Chemistry - A European Journal

Cover image for Vol. 20 Issue 20

May 12, 2014

Volume 20, Issue 20

Pages 5845–6191

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: From the Lindlar Catalyst to Supported Ligand-Modified Palladium Nanoparticles: Selectivity Patterns and Accessibility Constraints in the Continuous-Flow Three-Phase Hydrogenation of Acetylenic Compounds (Chem. Eur. J. 20/2014) (page 5845)

      Gianvito Vilé, Dr. Neyvis Almora-Barrios, Dr. Sharon Mitchell, Prof. Núria López and Prof. Javier Pérez-Ramírez

      Version of Record online: 7 MAY 2014 | DOI: 10.1002/chem.201490079

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      The evolutionary tale of palladium-based catalysts for selective alkyne hydrogenation, from bare to lead-alloyed, and, most recently, ligand-modified nanoparticles, is unlocked using flow chemistry. Distinctions in the performance of each catalyst system as well as accessibility constraints arising from the use of ligands are identified and rationalized. For more details, see the Full Paper by J. Pérez-Ramírez, N. López et al. on page 5926 ff.

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      Back Cover: Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field-Effect Transistors (Chem. Eur. J. 20/2014) (page 6196)

      Crystalann Jones, Dr. Damien Boudinet, Dr. Yu Xia, Mitch Denti, Adita Das, Dr. Antonio Facchetti and Prof. Dr. Tom G. Driver

      Version of Record online: 7 MAY 2014 | DOI: 10.1002/chem.201490082

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      Semiconducting bispyrrolothiophenes for thin film organic field effect transistors were constructed from vinyl azides using transition-metal-catalyzed C[BOND]H bond functionalization. Pictured is an AFM image of one of the polycrystalline bispyrrolothiophenes that exhibited good field effect transistor performance despite its amorphous nature. For more information see the Full Paper by A. Facchetti, T. G. Driver et al. on page 5938 ff.

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      From the Lindlar Catalyst to Supported Ligand-Modified Palladium Nanoparticles: Selectivity Patterns and Accessibility Constraints in the Continuous-Flow Three-Phase Hydrogenation of Acetylenic Compounds (page 5849)

      Gianvito Vilé, Dr. Neyvis Almora-Barrios, Dr. Sharon Mitchell, Prof. Núria López and Prof. Javier Pérez-Ramírez

      Version of Record online: 15 APR 2014 | DOI: 10.1002/chem.201400431

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      “Our inspiration was the increasing complexity in the design of alkyne hydrogenation catalysts…” Read more about the story behind the cover in the Cover Profile and about the research itself on page 5926 ff. (DOI: 10.1002/chem.201304795).

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
  4. News

    1. Top of page
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    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
  5. Concept

    1. Top of page
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    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Nucleic Acids

      Nucleic Acid Based Logical Systems (pages 5866–5873)

      Dr. Da Han, Dr. Huaizhi Kang, Dr. Tao Zhang, Cuichen Wu, Dr. Cuisong Zhou, Dr. Mingxu You, Prof. Dr. Zhuo Chen, Prof. Dr. Xiaobing Zhang and Prof. Dr. Weihong Tan

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201304891

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      It′s logical captain! Nucleic acid (NA) has become a fascinating construction material for various logical devices (see figure) with more and more widespread applications in biology, biotechnology, and biomedicine. This article highlights the most recent and important developments in NA-based logical devices and their evolution from in vitro through cellular and even towards in vivo biological applications.

  6. Communications

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    8. Full Papers
    1. Nanorods

      A Single-Step Reaction for Silicon and Germanium Nanorods (pages 5874–5879)

      Xiaotang Lu and Prof. Brian A. Korgel

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/chem.201402230

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      One small step for nanorods: A single-step reaction for crystalline Si and Ge nanorods has been developed. Nanorods grow by solution–liquid–solid (SLS) growth from Sn seeds formed in situ from a Sn reactant (see figure; DPG=diphenyl germane, PVP-HDE=poly(vinylpyrrolidinone)hexadecane). The nanorod dimensions are controlled by varying reactant concentrations.

