Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 29

July 15, 2013

Volume 52, Issue 29

Pages 7323–7603

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Evidence for Low-Temperature Melting of Mercury owing to Relativity (Angew. Chem. Int. Ed. 29/2013) (page 7323)

      Dr. Florent Calvo, Dr. Elke Pahl, Dr. Michael Wormit and Prof. Dr. Peter Schwerdtfeger

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304862

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      The generalized theory of relativity gives a correct explanation of the residual motion of the perihelion of planet mercury. As F. Calvo, P. Schwerdtfeger, et al. show in their Communication on page 7583 ff., the special theory of relativity has furnished an even more remarkable result. It gives the correct explanation as to why mercury is the only liquid metal at room temperature, as demonstrated by parallel-tempering Monte Carlo simulations (Picture: Cameron Smorenburg).

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      Inside Cover: Enantioselective Isomerization of Primary Allylic Alcohols into Chiral Aldehydes with the tol-binap/dbapen/Ruthenium(II) Catalyst (Angew. Chem. Int. Ed. 29/2013) (page 7324)

      Prof. Dr. Noriyoshi Arai, Keisuke Sato, Keita Azuma and Prof. Dr. Takeshi Ohkuma

      Article first published online: 2 JUL 2013 | DOI: 10.1002/anie.201304864

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      Enantioselective isomerization of γ-substituted primary allylic alcohols into the β-substituted aldehydes with the [RuCl2{(S)-tol-binap}{(R)-dbapen}]/KOH catalyst system is described by T. Ohkuma and co-workers in their Communication on page 7500 ff. A series of E- and Z-configured aromatic and aliphatic allylic alcohols, including a simple primary-alkyl-substituted compound (E)-3-methyl-2-hepten-1-ol, is transformed to the aldehydes in almost enantiomerically pure form.

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      Inside Back Cover: Odorless Isocyanide Chemistry: An Integrated Microfluidic System for a Multistep Reaction Sequence (Angew. Chem. Int. Ed. 29/2013) (page 7605)

      Dr. Siddharth Sharma, Dr. Ram Awatar Maurya, Kyoung-Ik Min, Guan-Young Jeong and Prof. Dr. Dong-Pyo Kim

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304980

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      Despite the long history of isocyanide chemistry, the full utilization of these compounds has been hindered by their distressing odor. In their Communication on page 7564 ff., D.-P. Kim et al. report the development of an automated continuous microfluidic system that produces products through the serial synthesis, purification, and in situ consumption of isocyanides, with little exposure of these compounds to the surroundings.

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      Back Cover: Metal-Free HB(C6F5)2-Catalyzed Hydrogenation of Unfunctionalized Olefins and Mechanism Study of Borane-Mediated σ-Bond Metathesis (Angew. Chem. Int. Ed. 29/2013) (page 7606)

      Yuwen Wang, Weiqiang Chen, Zhenpin Lu, Prof. Zhen Hua Li and Prof. Huadong Wang

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201304866

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      Metal-free hydrogenation of unfunctionalized olefins is described by Z. H. Li, H. Wang and co-workers in their Communication on page 7496 ff. Highly Lewis-acidic hydroborane HB(C6F5)2 was employed as the catalyst. The key step in the catalytic reaction is proposed to involve a borane-mediated σ-bond metathesis through a four-membered ring transition state which resembles the traditional Chinese residential house, Siheyuan, shown in the middle of the picture.

  2. Graphical Abstract

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 29/2013 (pages 7327–7342)

      Article first published online: 11 JUL 2013 | DOI: 10.1002/anie.201390029

  3. Corrigenda

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
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    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: Shape Control of Thermodynamically Stable Cobalt Nanorods through Organometallic Chemistry (page 7342)

      Frédéric Dumestre, Bruno Chaudret, Catherine Amiens, Marie-Claire Fromen, Marie-José Casanove, Philippe Renaud and Peter Zurcher

      Article first published online: 11 JUL 2013 | DOI: 10.1002/anie.201304166

    2. You have free access to this content
      Corrigendum: Highly Enantioselective Catalytic [6+3] Cycloadditions of Azomethine Ylides (page 7342)

      Marco Potowski, Jonathan O. Bauer, Prof. Dr. Carsten Strohmann, Dr. Andrey P. Antonchick and Prof. Dr. Herbert Waldmann

      Article first published online: 11 JUL 2013 | DOI: 10.1002/anie.201304263

      This article corrects:

      Highly Enantioselective Catalytic [6+3] Cycloadditions of Azomethine Ylides1

      Vol. 51, Issue 38, 9512–9516, Article first published online: 14 AUG 2012

  4. News

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
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    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    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. Meeting Review
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Chien-Hong Cheng (page 7348)

      Article first published online: 7 MAR 2013 | DOI: 10.1002/anie.201300198

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      “My biggest motivation is curiosity. Guaranteed to make me smile is when my predictions come true. …” This and more about Chien-Hong Cheng can be found on page 7348.

