Chemistry - A European Journal

Cover image for Vol. 21 Issue 11

Early View (Online Version of Record published before inclusion in an issue)

Editor: Neville Compton, Deputy Editors: Anne Deveson, Elisabeth Roedern

Impact Factor: 5.696

ISI Journal Citation Reports © Ranking: 2013: 22/148 (Chemistry Multidisciplinary)

Online ISSN: 1521-3765

Associated Title(s): Angewandte Chemie International Edition, Chemistry – An Asian Journal, ChemistryOpen, ChemBioChem, ChemCatChem, ChemElectroChem, ChemMedChem, ChemPhysChem, ChemPlusChem, ChemSusChem, European Journal of Inorganic Chemistry, European Journal of Organic Chemistry

VIEW

  1. 1 - 100
  2. 101 - 173
  1. Communications

    1. Metal–Organic Frameworks

      Structural Transformation and Hysteretic Sorption of Light Hydrocarbons in a Flexible Zn–Pyrazole–Adenine Framework

      Hong-Ru Fu and Prof. Dr. Jian Zhang

      Article first published online: 27 FEB 2015 | DOI: 10.1002/chem.201406323

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      Breathtaking: A flexible metal–organic framework based on the pyrazole–adenine module exhibits a breathing effect on the sorption of light hydrocarbons. The flexibility of the framework is demonstrated by single-crystal structural studies at different temperatures.

    2. Cross-Coupling | Hot Paper

      Asymmetric Suzuki–Miyaura Cross-Coupling for the Synthesis of Chiral Biaryl Compounds as Potential Monophosphine Ligands

      Yan-Na Ma and Prof. Shang-Dong Yang

      Article first published online: 27 FEB 2015 | DOI: 10.1002/chem.201406554

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      To bear a cross: Efficient asymmetric Suzuki–Miyaura coupling reactions are employed to synthesize chiral biaryl compounds with phosphinate groups as chiral auxiliaries. A series of functionalized chiral biaryls are synthesized in excellent yields and good diastereoselectivities (up to >95:5 d.r.) and axially chiral monophosphorus ligands are obtained through further functionalizations.

    3. Hydrogen Bonds

      Control over Excited State Intramolecular Proton Transfer and Photoinduced Tautomerization: Influence of the Hydrogen-Bond Geometry

      Giovanny A. Parada, Dr. Todd F. Markle, Dr. Starla D. Glover, Prof. Dr. Leif Hammarström, Dr. Sascha Ott and Dr. Burkhard Zietz

      Article first published online: 27 FEB 2015 | DOI: 10.1002/chem.201500244

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      H-bond geometry rules! Correlations between H-bond structural parameters and the dynamics of ESIPT and photoinduced tautomerization have been investigated in a series of H-bonded phenols (see figure).

  2. Full Papers

    1. Synthesis Design

      (E)-,(Z)-Parallel Preparative Methods for Stereodefined β,β-Diaryl- and α,β-Diaryl-α,β-unsaturated Esters: Application to the Stereocomplementary Concise Synthesis of Zimelidine

      Yuichiro Ashida, Yuka Sato, Takeyuki Suzuki, Kanako Ueno, Ken-ichiro Kai, Dr. Hidefumi Nakatsuji and Prof. Dr. Yoo Tanabe

      Article first published online: 27 FEB 2015 | DOI: 10.1002/chem.201405150

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      Working together: Parallel synthetic methods for (E)- and (Z)-β-Ar1-β-Ar2-α,β-unsaturated esters 1 and (E)- and (Z)-α-Ar1-β-Ar2-α,β-unsaturated esters 2 (see scheme), involving accessible stereocomplementary N-methylimidazole (NMI)-mediated enol tosylations and stereoretentive Suzuki–Miyaura cross-couplings, are presented. Application to an expeditious parallel synthesis of the selective serotonin reuptake inhibitor (E)-, (Z)-zimelidine is presented.

    2. Layered Imidonitridophosphates

      MH4P6N12 (M=Mg, Ca): New Imidonitridophosphates with an Unprecedented Layered Network Structure Type

      Alexey Marchuk, Vinicius R. Celinski, Prof. Dr. Jörn Schmedt auf der Günne and Prof. Dr. Wolfgang Schnick

      Article first published online: 27 FEB 2015 | DOI: 10.1002/chem.201406240

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      Unprecedented layered structure: New imidonitridophosphates MH4P6N12 (M=Mg, Ca) have been synthesized by high-pressure/high-temperature reactions at 8 GPa and 1000 °C. Their crystal structures have been determined by single-crystal X-ray diffraction analyses and confirmed by Rietveld refinement, which reveal an unprecedented layered structure type (see graphic). The hydrogen contents of the samples have been quantified by solid-state NMR spectroscopy.

  3. Communications

    1. Carboarylation | Hot Paper

      Calcium-Catalyzed Carboarylation of Alkynes

      Liang Fu and Prof. Dr. Meike Niggemann

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201406503

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      Finally free: The first transition-metal-free one-step synthesis of highly congested, all-carbon tetrasubstituted olefins has been realized by a calcium-catalyzed carboarylation reaction. Internal alkynes react with alcohols as alkylating reagent under mild reaction conditions, which provides access to a variety of useful structural scaffolds via highly reactive trisubstituted vinyl cations.

  4. Full Papers

    1. Protein Folding | Hot Paper

      Randomizing the Unfolded State of Peptides (and Proteins) by Nearest Neighbor Interactions between Unlike Residues

      Dr. Siobhan E. Toal, Nina Kubatova, Dr. Christian Richter, Verena Linhard, Prof. Dr. Harald Schwalbe and Prof. Reinhard Schweitzer-Stenner

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201406539

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      Neighborhood watch: Intrinsic structural propensities of amino acids in unfolded peptides are affected by their nearest neighbors via solvent mediated interactions. At room temperature these interactions function as conformational randomizer by favoring a pPII/β-coil. Different enthalpic and entropic contributions to the pPII[LEFT RIGHT ARROW]β equilibrium cause structural preferences above and below the compensation temperature.

    2. NH Acids

      Fluoro- and Perfluoralkylsulfonylpentafluoroanilides: Synthesis and Characterization of NH Acids for Weakly Coordinating Anions and Their Gas-Phase and Solution Acidities

      Julius F. Kögel, Thomas Linder, Fabian G. Schröder, Jörg Sundermeyer, Sascha K. Goll, Daniel Himmel, Ingo Krossing, Karl Kütt, Jaan Saame and Ivo Leito

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201405391

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      A tale of acidities: Fluoro- and perfluoralkylsulfonyl pentafluoroanilides [HN(C6F5)(SO2X); X=F, CF3, C4F9, C8F17] are unsymmetrical NH acids with one fluorinated sulfonyl substituent and one pentafluorophenyl substituent. Their acidities are investigated experimentally and quantum-chemically, and their gas-phase acidities (GAs) and solution-phase pKa values are reported.

  5. Communications

    1. C[BOND]H Activation

      Cobalt-Catalyzed C[BOND]H Arylations with Weakly-Coordinating Amides and Tetrazoles: Expedient Route to Angiotensin-II-Receptor Blockers

      Jie Li and Prof. Dr. Lutz Ackermann

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201500552

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      Broadly applicable cobalt-catalyzed C[BOND]H arylations with weakly-coordinating amides or tetrazoles provided step-economical access to biaryl tetrazoles as key structural motifs of angiotensin-II-receptor blockers (ARBs), such as the blockbuster drug Losartan (see scheme).

    2. Carbohydrates

      Automated Synthesis of Arabinoxylan-Oligosaccharides Enables Characterization of Antibodies that Recognize Plant Cell Wall Glycans

      Deborah Schmidt, Frank Schuhmacher, Andreas Geissner, Prof. Dr. Peter H. Seeberger and Dr. Fabian Pfrengle

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201500065

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      Automated synthesis meets plant research: Automated synthesis of plant oligosaccharides provides molecular tools for the characterization of important biological probes in plant research. The binding specificities of a collection of xylan-directed monoclonal antibodies have been determined by means of carbohydrate microarrays equipped with synthetic arabinoxylan fragments (see figure).

  6. Full Papers

    1. Homogeneous Catalysis

      A Simple Iridicycle Catalyst for Efficient Transfer Hydrogenation of N-Heterocycles in Water

      Dinesh Talwar, Dr. Ho Yin Li, Emma Durham and Prof. Jianliang Xiao

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201500016

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      An easily accessible iridicycle catalyst effects the transfer hydrogenation of a wide variety of N-heterocycles in water, including quinolines, isoquinolines, indoles, quinoxalines, and pyridines. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), even with low catalyst loadings.

