9 Å resolution are tautomers related by a single proton transfer. The anomalous oxygen species, O(5), weakly bound to four metal centers in the 1.9 Å structure (see picture) is identified as a substrate water molecule balanced between the Jahn–Teller axes of Mn(1), Mn(3), and Mn(4).

    14. Host–Guest Systems

      A Remarkable Organometallic Transformation on a Cage-Incarcerated Dinuclear Ruthenium Complex (pages 12029–12031)

      Shinnosuke Horiuchi, Dr. Takashi Murase and Prof. Dr. Makoto Fujita

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206325

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      Under confinement: Photosubstitution of a CO ligand with an alkyne on a dinuclear ruthenium carbonyl complex within a self-assembled cage occurs without the cleavage of the photolabile Ru[BOND]Ru bond. The resulting Ru–alkyne π complex is a reaction intermediate stabilized inside the cage. Outside the cage, the π complex can be further transformed to a diruthenacyclopentenone framework by intramolecular CO insertion (see scheme).

      Corrected by:

      Corrigendum: Corrigendum: A Remarkable Organometallic Transformation on a Cage-Incarcerated Dinuclear Ruthenium Complex

      Vol. 52, Issue 8, 2147, Article first published online: 13 FEB 2013

    15. Heterogeneous Catalysis

      Tailored Mesostructured Copper/Ceria Catalysts with Enhanced Performance for Preferential Oxidation of CO at Low Temperature (pages 12032–12035)

      Hoang Yen, Yongbeom Seo, Serge Kaliaguine and Prof. Freddy Kleitz

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201206505

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      Porosity control: Mixed metal oxides (CuM/CeO2, M=Co, Fe) with tailored porosity were prepared by improved hard templating. These materials were highly active and selective catalysts for low-temperature oxidation of CO in the presence of excess H2 (see picture), a process which is central for the practical use of H2 in proton-exchange membrane fuel cells.

    16. Staudinger ligation

      Phosphine-Based Redox Catalysis in the Direct Traceless Staudinger Ligation of Carboxylic Acids and Azides (pages 12036–12040)

      Andrew D. Kosal, Erin E. Wilson and Prof. Dr. Brandon L. Ashfeld

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201206533

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      Redox catalysis: Aryl amides, imides, lactams, and dipeptides are obtained through a direct Staudinger ligation mediated by phosphine-based redox catalysis (see scheme). Mechanistic studies indicate the involvement of a phosphonium carboxylate intermediate that leads to a 1,3-acyl migration and thus results in C[BOND]N bond formation.

    17. Natural Product Synthesis

      Divergent Total Synthesis of the Antimitotic Agent Leiodermatolide (pages 12041–12046)

      Dipl.-Chem. Jens Willwacher, Dr. Nina Kausch-Busies and Prof. Alois Fürstner

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206670

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      Subtle but distinctive: The stereostructure of the biologically highly promising antimitotic agent leiodermatolide was uncertain. A short, efficient, and flexible total synthesis based on ring-closing alkyne metathesis as the key step has now solved the puzzle. Subtle differences in the 1H NMR spectra of the structure shown and the conceivable isomer proved invaluable for the assignment.

    18. Borometalation

      Frustrated Lewis Pair Induced Boroauration of Terminal Alkynes (pages 12047–12050)

      Hongyan Ye, Zhenpin Lu, Di You, Dr. Zhenxia Chen, Prof. Zhen Hua Li and Prof. Huadong Wang

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206927

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      Golden frustration: The facile activation of terminal alkynes with a frustrated Lewis pair (1 and 1,4-diazabicyclo[2.2.2]octane (DABCO)) enables the development of an efficient boroauration reaction. This process can be achieved directly from alkynes, a hydroborane, [PPh3AuCl], and an organic base. ArF=2,4,6-tris(trifluoromethyl)phenyl.

    19. Conjugated Polymers

      Highly Efficient Benzannulation of Poly(phenylene ethynylene)s (pages 12051–12054)

      Hasan Arslan, Jonathan D. Saathoff, David N. Bunck, Prof. Dr. Paulette Clancy and Prof. Dr. William R. Dichtel

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201206964

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      Put a ring on it: Sterically congested polyarylenes can be synthesized by benzannulation reactions at each C[TRIPLE BOND]C bond of a poly(phenylene ethynylene) (see picture), one of the most easily synthesized and versatile classes of conjugated polymers. The benzannulation reaction is highly specific and efficient, as determined by an isotopic labeling study and several complementary spectroscopic methods.