    2. Acenes

      Combining Electronic and Steric Effects for Highly Stable Unsymmetric Pentacenes (pages 5880–5884)

      Jingjing Zhang, Robert H. Pawle, Prof. Terry E. Haas and Prof. Samuel W. Thomas III

      Version of Record online: 13 MAR 2014 | DOI: 10.1002/chem.201402003

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      High fives! Highly stable pentacene derivatives are described, which combine an electronically deactivating alkyne substituent with a sterically-encumbering dialkylaryl substituent on the reactive 6- and 13-positions (see scheme). Resistance to photooxidation of these unsymmetrically substituted pentacenes is comparable to diethynylpentacenes, opening new chemical space for the discovery of stable organic semiconductors.

    3. Heterogeneous Catalysis

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      Efficient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides Using Palladium Nanoparticles Dispersed on Siliceous Mesocellular Foam (pages 5885–5889)

      Fredrik Tinnis, Oscar Verho, Karl P. J. Gustafson, Dr. Cheuk-Wai Tai, Prof. Dr. Jan-E. Bäckvall and Prof. Dr. Hans Adolfsson

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201402029

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      It's catchy! An efficient palladium-catalyzed protocol for the aminocarbonylation of aryl iodides is reported in which the palladium immobilized on the amino-functionalized mesocellular foam (MCF) was found to operate through a “release and catch” mechanism (see scheme). A very low content of palladium was found in solution upon completion of the reaction and a variety of different aryl iodides were converted to the corresponding amides under mild conditions.

    4. C[BOND]H Activation

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      Aerobic Double Dehydrogenative Cross Coupling between Cyclic Saturated Ketones and Simple Arenes (pages 5890–5894)

      Dr. Nicolas Gigant and Prof. Dr. Jan-E. Bäckvall

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/chem.201402063

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      A simple and sustainable one-pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β-position of cyclic ketones has been developed (see scheme). Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron-transfer mediators (ETMs) under ambient oxygen pressure.

    5. Cyclopropanation

      Hypoiodite-Mediated Cyclopropanation of Alkenes (pages 5895–5898)

      Dr. Akira Yoshimura, Steven R. Koski, Brent J. Kastern, Jonathan M. Fuchs, Prof. Dr. T. Nicholas Jones, Dr. Roza Y. Yusubova, Prof. Dr. Victor N. Nemykin and Prof. Dr. Viktor V. Zhdankin

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201402372

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      An efficient, transition-metal-free procedure for the cyclopropanation of alkenes using malononitrile and the LiI/tBuOCl combination under mild reaction conditions is described. The reaction mechanism most likely involves tBuOI generated in situ from LiI and tBuOCl. The utility of this new methodology has been demonstrated by the synthesis of a potential HIV-1 RT inhibitor (see scheme).

    6. Organocatalysis

      One-Pot Organocatalytic Enantioselective Michael/Povarov Domino Strategy for the Construction of Spirooctahydroacridine-3,3′-oxindole Scaffolds (pages 5899–5904)

      Hao Wu and Prof. Yong-Mei Wang

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/chem.201402002

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      Domino construction: An efficient organocatalytic one-pot domino Michael/intramolecular Povarov reaction has been developed to provide enantiomerically enriched spirooctahydroacridine-3,3′-oxindole derivatives containing five stereogenic centers in good to high yields with excellent diastereo- and enantioselectivities (see scheme). This strategy not only adds to the limited repertory of examples of asymmetric synthesis of chiral spirocyclohexaneoxindoles and octahydroacridines, but also demonstrates a one-pot consecutive synthesis with an ecological and economical protocol.

    7. Organic Synthesis

      Isocyanide-Based Multicomponent Reactions: Concise Synthesis of Spirocyclic Oxindoles with Molecular Complexity by Using a [1,5]-Hydrogen Shift as the Key Step (pages 5905–5909)

      Shikuan Su, Chunju Li, Prof. Dr. Xueshun Jia and Prof. Dr. Jian Li

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201402576

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      Shift your perspective! An unprecedented cascade reaction, under mild conditions, involving a double Michael addition, double cyclization, and double [1,5]-hydrogen shift, followed by group migration is disclosed. This reaction offers a fast and straightforward approach to unusual polycyclic spirooxindoles (see scheme).