    2. Radical Anion Dimers

      Orientational Preference of Long, Multicenter Bonds in Radical Anion Dimers: A Case Study of π-[TCNB]22− and π-[TCNP]22−

      Dr. Marçal Capdevila-Cortada, Prof. Joel S. Miller and Prof. Juan J. Novoa

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201406028

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      A principled approach: The similar shape and electronic structure of the radical anions of 1,2,4,5-tetracyanopyrazine (TCNP) and 1,2,4,5-tetracyanobenzene (TCNB) suggest a similar relative orientation for their long, multicenter carbon[BOND]carbon bond in π-[TCNP]22− and in π-[TCNB]22−, in good accord with Maximin Principle predictions. Instead, the two known structures of π-[TCNP]22− have a D2h(θ=0°) and a C2(θ=30°) orientation (see figure).

  7. Communications

    1. Self-Assembly

      Supramolecular Capsules from Bilayer Membrane Scission Driven by Corannulene

      Dr. Yongju Kim and Prof. Dr. Myongsoo Lee

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201500101

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      Self-assembly of polyaromatic systems has proved to be a powerful technique to construct nanoscale optoelectronic materials. However, attempts to develop self-assembled nanomaterials guided by pristine polyaromatic molecules have been limited. Here the construction of photoactive nanocapsules through the scission of an aromatic bilayer membrane driven by curved corannulene intercalation is reported (see figure).

  8. Full Papers

    1. Zeolites | Hot Paper

      Differences Between Individual ZSM-5 Crystals in Forming Hollow Single Crystals and Mesopores During Base Leaching

      Daniel Fodor, Dr. Frank Krumeich, Dr. Roland Hauert and Prof. Jeroen A. van Bokhoven

      Article first published online: 26 FEB 2015 | DOI: 10.1002/chem.201406182

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      Hollow crystals: Individual ZSM-5 crystals are leached differently during base treatment. Aluminum-zoned nano-sized crystals yield hollow crystals. As leaching time increases, the amount of hollow crystals increases relative to the non-leached crystals. Commercial zeolites show an uneven distribution of mesopores between individual crystals of the same batch.

    2. Endohedral Fullerenes | Hot Paper

      An Expanded Family of Dysprosium–Scandium Mixed-Metal Nitride Clusterfullerenes: The Role of Lanthanide Metal on the Carbon Cage Size Distribution

      Tao Wei, Fupin Liu, Song Wang, Xianjun Zhu, Dr. Alexey A. Popov and Prof. Dr. Shangfeng Yang

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201406265

      Thumbnail image of graphical abstract

      A large family of dysprosium–scandium (Dy-Sc) mixed-metal nitride clusterfullerenes (MMNCFs), DyxSc3−xN@C2n (x=1, 2, 2n=68, 70, 76–86) have been successfully synthesized and isolated. This is the largest MMNCF family reported to date. The medium-sized Dy metal plays a crucial role on the expanded cage size distribution of MMNCFs.

  9. Cover Profiles

    1. Ring Opening of Donor–Acceptor Cyclopropanes with the Azide Ion: A Tool for Construction of N-Heterocycles

      Konstantin L. Ivanov, Dr. Elena V. Villemson, Dr. Ekaterina M. Budynina, Dr. Olga A. Ivanova, Dr. Igor V. Trushkov and Prof. Mikhail Ya. Melnikov

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201500456

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      One of the main aims of this research was to create numerous synthetic opportunities and to achieve diverse synthetic outcomes by using different combinations of the same parent compounds. To us, this image of a simple yet exciting kaleidoscope provides a splendid visual metaphor for this approach.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201405551).

  10. Full Papers

    1. Cobalt Nanostructures

      Pure and Palladium-Loaded Co3O4 Hollow Hierarchical Nanostructures with Giant and Ultraselective Chemiresistivity to Xylene and Toluene

      Su-Jin Hwang, Kwon-Il Choi, Ji-Wook Yoon, Prof. Yun Chan Kang and Prof. Jong-Heun Lee

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201405076

      Thumbnail image of graphical abstract

      Unprecedented sensors! Giant response and unprecedented high selectivity towards methylbenzenes have been achieved by using pure and palladium-loaded Co3O4 hollow hierarchical nanostructures assembled from nanosheets (see figure).

  11. Communications

    1. Natural Products

      Total Synthesis of an Exceptional Brominated 4-Pyrone Derivative of Algal Origin: An Exercise in Gold Catalysis and Alkyne Metathesis

      Laura Hoffmeister, Dr. Tsutomu Fukuda, Gerit Pototschnig and Prof. Alois Fürstner

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201500437

      Thumbnail image of graphical abstract

      The gentle way: Certain red algae produce highly unusual 4-pyrone derivatives which cluster several remarkable functionalities into a macrocyclic frame. The first member of this series (see figure) has now been conquered and a biosynthetic hypothesis predicting its relative stereochemistry has been confirmed. The successful route is based on the selective transformation of an acyclic precursor containing six different sites of unsaturation, without scrambling the labile skipped π-systems.

  12. Full Papers

    1. Reaction Mechanism | Hot Paper

      Enantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations

      Dr. Fedor Romanov-Michailidis, Maria Romanova-Michaelides, Marion Pupier and Prof. Dr. Alexandre Alexakis

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201406133

      Thumbnail image of graphical abstract

      Scope and limitations of the fluorination-initiated semi-pinacol rearrangement of strained, prochiral allylic alcohols are described. This reaction is proposed to operate through anionic phase-transfer technology, and can be readily extended the heavier halogen (Br, I) congeneers. In comparison with the fluorination reaction, an intriguing inversion of the sense of absolute induction for the heavier halogens is described (see scheme).

    2. Surface Chemistry

      Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of C[BOND]Br and C[BOND]H bonds

      Dr. Lara Ferrighi, Dr. Igor Píš, Dr. Thanh Hai Nguyen, Mattia Cattelan, Silvia Nappini, Andrea Basagni, Dr. Matteo Parravicini, Prof. Antonio Papagni, Dr. Francesco Sedona, Elena Magnano, Dr. Federica Bondino, Prof. Cristiana Di Valentin and Dr. Stefano Agnoli

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201405817

      Thumbnail image of graphical abstract

      Scratching the surface: Easy control of the intermolecular coupling of 5,11-dibromotetracene on a Cu(110) surface by temperature has been achieved. Organometallic oligomers characterized by copper atoms that bridge the tetracene molecule in the 5,11 positions are formed at mild temperature (room temperature to 523 K), whereas the higher intrinsic stability of the radical sites at the 3,2 and 8,9 positions determines the formation of linear chains produced by C[BOND]C coupling between the ends of the molecules at higher temperature (see picture).

    3. Combinatorial Chemistry | Hot Paper

      Dynamic Combinatorial Enrichment of Polyconformational D-/L-Peptide Dimers

      Dr. Kirtikumar B. Jadhav , Dr. Roman J. Lichtenecker , Anke Bullach, Dr. Bhubaneswar Mandal and Prof. Dr. Hans-Dieter Arndt

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201405413

      Thumbnail image of graphical abstract

      Dip into the pool: By using a dynamic combinatorial approach applied to thiol-tagged D-/L-peptides, preferred arrangements were selected from a pool of β-helical dimeric structures (see figure).

  13. Communications

    1. Liquid DNA

      Solvent-free Liquid Crystals and Liquids from DNA

      Kai Liu, Dr. Min Shuai, Dr. Dong Chen, Michael Tuchband, Dr. Jennifer Y. Gerasimov, Juanjuan Su, Qing Liu, Wojciech Zajaczkowski, Dr. Wojciech Pisula, Prof. Dr. Klaus Müllen, Prof. Noel A. Clark and Prof. Dr. Andreas Herrmann

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201500159

      Thumbnail image of graphical abstract

      Liquefying DNA: A series of solvent-free DNA melts that exhibit both liquid-crystal ordering and melting into isotropic liquids have been generated by electrostatic complexation of DNA with surfactants. Stable smectic mesophases and liquid phases are obtained in the −20 °C to 200 °C temperature range without thermal degradation of the DNA.

  14. Full Papers

    1. Fullerenes | Hot Paper

      Understanding the Reactivity of Endohedral Metallofullerenes: C78 versus Sc3N@C78

      Prof. Dr. F. Matthias Bickelhaupt, Prof. Dr. Miquel Solà and Dr. Israel Fernández

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201500067

      Thumbnail image of graphical abstract

      Free versus encapsulated: The encapsulation of Sc3N into a C78 cage induces dramatic changes in both the exohedral Diels–Alder reactivity and the regioselectivity as compared with free C78 (see figure). By means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method, the origin of these reactivity/regioselectivity changes is analysed in detail.

  15. Communications

    1. Umpolung Reactions | Very Important Paper

      Titanium-Catalyzed Reductive Umpolung Reactions with a Metal-Free Terminal Reducing Agent

      Georg Frey, J. Niklas Hausmann and Dr. Jan Streuff

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201500102

      Thumbnail image of graphical abstract

      Replacing zinc: A protocol for titanium(III)-catalyzed reductive umpolung reactions is presented that enables the title reactions in the presence of an N,N′-disilylated tetramethyldihydropyrazine as an organic sacrificial reducing agent. It is successfully applied to carbonyl–nitrile, enone–acrylonitrile and pinacol coupling reactions. A remarkable effect of the titanocene counterion renders titanocene diiodide a superior catalyst.

