Chemistry - A European Journal

Cover image for Vol. 19 Issue 3

January 14, 2013

Volume 19, Issue 3

Pages 797–1133

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid-State NMR Spectroscopies and DFT Calculations (Chem. Eur. J. 3/2013) (page 797)

      Saad Sene, Marc Reinholdt, Dr. Guillaume Renaudin, Dr. Dorothée Berthomieu, Prof. Claudio M. Zicovich-Wilson, Prof. Christel Gervais, Dr. Philippe Gaveau, Prof. Christian Bonhomme, Dr. Yaroslav Filinchuk, Prof. Mark E. Smith, Prof. Jean-Marie Nedelec, Dr. Sylvie Bégu, Dr. P. Hubert Mutin and Dr. Danielle Laurencin

      Version of Record online: 7 JAN 2013 | DOI: 10.1002/chem.201390004

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      In contrast to boronic acids, RB(OH)2, which have been extensively studied for applications in catalysis and materials chemistry, boronate anions, RB(OH)3, have drawn much less attention. Their coordination chemistry in the context of alkaline earth metals has only recently been reported. D. Laurencin et al. present an in depth study of a new crystalline phase, calcium butylboronate, in their Full Paper on page 880 ff. A methodology combining high-resolution solid-state NMR spectroscopy, IR spectroscopy, and DFT calculations was developed for the analysis of the local structure around boronates in the solid state.

  2. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Metal–Organic Frameworks

      Mixed Linker Strategies for Organic Framework Functionalization (pages 818–827)

      David N. Bunck and Prof. Dr. William R. Dichtel

      Version of Record online: 27 DEC 2012 | DOI: 10.1002/chem.201203145

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      Providing a framework: Framework materials have attracted intense interest for gas storage, separations, catalysis, and other applications as a consequence of their periodicity, high specific surface area, and rational synthesis. Cocrystallizing multiple monomers with identical linking chemistry represents an emerging route to functionalized materials. This Concept Article highlights three strategies for framework functionalization that employ comonomers with identical, expanded, or reduced linking geometries.

  5. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Organoindium Reagents

      Preparation of Functionalized Organoindium Reagents by Means of Magnesium Insertion into Organic Halides in the Presence of InCl3 at Room Temperature (pages 828–833)

      Dr. Sebastian Bernhardt, Zhi-Liang Shen and Prof. Dr. Paul Knochel

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203795

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      Magnesium, indium, palladium: An efficient one-pot procedure for the direct preparation of triorganoindium reagents from organic halides by means of magnesium insertion in the presence of InCl3 and LiCl is reported (see scheme). The organoindium reagents are obtained in good yields from functionalized aryl, heteroaryl, and alkyl bromides and benzyl chlorides at 25 °C in THF within 4 h. Moreover, the resulting organoindium reagents could be efficiently used as reagents in Pd-catalyzed cross-coupling reactions with a wide functional group tolerance.

    2. Biocatalalysis

      Rapid Preparation of Mycobacterium N-Glycolyl Lipid I and Lipid II Derivatives: A Biocatalytic Approach (pages 834–838)

      Kuo-Ting Chen, Ye-Ching Kuan, Wei-Chen Fu, Prof. Pi-Hui Liang, Dr. Ting-Jen R. Cheng, Prof. Chi-Huey Wong and Prof. Wei-Chieh Cheng

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/chem.201203251

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      Breaking down barriers: A rapid, inexpensive preparation of the structurally complex mycobacterial N-glycolyl Lipid I, Lipid II, and their analogues from a range of different synthetic N-glycolyl and N-glycinyl Park's nucleotides is described (see scheme). The biotransformations were catalyzed by a readily available biocatalyst obtained from a bacterial cell-free membrane fraction. The unnatural N-glycinyl Lipid II was found to be a substrate of Mycobacterium tuberculosis (Mtb) transglycosylase, PonA, and N-glycolyl Lipid I was a weak inhibitor against PonA.