  6. News

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
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    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  7. Meeting Review

    1. Top of page
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    10. Highlight
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    12. Review
    13. Communications
    1. Conference Report

  8. Book Review

    1. Top of page
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    4. Corrigenda
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    13. Communications
    1. Enzyme Catalysis in Organic Synthesis. Third, Completely Revised and Enlarged Edition. 3 Volumes. Edited by Karlheinz Drauz, Harald Gröger and Oliver May. (page 7355)

      Stephan Lütz

      Article first published online: 20 JUN 2013 | DOI: 10.1002/anie.201304466

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      Wiley-VCH, Weinheim, 2012. 2038 pp., hardcover, € 492.00.—ISBN 978-3527325474

  9. Highlight

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
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    7. News
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    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Bioenergetics

      Inside View of a Giant Proton Pump (pages 7358–7360)

      Prof. Dr. Ulrich Brandt

      Article first published online: 23 MAY 2013 | DOI: 10.1002/anie.201303403

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      Inner workings: The X-ray crystal structure of the entire bacterial complex I at 3.3 Å resolution offers fascinating insights into a giant 536 kDa molecular machine. The respiratory chain complex seems to employ unique mechanisms of energetic coupling that are entirely different from those found in all other enzymes using redox energy to drive vectorial proton transport across a bioenergetic membrane.

  10. Minireview

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    12. Review
    13. Communications
    1. Cross-Coupling

      Transmetalation in the Suzuki–Miyaura Coupling: The Fork in the Trail (pages 7362–7370)

      Dr. Alastair J. J. Lennox and Prof. Dr. Guy C. Lloyd-Jones

      Article first published online: 18 JUN 2013 | DOI: 10.1002/anie.201301737

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      Indecision: The Suzuki–Miyaura coupling is ubiquitous, yet there remains a dichotomy of opinion as to which of two pathways is followed for the delivery of the organoboron component to palladium in the steps leading up to the transmetalation. The importance of deciding between the two pathways should not be underestimated, as it influences the design of optimal conditions for coupling.

  11. Review

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    13. Communications
    1. CO2 Photoreduction

      Photocatalytic Reduction of CO2 on TiO2 and Other Semiconductors (pages 7372–7408)

      Severin N. Habisreutinger, Prof. Lukas Schmidt-Mende and Dr. Jacek K. Stolarczyk

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201207199

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      It cuts both ways: The photocatalytic conversion of CO2 into valuable solar fuels such as methane or methanol has the potential to address the future energy supply demand and mitigate CO2 emissions. This Review presents the current state of the art of the heterogeneous photocatalytic reduction of CO2 on TiO2 and other metal oxides, oxynitrides, sulfides, and phosphides. The mechanisms and the measures of the efficiency of the process are discussed in detail.

  12. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
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    10. Highlight
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    12. Review
    13. Communications
    1. Self-Assembly on Surfaces

      “Magic” Surface Clustering of Borazines Driven by Repulsive Intermolecular Forces (pages 7410–7414)

      Simon Kervyn, Dr. Nataliya Kalashnyk, Massimo Riello, Ben Moreton, Jonathan Tasseroul, Prof. Dr. Johan Wouters, Prof. Dr. Tim S. Jones, Prof. Dr. Alessandro De Vita, Prof. Dr. Giovanni Costantini and Prof. Dr. Davide Bonifazi

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201300948

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      It's a kind of magic: Hydroxy pentaaryl borazine molecules self-assemble into small clusters (see structure) on Cu(111) surfaces, whereas with symmetric hexaaryl borazine molecules large islands are obtained. Simulations indicate that the observed “magic” cluster sizes result from long-range repulsive Coulomb forces arising from the deprotonation of the B[BOND]OH groups of the hydroxy pentaaryl borazine.

    2. Organoboron Surface Chemistry

      Facile Monolayer Formation on SiO2 Surfaces via Organoboron Functionalities (pages 7415–7418)

      Dr. Arunava Agarwala, Dr. Thangavel Subramani, Dr. Amir Goldbourt, Dr. David Danovich and Dr. Roie Yerushalmi

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201302655

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      More than they appear on the surface: The treatment of SiO2 nanoparticles under mild conditions with two organoboron derivatives led to boron-containing monolayers with different types of surface species (see picture) through the direct formation of Si[BOND]O[BOND]B bonds. The organoboron-modified SiO2 NPs showed selective reactivity towards diols.

    3. Nanoclusters

      Formation of a Pt12 Cluster by Single-Atom Control That Leads to Enhanced Reactivity: Hydrogenation of Unreactive Olefins (pages 7419–7421)

      Masaki Takahashi, Dr. Takane Imaoka, Yushi Hongo and Prof. Kimihisa Yamamoto

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201302860

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      A platinum subnanocluster catalyst composed of 12 atoms was synthesized using a phenylazomethine dendrimer, which can assemble twelve PtCl4 units by stepwise complexation, followed by reduction to Pt0. Unreactive olefins that were not activated by conventional 2 nm Pt nanoparticles were successfully hydrogenated by the subnanocluster. EWG=electron-withdrawing group.