  16. Full Papers

    1. Contrast Agents

      Interaction of PiB-Derivative Metal Complexes with Beta-Amyloid Peptide: Selective Recognition of the Aggregated Forms

      Dr. André F. Martins, David M. Dias, Dr. Jean-François Morfin, Dr. Sara Lacerda, Dr. Douglas V. Laurents, Dr. Éva Tóth and Prof. Carlos F. G. C. Geraldes

      Article first published online: 25 FEB 2015 | DOI: 10.1002/chem.201406152

      Thumbnail image of graphical abstract

      The lanthanide(III) chelates of two PiB-derivative ligands (LnL1 and LnL2; PiB=Pittsburgh compound B), used as imaging probes, interact with the aggregated Aβ1–40 peptide in solution with 67–160 μM affinities and affect Aβ fibril formation distinctly.

  17. Communications

    1. Host–Guest Systems

      Host–Guest Chemistry of a Bis-Calix[4]pyrrole Derivative Containing a trans/cis-Switchable Azobenzene Unit with Several Aliphatic Bis-Carboxylates

      Grazia Cafeo, Franz H. Kohnke, Giovanni Mezzatesta, Aldo Profumo, Camillo Rosano, Antonino Villari and Andrew J. P. White

      Article first published online: 24 FEB 2015 | DOI: 10.1002/chem.201406183

      Thumbnail image of graphical abstract

      Bind and switch: A trans/cis-switchable azobenzene unit of the bis-calix[4]pyrrole receptor (see scheme) provides a means to modulate the binding of bis-carboxylates of significant biological importance in cancer research. Conversely, the complexation of different bis-anionic guests has significant kinetic effects on both the photochemical and thermal trans/cis isomerization.

    2. Gold Leaves

      From Spherical to Leaf-Like Morphologies: Tunable Supramolecular Assembly of Alkynylgold(I) Complexes through Variations of the Alkyl Chain Length

      Eugene Yau-Hin Hong, Dr. Hok-Lai Wong and Prof. Vivian Wing-Wah Yam

      Article first published online: 24 FEB 2015 | DOI: 10.1002/chem.201500078

      Thumbnail image of graphical abstract

      Turnover a new leaf: A series of luminescent non-amphiphilic polynuclear alkynylgold(I) complexes has been synthesised and demonstrated to undergo self-assembly in a THF–water mixture through a cooperative growth mechanism. Simple modifications of the alkyl chain length were found to cause drastic morphological differences in the aggregates and to strongly affect the thermodynamic parameters of the self-assembly process (see figure).

  18. Full Papers

    1. Radiopharmaceuticals

      Copper-Mediated Aromatic Radiofluorination Revisited: Efficient Production of PET Tracers on a Preparative Scale

      Dr. Boris D. Zlatopolskiy, Johannes Zischler, Philipp Krapf, Fadi Zarrad, Elizaveta A. Urusova, Dr. Elena Kordys, Priv.-Doz. Dr. Heike Endepols and Prof. Dr. Bernd Neumaier

      Article first published online: 24 FEB 2015 | DOI: 10.1002/chem.201405586

      Thumbnail image of graphical abstract

      Less is more: Copper-mediated nucleophilic aromatic radiofluorination under “low base” and “minimalist” conditions affords radiolabeled arenes in reasonable to excellent yields on a preparative scale. In particular, the “minimalist” approach circumvents time-consuming azeotropic drying, avoids the application of base and other additives, and enables efficient production of clinical doses of positron emission tomography (PET) tracers such as, [18F]FDA, 4-[18F]FPhe and [18F]DAA1106.

    2. BODIPY Dyes

      An Optically and Thermally Switchable Electronic Structure Based on an Anthracene–BODIPY Conjugate

      Tatsuya Aotake, Dr. Mitsuharu Suzuki, Kazuaki Tahara, Dr. Daiki Kuzuhara, Prof. Dr. Naoki Aratani, Prof. Dr. Naoto Tamai and Prof. Dr. Hiroko Yamada 

      Article first published online: 24 FEB 2015 | DOI: 10.1002/chem.201406384

      Thumbnail image of graphical abstract

      Four-way switch: An optically and thermally switchable BODIPY dye was designed and synthesized (see figure). Separate photoexcitation for structure change and fluorescence monitoring was achieved by means of fluorescence quenching based on an intramolecular electron-transfer mechanism. As the absorption characteristic can be switched by thermal activation, the construction of a completely irreversible multifluorescence switching system is possible.

    3. Organic Chemistry | Hot Paper

      Catalyst Activation, Deactivation, and Degradation in Palladium-Mediated Negishi Cross-Coupling Reactions

      Katharina Böck, Dr. Julia E. Feil, Prof. Konstantin Karaghiosoff and Prof. Konrad Koszinowski

      Article first published online: 24 FEB 2015 | DOI: 10.1002/chem.201406408

      Thumbnail image of graphical abstract

      Catalytic Complexity: The Pd catalyst used in Negishi cross-coupling reactions shows an unexpected heterogeneity and complexity. Among the various species observed in solution, heterobimetallic Pd–Zn complexes are of particular interest (see figure). These species also seem key to understanding the kinetics of Negishi cross-coupling reactions.

  19. Communications

    1. Synthetic Methods

      CBr4-Mediated Cross-Dehydrogenative Coupling Reaction of Amines

      Dr. Congde Huo, Haisheng Xie, Mingxia Wu, Dr. Xiaodong Jia, Dr. Xicun Wang, Fengjuan Chen and Jing Tang

      Article first published online: 23 FEB 2015 | DOI: 10.1002/chem.201500453

      Thumbnail image of graphical abstract

      Go tandem! A novel CBr4-mediated dehydrogenative Povarov/aromatization tandem reaction of glycine derivatives with alkenes and CBr4-mediated dehydrogenative C[BOND]H functionalization of N-aryl tetrahydroisoquinolines is reported. The reactions were performed under simple and mild conditions, only CBr4 and a solvent are required (see scheme). A plausible mechanism involving a radical process is also proposed.

  20. Full Papers

    1. Reaction Mechanisms | Hot Paper

      Mechanism of Phosphine Borane Deprotection with Amines: The Effects of Phosphine, Solvent and Amine on Rate and Efficiency

      Prof. Dr. Guy C. Lloyd-Jones and Nicholas P. Taylor

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406585

      Thumbnail image of graphical abstract

      Efficient deprotection: Kinetic and thermodynamic data for amine-mediated deprotection of phosphine boranes under synthetically relevant conditions is consistent with an SN2-like rather than SN1-like mechanism. The amine, solvent, and phosphine substituents all strongly influence the reaction efficiency (see scheme). The data allow informed selection of optimal reaction conditions.

    2. Electrochemistry

      The Correlation of Electrochemical Measurements and Molecular Junction Conductance Simulations in β-Strand Peptides

      John R. Horsley, Dr. Jingxian Yu and Prof. Andrew D. Abell

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406451

      Thumbnail image of graphical abstract

      Peptide circuits: Vast differences in the electronic transport properties of the two new peptides, measured by electrochemical techniques as well as molecular junction conductance simulations, provide two distinctly different conductance states, in what is essentially a molecular switch (see figure).

  21. Communications

    1. N-Heterocyclic Carbenes | Hot Paper

      Cycloelimination of Imidazolidin-2-ylidene N-Heterocyclic Carbenes: Mechanism and Insights into the Synthesis of Stable “NHC-CDI” Amidinates

      Aleksandr V. Zhukhovitskiy, Julie Geng and Prof. Dr. Jeremiah A. Johnson

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500052

      Thumbnail image of graphical abstract

      Old NHCs, new tricks: 1,3-Bis(aryl)imidazolidin-2-ylidenes, one of the most widely studied classes of N-heterocyclic carbenes (NHCs), undergo quantitative conversion to zwitterionic “NHC-CDI” amidinates upon heating to ≈100 °C in solution. The mechanism of this novel NHC decomposition process is studied in detail. These studies enabled the rational synthesis of a new class of bench stable amidinates from a panel of NHCs and carbodiimides. These constructs are expected to find utility in a variety of applications.

  22. Full Papers

    1. Cross-Coupling

      On the Radical Nature of Iron-Catalyzed Cross-Coupling Reactions

      Dr. Anna Hedström, Dr. Zakieh Izakian, Irma Vreto, Dr. Carl-Johan Wallentin and Prof. Dr. Per-Ola Norrby

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406096

      Thumbnail image of graphical abstract

      Iron cross: The iron-catalyzed cross-coupling reaction between alkyl halides and Grignard reagents has been investigated by competitive Hammett studies and DFT calculations. The results support the presence of radical intermediates in an FeI–FeIII cycle with an atom-transfer (AT) mechanism as the rate-limiting step (see figure; TM=transmetalation, RE=reductive elimination).