    3. Spin Crossover

      High Intrinsic Barriers against Spin-State Relaxation in Iron(II)-Complex Solutions (pages 839–842)

      Dr. Philipp Stock, Dr. Tomasz Pędziński, Nicole Spintig, Prof. Dr. Andreas Grohmann and Dr. Gerald Hörner

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/chem.201203784

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      Slow relaxation: Exergonic high-spin[RIGHTWARDS ARROW]low-spin relaxation after photoexcitation has been found to be exceedingly slow in a class of iron(II) complexes with hexadentate imine ligands. The thermal activation barriers that arise between the quintet- and singlet-spin manifolds are the highest ever recorded for spin crossover of isolated molecules in free solution (see figure).

    4. Palladium Catalysis

      Pd-PEPPSI-IPentCl: An Effective Catalyst for the Preparation of Triarylamines (pages 843–845)

      Ka Hou Hoi, Jennifer A. Coggan and Prof. Michael G. Organ

      Version of Record online: 18 DEC 2012 | DOI: 10.1002/chem.201203379

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      Third times a charm: A new Pd–NHC catalyst, Pd-PEPPSI-IPentCl, has been developed for applications in amination reactions for the preparation of triarylamines. The catalyst can be used under mild conditions (carbonate base/dioxane, 80 °C) to perform multiple aminations in sequence from simple aniline derivatives that contain highly base-sensitive functional groups.

    5. Glycosylation

      Highly Stereoselective Glycosyl-Chloride-Mediated Synthesis of 2-Deoxyglucosides (pages 846–851)

      Dr. Ved Prakash Verma and Dr. Cheng-Chung Wang

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/chem.201203418

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      Cl intermediates: The glycosylation of per-O-benzylated 2-deoxy- and 2,6-dideoxythioglycosides, promoted by the combination of para-toluenesulfenyl chloride (p-TolSCl) and silver triflate (AgOTf), furnished the products in high yields and high stereoselectivity. The glycosyl chloride was the intermediate (see scheme).

    6. Functionalized Nanotubes

      Radical Addition of Xanthates on Carbon Nanotubes as an Efficient Covalent Functionalization Method (pages 852–856)

      Béatrice Vanhorenbeke, Charles Vriamont, Florence Pennetreau, Prof. Michel Devillers, Prof. Olivier Riant and Prof. Sophie Hermans

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/chem.201203207

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      Radical-initiated support: Xanthates were used as chemical reagents for the sidewall covalent functionalization of carbon nanotubes (see figure). The best grafting yields were obtained with stoichiometric ratios of xanthate and the radical initiator lauroyl peroxide. One grafted function was used as a tether for bimetallic cluster compounds, which were converted into very small (1–2 nm) supported nanoparticles upon heating.

    7. Cyclization

      Solvent-Free, Metal-Free, Aza-Prins Cyclization: Unprecedented Access to δ-Sultams (pages 857–860)

      Damien Clarisse, Dr. Béatrice Pelotier and Dr. Fabienne Fache

      Version of Record online: 18 DEC 2012 | DOI: 10.1002/chem.201203415

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      Aza-Prins and the pauper: Aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes was successfully performed under solvent-free and metal-free conditions. When applied to β,γ-unsaturated sulfonamides, the corresponding δ-sultams were isolated in good yields (see scheme). This approach constitutes a new route to cyclic sulfonamides.

    8. C[BOND]H Activation

      Ruthenium-Catalyzed Intermolecular Hydroacylation of Internal Alkynes: The Use of Ceria-Supported Catalyst Facilitates the Catalyst Recycling (pages 861–864)

      Dr. Hiroki Miura, Dr. Kenji Wada, Dr. Saburo Hosokawa and Prof. Dr. Masashi Inoue

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/chem.201203530

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      Versatile and practical: Intermolecular hydroacylation of internal alkynes takes place in the presence of Ru catalysts together with HCO2Na and Xantphos to give the corresponding conjugated enones. Aromatic aldehydes with or without coordinating groups could be used in the present catalytic system. The solid Ru/CeO2 catalysts can be recycled for several times without significant decreases in yield (see scheme).