    8. Zinc-Catalyzed [4+3] Cycloaddition with Concomitant Furan Annulation: Formation of Cyclohepta[b]Furans (pages 5910–5913)

      Bo Song, Lian-Hua Li, Xian-Rong Song, Yi-Feng Qiu, Mei-Jin Zhong, Ping-Xin Zhou and Prof. Dr. Yong-Min Liang

      Version of Record online: 11 APR 2014 | DOI: 10.1002/chem.201402513

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      Go tandem! A first zinc-catalyzed tandem [4+3] cycloaddition is presented herein. Various substituted cyclohepta[b]furans were synthesized from carbonyl ene–yne and diene in moderate to good yield. Furan rings and seven-membered rings were prepared in one single step (see scheme; TBS=tert-butyldimethyl).

  7. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Hydrogen Bonds

      Redox-Controlled Hydrogen Bonding: Turning a Superbase into a Strong Hydrogen-Bond Donor (pages 5914–5925)

      Ute Wild, Dr. Christiane Neuhäuser, Sven Wiesner, Dr. Elisabeth Kaifer, Prof. Dr. Hubert Wadepohl and Prof. Dr. Hans-Jörg Himmel

      Version of Record online: 22 APR 2014 | DOI: 10.1002/chem.201304882

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      Hydrogen-bond sandwich, anyone? After oxidation of guanidinyl-functionalized aromatic compounds, the superbase is turned into a strong hydrogen-bond donor and forms hydrogen-bonded aggregates, which could be described as frozen stages on the way to hydrogen transfer (see figure).

    2. Heterogeneous Catalysis

      From the Lindlar Catalyst to Supported Ligand-Modified Palladium Nanoparticles: Selectivity Patterns and Accessibility Constraints in the Continuous-Flow Three-Phase Hydrogenation of Acetylenic Compounds (pages 5926–5937)

      Gianvito Vilé, Dr. Neyvis Almora-Barrios, Dr. Sharon Mitchell, Prof. Núria López and Prof. Javier Pérez-Ramírez

      Version of Record online: 17 APR 2014 | DOI: 10.1002/chem.201304795

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      Hybrid nanocatalysts: The classical Lindlar and the newly developed NanoSelectTM catalysts are confronted in the semi-hydrogenation of alkynes (see figure). Systematic testing under continuous-flow three-phase conditions, coupled with detailed characterization analyses and molecular simulations, enable the understanding of the structure of the catalysts and the associated activity and selectivity patterns for a wide range of acetylenic compounds.

    3. Organic Semiconductors

      Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field-Effect Transistors (pages 5938–5945)

      Crystalann Jones, Dr. Damien Boudinet, Dr. Yu Xia, Mitch Denti, Adita Das, Dr. Antonio Facchetti and Prof. Dr. Tom G. Driver

      Version of Record online: 23 APR 2014 | DOI: 10.1002/chem.201304914

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      Highly soluble bispyrrolothiophenes have been synthesized from vinyl azides by using transition-metal-catalyzed C[BOND]H bond functionalization (see scheme; TFT=thin-film transistor). The solution-state properties and field-effect-transistor (FET) electrical behavior of these compounds were investigated.

    4. Polyoxometalates

      Synthesis of α-Dawson-Type Silicotungstate [α-Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds (pages 5946–5952)

      Takuo Minato, Dr. Kosuke Suzuki, Dr. Keigo Kamata and Prof. Dr. Noritaka Mizuno

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201400390

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      Give and take: An inorganic anionic cage, TBA8[α-Si2W18O62] (TBA=tetra- n-butylammonium), was successfully synthesized by using the precursor TBA4H6[α-SiW9O34] under mild conditions and in an organic solvent in which it was soluble. The aperture of TBA8[α-Si2W18O62] was able to be protonated and deprotonated by means of intramolecular hydrogen bonds (see figure).

    5. Donor–Acceptor Systems

      Carborane Dyads for Photoinduced Electron Transfer: Photophysical Studies on Carbazole and Phenyl-o-carborane Molecular Assemblies (pages 5953–5960)

      Soonnam Kwon, Kyung-Ryang Wee, Yang-Jin Cho and Prof. Sang Ook Kang

      Version of Record online: 7 MAY 2014 | DOI: 10.1002/chem.201304474

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      Nothing acts in isolation: o-Carborane-based donor–acceptor dyads (see figure; HSOMO=highest singly occupied molecular orbital) have been prepared. The absorption and electrochemical properties of the dyads are essentially the sum of those of the carbazole and o-carboranyl phenyl units; this indicates negligible interactions between the carbazole and o-carborane units in the ground state.