    2. Main Group Elements

      Unusual Bonding and Properties in Main Group Element Chemistry: Rational Synthesis, Characterization, and Experimental Electron Density Determination of Mixed-Valent Tetraphosphetes

      Verena Breuers, Prof. Dr. Christian W. Lehmann and Prof. Dr. Walter Frank

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406131

      Thumbnail image of graphical abstract

      Remarkable molecular properties are exhibited by the mixed-valent tetraphosphetes made available in almost quantitative yields by using a simple synthetic protocol. Pronounced anisotropic absorption of visible light, unusual 31P NMR spectra and a unique bonding situation in their central P4 ring characterized by polar σ-bonding, pronounced out-of-ring activity by a nonbonding lone pair of electrons, and an additional non-classical three-center back-bonding contribution have been shown.

    3. DNA Recognition

      Resolution of Mixed Site DNA Complexes with Dimer-Forming Minor-Groove Binders by Using Electrospray Ionization Mass Spectrometry: Compound Structure and DNA Sequence Effects

      Sarah Laughlin, Dr. Siming Wang, Dr. Arvind Kumar, Dr. Abdelbasset A. Farahat, Prof. David W. Boykin and Prof. W. David Wilson

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406322

      Thumbnail image of graphical abstract

      Dimer system in DNA minor groove: A developed competitive ESI mass spectrometry method was used in the discovery of a new binding mode by a synthetic minor groove binding compound. The compound recognizes mixed DNA base pair sites as a cooperative dimer complex through stacking as an antiparallel system within the minor groove of mixed base pair sequences (see figure).

    4. Electrochemical Synthesis

      Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3-Azabicyclo[4.1.0]hept-4-enes

      Dr. Frédérick Nuter, Dr. Abdou Khadre Djily Dimé, Dr. Cheng Chen, Dr. Lotfi Bounaadja, Dr. Elisabeth Mouray, Dr. Isabelle Florent, Dr. Yvan Six, Dr. Olivier Buriez, Dr. Angela Marinetti and Dr. Arnaud Voituriez

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406138

      Thumbnail image of graphical abstract

      A series of substituted 3-azabicyclo[4.1.0]hept-4-ene derivatives were prepared (see scheme) and analysed by cyclic voltammetry. Three original endoperoxides were isolated, characterised and evaluated against two strains of Plasmodium falciparum and significant anti-plasmodial activities were noted.

  23. Communications

    1. Fluorescence

      High Excimer-State Emission of Perylene Bisimides and Recognition of Latent Fingerprints

      Prof. Dr. Ke-Rang Wang, Zi-Bo Yang and Prof. Dr. Xiao-Liu Li

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406447

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      Fluorescent fingerprints: High excimer-state emission in the H-type aggregate of a novel asymmetric perylene bisimide derivative was achieved in water. Furthermore, its application for enhancing the visualization of latent fingerprints transferred from glass slides to poly- (vinylidene fluoride) membrane was explored, with clear visualization of the fingerprints in daylight and with ultraviolet illumination.

    2. Molecular Rotation

      Restriction of Molecular Twisting on a Gold Nanoparticle Surface

      Tushar Debnath, Jayanta Dana, Partha Maity, Dr. Hyacintha Lobo, Prof. Ganapati S. Shankarling and Prof. Hirendra N. Ghosh

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500044

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      TICT off: The coumarin 3 (C3) molecule is found to have dual emitting intramolecular charge transfer (ICT) and twisted ICT (TICT) states. Rotation of the free 7-amino substituent in the excited state generates the twisted structure, which gives the TICT state. Au NPs restrict the rotation of the 7-amino substituent of C3; dual emitting C3 on the Au NP surface gives emission that is only due to the ICT state.

    3. Aluminum | Hot Paper

      Homocatenation of Aluminum: Alkane-like Structures of Li2Al2H6 and Li3Al3H8

      J. Tyler Gish, Ivan A. Popov and Prof. Alexander I. Boldyrev

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500298

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      Opening up the realms of possibility: Side-by-side comparison of structures of Li2Al2H6 and Li3Al3H8 with molecules of ethane and propane, respectively (see figure).

    4. Synthetic Methods

      Synthesis and Characterization of a Cu14 Hydride Cluster Supported by Neutral Donor Ligands

      Thuy-Ai D. Nguyen, Bryan R. Goldsmith, Homaira T. Zaman, Dr. Guang Wu, Prof. Dr. Baron Peters and Prof. Dr. Trevor W. Hayton

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500422

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      The copper hydride clusters [Cu14H12(phen)6(PPh3)4][X]2 (X=Cl or OTf; OTf=trifluoromethanesulfonate, phen=1,10-phenanthroline) were obtained in good yields by the reaction of [(Ph3P)CuH]6 with phen, in the presence of a halide or pseudohalide source. This work demonstrates that [(Ph3P)CuH]6 is a viable precursor for the generation of high nuclearity copper clusters.

    5. Electrochemistry

      Synthesis of Mesoporous Wall-Structured TiO2 on Reduced Graphene Oxide Nanosheets with High Rate Performance for Lithium-Ion Batteries

      Mengmeng Zhen, Meiqing Sun, Prof. Guandao Gao, Prof. Lu Liu and Prof. Zhen Zhou

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406678

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      Mesoporous wall-structured TiO2 on reduced graphene oxide nanosheets was successfully fabricated through a simple and steerable two-step hydrothermal process without any surfactants. The obtained mesoporous structured TiO2–reduced graphene oxide composites have high surface areas and exhibit excellent electrochemical cycling (a reversible capacity of 260 mAh g−1 at 1.2 C and 180 mAh g−1 at 5 C after 400 cycles).

  24. Full Papers

    1. Gold Catalysis

      Gold-Catalyzed Tandem Hydroamination/Formal Aza-Diels–Alder Reaction of Homopropargyl Amino Esters: A Combined Computational and Experimental Mechanistic Study

      Javier Miró, Dr. María Sánchez-Roselló, Dr. Javier González, Dr. Carlos del Pozo and Prof. Santos Fustero

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406224

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      Gold-catalyzed tandem reaction: In the presence of gold salts, homopropargyl amino esters that bear a quaternary stereocenter attached to the nitrogen atom undergo an unusual tandem hydroamination/formal aza-Diels–Alder reaction, which gives rise to complex tetracyclic scaffolds. By means of theoretical calculations, a plausible mechanistic pathway has been proposed. In combination with a ligand screening, this was crucial for broadening the reaction scope.

    2. Gold

      Gold–Acetonyl Complexes: From Side-Products to Valuable Synthons

      Danila Gasperini, Dr. Alba Collado, Dr. Adrián Goméz-Suárez, Dr. David B. Cordes, Prof. Dr. Alexandra M. Z. Slawin and Prof. Dr. Steven P. Nolan

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406543

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      Organogold: A library of [Au(NHC)(acetonyl)] complexes (NHC=N-heterocyclic carbene) has been easily synthesized. These complexes represent valuable synthetic precursors to a plethora of organogold species, as well as active catalysts for gold(I)-catalyzed reactions (see scheme).

  25. Communications

    1. Synthetic Methods

      Regio- and Chemoselective N-1 Acylation of Indoles: Pd-Catalyzed Domino Cyclization to Afford 1,2-Fused Tricyclic Indole Scaffolds

      Yongxian Liu, Yuanqiong Huang, Hongjian Song, Yuxiu Liu and Prof. Qingmin Wang

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406617

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      Domino route: A concise method for the synthesis of 1,2-fused tricyclic indole scaffolds by domino cyclization is reported. This method provides straightforward access to tetrahydro[1,4]diazepino[1,2-a]indole and hexahydro[1,5]diazocino[1,2-a]indole scaffolds (see figure).

  26. Full Papers

    1. Solvent Effects

      Morphology-Controlled Self-Assembly of an Organic/Inorganic Hybrid Porphyrin Derivative Containing Polyhedral Oligomeric Silsesquioxane (POSS)

      Prof. Feng Liu, Yuan Zhang, Lei Xu and Prof. Weian Zhang

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201405334

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      Get in shape! The self-assembly of metal-free tetrakisphenyl porphyrin–polyhedral oligomeric silsesquioxanes (H2TPP-POSS) in various solvents with different polarities was investigated. A series of assembled morphologies, including crescent-shaped micelles, spherical micelles, doughnut-shaped vesicles, and ordered square sheets, was obtained (see figure).

    2. Electroluminescent Devices | Hot Paper

      Sterically Hindered Luminescent PtII–Phosphite Complexes for Electroluminescent Devices

      Dr. Mathias Mydlak, Dr. Cheng-Han Yang, Dr. Federico Polo, Dr. Anzhela Galstyan, Dr. Constantin G. Daniliuc, Michael Felicetti, Jens Leonhardt, Dr. Cristian A. Strassert and Prof. Luisa De Cola

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201405839

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      Bright device: Efficient PtII-based emitters with inhibited aggregation are presented, with emission colors ranging from blue to green. Aggregation is avoided by the use of a sterically demanding bidentate phosphite ligand (see figure). It provides solubility and the emission properties are controlled by the second bidentate ligand.