    9. Domino Reactions

      Rhodium-Catalyzed Enantioselective Addition to Unsymmetrical α-Diketones: Tandem One-Pot Synthesis of Optically Active 3-Tetrasubstituted Isochroman Derivatives (pages 865–869)

      Ting-Shun Zhu, Jian-Ping Chen and Prof. Dr. Ming-Hua Xu

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/chem.201203701

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      The domino effect: An efficient and general catalytic one-pot synthesis of quaternary-substituted isochroman derivatives has been developed (see scheme). The cascade transformation relies on rhodium-catalyzed highly regio- and enantioselective 1,2-addition of arylboronic acids to unsymmetrical α-diketones and intramolecular etherification or esterification, and provides a variety of enantioenriched isochromanones under exceptionally mild conditions.

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Structure Elucidation

      Structure of the O-Glycosylated Conopeptide CcTx from Conus consors Venom (pages 870–879)

      Dr. Henry G. Hocking, Dr. Gerrit J. Gerwig, Dr. Sébastien Dutertre, Dr. Aude Violette, Dr. Philipe Favreau, Dr. Reto Stöcklin, Prof. Dr. Johannis P. Kamerling and Prof. Dr. Rolf Boelens

      Version of Record online: 27 DEC 2012 | DOI: 10.1002/chem.201202713

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      Name your poison: A new O-glycan was found in a conopeptide isolated from the venom of the piscivorous cone snail Conus consors. The glycopeptide, CcTx, belongs to the κA-family of conotoxins and contains a new type of glycopeptide O-glycan core structure, here registered as core type 9, containing two terminal L-galactose units (see figure).

    2. Solid-State Structures

      Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid-State NMR Spectroscopies and DFT Calculations (pages 880–891)

      Saad Sene, Marc Reinholdt, Dr. Guillaume Renaudin, Dr. Dorothée Berthomieu, Prof. Claudio M. Zicovich-Wilson, Prof. Christel Gervais, Dr. Philippe Gaveau, Prof. Christian Bonhomme, Dr. Yaroslav Filinchuk, Prof. Mark E. Smith, Prof. Jean-Marie Nedelec, Dr. Sylvie Bégu, Dr. P. Hubert Mutin and Dr. Danielle Laurencin

      Version of Record online: 27 DEC 2012 | DOI: 10.1002/chem.201203560

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      Boronate ligands in materials: A combined experimental/computational approach is used to define the IR and NMR spectroscopic signatures of boronate ligands in the solid state. OH stretching frequencies and 1H chemical shifts can now be related to the local environments around the OH groups (see figure).

    3. Ionic liquids

      Chiral Triazolium Salts and Ionic Liquids: From the Molecular Design Vectors to Their Physical Properties through Specific Supramolecular Interactions (pages 892–904)

      Dr. Raul Porcar, Dr. Nicolás Ríos-Lombardía, Dr. Eduardo Busto, Dr. Vicente Gotor-Fernández, Dr. Jose Montejo-Bernardo, Prof. Santiago García-Granda, Prof. Santiago V. Luis, Prof. Vicente Gotor, Dr. Ignacio Alfonso and Dr. Eduardo García-Verdugo

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202274

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      The importance of being liquid: The non-covalent intermolecular network of contacts is a key aspect to explain structure–property relationships of new chiral triazolium salts (see figure). To understand how these contacts influence such relationships and their correlation with macroscopic properties (e.g., the melting point), an exhaustive experimental study based on X-ray diffraction analysis, NMR, FTIR and Raman spectroscopy, as well as theoretical calculations is presented.

    4. Bimetallic Nanoparticles

      Relating the Composition of PtxRu100−x/C Nanoparticles to Their Structural Aspects and Electrocatalytic Activities in the Methanol Oxidation Reaction (pages 905–915)

      Dr. Fadlilatul Taufany, Dr. Chun-Jern Pan, Feng-Ju Lai, Dr. Hung-Lung Chou, Loka Subramanyam Sarma, Dr. John Rick, Jhih-Min Lin, Dr. Jyh-Fu Lee, Dr. Mau-Tsu Tang and Prof. Bing-Joe Hwang

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202473

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      Control and catalysis: This study reports a controlled composition-based synthesis and characterization of selected bimetallic PtxRu100−x/C nanoparticles and simultaneously demonstrates their physiochemical properties—that is, their alloying extent and electronic structure—by focusing on the catalytic activity (see figure). A methanol oxidation reaction was used as a model system.