    20. Heterocycles

      Synthetic Strategy for Cyclic Amines: A Stereodefined Cyclic N,O-Acetal as a Stereocontrol and Diversity-Generating Element (pages 12055–12058)

      Haejin Kim, Wontaeck Lim, Donghong Im, Dong-gil Kim and Prof. Young Ho Rhee

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201206967

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      In control: A new synthetic strategy towards cyclic amines was developed and exploits a stereodefined cyclic N,O-acetal as the key stereocontrol and diversity-generating element. The cyclic N,O-acetal was prepared from the sequential asymmetric hydroamination of an alkoxyallene with the chiral ligand L*, and ring-closing metathesis. The stereochemical integrity of the labile N,O-acetal was conserved in all catalytic transformations.

    21. Heterocycle Formation

      Substitution of Two Fluorine Atoms in a Trifluoromethyl Group: Regioselective Synthesis of 3-Fluoropyrazoles (pages 12059–12062)

      Dr. Kohei Fuchibe, Masaki Takahashi and Prof. Junji Ichikawa

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201206946

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      Replacing the fluorine: 3-Fluorinated pyrazoles were regioselectively synthesized by sequential substitution reactions of 2-trifluoromethyl-1-alkenes (see scheme). SN2′-type reactions of 2-trifluoromethyl-1-alkenes with deprotonated tert-butoxylcarbonyl- or arylhydrazines afforded 1,1-difluoro-1-alkenes, which were tosylated and then treated with NaH to give the desired 3-fluoropyrazoles.

    22. Iron Fluorides

      A Matrix-Isolation and Quantum-Chemical Investigation of FeF4 (pages 12063–12067)

      Tobias Schlöder, Thomas Vent-Schmidt and Dr. Sebastian Riedel

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201206464

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      Beyond iron trifluoride: Matrix-isolation IR spectroscopy and state-of-the-art quantum-chemical calculations have led to the characterization of iron tetrafluoride, a previously unknown species. FeF4 has been prepared by co-deposition of laser-ablated iron atoms with fluorine under excess of noble gases (neon and argon) at cryogenic temperatures.

    23. Kinetic Probes

      Chiral Bases as Useful Probes of Lithium Amide Reactivity (pages 12068–12071)

      Mark R. Prestly and Prof. Nigel S. Simpkins

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201206558

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      Experiments involving competition between chiral and achiral lithium amides provide a qualitative impression of the kinetics of different amide motifs in enolization reactions. The level of enantioselectivity was not diminished by the inclusion of lithium diisopropylamide (LDA; see scheme) into asymmetric enolizations mediated by a chiral lithium amide base, derived from a 1,2-diamine.

    24. Natural Product Synthesis

      Total Synthesis of (±)-Pentalenolactone A Methyl Ester (pages 12072–12076)

      Dr. Qi Liu, Guozong Yue, Na Wu, Guang Lin, Dr. Yuanzhen Li, Prof. Dr. Junmin Quan, Prof. Dr. Chuang-chuang Li, Dr. Guoxin Wang and Prof. Dr. Zhen Yang

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201206705

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      Ringing it up: The methyl ester of pentalenolactone A has been obtained through the stereoselective synthesis of a cyclopentenone by a combination of the Co-mediated Pauson–Khand reaction (PKR) of enyne 1, and the construction of a quaternary-carbon-based strained α-methylidene-δ-pentyrolactone core through a trimethylsilyl (TMS) mediated, telescoped intramolecular Michael olefination (TIMO) reaction of keto-phosphonate 2.

    25. Gold Clusters

      Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+ (pages 12077–12080)

      Dr. Thomas J. Robilotto, Dr. John Bacsa, Prof. Dr. Thomas G. Gray and Prof. Dr. Joseph P. Sadighi

      Article first published online: 4 OCT 2012 | DOI: 10.1002/anie.201206712

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      Isolobal and isolatable: A triangular [L3Au3]+ ion, bearing N-heterocyclic carbene ligands (L), is crystallographically characterized (see structure; Au yellow, C gray, N blue). Density functional theory suggests full valence delocalization among the gold atoms, with the HOMO composed largely of gold 6s orbitals and the LUMO comprising a degenerate pair. This orbital picture is analogous to that of [H3]+.