  27. Communications

    1. Bioinspired Synthesis

      Site-Selective and Metal-Free Aliphatic C[BOND]H Oxidation Enabled Synthesis of [5,24,25-D3]-(25S)-Δ7-Dafachronic acid

      Weilong Liu, Xiangke Li, Jie Chen, Tiemei Li, Prof.Dr. Mengqiu Dong and Prof.Dr. Xiaoguang Lei

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500324

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      Bio is best! [5,24,25-D3]-(25S)-Δ7-Dafachronic acid, an isotope-labeled steroid hormone has been synthesized in 14 steps from cholesterol inspired by biosynthesis. Key steps include a site-selective and metal-free aliphatic C[BOND]H oxidation and a late-stage catalytic asymmetric deuteration (see scheme). [5,24,25-D3]-(25S)-Δ7-Dafachronic acid will be severed as an effective chemical tool for the illumination of novel molecular mechanisms of longevity.

  28. Full Papers

    1. Coordination Polymers

      Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis, Crystal Structures, and Magnetic Properties

      Dr. Maria-Gabriela Alexandru, Dr. Diana Visinescu, Prof. Marius Andruh, Dr. Nadia Marino, Dr. Donatella Armentano, Dr. Joan Cano, Prof. Francesc Lloret and Prof. Miguel Julve

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201406088

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      Heterotrimetallic complexes of various dimensionality and topology were synthesized from {Fe(AA)(CN)4} metalloligands and 3d–4f heterobimetallic building blocks, with Schiff base compartmental ligands: {CuIILnIIIFeIII} chains (see figure; compounds 13), a {CuIILaIIIFeIII} discrete molecule (4), and {NiIILnIIIFeIII} 2D coordination polymers (57). Magnetic measurements in ac field indicated the presence of the slow relaxation of the magnetization for 6.

  29. Communications

    1. Ligand Design

      Single Oxygen-Atom Insertion into P[BOND]B Bonds: On- and Off-Metal Transformation of a Borylphosphine into a Borylphosphinite

      Jonathan A. Bailey, Dr. Hazel A. Sparkes and Prof. Dr. Paul G. Pringle

      Article first published online: 20 FEB 2015 | DOI: 10.1002/chem.201500378

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      What a difference an atom makes: A single O atom can be readily incorporated into a borylphosphine-rhodium catalyst to produce a borylphosphinite-rhodium catalyst with sharply contrasting activity and selectivity.

  30. Concepts

    1. Sensors

      Self-Assembled Discrete Molecules for Sensing Nitroaromatics

      Dr. Sankarasekaran Shanmugaraju and Prof. Dr. Partha Sarathi Mukherjee

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406092

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      Molecular “sniffer dog”: This article summarizes the recent developments on rational design of electron-rich self-assembled discrete molecular sensors for nitroaromatic explosives (see figure), for sensing both in solution as well as in vapor phase.

  31. Communications

    1. Cyclodepsipeptides

      Divergent Solid-Phase Synthesis of Natural Product-Inspired Bipartite Cyclodepsipeptides: Total Synthesis of Seragamide A

      Prof. Dr. Hans-Dieter Arndt, Dr. Stefano Rizzo, M. Sc. Christina Nöcker, Dr. Vijay N. Wakchaure, Dr. Lech-Gustav Milroy, B. Sc. Vanessa Bieker, Dr. Abram Calderon, Dr. Tuyen T. N. Tran, Dr. Silke Brand, Dr. Leif Dehmelt and Prof. Dr. Herbert Waldmann

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201500368

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      An efficient solid-phase/cyclorelease method for the synthesis of a collection of macrocyclic depsipeptides with bipartite peptide/polyketide structure inspired by the very potent F-actin stabilizing depsipeptides of the jasplakinolide/geodiamolide class is described. The method was validated in the first total synthesis of the actin-stabilizing cyclodepsipeptide seragamide A and the synthesis of a collection of structurally diverse bipartite depsipeptides. RRCM = relay-ring-closing metathesis.

  32. Concepts

    1. Mechanochemistry

      You have free access to this content
      Mechanosensitive Membrane Probes

      Dr. Marta Dal Molin, Quentin Verolet, Saeideh Soleimanpour and Prof. Stefan Matile

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406320

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      Lobsters, flippers, disorder, tension and potential: The origins of the concept of mechanosensitive membrane probes—from fishmarket and scuba diving to the chemistry of vision, mechanochromic organic materials and mechanosensitive channels—are briefly reviewed (see scheme).

  33. Communications

    1. Organic Synthesis

      Saccharin-Based μ-Oxo Imidoiodane: A Readily Available and Highly Reactive Reagent for Electrophilic Amination

      Dr. Akira Yoshimura, Steven R. Koski, Jonathan M. Fuchs, Prof. Dr. Akio Saito, Prof. Dr. Victor N. Nemykin and Prof. Dr. Viktor V. Zhdankin

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201500335

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      Sweet saccharin: Three new saccharin-derived hypervalent iodine compounds were prepared by the reaction of saccharine with (diacetoxyiodo)arenes or acetoxybenziodoxole. The saccharin-based μ-oxo-bridged imidoiodane readily reacts with silyl enol ethers to give the corresponding α-aminated carbonyl compounds in moderate yields.

    2. Flow Chemistry

      Immobilization and Continuous Recycling of Photoredox Catalysts in Ionic Liquids for Applications in Batch Reactions and Flow Systems: Catalytic Alkene Isomerization by Using Visible Light

      M. Sc. David C. Fabry, B. Sc. Meria A. Ronge and Prof. Dr. Magnus Rueping

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406653

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      Catalytic (E)- to (Z)-isomerizations of olefins under mild conditions can be achieved by use of a photosensitizer and visible light. A new reaction system such as depicted allows an easy and efficient scale-up, as well as continuous flow processes in which the photocatalyst is immobilized in an ionic liquid and continuously recycled by phase separation.

  34. Full Papers

    1. Chiral Helical Structures

      Supramolecular Assembly of Achiral Alkynylplatinum(II) Complexes and Carboxylic β-1,3-Glucan into Different Helical Handedness Stabilized by Pt⋅⋅⋅Pt and/or π–π Interactions

      Dr. Clive Yik-Sham Chung, Prof. Shun-ichi Tamaru, Prof. Seiji Shinkai and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201405035

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      Two handed: Two-component ensembles of alkynylplatinum(II) terpyridine complexes and carboxylic β-1,3-glucan have been found to form supramolecular helical assemblies that are stabilized by Pt⋅⋅⋅Pt and/or π–π interactions (see figure). The systems show different handedness and even demonstrate a change in handedness over time under different experimental conditions. The results have been rationalized by considering the competing kinetic and thermodynamic assembly–elongation processes.

    2. Frustrated Lewis Pairs

      Conceptual Quantum Chemical Analysis of Bonding and Noncovalent Interactions in the Formation of Frustrated Lewis Pairs

      Gabriella Skara, Dr. Balazs Pinter, Jens Top, Prof. Dr. Paul Geerlings, Dr. Frank De Proft and Dr. Freija De Vleeschouwer

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201405891

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      Frustration explained: A combination of several state-of-the-art quantum chemical methods was used to analyze and visualize the nature of bonding in frustrated Lewis pairs (FLPs), which was compared to that of similar classical Lewis adducts (see figure). For the acid–base adducts, orbital (46–49 %) and electrostatic (46–49 %) interactions are the most stabilizing terms, whereas dispersion becomes the dominant term (41–50 %) in stabilizing FLPs.

    3. Nanostructures

      Boron-Doped, Carbon-Coated SnO2/Graphene Nanosheets for Enhanced Lithium Storage

      Yuxin Liu, Prof. Ping Liu, Prof. Dongqing Wu, Yanshan Huang, Yanping Tang, Prof. Yuezeng Su, Prof. Fan Zhang and Prof. Xinliang Feng

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406029

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      Doping for better anodes: Boron-doped carbon-coated SnO2/graphene hybrids (BCTGs) were fabricated by hydrothermal carbonization of sucrose in the presence of SnO2/graphene (TG) nanosheets and phenylboronic acid or boric acid as dopant source to give BSTGs and subsequent thermal treatment (see figure; GO: graphene oxide). Owing to the dopant B atoms in the hybrid and its 2D core–shell architecture, the hybrid obtained with phenylboronic acid as B source exhibits outstanding cycle stability after 360 cycles and an excellent rate capability at high current density.