    6. Fullerenes

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      Hierarchically Ordered Self-Assembly of Amphiphilic Bifullerenes (pages 5961–5966)

      Lennard Wasserthal, Dr. Boris Schade, Dr. Kai Ludwig, Dr. Christoph Böttcher and Prof. Andreas Hirsch

      Version of Record online: 7 MAY 2014 | DOI: 10.1002/chem.201400153

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      Nanoscopic dumbbell exercises: Studying the assembly behaviour of novel synthesised amphiphilic bifullerene derivatives in aqueous solution by cryogenic transmission electron microscopy reveals an unprecedented hierarchical self-assembly towards spherical and rod-like aggregates (see graphic).

    7. Dehydrogenation

      Hydrogen Release from Dialkylamine–Boranes Promoted by Mg and Ca Complexes: A DFT Analysis of the Reaction Mechanism (pages 5967–5976)

      Dr. Valeria Butera, Prof. Nino Russo  and Prof. Dr. Emilia Sicilia

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201304329

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      Dehydrocoupling of amine–boranes assisted by Mg- and Ca-based complexes was studied by DFT calculations to assess the viability of the pathways of the mechanistic scheme proposed on the basis of experimental evidence and to determine whether different ionic radii and charge densities are responsible for the observed differences in reactivity of Mg and Ca complexes (see scheme). The influence of the steric demand of amine–boranes on the course of the reaction was examined by performing calculations on the dehydrogenation of dimethylamine–borane, pyrrolidine–borane, and diisopropylamine–borane.

    8. Materials Design

      Quaternary Sulfide Ba6Zn6ZrS14: Synthesis, Crystal Structure, Band Structure, and Multiband Physical Properties (pages 5977–5982)

      Xian Zhang, Jianqiao He, Wei Chen, Ketian Zhang, Prof. Chong Zheng, Prof. Dr. Junliang Sun, Fuhui Liao, Prof. Dr. Jianhua Lin and Prof. Dr. Fuqiang Huang 

      Version of Record online: 3 APR 2014 | DOI: 10.1002/chem.201304525

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      Bandgap engineering: ZnS- and ZrS-based building blocks were combined to construct multicomponent material Ba6Zn6ZrS14, which features two types of one-dimensional chains parallel to the c axis and shows a much more complex absorption character than simple ZnS and ZrS2 materials, with three optical absorption edges around 1.78, 2.50, and 2.65 eV (see figure).

    9. Enantioselectivity

      Mukaiyama–Michael Reactions with trans-2,5-Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions, Not from Steric Hindrance (pages 5983–5993)

      Dr. Eeva K. Kemppainen, Dr. Gokarneswar Sahoo, Antti Piisola, Andrea Hamza, Bianka Kótai, Dr. Imre Pápai and Prof. Petri M. Pihko

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201304240

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      Embraced enantioselectivity: Mukaiyama–Michael reactions catalyzed by trans-2,5-diphenylpyrrolidine catalyst are highly enantioselective, but why? The answer appears to lie in the attractive, not repulsive, noncovalent interactions in the transition states leading to the major product(s) (see scheme; TIPS=triisopropylsilyl).

    10. Organocatalysis

      Constrained-Geometry Bisphosphazides Derived from 1,8-Diazidonaphthalene: Synthesis, Spectroscopic Characteristics, Structural Features, and Theoretical Investigations (pages 5994–6009)

      Julius F. Kögel, Nuri C. Abacılar, Felicia Weber, Dr. Benjamin Oelkers, Dr. Klaus Harms, Dr. Borislav Kovačević and Prof. Dr. Jörg Sundermeyer

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201304498

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      New bisphosphazides with a rigid naphthalene scaffold show different binding sites for proton and Lewis acids, opening up interesting perspectives in coordination chemistry and organocatalysis (see figure).