    4. Asymmetric Catalysis

      Chiral N-Heterocyclic Carbene/Pyridine Ligands for the Iridium-Catalyzed Asymmetric Hydrogenation of Olefins (pages 7422–7425)

      Dr. Andreas Schumacher, Maurizio Bernasconi and Prof. Dr. Andreas Pfaltz

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201301251

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      Swapping N,P for C,N: Iridium complexes of bidentate pyridine-based C,N ligands with an N-heterocylic carbene (NHC) unit proved to be efficient and highly enantioselective hydrogenation catalysts. As a result of the lower acidity of iridium hydride intermediates produced from NHC-based complexes, these catalysts are much better suited than analogous N,P-ligand complexes for the hydrogenation of acid-sensitive substrates.

    5. Carbohydrates

      Top-Down Chemoenzymatic Approach to a High-Mannose-Type Glycan Library: Synthesis of a Common Precursor and Its Enzymatic Trimming (pages 7426–7431)

      Dr. Akihiko Koizumi, Prof. Ichiro Matsuo, Maki Takatani, Dr. Akira Seko, Dr. Masakazu Hachisu, Dr. Yoichi Takeda and Dr. Yukishige Ito

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301613

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      From the stacks: A novel method for construction of a high-mannose-type glycan library by systematic enzymatic trimming of a single synthetic Man9-based precursor was developed. Efficient chemical synthesis of the tetradecasaccharide common precursor and orthogonal enzymatic trimming to obtain all M8-9 and G1M8-9 derivatives was demonstrated. G=glucose, M=mannose.

    6. DNA Repair

      Repair of the (6–4) Photoproduct by DNA Photolyase Requires Two Photons (pages 7432–7436)

      Dr. Junpei Yamamoto, Ryan Martin, Prof. Shigenori Iwai, Dr. Pascal Plaza and Dr. Klaus Brettel

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201301567

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      It takes two (photons) to tango: Single-turnover flash experiments showed that the flavoenzyme (6–4) photolyase uses a successive two-photon mechanism to repair the UV-induced T(6–4)T lesion in DNA (see picture). The intermediate (X) formed by the first photoreaction is likely to be the oxetane-bridged dimer T(ox)T. The enzyme could stabilize the normally short-lived T(ox)T, allowing repair to be completed by the second photoreaction.

    7. Supramolecular Self-Sorting

      Pseudorotaxanes with Self-Sorted Sequence and Stereochemical Orientation (pages 7437–7441)

      Dr. Carmen Talotta, Dr. Carmine Gaeta, Zhenhui Qi, Prof. Christoph A. Schalley and Prof. Placido Neri

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301570

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      Partner preferences in pseudorotaxane formation were exploited to establish an integrative self-sorting system able to discriminate simultaneously at the sequence and stereochemical level (see picture). It was found that calix[6]arenes were threaded selectively with a preferred orientation onto bisammonium axles, even when the structural differences between the possible building blocks were small and located remote from the binding sites.

    8. Surface Chemistry

      Identification of Molecular-Adsorption Geometries and Intermolecular Hydrogen-Bonding Configurations by In Situ STM Manipulation (pages 7442–7445)

      Prof. Dr. Wei Xu, Huihui Kong, Chi Zhang, Qiang Sun, Henkjan Gersen, Liang Dong, Prof. Dr. Qinggang Tan, Prof. Erik Lægsgaard and Prof. Dr. Flemming Besenbacher

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201301580

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      Don't be dim! By combining the technique with DFT calculations, STM manipulation was extended to the probing of intermolecular hydrogen-bonding configurations in self-assembled nanostructures. It was also possible to convert one configuration into another in a controlled fashion through the careful manipulation of a particular structural unit (see picture).

    9. Plasmonic Catalysis

      The Synthesis of Size- and Color-Controlled Silver Nanoparticles by Using Microwave Heating and their Enhanced Catalytic Activity by Localized Surface Plasmon Resonance (pages 7446–7450)

      Kojirou Fuku, Ryunosuke Hayashi, Shuhei Takakura, Dr. Takashi Kamegawa, Dr. Kohsuke Mori and Prof. Dr. Hiromi Yamashita

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301652

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      Silver nanoparticles (Ag NPs) of various colors were synthesized within the mesopore structure of SBA-15 by using microwave-assisted alcohol reduction. The charge density is partially localized on the surface of these Ag NPs owing to localized surface plasmon resonance. This charge localization results in them having enhanced catalytic activity under visible light irradiation compared to Ag NPs obtained by thermal processes.

    10. Molecular Imprinting

      Photolithographic Boronate Affinity Molecular Imprinting: A General and Facile Approach for Glycoprotein Imprinting (pages 7451–7454)

      Li Li, Yue Lu, Zijun Bie, Prof. Hong-Yuan Chen and Dr. Zhen Liu

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201207950

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      Better than expected: With a regular boronic acid as the functional monomer, a general and facile approach for glycoprotein imprinting exhibited several highly favorable features that are beyond normal expectation, which make the prepared MIPs feasible for the recognition of trace glycoproteins in complicated real samples.