    5. Natural Products

      Jozimine A2: The First Dimeric Dioncophyllaceae-Type Naphthylisoquinoline Alkaloid, with Three Chiral Axes and High Antiplasmodial Activity (pages 916–923)

      Prof. Dr. Gerhard Bringmann, Guoliang Zhang, Tobias Büttner, Gabi Bauckmann, Dr. Thomas Kupfer, Prof. Dr. Holger Braunschweig, Prof. Dr. Reto Brun and Prof. Dr. Virima Mudogo

      Version of Record online: 5 DEC 2012 | DOI: 10.1002/chem.201202755

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      Jozimine A2 is a new dimeric naphthylisoquinoline alkaloid, discovered in an Ancistrocladus plant (see scheme). Its stereostructure, including three consecutive chiral axes, was assigned by chemical and spectroscopic methods, and confirmed by X-ray crystallography. It exhibits a high antiplasmodial activity, better than any other naphthylisoquinoline alkaloid. Its synthesis is achieved by biomimetic phenol-oxidative coupling of its monomeric precursor.

    6. Fluorescence

      Tuning the Nature of the Fluorescent State: A Substituted Polycondensed Dye as a Case Study (pages 924–935)

      Dr. Cristina Sissa, Dr. Valentina Calabrese, Dr. Marco Cavazzini, Dr. Luca Grisanti, Prof. Francesca Terenziani, Dr. Silvio Quici and Prof. Anna Painelli

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202154

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      Charge-transfer or local excitations? Fluorescence emission from a substituted azachrysene chromophore is shown to change its nature according to solvent polarity. The different polarization of the low-energy local and charge-transfer excitations (see scheme) is responsible for highly informative fluorescence anisotropy spectra. Experimental results are interpreted and reproduced based on an original three-state model.

    7. Sensors

      A PEGylated Fluorescent Turn-On Sensor for Detecting Fluoride Ions in Totally Aqueous Media and Its Imaging in Live Cells (pages 936–942)

      Fangyuan Zheng, Prof. Fang Zeng, Changmin Yu, Xianfeng Hou and Prof. Shuizhu Wu

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202732

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      Shining to track fluoride: A fluorescent turn-on sensor for the fluoride anion was developed. The sensor is responsive, highly selective, has low cytotoxicity, and is capable of functioning in a totally aqueous solution. Moreover, this sensor is highly sensitive with a low detection limit of 19 ppb. It is operative in real samples, such as running water, urine, and serum, and it also can be utilized to track fluoride-level changes inside live cells (see figure).

    8. Imaging Nanoprobes

      Thiol-Directed Synthesis of Highly Fluorescent Gold Clusters and Their Conversion into Stable Imaging Nanoprobes (pages 943–949)

      Sharbari Palmal, SK Basiruddin, Amit Ranjan Maity, Dr. Sekhar C. Ray and Dr. Nikhil R. Jana

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/chem.201203083

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      Tunable emission: Fluorescent gold clusters with tunable emission from blue to red (see figure) and quantum yields in the range of 6–17 % have been synthesized and transformed into imaging nanoprobes with hydrodynamic diameters of 5–12 nm.

    9. Magnetic Properties

      Origin of the Magnetic Anisotropy in Heptacoordinate NiII and CoII Complexes (pages 950–956)

      Renaud Ruamps, Dr. Luke J. Batchelor, Dr. Rémi Maurice, Dr. Nayanmoni Gogoi, Pablo Jiménez-Lozano, Prof. Nathalie Guihéry, Prof. Coen de Graaf, Dr. Anne-Laure Barra, Dr. Jean-Pascal Sutter  and Prof. Talal Mallah

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202492

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      The nature and magnitude of the magnetic anisotropy of heptacoordinate mononuclear NiII and CoII complexes [Ni(DAPBH)(H2O)2](NO3)22 H2O (1) and [Co(DAPBH)(H2O)(NO3)](NO3) [2; H2DAPBH=2,6-diacetylpyridine bis(benzoyl hydrazone)] were investigated experimentally and theoretically. The zero-field splitting (ZFS) parameters were estimated by means of magnetization measurements and EPR spectroscopy, and then ab initio calculations were carried out to rationalize the origin of the experimentally observed anisotropy and develop simple rules to tune the ZFS through small modifications of the complexes.