    26. Mechanistic Studies

      Amidocuprates for Directed ortho Cupration: Structural Study, Mechanistic Investigation, and Chemical Requirements (pages 12081–12085)

      Dr. Shinsuke Komagawa, Dr. Shinya Usui, Dr. Joanna Haywood, Philip J. Harford, Dr. Andrew E. H. Wheatley, Dr. Yotaro Matsumoto, Dr. Keiichi Hirano, Prof. Dr. Ryo Takita and Prof. Dr. Masanobu Uchiyama

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201204923

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      The name of the game: X-ray crystallographic analysis of Gilman- and Lipshutz-type amidocuprates indicates that the presence of LiX (X=CN, I) and THF shifts the equilibrium between the two toward the Lipshutz-type cuprate and that this is important in generating the active species for directed ortho cupration. DFT calculations show that monomeric Gilman-type cuprates have an unprecedentedly high reactivity (see scheme, DG=directing group).

    27. Biosynthetic Pathway

      Reciprocal Cross Talk between Fatty Acid and Antibiotic Biosynthesis in a Nematode Symbiont (pages 12086–12089)

      Dr. Alexander O. Brachmann, M. Sc. Daniela Reimer, Wolfram Lorenzen, Eduardo Augusto Alonso, Yannick Kopp, Prof. Dr. Jörn Piel and Prof. Dr. Helge B. Bode

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201205384

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      Don't play the second fiddle! The identification of different arrangements of branched-chain keto acid dehydrogenases usually involved in the biosynthesis of cellular building blocks is demonstrated (see scheme). Direct cross talk between secondary metabolism ketosynthases (KS) and fatty acid biosynthesis is shown and the biosynthesis of odd-numbered iso-fatty acids is found to be connected to the production of pristinamycin IIa.

    28. Organofluorine Compounds

      Copper-Mediated Difluoromethylation of (Hetero)aryl Iodides and β-Styryl Halides with Tributyl(difluoromethyl)stannane (pages 12090–12094)

      Prof. Dr. G. K. Surya Prakash, Dr. Somesh K. Ganesh, John-Paul Jones, Dr. Aditya Kulkarni, Kamil Masood, Joseph K. Swabeck and Prof. Dr. George A. Olah

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201205850

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      Owing to their unique properties, molecules containing the difluoromethyl group (CF2H) are of great interest. Tributyl(difluoromethyl)stannane has now been used for the selective and efficient direct ipso difluoromethylation of aryl iodides, heterocyclic iodides, and β-styryl halides (see scheme). The straightforward preparation of the difluoromethylating reagent makes this approach particularly valuable.

    29. Ribosomes

      Ligand- and pH-Induced Conformational Changes of RNA Domain Helix 69 Revealed by 2-Aminopurine Fluorescence (pages 12095–12098)

      Dr. Yogo Sakakibara, Dr. Sanjaya C. Abeysirigunawardena, Dr. Anne-Cécile E. Duc, Danielle N. Dremann and Prof. Christine S. Chow

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201206000

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      Loop conformation: The loop of the RNA domain helix 69 (H69) was modified with the fluorescent analogue 2-aminopurine (2AP), thus showing different conformational states under various conditions. The application of this model RNA reveals the unique impact of aminoglycoside neomycin, which differs from the effects of structurally related compounds paromomycin and gentamicin, on the H69 loop conformation in solution (see picture).

    30. Peptide Switches

      Reversible Redox Reconfiguration of Secondary Structures in a Designed Peptide (pages 12099–12101)

      Xiaojian Wang, Irina Bergenfeld, Prof. Dr. Paramjit S. Arora and Prof. Dr. James W. Canary

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201206009

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      Secondary structures are critical regulators of protein structure and function. Switchable peptides that can adopt multiple defined conformations in response to stimuli are attractive model systems for the study of protein folding and misfolding. A peptide is presented that can be reversibly reconfigured between an α-helical monomer and a β-sheet aggregate upon one-electron oxidation and reduction in the presence of CuI/CuII.

    31. Cobalt Catalysts

      Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of C[DOUBLE BOND]C, C[DOUBLE BOND]O, and C[DOUBLE BOND]N Bonds (pages 12102–12106)

      Dr. Guoqi Zhang, Dr. Brian L. Scott and Dr. Susan K. Hanson

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201206051

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      A cationic cobalt(II)–alkyl complex is an effective precatalyst for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (1–4 atm H2; see scheme). The catalyst shows a high functional-group tolerance across a broad range of substrates. Experiments suggest that the active catalytic species is a cobalt(II)–hydride complex.