    4. Reaction Mechanisms

      Experimental and Computational Insights into Carbon Dioxide Fixation by RZnOH Species

      Kamil Sokołowski, Dr. Wojciech Bury, Adam Tulewicz, Anna M. Cieślak, Dr. Iwona Justyniak, Dominik Kubicki, Elżbieta Krajewska, Prof. Anne Milet, Prof. Robert Moszyński and Prof. Janusz Lewiński

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406271

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      Tracking progress: Comprehensive experimental and computational investigations of the solution and solid-state behavior of tBuZnOH species in the presence of THF and 4-methylpyridine, a step-by-step sequence of the reaction between tBuZnOH and CO2, and the effect of a donor ligand and/or an excess of tBu2Zn as an external proton acceptor on the reaction course, are described (see figure).

    5. Fluorescent Carbon Dots

      Carbon Dots (C-dots) from Cow Manure with Impressive Subcellular Selectivity Tuned by Simple Chemical Modification

      Cintya D'Angelis do E. S. Barbosa, Dr. José R. Corrêa, Gisele A. Medeiros, Gabrielle Barreto, Dr. Kelly G. Magalhães, Dr. Aline L. de Oliveira, Prof. Dr. John Spencer, Prof. Dr. Marcelo O. Rodrigues and Prof. Dr. Brenno A. D. Neto

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201406330

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      Cow dots: Improved cellular selectivity for nucleoli staining was achieved by simple amine passivation of carbon dots (C-dots) synthesized from cow manure. The modified C-dots were successfully applied as selective live-cell fluorescence imaging probes with impressive subcellular selectivity and the ability to selectively stain nucleoli in breast cancer and other cell lines.

    6. Donor–Acceptor Systems

      Pyrene-Based Dyad and Triad Leading to a Reversible Chemical and Redox Optical and Magnetic Switch

      Carlos Franco, Dr. Marta Mas-Torrent, Dr. Antonio Caballero, Dr. Arturo Espinosa, Prof. Pedro Molina, Prof. Jaume Veciana and Prof. Concepció Rovira

      Article first published online: 18 FEB 2015 | DOI: 10.1002/chem.201405993

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      Switching properties: The synthesis of new pyrene–polychlorotriphenylmethyl (PTM) dyads and triads has permitted study of the interplay between the different electronic states of the PTM moiety and the optical and magnetic properties of the molecules, as well as their switching properties (see figure).

    7. Chiral Molecular Networks

      Chemistry of Anthracene–Acetylene Oligomers XXV: On-Surface Chirality of a Self-Assembled Molecular Network of a Fan-Blade-Shaped Anthracene–Acetylene Macrocycle with a Long Alkyl Chain

      Dr. Takuya Tsuya, Kohei Iritani, Dr. Kazukuni Tahara, Prof. Yoshito Tobe, Dr. Tetsuo Iwanaga and Prof. Shinji Toyota

      Article first published online: 17 FEB 2015 | DOI: 10.1002/chem.201405638

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      Networking: A chiral molecular network was constructed from prochiral molecules at the 1-phenyloctane/graphite interface as revealed by STM observations (see figure). The molecular packing mode that involves the chirality and the conformation of the alkyl chain was reasonably simulated by MM3 calculations.

  35. Communications

    1. Synthetic Methods

      Room Temperature C[BOND]P Bond Formation Enabled by Merging Nickel Catalysis and Visible-Light-Induced Photoredox Catalysis

      Jun Xuan, Ting-Ting Zeng, Prof. Dr. Jia-Rong Chen, Dr. Liang-Qiu Lu and Prof. Dr. Wen-Jing Xiao

      Article first published online: 17 FEB 2015 | DOI: 10.1002/chem.201500227

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      Dual catalysis: A novel and efficient C[BOND]P bond formation reaction of diarylphosphine oxides with aryl iodides was achieved by combining nickel catalysis and visible-light-induced photoredox catalysis (see scheme). This dual-catalytic reaction showed a broad substrate scope, excellent functional-group tolerance, and afforded the corresponding products in good to excellent yields. Compared with previously reported photoredox/nickel dual catalytic systems, this methodology is the first to allow for C[BOND]heteroatom bond formation.

  36. Full Papers

    1. Reaction Mechanisms

      Solvent Influence on Cellulose 1,4-β-Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

      Claudia Loerbroks, Eliot Boulanger and Prof. Dr. Walter Thiel

      Article first published online: 17 FEB 2015 | DOI: 10.1002/chem.201405507

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      A question of angles: How does solvation influence the acid hydrolysis mechanism of cellulose? This question is addressed with the help of molecular dynamics and metadynamics simulations for two solvents: water and 1-ethyl-3-methylimidazolium acetate. Solvent effects are compared in detail for cellobiose (see scheme; α1, β1, β2 and φ represent dihedral angles) and a chain of 40 glucose units. The simulations for the latter indicate that hydrolysis will start at the ends of the chain.

    2. Enzyme Models

      Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

      Roman Goy, Dr. Luca Bertini, Dr. Helmar Görls, Prof. Dr. Luca De Gioia, Dr. Jean Talarmin, Dr. Giuseppe Zampella, Prof. Dr. Philippe Schollhammer and Prof. Dr. Wolfgang Weigand

      Article first published online: 17 FEB 2015 | DOI: 10.1002/chem.201406087

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      H2ase mimics: A series of [FeFe]-H2ase mimics were synthesized and characterized in detail containing different bulky Si-heteroaromatic systems at the dithiolate moiety as well as their mono-PPh3-substituted derivatives (see figure). The experimental results and the theoretical studies confirm that the μ-sulfur atom directed to the PPh3 ligand acts as a favored basic site upon addition of an excess triflic acid.

    3. Catalytic C[BOND]H Functionalisation

      Ru-Catalysed C[BOND]H Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies

      Carina Sollert, Karthik Devaraj, Dr. Andreas Orthaber, Dr. Paul J. Gates and Dr. Lukasz T. Pilarski

      Article first published online: 17 FEB 2015 | DOI: 10.1002/chem.201405931

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      High tolerance: An oxidative, Ru-catalysed, and highly selective C[BOND]H arylation of indoles and pyrroles is accomplished by using boronic acids (see picture; pym=2-pyrimidyl). The reaction tolerates a wide range of functional groups, including aryl iodides and tryptophan derivatives. New indole-based ruthenacycles are described and their role in the mechanism is investigated.

    4. Helical Structures | Hot Paper

      Self-Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

      Partha Malakar and Prof. Dr. Edamana Prasad

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201405488

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      How will it gel? The J-type aggregation propensity, hydrogen-bond donor/acceptor ability of solvents, as well as the polarity of the medium have been identified as the main factors that control the self-assembly of helical structures by poly(aryl ether) based dendron derivatives with acyl hydrazone/hydrazide units.

    5. Ionic Liquids

      Tuning the Basicity of Cyano-Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interaction

      Dr. Guokai Cui , Fengtao Zhang, Xiuyuan Zhou , Prof. Haoran Li, Prof. Jianji Wang and Prof. Congmin Wang

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201405683

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      SO2 sorption strategy: A new approach has been developed for improving SO2 sorption by cyano-containing ionic liquids with different basicities. The dramatic effect of the cyano group on SO2 capacity originates from the basicity of the ionic liquids and the enhanced cyano–sulfur interaction (see picture), as revealed by a combination of sorption experiments, spectroscopic investigations, and quantum chemical calculations.

    6. Ethylene/Propylene Copolymerisation

      Vanadium(V) Oxo and Imido Calix[8]arene Complexes: Synthesis, Structural Studies, and Ethylene Homo/Copolymerisation Capability

      Prof. Dr. Carl Redshaw, Dr. Mark J. Walton, Dr. Darren S. Lee, Chengying Jiang, Dr. Mark R. J. Elsegood and Dr. Kenji Michiue

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406084

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      Interaction of p-tert-butylcalix[8]areneH8 with MOtBu and VOCl3 (M=Li, Na, K) affords vanadium(V) oxo calix[8]arene complexes. Imido complexes were also formed with [V(NR)(OtBu)3] (R=tBu, p-tolyl). Molecular structures are presented, along with activities as precatalysts for the polymerisation of ethylene and copolymerisation with propylene (see picture; stand=benchmark [VO(OEt)Cl2]). Higher molecular weight polymers could be obtained versus the benchmark. For copolymerisation, incorporation of propylene was 7.1–10.9 mol % (compare 10 mol % for [VO(OEt)Cl2]), although catalytic activities were lower than [VO(OEt)Cl2].

    7. Helical Superstructures

      Chiral Perylene Diimides: Building Blocks for Ionic Self-Assembly

      Dr. Geraldine Echue, Prof. Guy C. Lloyd-Jones and Dr. Charl F. J. Faul

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406094

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      Chirality for construction! A chiral perylene diimide building block has been prepared based on an amine derivative of the amino acid L-phenylalanine. Detailed studies were carried out into the self-assembly behaviour of the material in solution and the solid state using UV/Vis, circular dichroism (CD) and fluorescence spectroscopy, as well as polarised light microscopy (see figure).