    11. Solar Cells

      Performance Enhancement of Bulk Heterojunction Solar Cells with Direct Growth of CdS-Cluster-Decorated Graphene Nanosheets (pages 6010–6018)

      Kai Yuan, Prof. Dr. Lie Chen, Dr. Licheng Tan and Prof. Dr. Yiwang Chen

      Version of Record online: 7 APR 2014 | DOI: 10.1002/chem.201400119

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      Two-dimensional exciton dissociation centers were fabricated in situ. By incorporating these centers into active layers (see figure, ITO=indium tin oxide, GO=graphene oxide), exciton dissociation and separation was dramatically improved with remarkably enhanced collecting and transporting efficiency of photoinduced electrons and holes, and thus elevated device performance.

    12. Protein Engineering

      Site-Specific Protection and Dual Labeling of Human Epidermal Growth Factor (hEGF) for Targeting, Imaging, and Cargo Delivery (pages 6019–6026)

      Dr. Michael H. Sonntag, Jenny Ibach, Dr. Lidia Nieto, Dr. Peter J. Verveer and Prof. Dr. Luc Brunsveld

      Version of Record online: 3 APR 2014 | DOI: 10.1002/chem.201304090

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      A protein expression and dual labeling approach provides access to the human epidermal growth factor (hEGF) with one or two thiol-based ligation sites, thus enabling sequential orthogonal dual hEGF labeling for targeting, imaging, and cargo delivery (see picture). The dual-coupling strategy involving two independent probes for hEGF with full control over location and stoichiometry by using standard thiol chemistry enables the site-specific cargo targeting of epidermal-growth-factor receptor (EGFR)-overexpressing cancer cells with these well-defined hEGF constructs.

    13. Self-Assembly

      Synthesis of Mesoporous TiO2/SiO2 Hybrid Films as an Efficient Photocatalyst by Polymeric Micelle Assembly (pages 6027–6032)

      Yunqi Li, Dr. Bishnu Prasad Bastakoti, Dr. Masataka Imura, Dr. Soo Min Hwang, Dr. Ziqi Sun, Prof. Jung Ho Kim, Prof. Shi Xue Dou and Prof. Yusuke Yamauchi

      Version of Record online: 7 APR 2014 | DOI: 10.1002/chem.201304689

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      Photoactive hybrids: Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles (see figure).

    14. Transition-Metal Complexes

      C[BOND]H Bond Activation during and after the Reactions of a Metallacyclic Amide with Silanes: Formation of a μ-Alkylidene Hydride Complex, Its H–D Exchange, and β-H Abstraction by a Hydride Ligand (pages 6033–6039)

      Li Wang, Seth C. Hunter, Zhimin Song, Dr. Carlos A. Steren, Tianniu Chen, Prof. Dr. Zhenhong Wei, Prof. Dr. Hu Cai  and Prof. Dr. Zi-Ling Xue

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201303166

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      A tantalum metallacyclic complex undergoes intramolecular C[BOND]H activation upon reaction with H3SiPh to give a Ta/μ-alkylidene/hydride complex, which then undergoes β-H abstraction to form a complex with a bridging tantalaaziridine ligand (see scheme).

    15. Sensors

      CuO–ZnO Micro/Nanoporous Array-Film-Based Chemosensors: New Sensing Properties to H2S (pages 6040–6046)

      Zongke Xu, Dr. Guotao Duan , Prof. Yue Li, Dr. Guangqiang Liu, Dr. Hongwen Zhang, Zhengfei Dai and Prof. Weiping Cai

      Version of Record online: 7 APR 2014 | DOI: 10.1002/chem.201304722

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      Extra-sensitive films: The CuO–ZnO micro/nanoporous array-film-based chemosensor is fabricated by using a solution-dipping colloidal template. The obtained CuO–ZnO films exhibit a more homogeneous structure, higher H2S sensitivity, shorter recovery time, and better selectivity than those of the pure ZnO thin film (see figure).

    16. Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris (pages 6047–6053)

      Sandeep Nadella, Jashobanta Sahoo, Dr. Palani S. Subramanian, Abhishek Sahu, Dr. Sandhya Mishra and Prof. Dr. Markus Albrecht

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201304664

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      Lanthanide phosphate sensor: Luminescent complexes [EuL2] and [TbL2] (L2=2,2′-(((1,10-phenanthroline-2,9-diyl)bis(methylene))bis(azanediyl))bis(3-methylbutanamide) are selective sensors for phosphates, that is, adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP), and can be applied in the luminescent staining agents of cells (see figure). The complexes are found to penetrate into the cell wall upon which they are quenched by phosphates.