    11. Emulsion Catalysis

      A Strategy for Separating and Recycling Solid Catalysts Based on the pH-Triggered Pickering-Emulsion Inversion (pages 7455–7459)

      Prof. Dr. Hengquan Yang, Ting Zhou and Wenjuan Zhang

      Article first published online: 7 JUN 2013 | DOI: 10.1002/anie.201300534

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      Turn you inside out: A novel method for performing in situ separation and recycling of submicrometer-sized solid catalysts is developed based on the pH-triggered inversion of Pickering emulsions (see scheme; o=oil, w=water). Solid catalysts can be recycled 36 times without significant loss of activity. The method differs from conventional methods in terms of speed, energy consumption, catalyst separation, and recycling effectiveness.

    12. Lithium Batteries

      Lithium Polysulfidophosphates: A Family of Lithium-Conducting Sulfur-Rich Compounds for Lithium–Sulfur Batteries (pages 7460–7463)

      Dr. Zhan Lin, Dr. Zengcai Liu, Dr. Wujun Fu, Dr. Nancy J. Dudney and Dr. Chengdu Liang

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201300680

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      Sulfur-rich lithium polysulfidophosphates (LPSPs) act as an enabler for long-lasting and efficient lithium–sulfur batteries. LPSPs have ionic conductivities of 3.0×10−5 S cm−1 at 25 °C, which is 8 orders of magnitude higher than that of Li2S. The high lithium ion conductivity imparts excellent cycling performance, and the batteries are configured in an all-solid state, which promises safe cycling with metallic lithium anodes.

    13. Reaction Dynamics

      Dynamics of a Nanometer-Sized Uranyl Cluster in Solution (pages 7464–7467)

      Rene L. Johnson, Dr. C. André Ohlin, Kristi Pellegrini, Prof. Peter C. Burns and Prof. William H. Casey

      Article first published online: 6 JUN 2013 | DOI: 10.1002/anie.201301973

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      A class of uranyl peroxide clusters was discovered before as nanometer-sized ions that form spontaneously in aqueous solutions. The uranyl(VI) cluster investigated here is approximately 2 nm in diameter, contains 24 uranyl moieties, and 12 pyrophosphate units. NMR spectroscopy shows that the ion has two distinct forms that interconvert in milliseconds to seconds depending on the temperature and the size of the counterions. P blue, O red, U yellow.

    14. Functional Surfaces

      Self-Oscillating Polymer Brushes (pages 7468–7471)

      Tsukuru Masuda, Mio Hidaka, Dr. Yoko Murase, Dr. Aya Mizutani Akimoto, Dr. Kenichi Nagase, Prof. Dr. Teruo Okano and Prof. Dr. Ryo Yoshida

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201301988

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      An autonomous functional surface has been designed by using self-oscillating polymers that convert the chemical energy of the Belousov–Zhabotinsky reaction into conformational changes of the polymer chains (see picture: red: hydrophobic/collapsed, green: hydrophilic/extended). Self-oscillating polymer brushes were grafted onto the inner surface of a glass capillary, and autonomous propagation of a chemical wave was observed.

    15. Electrocatalysts

      Ultrathin PtPdTe Nanowires as Superior Catalysts for Methanol Electrooxidation (pages 7472–7476)

      Hui-Hui Li, Shuo Zhao, Prof. Dr. Ming Gong, Dr. Chun-Hua Cui, Da He, Dr. Hai-Wei Liang, Liang Wu and Prof. Dr. Shu-Hong Yu

      Article first published online: 6 JUN 2013 | DOI: 10.1002/anie.201302090

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      Ultrathin and ultralong: Highly uniform, ultrathin (diameter 5–7 nm), and ultralong (aspect ratio >104) PtPdTe nanowires (NWs) were synthesized by using a facile method employing Te NWs as both sacrificial templates and reducing agents. Fine-tuning of the molar ratios of Pt and Pd precursors afforded PtPdTe NWs with different compositions and enhanced electroactivity in the methanol oxidation reaction in comparison with a commercial Pt/C catalyst.

    16. Proteomics

      Analysis of Microarrays by MALDI-TOF MS (pages 7477–7481)

      Dr. Ana Beloqui, Dr. Javier Calvo, Dr. Sonia Serna, Dr. Shi Yan, Prof. Dr. Iain B. H. Wilson, Prof. Dr. Manuel Martin-Lomas and Dr. Niels Christian Reichardt

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201302455

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      Ligand libraries can be printed onto a sandwich composed of activated lipids embedded in a hydrophobic layer conjugated to an indium–tin oxide (ITO) surface. Arrays produced this way can be analyzed by fluorescence spectroscopy and mass spectrometry. Applications include the assignment of enzyme specificity, the profiling of glycoforms and the identification of lectins.