    10. Dimerization

      Selective Dimerization of Lewis-Acid/Base-Stabilized Phosphanylalanes (pages 957–963)

      Dr. Michael Bodensteiner, Prof. Dr. Alexey Y. Timoshkin, Dr. Eugenia V. Peresypkina, Dr. Ulf Vogel and Prof. Dr. Manfred Scheer

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201203074

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      Basic changes: Minor changes in the amine base and the phosphorus substituent of phosphanylalanes significantly affect the reaction outcome and the behavior of the products in solution. A fast equilibrium between different isomers is observed by NMR spectroscopy (see scheme).

    11. Surface Chemistry

      Small Changes Have Consequences: Lessons from Tetrabenzyltitanium and -zirconium Surface Organometallic Chemistry (pages 964–973)

      Dr. Nicolas Popoff, Dr. Jeff Espinas, Dr. Jérémie Pelletier, Benoît Macqueron, Dr. Kai C. Szeto, Olivier Boyron, Dr. Christophe Boisson, Dr. Iker Del Rosal, Dr. Laurent Maron, Dr. Aimery De Mallmann, Dr. Régis M. Gauvin and Dr. Mostafa Taoufik

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/chem.201202737

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      From little acorns: [M(CH2Ph)4] (M=Ti, Zr) species that were grafted onto SiO2−200 and SiO2−700 afforded well-defined mono- and bi-grafted species. The supported benzyl-zirconium derivatives are active catalysts for ethylene polymerization.

    12. Oxygen-Reduction Reaction

      Porous-Organic-Framework-Templated Nitrogen-Rich Porous Carbon as a More Proficient Electrocatalyst than Pt/C for the Electrochemical Reduction of Oxygen (pages 974–980)

      Pradip Pachfule, Vishal M. Dhavale, Sharath Kandambeth, Dr. Sreekumar Kurungot and Dr. Rahul Banerjee

      Version of Record online: 30 NOV 2012 | DOI: 10.1002/chem.201202940

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      What a ri-POF: Porous, nitrogen-rich carbon (POF-C-1000) has a high degree of graphitization in an ordered structure with large domains and well-ordered arrays of carbon sheets. POF-C-1000 has favorable electrocatalytic activity for oxygen reduction.

    13. Drug Delivery

      Highly Stable Amorphous Calcium Phosphate Porous Nanospheres: Microwave-Assisted Rapid Synthesis Using ATP as Phosphorus Source and Stabilizer, and Their Application in Anticancer Drug Delivery (pages 981–987)

      Chao Qi, Prof. Dr. Ying-Jie Zhu, Xin-Yu Zhao, Bing-Qiang Lu, Dr. Qi-Li Tang, Jing Zhao and Feng Chen

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202829

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      Stabilized nanospheres: Highly stable amorphous calcium phosphate (ACP) porous nanospheres with an average pore diameter of about 10 nm have been synthesized by using a microwave-assisted hydrothermal method with adenosine 5′-triphosphate disodium salt (ATP) as the phosphorus source and stabilizer (see scheme). The as-prepared ACP porous nanospheres show a high ability to damage tumor cells after loading docetaxel, thus, are promising for application in anticancer drug delivery.

    14. Fullerenes

      Mapping the Metal Positions inside Spherical C80 Cages: Crystallographic and Theoretical Studies of Ce2@D5h-C80 and Ce2@Ih-C80 (pages 988–993)

      Prof. Dr. Lai Feng, Mitsuaki Suzuki, Dr. Naomi Mizorogi, Dr. Xing Lu, Dr. Michio Yamada, Prof. Dr. Takeshi Akasaka and Prof. Dr. Shigeru Nagase

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201202341

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      Acting cagey: Dynamic metal positions inside spherical C80 cages can be visualized by using crystallographic methods. A comparison study between Ce2@D5h-C80 and Ce2@Ih-C80 (see figure) shows us how changes in the cage structure can influence the motional behaviors of the Ce2 cluster.