    17. Photodynamic Therapy

      Silylation Improves the Photodynamic Activity of Tetraphenylporphyrin Derivatives In Vitro and In Vivo (pages 6054–6060)

      Prof. Hiroaki Horiuchi, Prof. Masahiro Hosaka, Hiroyuki Mashio, Motoki Terata, Prof. Shintaro Ishida, Prof. Soichiro Kyushin, Prof. Tetsuo Okutsu, Prof. Toshiyuki Takeuchi and Prof. Hiroshi Hiratsuka

      Version of Record online: 7 APR 2014 | DOI: 10.1002/chem.201303120

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      Improved photosensitizers: Silylation improves the quantum yield of singlet oxygen sensitization, cellular uptake efficiency, and selective accumulation efficiency in tumors. As a result of these improvements, silylation significantly enhances photodynamic activity (see figure). The results of this work suggest that silylation is a promising strategy for improving photosensitizers for photodynamic therapy.

    18. Cluster Compounds

      Hydroxo-Bridged Dimers of Oxo-Centered Ruthenium(III) Triangle: Synthesis and Spectroscopic and Theoretical Investigations (pages 6061–6070)

      Apoorva Upadhyay, Jitendrasingh Rajpurohit, Mukesh Kumar Singh, Richa Dubey, Anant Kumar Srivastava, Prof. Dr. Ashutosh Kumar, Prof. Dr. Gopalan Rajaraman and Prof. Dr. Maheswaran Shanmugam

      Version of Record online: 3 APR 2014 | DOI: 10.1002/chem.201304826

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      Ruthenium exchanges better: A one-pot synthetic method has been developed to isolate a trivalent hexameric RuIII cluster, which registers with one of the largest J values (−800.6 cm−1) known to date with a singlet ground state (see figure). The study reveals the importance of having a 4d ion to have a strong exchange interaction even at room temperature. Theoretical calculations shed light on the origin of these strong exchange interactions, which are further supported by detailed NMR studies.

    19. Natural Products

      Access to the Aeruginosin Serine Protease Inhibitors through the Nucleophilic Opening of an Oxabicyclo[2.2.1]heptane: Total Synthesis of Microcin SF608 (pages 6071–6080)

      Stefan Diethelm, Corinna S. Schindler and Prof. Dr. Erick M. Carreira

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201400046

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      Expect the unexpected! An entry route to the aeruginosin protease inhibitors is reported and showcased on the total synthesis of microcin SF608 (see scheme). Detailed experimental studies of an unusual regioselective epoxide reduction observed during this synthesis suggests a mechanistic rationale for this transformation involving intramolecular hydrogen atom delivery by a carbamate NH to direct the regioselectivity of the homolytic epoxide cleavage.

    20. Host–Guest Systems

      Systematic Dissection of an Aminopyrrolic Cage Receptor for β-Glucopyranosides Reveals the Essentials for Effective Recognition (pages 6081–6091)

      Dr. Oscar Francesconi, Matteo Gentili, Prof. Cristina Nativi, Dr. Ana Ardá, Prof. F. Javier Cañada, Prof. Jesús Jiménez-Barbero and Dr. Stefano Roelens

      Version of Record online: 3 APR 2014 | DOI: 10.1002/chem.201400365

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      Comfort is paramount! A set of structures designed for the recognition of glucosides has been obtained by systematically destructuring a tripodal aminopyrrolic cage receptor. A β-glucoside is more effectively recognized by an adaptive cleft than by a preorganized cage, if a more comfortable fit can be achieved (see picture).

    21. Quintuple Bonds

      Experimental and Theoretical Studies on Arene-Bridged Metal–Metal-Bonded Dimolybdenum Complexes (pages 6092–6102)

      Dr. Mario Carrasco, Natalia Curado, Dr. Eleuterio Álvarez, Dr. Celia Maya, Dr. Riccardo Peloso, Prof. Dr. Manuel L. Poveda, Dr. Amor Rodríguez, Prof. Dr. Eliseo Ruiz, Prof. Dr. Santiago Álvarez and Prof. Dr. Ernesto Carmona

      Version of Record online: 11 APR 2014 | DOI: 10.1002/chem.201400236

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      Quintuply bound [Mo2{HC(N-2,6-iPr2C6H3)2}2(arene)] complexes (arene=C6H6, C6H5Me, C6H5OMe, p-C6H4Me2, C6H5F, and p-C6H4F2 and Dipp=2,6-iPr2C6H3) have been prepared and structurally characterized by experimental and theoretical methods (see figure). Coordination of the arene to the quintuple MoI–MoI bond results in an effective metal–metal bond order substantially lower than five as a consequence of a strong electronic interaction between δ and δ* dimetal orbitals and the π and π* orbitals of the arene.