    17. Supramolecular Chemistry

      Quadruple π Stack of Two Perylene Bisimide Tweezers: A Bimolecular Complex with Kinetic Stability (pages 7482–7486)

      Dr. Changzhun Shao, Dr. Matthias Stolte and Prof. Dr. Frank Würthner

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201302479

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      Self-assembly: A tweezer-type perylene bisimide (PBI) dyad self-assembles into a defined bimolecular complex composed of a quadruple PBI π stack with remarkable kinetic stability, which is unprecedented for π-stacked dye aggregates (see picture). These persistent supramolecular species are of considerable interest for the elucidation of functional properties of dye aggregates.

    18. Drug Delivery

      A Controlled-Release Nanocarrier with Extracellular pH Value Driven Tumor Targeting and Translocation for Drug Delivery (pages 7487–7491)

      Dr. Zilong Zhao, Hongmin Meng, Nannan Wang, Michael J. Donovan, Ting Fu, Dr. Mingxu You, Prof. Zhuo Chen, Prof. Xiaobing Zhang and Prof. Weihong Tan

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201302557

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      This pHLIP is no flop: Functionalizing mesoporous silica nanoparticles (MSNs) with pHLIPss peptide provides a controlled-release nanoparticle drug delivery system targeting the acidic tumor microenvironment. At low pH values, pHLIPss inserts into the cell membrane and translocates carriers into cells, where the cargo is released by the cleavage of the pHLIPss disulfide bonds (see scheme).

    19. Frustrated Lewis Pairs

      Combinations of Ethers and B(C6F5)3 Function as Hydrogenation Catalysts (pages 7492–7495)

      Dr. Lindsay J. Hounjet, Christoph Bannwarth, Dr. Christian N. Garon, Christopher B. Caputo, Prof. Dr. Stefan Grimme and Prof. Dr. Douglas W. Stephan

      Article first published online: 14 JUN 2013 | DOI: 10.1002/anie.201303166

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      It works ether way: Labile adducts of dialkyl ethers with the electrophilic borane B(C6F5)3 are shown to scramble HD to H2 and D2 and catalyze the hydrogenation of 1,1-diphenylethylene.

    20. Synthetic Methods

      Metal-Free HB(C6F5)2-Catalyzed Hydrogenation of Unfunctionalized Olefins and Mechanism Study of Borane-Mediated σ-Bond Metathesis (pages 7496–7499)

      Yuwen Wang, Weiqiang Chen, Zhenpin Lu, Prof. Zhen Hua Li and Prof. Huadong Wang

      Article first published online: 18 JUN 2013 | DOI: 10.1002/anie.201303500

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      Out with the metal: Metal-free hydrogenation of unfunctionalized olefins can be achieved by employing HB(C6F5)2 as the catalyst. The key step in the catalytic reaction is believed to involve a novel borane-mediated σ-bond metathesis, which has been investigated both experimentally and theoretically.

    21. Asymmetric Catalysis

      Enantioselective Isomerization of Primary Allylic Alcohols into Chiral Aldehydes with the tol-binap/dbapen/Ruthenium(II) Catalyst (pages 7500–7504)

      Prof. Dr. Noriyoshi Arai, Keisuke Sato, Keita Azuma and Prof. Dr. Takeshi Ohkuma

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303423

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      Efficient isomerization: The title reaction was catalyzed by the [RuCl2{(S)-tol-binap}{(R)-dbapen}]/KOH system in ethanol at 25 °C (see scheme). A series of E- and Z-configured aromatic and aliphatic allylic alcohols, including a simple primary alkyl-substituted compound (E)-3-methyl-2-hepten-1-ol, were transformed into the chiral aldehydes with at least 99 % ee. dbapen=2-dibutylamino-1-phenylethylamine, tol-binap=2,2′-bis(di-4-tolylphosphanyl)-1,1′-binaphthyl.

    22. Electron Acceptors

      C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60 (pages 7505–7508)

      Dr. Igor V. Kuvychko, Cristina Dubceac, Dr. Shihu H. M. Deng, Dr. Xue-Bin Wang, Dr. Alexander A. Granovsky, Dr. Alexey A. Popov, Prof. Marina A. Petrukhina, Prof. Steven H. Strauss and Dr. Olga V. Boltalina

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201300796

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      At sixes and sevens: The reaction of corannulene with 35 equivalents of 1,4-C4F8I2 is an efficient and a relatively selective process that yields two main products in which six H atoms are substituted with three C4F8 moieties that form six- and seven-membered rings. Low-temperature photoelectron spectroscopy showed the electron affinity of the major isomer (shown) exceeds that of C60 (2.74±0.02 and 2.689±0.008 eV, respectively).

    23. Synthetic Methods

      Base-Catalyzed Synthesis of Substituted Indazoles under Mild, Transition-Metal-Free Conditions (pages 7509–7513)

      Isabelle Thomé, Dr. Claire Besson, Dr. Tillmann Kleine and Prof. Dr. Carsten Bolm

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201300917

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      Back to basics: A transition-metal-free method developed for the synthesis of indazoles involves an inexpensive catalytic system composed of a diamine and K2CO3. Various (Z)-2-bromoacetophenone tosylhydrazones were converted into indazoles at room temperature in excellent yields (see example; Ts=p-toluenesulfonyl). The yield was improved by photoisomerization with UV light when E/Z isomeric mixtures of the starting material were used.