    8. Graphene Oxide

      Graphene Oxide Nanoribbons: Improved Synthesis and Application in MALDI Mass Spectrometry

      Dr. Qian Liu, Mengting Cheng, Jing Wang and Prof. Guibin Jiang

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406280

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      Tie a nanoribbon: Graphene oxide nanoribbons were synthesized with a one-step, one-pot pressurized oxidation method. They were demonstrated to be an excellent matrix or probe for matrix-assisted or surface-enhanced laser desorption/ionization mass spectrometry (MALDI or SELDI MS) in the detection of small molecules (see figure).

    9. Synthesis Design

      tert-Butyl(tert-Butoxy)zinc Hydroxides: Hybrid Models for Single-Source Precursors of ZnO Nanocrystals

      Kamil Sokołowski, Dr. Iwona Justyniak, Dr. Wojciech Bury, Dr. Justyna Grzonka, Prof. Zbigniew Kaszkur, Łukasz Mąkolski, Michał Dutkiewicz, Agnieszka Lewalska, Elżbieta Krajewska, Dominik Kubicki, Dr. Katarzyna Wójcik, Prof. Krzysztof J. Kurzydłowski and Prof. Janusz Lewiński

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406245

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      Get it together: A new family of tert-butyl(tert-butoxy)zinc hydroxides [(tBu)4Zn43-OtBu)x3-OH)4−x] as model single-source precursors of ZnO nanoparticles (NPs; see figure) are described. Zn[BOND]OH groups within the “Zn4O4” core appear to be a desirable feature that lowers the decomposition temperature of crystalline precursors significantly.

    10. Perovskite Phases

      Pyrochlore and Perovskite Potassium Tantalate: Enthalpies of Formation and Phase Transformation

      Sebastian Zlotnik, Dr. Sulata K. Sahu, Prof. Alexandra Navrotsky and Prof. Paula M. Vilarinho

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201405666

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      A meltdown: The formation and decomposition energetics for K2O[BOND]Ta2O5 compounds were measured by high-temperature oxide melt calorimetry. The enthalpies of formation were determined (experimentally for the first time) for perovskite KTaO3 and pyrochlores K2−xTa2+x/5O6 with different stoichiometries (see figure).

    11. Boron Complexes

      First-Row Transition-Metal–Diborane and –Borylene Complexes

      Dudekula Sharmila, Bijan Mondal, Rongala Ramalakshmi, Sangita Kundu, Dr. Babu Varghese and Prof. Sundargopal Ghosh

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201405585

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      Building bridges: The synthesis and full characterization of a new manganaborane containing a diborane(6) dianion ligand has been described. In addition, the synthesis and characterization of new hetero- and homotrinuclear triply bridged borylene complexes from the reaction of a cobalt intermediate with metal carbonyls ({M2(CO)10}, (M=Mn, Re); see figure) is also reported. DFT computations were used to shed light into the bonding and electronic structures of these new compounds.

  37. Communications

    1. Organocatalysis

      An NHC-Catalyzed In Situ Activation Strategy to β-Functionalize Saturated Carboxylic Acid: An Enantioselective Formal [3+2] Annulation for Spirocyclic Oxindolo-γ-butyrolactones

      Yuanwei Xie, Prof. Chenxia Yu, Tuanjie Li, Prof. Dr. Shujiang Tu and Prof. Dr. Changsheng Yao

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201500345

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      Top cat: An in situ NHC-catalyzed activation strategy to β-functionalize saturated carboxylic acid was developed (see scheme). This asymmetric formal [3+2] annulation delivered spirocyclic oxindolo-γ-butyrolactones from saturated carboxylic acid and isatin in good yields with high to excellent enantioselectivities. The availability of the starting materials, direct installation of functional units at unreactive carbon atom and the convergent assembly make this protocol attractive for organic synthesis.

    2. Organic Synthesis

      Direct C[BOND]H Amidation of Benzoic Acids to Introduce meta- and para-Amino Groups by Tandem Decarboxylation

      Donggun Lee and Prof. Sukbok Chang

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201500331

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      Without a trace: Carboxylic acids are used as traceless directing groups in the Ir-catalyzed direct C[BOND]H amidation of arenes with sulfonyl azides under mild conditions. The tandem protodecarboxylation of the ortho-amidated benzoic acid products afforded meta- or para-substituted (N-sulfonyl)anilines, which are difficult to obtain by other C[BOND]H functionalization approaches.

    3. Calcium Catalysis

      Calcium-Catalyzed Formal [2+2+2] Cycloaddition

      Dr. Vera J. Meyer, Christoph Ascheberg and Prof. Meike Niggemann

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201500181

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      A simple catalyst for a complex task: A formal intermolecular [2+2+2] cycloaddition reaction of enynes to aldehydes was realized in the presence of a simple and benign calcium catalyst (see scheme). The reaction proceeds with excellent chemo-, regio- and diastereoselectivity and leads to a one-step assembly of highly interesting bicyclic building blocks containing up to three stereocenters from simple precursors via a new type of skeletal rearrangement of enynes.

    4. Bioorganometallic chemistry

      Selective Ruthenium Labeling of the Tryptophan Residue in the Bee Venom Peptide Melittin

      Dr. Dmitry S. Perekalin, Dr. Valentin V. Novikov, Alexander A. Pavlov, Igor A. Ivanov, Dr. Natalia Yu. Anisimova, Alexey N. Kopylov, Dr. Dmitry S. Volkov, Dr. Irina F. Seregina, Prof. Dr. Michail A. Bolshov and Prof. Dr. Alexander R. Kudinov

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406510

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      Busy as bees: Selective tryptophan labeling in bee venom peptide melittin by organometallic fragment [(C5H5)Ru]+ was carried out in aqueous solution in air. The ruthenium coordination converted a hydrophobic tryptophan residue into cationic complex, thus changing the quaternary structure and biological activity of the peptide. High stability of the label allowed the establishment of the biodistribution of melittin in mice, using inductively coupled plasma MS analysis of ruthenium.

    5. Hydrothiolation | Hot Paper

      Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

      Krzysztof Kuciński, Dr. Piotr Pawluć, Prof. Dr. Bogdan Marciniec and Dr. Grzegorz Hreczycho

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406412

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      Stick to the rules: The use of Lewis acid as a catalyst in the addition of thiols to unsaturated organosilicon compounds is reported. Scandium(III) triflate demonstrates high catalytic activity in this process. The use of allylsilanes leads to products that are consistent with the Markovnikov’s rule. This is the first example of allylsilane hydrothiolation that gives the Markovnikov regioisomer as the main product.

    6. Diamondoid Metal–Organic Framework

      Encapsulation of an Interpenetrated Diamondoid Inorganic Building Block in a Metal–Organic Framework

      Dr. Huabin Zhang, Dr. Ping Lin, Dr. Erxia Chen, Dr. Yanxi Tan, Dr. Tian Wen, Prof. Ali Aldalbahi, Prof. Saad M. Alshehri, Prof. Yusuke Yamauchi, Prof. Shaowu Du and Prof. Jian Zhang

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201405710

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      Diamondoid inorganic building block: The first example of an inorganic–organic composite framework with an interpenetrated diamondoid inorganic building block, featuring unique {InNa}n helices and {In12Na16} nano-rings, has been constructed and structurally characterized (see graphic). This framework also represents a unique example of encapsulation of an interpenetrated diamondoid inorganic building block in a metal–organic framework.

    7. Biochemistry

      Photobiochemical Production of Carbon Monoxide by Thermus thermophilus ba3-Cytochrome c Oxidase

      Dr. Constantinos Koutsoupakis, Prof. Tewfik Soulimane and Prof. Constantinos Varotsis

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406239

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      Carbon monoxide: Spectroscopic evidence for the photochemical production of carbon monoxide by ba3-oxidoreductase is presented (see figure). FTIR and time-resolved step-scan FTIR spectroscopies were combined to probe this process and also monitor the concomitant binding of the produced gas to other intact ba3 molecules forming the ba3–CO complex.

    8. Decarbonylation

      Decarbonylative C[BOND]C Bond-Forming Reactions of Saccharins by Nickel Catalysis: Homocoupling and Cycloaddition

      Pengbing Mi, Dr. Peiqiu Liao, Prof. Tao Tu and Prof. Xihe Bi

      Article first published online: 16 FEB 2015 | DOI: 10.1002/chem.201406227

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      Decarbonylation of saccharins by nickel catalysis has led to the discovery of two novel C[BOND]C bond-forming reactions; homocoupling to form biaryls, and cycloaddition with alkynes to give benzosultams. The former represents the first nickel-catalyzed decarbonylative C[BOND]C homocoupling reaction, whereas the latter constitutes a powerful method to pharmaceutically relevant benzosultams with good functional-group tolerance and excellent regioselectivity.