    22. Memory Switches

      Redox Non-Innocence of Coordinated 2-(Arylazo) Pyridines in Iridium Complexes: Characterization of Redox Series and an Insight into Voltage-Induced Current Characteristics (pages 6103–6111)

      Sreetosh Goswami, Debabrata Sengupta, Dr. Nanda D. Paul, Dr. Tapan K. Mondal and Prof. Dr. Sreebrata Goswami

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201304369

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      A systematic exploration of transition-metal complexes in the arena of redox-induced switches has been carried out. A number of similar systems with significant I-V characteristics have been analyzed to reveal the mystery of redox dynamics in action at the backbone of such current responses (see figure).

    23. Alkaloid Synthesis

      Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine-type Amaryllidaceae Alkaloids (+)-α-Lycorane and (+)-Lycorine (pages 6112–6119)

      Zhongwen Sun, Mingtao Zhou, Xiang Li, Xueling Meng, Fangzhi Peng, Prof. Hongbin Zhang and Prof. Zhihui Shao

      Version of Record online: 3 APR 2014 | DOI: 10.1002/chem.201400178

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      Octahydroindolone motifs are constructed diastereo- and enantioselectively through a catalytic enantioselective 1,4-conjugate addition of nitro dienynes, followed by a TsOH-catalyzed cascade reaction. This methodology has been applied in the divergent enantioselective synthesis of perhydroindole alkaloids, as exemplified by lycorine-type Amaryllidaceae alkaloids (+)-α-lycorane and (+)-lycorine (see scheme; Ts=p-toluenesulfonyl), from a common intermediate by using a highly concise synthetic route.

    24. Photocatalysis

      Visible-Light-Mediated Addition of α-Aminoalkyl Radicals to [60]Fullerene by Using Photoredox Catalysts (pages 6120–6125)

      Dr. Yoshihiro Miyake, Yuya Ashida, Dr. Kazunari Nakajima and Prof. Dr. Yoshiaki Nishibayashi

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201304731

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      Let there be light: The functionalization of [60]fullerene by using α-aminoalkyl radicals generated by visible-light-mediated single-electron oxidation of α-silylamines as synthetic intermediates (see picture) has been realized. In these reactions, the introduction of diarylamino groups, which are useful electron donors, was easily achieved.

    25. Electrochemistry

      Facile Synthesis of Porous Mn2O3 Nanoplates and Their Electrochemical Behavior as Anode Materials for Lithium Ion Batteries (pages 6126–6130)

      Dr. Yanjun Zhang, Dr. Yang Yan, Dr. Xueyun Wang, Dr. Gen Li, Dr. Dingrong Deng, Dr. Li Jiang, Prof. Chunying Shu and Prof. Chunru Wang

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201304935

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      Go nano! Porous Mn2O3 nanoplates were prepared by a facile polyol solution method combined with a simple post-annealing process. These porous nanoplates exhibited improved electrochemical performance with excellent cycling stability and good rate capability when used as anode materials for lithium ion batteries (see figure).

    26. Ring-Opening Polymerisation

      Chiral (1,2)-Diphenylethylene-Salen Complexes of Triel Metals: Coordination Patterns and Mechanistic Considerations in the Isoselective ROP of Lactide (pages 6131–6147)

      Nicolas Maudoux, Dr. Thierry Roisnel, Dr. Vincent Dorcet, Prof. Dr. Jean-François Carpentier and Dr. Yann Sarazin

      Version of Record online: 7 APR 2014 | DOI: 10.1002/chem.201304788

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      Class act: A new range of monometallic chiral salen–aluminium complexes based on a less-classical chiral backbone has been developed. These constitute efficient precatalysts for the isoselective ring-opening polymerisation of racemic lactide. According to chain-end control, they afford poly(lactide) (PLA) featuring high isotacticity (Pm≈0.80–0.90) in the upper range reported to date (see figure).