    15. Magnetic Materials

      Magnetic Blocking from Exchange Interactions: Slow Relaxation of the Magnetization and Hysteresis Loop Observed in a Dysprosium–Nitronyl Nitroxide Chain Compound with an Antiferromagnetic Ground State (pages 994–1001)

      Tian Han, Dr. Wei Shi, Zheng Niu, Bo Na and Prof. Dr. Peng Cheng

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202708

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      Mag-neato! Paramagnetic mononuclear dysprosium–nitronyl nitroxide 1 was successfully assembled to form superparamagnetic one-dimensional dysprosium–nitronyl nitroxide 2. Compound 2 shows the unusual coexistence of superparamagnetic and two-step field-induced metamagnetic behaviors with an antiferromagnetic ground state (see figure).

    16. Ring-Closing Metathesis

      Low Catalyst Loading in Ring-Closing Metathesis Reactions (pages 1002–1012)

      Dr. Renat Kadyrov

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202207

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      Getting some closure: An efficient procedure is described for ring-closing metathesis reactions in which only 50 to 250 ppm of catalyst is required to effect almost-quantitative conversion into a broad range of 5–16-membered heterocyclic compounds. The practicality of this procedure was illustrated in the synthesis of 5–8-membered N-protected cyclic amines, 9–16-membered lactones, and 11–16-membered proline-based lactams.

    17. Energy Storage

      Encapsulating Sulfur into Hierarchically Ordered Porous Carbon as a High-Performance Cathode for Lithium–Sulfur Batteries (pages 1013–1019)

      Bing Ding, Dr. Changzhou Yuan, Laifa Shen, Guiyin Xu, Ping Nie and Prof. Xiaogang Zhang

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202127

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      Taking charge: Hierarchically ordered porous carbon (HOPC) was prepared by self-assembly to serve as a scaffold to prepare a carbon/sulfur nanocomposite for lithium–sulfur battery cathodes. The excellent electrochemical properties of the nanocomposite (see figure) are attributed to the integration of mesopores for sulfur lithiation and macropores for ion transport.

    18. Hydroamination Catalysts

      Analysis of Potential Molecular Catalysts for the Hydroamination of Ethylene with Ammonia: A DFT Study with [Ir(PCP)] and [Ir(PSiP)] Complexes (pages 1020–1027)

      Andreas Uhe, Dr. Markus Hölscher and Prof. Dr. Walter Leitner

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/chem.201202185

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      A careful computational design is necessary to understand the strict energetic limitations of the hydroamination of ethylene with ammonia, with rhodium and iridium pincer catalysts. According to DFT computations, the iridium catalyst (see figure) with a finely tuned pincer ligand enables this challenging reaction.

    19. Solar Cells

      Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes (pages 1028–1034)

      Prof. Dr. Mutsumi Kimura, Junya Masuo, Yuki Tohata, Kazumichi Obuchi, Naruhiko Masaki, Takurou N. Murakami, Nagatoshi Koumura, Kojiro Hara, Atsushi Fukui, Ryohsuke Yamanaka and Prof. Dr. Shogo Mori

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202709

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      An unsymmetric terpyridine ligand having a bromo group as a connection point for the introduction of various substituents by Suzuki coupling reactions with boronic acids was used to explore the effect of substituents on the energy-conversion efficiency of dye-sensitized solar cells (DSSCs). Introduction of a peripheral bulky substituent improved the DSSC performance, and MJ-10 (see figure) harvests visible and near-infrared light, whereas solar cells sensitized by MJ-10 exhibit an efficiency of 9.1 % under 1 sun irradiation.

    20. Capillary Liquid Chromatography

      Preparation of a Hyper-cross-linked Polymer Monolithic Column and Its Application to the Sensitive Determination of Genomic DNA Methylation (pages 1035–1041)

      Ming-Luan Chen, Yu-Li Liu, Xi-Wen Xing, Prof. Xiang Zhou, Prof. Yu-Qi Feng and Prof. Bi-Feng Yuan

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201203129

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      5-Methylcytosine determination: We have developed a capillary liquid chromatography method based on a hyper-cross-linked poly(MATE-co-VBC-co-DVB) monolithic column for the rapid and sensitive detection of 5-methylcytosine (5-mC). By using this method, six nucleobases were baseline separated (see figure).