    24. Photocatalysts

      Self-Organized Arrays of Single-Metal Catalyst Particles in TiO2 Cavities: A Highly Efficient Photocatalytic System (pages 7514–7517)

      Jeong Eun Yoo, Kiyoung Lee, Marco Altomare, Prof. Dr. Elena Selli and Prof. Dr. Patrik Schmuki

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201302525

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      Peas in a pod: A highly aligned Aunp@TiO2 photocatalyst was formed by self-organizing anodization of a Ti substrate followed by dewetting of a gold thin film. This leads to exactly one Au nanoparticle (np) per TiO2 nanocavity. Such arrays are highly efficient photocatalysts for hydrogen generation from ethanol.

    25. Alkene Synthesis

      You have full text access to this OnlineOpen article
      Haloboration of Internal Alkynes with Boronium and Borenium Cations as a Route to Tetrasubstituted Alkenes (pages 7518–7522)

      James R. Lawson, Dr. Ewan R. Clark, Dr. Ian A. Cade, Dr. Sophia A. Solomon and Dr. Michael J. Ingleson

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201302609

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      Hail boration! 2-Dimethylaminopyridine-ligated dihaloborocations [X2B(2-DMAP)]+ with a strained four-membered boracycle were used for the haloboration of terminal and dialkyl internal alkynes (see scheme). Esterification then provided vinyl boronate esters as useful precursors to tetrasubstituted alkenes. Following mechanistic studies, the scope of the haloboration was expanded simply by variation of the amine. Pin=2,3-dimethyl-2,3-butanedioxy.

    26. Homogeneous Catalysis

      A Robust Nickel Catalyst for Cyanomethylation of Aldehydes: Activation of Acetonitrile under Base-Free Conditions (pages 7523–7526)

      Dr. Sumit Chakraborty, Yogi J. Patel, Dr. Jeanette A. Krause and Prof. Hairong Guan

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201302613

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      Nick of time: The nickel cyanomethyl complex 1 catalyzes the room temperature coupling of aldehydes with acetonitrile under base-free conditions. The catalytic system is long-lived and remarkably efficient with high turnover numbers (TONs) and turnover frequencies (TOFs) achieved. The mild reaction conditions allow a wide variety of aldehydes, including base-sensitive ones, to catalytically react with acetonitrile.

    27. B,N Heterocycles

      Boron-Substituted 1,3-Dihydro-1,3-azaborines: Synthesis, Structure, and Evaluation of Aromaticity (pages 7527–7531)

      Dr. Senmiao Xu, Tanya C. Mikulas, Dr. Lev N. Zakharov, Prof. Dr. David A. Dixon and Prof. Shih-Yuan Liu

      Article first published online: 7 JUN 2013 | DOI: 10.1002/anie.201302660

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      Getting the family together: A general synthetic strategy based on nucleophilic substitution provided B-substituted 1,3-dihydro-1,3-azaborines (see scheme), BN isosteres of arenes with potential for application in biomedicine and materials science. Experimental structural analysis and calculations suggest that the aromaticity of the 1,3-dihydro-1,3-azaborine heterocycle is intermediate between that of benzene and that of 1,2-dihydro-1,2-azaborine.

    28. Asymmetric Catalysis

      Iridium-Catalyzed Enantioselective Allylic Alkynylation (pages 7532–7535)

      James Y. Hamilton, Dr. David Sarlah and Prof. Dr. Erick M. Carreira

      Article first published online: 27 MAY 2013 | DOI: 10.1002/anie.201302731

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      No leaving group needed: With an Ir(P,olefin) complex as catalyst, the direct enantioselective allylic alkynylation of secondary allylic alcohols with potassium alkynyltrifluoroborates as alkynylating reagents has been achieved. High levels of enantioselectivity and high yields were achieved with this operationally easy and robust protocol, the use of which was demonstrated in the synthesis of GPR40 receptor agonist AMG 837. cod=1,5-cyclooctadiene.

    29. Heterocycles

      Oxazepine Synthesis by Copper-Catalyzed Intermolecular Cascade Reactions between O-Propargylic Oximes and Dipolarophiles (pages 7536–7539)

      Prof. Dr. Itaru Nakamura, Yu Kudo and Prof. Dr. Masahiro Terada

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201302751

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      Three-step cascade: Oxazepine derivatives were efficiently prepared from O-propargylic oximes and dipolarophiles through copper-catalyzed cascade reactions which proceed through a 2,3-rearrangement, [3+2] cycloaddition, and subsequent 1,3-oxygen rearrangement. The process involves the cleavage of C[BOND]O and N[BOND]O bonds.