    27. Perfluorinated Compounds

      Perfluorobutyric Acid and Its Monohydrate: A Chirped Pulse and Cavity Based Fourier Transform Microwave Spectroscopic Study (pages 6148–6153)

      Javix Thomas, Agapito Serrato III, Prof. Dr. Wei Lin, Prof. Dr. Wolfgang Jäger and Prof. Dr. Yunjie Xu

      Version of Record online: 22 APR 2014 | DOI: 10.1002/chem.201304321

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      Hydration of acid: Conformational preferences of perfluorobutyric acid and its monohydrate are established with rotational spectroscopy and ab initio calculations. The monohydrate takes on an insertion H-bonding topology, shows a unique orientation for the nonbonded [BOND]OH group, and behaves as a semirigid rotor (see figure), in contrast to the hydrates of di- and trifluoroacetic acid, for which large amplitude and tunnelling motions are present.

    28. Heterogeneous Catalysis

      Cobalt Phthalocyanine Immobilized on Graphene Oxide: An Efficient Visible-Active Catalyst for the Photoreduction of Carbon Dioxide (pages 6154–6161)

      Pawan Kumar, Arvind Kumar, Dr. Bojja Sreedhar, Dr. Bir Sain, Dr. Siddharth S. Ray and Dr. Suman L. Jain

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201304189

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      Very photoactive! Cobalt phthalocyanine grafted to the chemically functionalized graphene oxide was found to be an efficient heterogeneous visible-light-induced photoredox catalyst for the photoreduction of carbon dioxide to methanol in a very good yield. The developed photocatalyst exhibited superior activity compared with the existing photocatalytic systems and gave methanol as the major reaction product (see scheme).

    29. Intramolecular Hydroamination

      Expanded-Ring N-Heterocyclic Carbenes Efficiently Stabilize Gold(I) Cations, Leading to High Activity in π-Acid-Catalyzed Cyclizations (pages 6162–6170)

      Oleg S. Morozov, Andrey V. Lunchev, Alexander A. Bush, Aleksandr A. Tukov, Andrey F. Asachenko, Victor N. Khrustalev, Sergey S. Zalesskiy, Valentine P. Ananikov and Mikhail S. Nechaev

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201303760

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      What a difference a ring makes: Expanded-ring N-heterocyclic carbenes (er-NHC) surpass their five-membered ring counterparts, as well as Ph3P and Me2S, in the stabilization of cationic gold(I) species due to increased steric protection and electron-donating properties. A monoligand cationic [(THD-Dipp)Au]BF4 (Dipp=2,6-diisopropylphenyl) complex bearing a seven-membered ring carbene and bulky Dipp substituents exhibits unprecedentedly high catalytic activity in indole and benzofuran synthesis (see scheme).

    30. Hydrogen Production

      Photo- and Electrocatalytic H2 Production by New First-Row Transition-Metal Complexes Based on an Aminopyridine Pentadentate Ligand (pages 6171–6183)

      Arnau Call, Zoel Codolà, Ferran Acuña-Parés and Dr. Julio Lloret-Fillol

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201303317

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      Cobalt is king! The Fe, Co, and Ni complexes based on the same ligand have shown excellent electrocatalytic H2 activity (see figure). While only the Co complex has excellent H2 photoproduction catalytic activity, when using [Ir(ppy)2(bpy)]PF6 (PSIr) as photosensitiser and Et3N as electron donor. Analytic and kinetic studies show that the catalytic activity is molecular. The lack of photochemical activity of the Fe and Ni complexes is ascribed to their redox chemistry and the pKa, respectively.

    31. Functionalized Nanoparticles

      Inhibition of Amyloid Fibril Growth and Dissolution of Amyloid Fibrils by Curcumin–Gold Nanoparticles (pages 6184–6191)

      Sharbari Palmal, Amit Ranjan Maity, Brijesh Kumar Singh, Sreetama Basu, Prof. Nihar R. Jana and Dr. Nikhil R. Jana

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201400079

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      Nanoparticles in amyloid therapy: Curcumin-functionalized water-soluble gold nanoparticles have been found to efficiently inhibit amyloid fibril growth and to disintegrate preformed amyloid fibrils (see figure). Consequently, they serve to reduce amyloid-induced neurotoxicity.

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