    21. Olefin Complexes

      Copper(I) and Silver(I) Bis(trifluoromethanesulfonyl)imide and Their Interaction with an Arene, Diverse Olefins, and an NTf2-Based Ionic Liquid (pages 1042–1057)

      Dr. Marion Stricker, Dr. Benjamin Oelkers, Carl Philipp Rosenau and Prof. Dr. Jörg Sundermeyer

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201201740

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      Chemisorbing coinage: The crystal structures of two solvent adducts of CuNTf2 and the solid-state structure of [AgNTf2] are presented (see figure). The reactivity of these versatile compounds towards [emim]NTf2 ([emim]+=1-ethyl-3-methylimidazolium), 1,5-cyclooctadiene (COD), 2,5-norbornadiene (NBD), isoprene, and ethylene has been studied. Finally, their potential as reversible chemisorbers for ethylene has been investigated through NMR experiments.

    22. Gold

      Dual Gold Catalysis: σ,π-Propyne Acetylide and Hydroxyl-Bridged Digold Complexes as Easy-To-Prepare and Easy-To-Handle Precatalysts (pages 1058–1065)

      Prof. Dr. A. Stephen K. Hashmi, Tobias Lauterbach, Dipl.-Chem. Pascal Nösel, Dr. Mie Højer Vilhelmsen, Dr. Matthias Rudolph and Dr. Frank Rominger

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203010

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      Traceless dual-activation catalysts: Air-stable π-coordinated propyne acetylide gold complexes proved to be powerful precatalysts for dual gold catalysis (see scheme). A fast catalyst transfer to the starting substrates initiates the catalytic cycle. Reaction yields and selectivity were improved without the need for basic additives or activation by silver salts.

    23. Photooxidation

      Aggregation Effects in Visible-Light Flavin Photocatalysts: Synthesis, Structure, and Catalytic Activity of 10-Arylflavins (pages 1066–1075)

      Jitka Daďová, Susanne Kümmel, Christian Feldmeier, Jana Cibulková, Dr. Richard Pažout, Dr. Jaroslav Maixner, Prof. Dr. Ruth M. Gschwind, Prof. Dr. Burkhard König and Dr. Radek Cibulka

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201202488

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      Shining light on increased activity: Aryl rings that are perpendicularly oriented relative to the flavin chromophore substantially decrease aggregation relative to nonsubstituted derivatives. These 10-arylflavin derivatives are more efficient photocatalysts for the oxidation of 4-methoxybenzyl alcohol (see scheme).

    24. Supramolecular Chemistry

      Construction of Supramolecular Self-Assembled Microfibers with Fluorescent Properties through a Modified Ionic Self-Assembly (ISA) Strategy (pages 1076–1081)

      Dr. Mingwei Zhao, Dr. Yurong Zhao, Prof. Liqiang Zheng and Prof. Caili Dai

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/chem.201203062

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      Fantastic fibers: Highly ordered supramolecular microfibers were constructed through a simple modified ionic self-assembly strategy from complexes of a surface-active ionic liquid (N-tetradecyl-N-methylpyrrolidinium bromide) and a small dye molecule (methyl orange), with the aid of patent blue VF sodium salt. These microfibers show strong fluorescent properties (see figure).

    25. Supramolecular Interactions

      FeIII Quinolylsalicylaldimine Complexes: A Rare Mixed-Spin-State Complex and Abrupt Spin Crossover (pages 1082–1090)

      Prof. Dr. David J. Harding, Darunee Sertphon, Prof. Dr. Phimphaka Harding, Prof. Dr. Keith S. Murray, Dr. Boujemaa Moubaraki, Prof. Dr. John D. Cashion and Harry Adams

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202053

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      Time to step up! Two novel FeIII complexes, [Fe(qsal-5-OMe)2]Clsolvent {qsal-5-OMe=5-methoxy-N-(8-quinolyl) salicylaldiminate, solvent=2 MeOH0.5 H2O (1) and MeCNH2O (2)} are reported. The structure of 1 reveals crystallographically independent high-spin and low-spin FeIII centres, with 1 and 2 undergoing abrupt half-spin crossover and spin crossover in two steps, respectively (see figure).