    30. Asymmetric Catalysis

      A Palladium-Catalyzed Enantioselective Addition of Arylboronic Acids to Cyclic Ketimines (pages 7540–7544)

      Dr. Guoqiang Yang and Prof. Wanbin Zhang

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201302861

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      Sly as Nicox: A palladium-catalyzed addition of arylboronic acids to ketimines has been developed to efficiently provide products in up to 99 % yield and 96 % ee. The reactions could be run under aerobic conditions and with unpurified trifluoroethanol (TFE). A pyrrolidine compound bearing a chiral α-tertiary amine was synthesized in several steps without loss of enantioselectivity. TFA=trifluoroacetate.

    31. Photovoltaics

      Photovoltaic Wire Derived from a Graphene Composite Fiber Achieving an 8.45 % Energy Conversion Efficiency (pages 7545–7548)

      Zhibin Yang, Hao Sun, Dr. Tao Chen, Longbin Qiu, Dr. Yongfeng Luo and Prof. Huisheng Peng

      Article first published online: 28 MAY 2013 | DOI: 10.1002/anie.201301776

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      Wired for light: Novel wire-shaped photovoltaic devices have been developed from graphene/Pt composite fibers. The high flexibility, mechanical strength, and electrical conductivity of graphene composite fibers resulted in a maximum energy conversion efficiency of 8.45 %, which is much higher than that of other wire-shaped photovoltaic devices.

    32. Synthetic Methods

      Copper-Catalyzed Regioselective Fluorination of Allylic Halides (pages 7549–7553)

      Zuxiao Zhang, Fei Wang, Xin Mu, Dr. Pinhong Chen and Prof. Dr. Guosheng Liu

      Article first published online: 14 JUN 2013 | DOI: 10.1002/anie.201301891

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      Group activity: A novel copper-catalyzed fluorination of internal allylic bromides and chlorides has been developed by using Et3N⋅3 HF as the fluorine source. A functional group (FG) within the substrate is required to achieve the allylic fluorination, and a variety of secondary allylic fluoride compounds can be accessed in good yield with excellent regioselectivity.

    33. Nanosheets

      Ultrathin Nanosheets of Half-Metallic Monoclinic Vanadium Dioxide with a Thermally Induced Phase Transition (pages 7554–7558)

      Dr. Tao Yao, Dr. Liang Liu, Chong Xiao, Xiaodong Zhang, Dr. Qinghua Liu, Prof. Shiqiang Wei and Prof. Yi Xie

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201302891

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      Only the half of it: A modified intercalation–deintercalation strategy that takes advantage of the characteristic thermally induced phase transition of monoclinic VO2 has been developed for the preparation of ultrathin VO2 nanosheets. The resultant nanosheets exhibit half-metallic character and a temperature-dependent phase transition. The half-metallicity could lead to applications in spintronic nanodevices.

    34. Synthetic Methods

      Gold-Catalyzed Formal Cycloaddition of 2-Ethynylbenzyl Ethers with Organic Oxides and α-Diazoesters (pages 7559–7563)

      Samir Kundlik Pawar, Chiou-Dong Wang, Dr. Sabyasachi Bhunia, Appaso Mahadev Jadhav and Prof. Dr. Rai-Shung Liu

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201303016

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      A world of possibilities: Gold-catalyzed reactions of 2-ethynylbenzyl ethers with organic oxides and α-diazoesters gave 1,3-dihydroisobenzofuran and naphthalene derivatives, respectively (see scheme; EWG=electron-withdrawing group). Mechanisms for the formation of the formal cycloadducts were elucidated by isotope labeling.

    35. Continuous-Flow Microreactors

      Odorless Isocyanide Chemistry: An Integrated Microfluidic System for a Multistep Reaction Sequence (pages 7564–7568)

      Dr. Siddharth Sharma, Dr. Ram Awatar Maurya, Kyoung-Ik Min, Guan-Young Jeong and Prof. Dr. Dong-Pyo Kim

      Article first published online: 18 JUN 2013 | DOI: 10.1002/anie.201303213

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      Can't smell this: An integrated continuous-flow microfluidic setup enables in situ generation, extraction, separation, and reaction of foul-smelling isocyanides with little exposure to the surroundings. Isocyanides were generated by dehydration of the corresponding N-substituted formamides, and several representative isocyanide-based organic reactions were successfully performed. DIPEA=N,N-diisopropylethylamine.

    36. Natural Product Synthesis

      Total Syntheses of (−)-Scabronines G and A, and (−)-Episcabronine A (pages 7569–7573)

      Yu Kobayakawa and Prof. Masahisa Nakada

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201303224

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      Making scab(ronine)s: The total synthesis of (−)-scabronine G features a highly stereoselective oxidative dearomatization/intramolecular inverse-electron-demand Diels–Alder reaction cascade, and the first total synthesis of (−)-scabronine A comprises a highly stereoselective oxa-Michael/protonation/acetalization cascade. The first total synthesis of (−)-episcabronine A includes another highly stereoselective cascade.