    32. DNA Binding

      Temperature-Switched Binding of a RuII(dppz)/DNA Light-Switch Complex (pages 12107–12110)

      Michael G. Walker, Dr. Veronica Gonzalez, Dr. Elena Chekmeneva and Dr. Jim A Thomas

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206260

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      Cool to switch on: Although a Ru(dppz)-based complex binds to the grooves of duplex DNA at room temperature and above, it intercalates into duplex DNA at 10 °C, thus displaying a light-switch effect (see picture, dppz=dipyridylphenazine). Furthermore, once intercalated at low temperatures, emission does not disappear, even after the bound complex is warmed up to 35 °C for several hours.

    33. Palladium Complexes

      A Two-Coordinate Palladium Complex with Two Dialkylphosphinyl Ligands (pages 12111–12114)

      Prof. Dr. Takeaki Iwamoto, Fumiya Hirakawa and Dr. Shintaro Ishida

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201206997

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      Navy blue crystals of a two-coordinate homoleptic palladium complex with two phosphinyl radical ligands was synthesized by a simple ligand-exchange reaction. Significant π interactions between orbitals of Pd and the SOMO of phosphinyl radicals are responsible for the diamagnetic character, the intense blue color, and short P[BOND]Pd distances. Hydrogenation of the complex gave the corresponding bis(dialkylhydrophosphine)palladium complex.

    34. C[BOND]H Functionalization

      Functionalization of Cmath image[BOND]H and Cmath image[BOND]H Bonds: Synthesis of Spiroindenes by Enolate-Directed Ruthenium-Catalyzed Oxidative Annulation of Alkynes with 2-Aryl-1,3-dicarbonyl Compounds (pages 12115–12119)

      Dr. Suresh Reddy Chidipudi, Imtiaz Khan and Dr. Hon Wai Lam

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201207170

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      Ru(de) awakening: The synthesis of carbocycles by the ruthenium-catalyzed oxidative annulation of alkynes with 2-aryl cyclic 1,3-dicarbonyl substrates is described. Proceeding by the functionalization of Cmath image[BOND]H and Cmath image[BOND]H bonds, and the formation of an all-carbon quaternary center, the reaction provides a diverse range of spiroindenes in good yields with high levels of regioselectivity.

    35. Synthetic Methods

      Asymmetric (4+3) Cycloadditions of Enantiomerically Enriched Epoxy Enolsilanes (pages 12120–12123)

      Brian Lo, Sarah Lam, Prof. Wing-Tak Wong and Prof. Pauline Chiu

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201207427

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      A f(oxy) allyl: The intermolecular (4+3) cycloaddition of enantiomerically enriched epoxy enolsilanes produces cycloadducts with up to 99 % ee, thus implying the reaction does not proceed by the putative achiral oxyallyl cation intermediate, but through a transiently chiral electrophile which retains the stereochemical information of the epoxide (see scheme; TES=triethylsilyl, Tf=trifluoromethanesulfonyl).

    36. Energy Conversion

      Nitrogen-Doped Graphene Foams as Metal-Free Counter Electrodes in High-Performance Dye-Sensitized Solar Cells (pages 12124–12127)

      Dr. Yuhua Xue, Dr. Jun Liu, Dr. Hao Chen, Dr. Ruigang Wang, Dr. Dingqiang Li, Dr. Jia Qu and Prof. Liming Dai

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201207277

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      Efficient without metal: Nitrogen-doped graphene foams with a nitrogen content up to 7.6 % have been prepared and used as counter electrodes in dye-sensitized solar cells (DSSCs; see picture). The doping with nitrogen leads to a power conversion efficiency of 7.07 %. This is one of the highest values reported for DSSCs with carbon-based metal-free counter electrodes.

    37. Organocatalysis

      Organocatalytic Synthesis of Highly Substituted Furfuryl Alcohols and Amines (pages 12128–12131)

      Prof. Dr. J. Stephen Clark, Dr. Alistair Boyer, Anthony Aimon, Paloma Engel García, Dr. David M. Lindsay, Andrew D. F. Symington and Yves Danoy

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201207300

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      Top cat! Tetrahydrothiophene is an efficient organocatalyst for the synthesis of highly substituted furfuryl products from readily accessible electron-poor enynes under neutral reaction conditions. This process is applicable to a wide range of nucleophiles and enynes and can be used in a domino organocatalysis sequence.

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