    26. Nanostructures

      Expanding the Applications of the Ilmenite Mineral to the Preparation of Nanostructures: TiO2 Nanorods and their Photocatalytic Properties in the Degradation of Oxalic Acid (pages 1091–1096)

      Dr. Tao Tao, Prof. Ying Chen, Dan Zhou, Dr. Hongzhou Zhang, Dr. Sanly Liu, Prof. Rose Amal, Dr. Neeraj Sharma and Dr. Alexey M. Glushenkov

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202451

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      Hot rods: Ilmenite (FeTiO3) is a major source of bulk TiO2 but ways to convert it into nanostructures of titanium oxide are scarce. Single-crystal TiO2 nanorods were synthesized from natural ilmenite by simple ball milling and acid treatment (see figure).

    27. Protein Labeling

      Site-Specific Labeling of Proteins with a Chemically Stable, High-Affinity Tag for Protein Study (pages 1097–1103)

      Yin Yang, Qing-Feng Li, Chan Cao, Feng Huang and Prof. Xun-Cheng Su

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/chem.201202495

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      NMR tag: Site-specific labeling of proteins with a high affinity, chemically stable lanthanide-binding tag for structural biology is presented (see figure). The protein–tag construct is an ideal system for the study of protein stability and self-assembly processes under in situ conditions.

    28. Nanostructures

      Rapid, General Synthesis of PdPt Bimetallic Alloy Nanosponges and Their Enhanced Catalytic Performance for Ethanol/Methanol Electrooxidation in an Alkaline Medium (pages 1104–1111)

      Chengzhou Zhu, Shaojun Guo and Prof. Shaojun Dong

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202909

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      Soak it up: A rapid and general strategy is demonstrated for the preparation of novel three-dimensional PdPt bimetallic alloy nanosponges (see figure) that exhibit greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium.

    29. Sensors

      Interfacing Click Chemistry with Automated Oligonucleotide Synthesis for the Preparation of Fluorescent DNA Probes Containing Internal Xanthene and Cyanine Dyes (pages 1112–1122)

      Prof. Dr.  I. Kira Astakhova and Prof. Dr. Jesper Wengel

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/chem.201202621

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      It just clicks: Oligonucleotide probes containing internally positioned xanthene and cyanine dye pairs were prepared by a novel CuAAC click chemistry approach (see scheme). Their unusual and promising photophysical properties result from energy-transfer interactions between the fluorophores controlled by nucleic acid assembly.

    30. Organic Synthesis

      One-Step Synthesis of Racemic α-Amino Acids from Aldehydes, Amine Components, and Gaseous CO2 by the Aid of a Bismetal Reagent (pages 1123–1128)

      Dr. Tsuyoshi Mita, Yuki Higuchi and Prof. Dr. Yoshihiro Sato

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/chem.201202332

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      Go retro! α-Amino acids are essential resources for human life and are highly useful as building blocks for organic synthesis. The core framework of an α-amino acid is retrosynthesized to an aldehyde, an amine, and carbon dioxide. A one-step synthesis of α-amino acids has been successfully achieved from these three simple and commercially available chemicals with a single operation (see scheme).

    31. C[BOND]H Functionalization

      Synthesis of Imides by Palladium-Catalyzed C[BOND]H Functionalization of Aldehydes with Secondary Amides (pages 1129–1133)

      Yong-Jun Bian, Chao-Yue Chen and Prof. Zhi-Zhen Huang 

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/chem.201202601

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      An efficient palladium-catalyzed C[BOND]H functionalization of aldehydes with various N-substituted N-heteroarene-2-carboxamides has been developed for the synthesis of secondary imides (see scheme; TBHP=tert-butyl hydroperoxide). The reaction tolerates various functional groups. A tentative radical mechanism for a PdII/PdIV catalytic cycle is proposed.

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