    37. Radical Reactions

      Direct Vicinal Disubstitution of Diaryliodonium Salts by Pyridine N-oxides and N-amidates by a 1,3-Radical Rearrangement (pages 7574–7578)

      Jing Peng, Prof. Dr. Chao Chen, Yong Wang, Zhenbang Lou, Prof. Dr. Ming Li, Prof. Dr. Chanjuan Xi and Prof. Dr. Hui Chen

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201303347

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      Paired off: The title reaction leads to a series of o-pyridinium phenols (1) and anilines (2). The experimental and computational studies indicate that the key step involves homolytic cleavage to give a radical pair, which undergoes solvent-cage recombination to give the product.

    38. Alkyne Halosilylation

      Stereoselective Synthesis of Tetrasubstituted Olefins through a Halogen-Induced 1,2-Silyl Migration (pages 7579–7582)

      Dr. Nicholas T. Barczak, Douglas A. Rooke, Zachary A. Menard and Prof. Eric M. Ferreira

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201303007

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      Migrating through Si valley: The highly stereoselective formation of α-silyl-β- haloenones by way of silicon group migration is described. Electrophilic activation of the alkyne by N-halosuccinimides induced an anti-selective migration to give highly substituted enones (see scheme). These enone products can be readily converted to the all-carbon tetrasubstituted alkenes while maintaining their geometry.

    39. Relativistic Effects

      Evidence for Low-Temperature Melting of Mercury owing to Relativity (pages 7583–7585)

      Dr. Florent Calvo, Dr. Elke Pahl, Dr. Michael Wormit and Prof. Dr. Peter Schwerdtfeger

      Article first published online: 18 JUN 2013 | DOI: 10.1002/anie.201302742

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      An old problem solved: Monte Carlo simulations using the diatomic-in-molecule method derived from accurate ground- and excited-state relativistic calculations for Hg2 show that the melting temperature for bulk mercury is lowered by 105 K, which is due to relativistic effects.

    40. Gold Catalysis

      In Situ Generation of Nucleophilic Allenes by the Gold-Catalyzed Rearrangement of Propargylic Esters for the Highly Diastereoselective Formation of Intermolecular C(sp3)[BOND]C(sp2) Bonds (pages 7586–7589)

      M. Sc. Yang Yu, M. Sc. Weibo Yang, Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201302402

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      New perspectives, in particular for the synthesis of isochromane derivatives (see scheme), are provided by the title reaction. Excellent diastereoselectivites are achieved in this reaction which proceeds through a gold-catalyzed 1,3-acyloxy migration. In some cases exclusively the Z isomer is detected.

    41. Nucleophilic Boron

      Deprotonation of a Borohydride: Synthesis of a Carbene-Stabilized Boryl Anion (pages 7590–7592)

      David A. Ruiz, Gaël Ung, Dr. Mohand Melaimi and Prof. Guy Bertrand

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201303457

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      An acidic hydride! Thanks to the presence of a π-acceptor cyclic alkyl amino carbene and of two electron-withdrawing nitrile groups, a borohydride reacts with a base to give a carbene-stabilized boryl anion, which reacts with carbon and metal electrophiles at the boron center. Dipp=2,6-diisopropylphenyl, KHMDS=potassium bis(trimethylsilyl)amide.

    42. Bioinorganic Chemistry

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      Cobalt(III) as a Stable and Inert Mediator Ion between NTA and His6-Tagged Proteins (pages 7593–7596)

      Dr. Seraphine V. Wegner and Prof. Dr. Joachim P. Spatz

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201210317

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      Don't let go! The Co3+-mediated interaction between nitrilotriacetic acid (NTA) and the His6-tag is so stable and inert towards ligand exchange that it has a half-life of 7 days in the presence of imidazole and survives even under strongly chelating as well as reducing conditions, unlike the commonly used Ni2+ or Co2+ complexes. Possible applications include the separation of labeled proteins and the stable immobilization of proteins on surfaces.

    43. PEGylated Prodrugs

      Controlled Systemic Release of Therapeutic Peptides from PEGylated Prodrugs by Serum Proteases (pages 7597–7599)

      Friederike Inga Nollmann, Tina Goldbach, Nicole Berthold and Prof. Ralf Hoffmann

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201301533

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      A novel concept to release peptidic drugs systemically by serum proteases from a PEGylated precursor makes it possible to tune release kinetics to fit the medical needs. Drug release depends on the size of the PEG polymer and the sequence and length of the peptide linker. The antimicrobial activities of the prodrugs were even better than those of the free peptides, whereas direct PEGylation abolished the peptide activity.

    44. As4 Complexes

      An End-on-Coordinated As4 Tetrahedron (pages 7600–7603)

      Dr. Christoph Schwarzmaier, Prof. Dr. Alexey Y. Timoshkin and Prof. Dr. Manfred Scheer

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201302882

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      One time only: The reaction of [Cp*Ru(dppe)Cl] with the potent As4 transfer reagent [Ag(η2-As4)2]+[pftb] leads to [Cp*Ru(dppe)(η1-As4)]+[pftb] with an unprecedented end-on-coordinated As4 tetrahedron. Reaction with a second cationic ruthenium complex fragment does not lead to a second end-on coordination but to the cleavage of one basal As[BOND]As bond. This behavior, which differs from its phosphorus analogues, is rationalized by DFT calculations.

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