  38. Full Papers

    1. Macrocycles | Hot Paper

      Palladium-Catalyzed Annulation of 9-Halophenanthrenes with Alkynes: Synthesis, Structural Analysis, and Properties of Acephenanthrylene-Based Derivatives

      En-Chih Liu, Min-Kuan Chen, Jen-Yi Li and Prof. Yao-Ting Wu

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201405763

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      Put a ring on it: The palladium-catalyzed annulation of 9-halophenanthrenes with alkynes produced 4,5-disubstituted acephenanthrylenes (see scheme). The annulated diphenyl-substituted acephenanthrylene derivatives were converted into phenanthro[9,10-e]acephenanthrylenes by oxidative cyclodehydrogenation. The photophysical and electrochemical properties of selected compounds were investigated.

    2. Pd Nanocrystals

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      Polyoxometalate-Mediated One-Pot Synthesis of Pd Nanocrystals with Controlled Morphologies for Efficient Chemical and Electrochemical Catalysis

      Dr. Dongheun Kim, Ji Hyun Seog, Minjune Kim, MinHo Yang, Eleanor Gillette, Prof. Dr. Sang Bok Lee and Prof. Dr. Sang Woo Han

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201406400

      Thumbnail image of graphical abstract

      Single-crystalline Pd nanocrystals with controlled shapes and sizes were synthesized by a polyoxometalate-mediated one-pot aqueous synthesis method. The prepared Pd nanocrystals exhibited enhanced catalytic properties toward electrochemical and chemical reactions (see figure).

    3. DNA | Hot Paper

      Isoguanine and 5-Methyl-Isocytosine Bases, In Vitro and In Vivo

      Dr. Omprakash Bande, Rania Abu El Asrar, Dr. Darren Braddick, Dr. Shrinivas Dumbre, Dr. Valérie Pezo, Guy Schepers, Prof. Vitor B. Pinheiro, Prof. Eveline Lescrinier, Prof. Philipp Holliger, Dr. Philippe Marlière and Prof. Piet Herdewijn

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201406392

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      Synthesis and base-pairing properties of 5-methyl-isocytosine and isoguanine nucleosides incorporated in a hexitol nucleic acid (HNA)–DNA mosaic backbone are described. Enzymatic incorporation experiments show that the hexitol backbone has a variable effect on selectivity. Results in vivo demonstrated that mispairing and misincorporation was dependent on the backbone scaffold of the base (see scheme).

    4. Reaction Mechanisms | Very Important Paper

      Reactivity and Operational Stability of N-Tailed TAMLs through Kinetic Studies of the Catalyzed Oxidation of Orange II by H2O2: Synthesis and X-ray Structure of an N-Phenyl TAML

      Genoa R. Warner, Matthew R. Mills, Clarissa Enslin, Shantanu Pattanayak, Chakadola Panda, Tamas Kumar Panda, Prof. Sayam Sen Gupta, Prof. Alexander D. Ryabov and Prof. Terrence J. Collins

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201406061

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      N-Tailed TAMLs in water: Iron–TAML (tetraamido macrocyclic ligand) activators with N-methyl tail adopt a similar mechanism of oxidative catalysis and display comparable reactivity in water as their earlier prototypes despite their compactness (see scheme).

    5. Oligomerization

      CaO as Drop-In Colloidal Catalysts for the Synthesis of Higher Polyglycerols

      Dr. Fiona Kirby, Anne-Eva Nieuwelink, Bonny W. M. Kuipers, Dr. Anton Kaiser, Dr. Pieter C. A. Bruijnincx and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201405906

      Thumbnail image of graphical abstract

      Drop-in CaO colloidal catalyst: An elegant method for the use of CaO colloidal particles in glycerol oligomerization has been developed. Firstly, CaO nanoparticles are stabilized/dispersed on carbon nanofibers. Secondly, the colloids are dispensed from the carbon nanofibers into the reaction medium (see scheme). These CaO colloids are highly active for the etherification of glycerol to linear polyglycerols containing more than three glycerol units and with a low Gardner color number.

    6. Carboxylate Receptors

      Towards the Discrimination of Carboxylates by Hydrogen-Bond Donor Anion Receptors

      Sandip A. Kadam, Kerli Martin, Kristjan Haav, Dr. Lauri Toom, Dr. Charly Mayeux, Astrid Pung, Prof. Philip A. Gale, Dr. Jennifer R. Hiscock, Dr. Simon J. Brooks, Dr. Isabelle L. Kirby, Dr. Nathalie Busschaert and Prof. Ivo Leito

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201405858

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      Can we discriminate? Comprehensive binding studies of four carboxylate anions with a number of anion receptors (see figure) reveals that the binding strength is largely determined by the basicity of the anion (leading to the general binding order lactate <benzoate<acetate≤trimethylacetate) and modulated by additional effects, such as the steric fit between the anion and the receptor as well as the hydrophilicity/hydrophobicity of the anion.

    7. Solar Energy Conversion

      Layer-by-Layer Assemblies of Catechol-Functionalized TiO2 Nanoparticles and Porphyrins through Electrostatic Interactions

      Alexandra Burger, Dr. Rubén D. Costa, Dr. Volodymyr Lobaz, Prof. Dr. Wolfgang Peukert, Prof. Dr. Dirk M. Guldi and Prof. Dr. Andreas Hirsch

      Article first published online: 13 FEB 2015 | DOI: 10.1002/chem.201405039

      Thumbnail image of graphical abstract

      Multilayer assemblies: Layer-by-layer assemblies of positively charged TiO2 nanoparticles (NPs) and anionic porphyrins are applied in solar-energy conversion schemes. TiO2 NPs are functionalized with permanent positively charged catechol molecules, leading to stable ethanolic NP suspensions. Alternate deposition of these NPs and anionic porphyrins through simple dip coating results in multilayer assemblies formed through electrostatic attraction (see figure).

    8. Asymmetric Synthesis

      Absolute Asymmetric Synthesis: Protected Substrate Oxidation

      Dr. Susanne Olsson, Per Martin Björemark, Dr. Theonitsa Kokoli, Dr. Jonas Sundberg, Dr. Anders Lennartson, Prof. Christine J. McKenzie and Prof. Mikael Håkansson

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406354

      Thumbnail image of graphical abstract

      Optical activity is created when enantiopure ruthenium(II) complexes are crystallized from achiral starting materials. This process, total spontaneous resolution, enables enantioselective ligand oxidation, as demonstrated by the oxidation of sulfide ligands to give chiral RuII sulfoxide complexes with >98 % ee.

  39. Communications

    1. Fullerenes | Hot Paper

      C100 is Converted into C94Cl22 by Three Chlorination-Promoted C2 Losses under Formation and Elimination of Cage Heptagons

      Dr. Ilya N. Ioffe, Prof. Dr. Shangfeng Yang, Song Wang, Prof. Dr. Erhard Kemnitz, Prof. Dr. Lev N. Sidorov and Prof. Dr. Sergey I. Troyanov

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406487

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      Loss in three acts: Three acts of C2 loss occur upon high-temperature chlorination of the C100 fullerene. The resulting C94Cl22 (see picture) contains 13 pentagons and one heptagon in a non-classical C94 carbon cage. Although two successive C2 losses of 5:6 C[BOND]C bonds introduce two heptagons, the concluding abstraction of a 5:5 C[BOND]C bond destroys one of them. Theoretical calculations reveal that C2 elimination proceeds with relatively low activation energy.

    2. Nanoparticles

      Ultrasensitive Biosensing Platform Based on Luminescence Quenching Ability of Plasmonic Palladium Nanoparticles

      Hui Li, De-en Sun and Prof. Zhihong Liu

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406633

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      Performing particles: An ultrasensitive biosensing platform for DNA and protein detection is constructed based on the luminescence quenching ability of plasmonic palladium nanoparticles (PdNPs see scheme in gray; yellow ribbon=fluorescein tagged ssDNA chain; FRET=Förster resonance energy transfer) for the first time. It offers pronounced sensing performances and can be reasonably expected to be of use for a wide range of applications.

    3. Homogeneous Catalysis

      Simultaneous Induction of Axial and Planar Chirality in Arene–Chromium Complexes by Molybdenum-Catalyzed Enantioselective Ring-Closing Metathesis

      Prof.Dr. Ken Kamikawa, Dr. Sachie Arae, Dr. Wei-Yi Wu, Chihiro Nakamura, Prof.Dr. Tamotsu Takahashi and Prof.Dr. Masamichi Ogasawara

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201500226

      Thumbnail image of graphical abstract

      Enantiomerically enriched planar-chiral (π-arene)chromium complexes were prepared by Mo-catalyzed asymmetric ring-closing metathesis (RCM) desymmetrization of Cs-symmetric substrates. The axial chirality of indolyl- or naphthyl-containing substrates was retained after removal of the Cr(CO)2 fragment, and biaryl/heterobiaryl compounds were obtained in high enantiopurity.

  40. Full Papers

    1. NMR Spectroscopy | Hot Paper

      Generation of Pseudocontact Shifts in Proteins with Lanthanides Using Small “Clickable” Nitrilotriacetic Acid and Iminodiacetic Acid Tags

      Dr. Choy-Theng Loh, Dr. Bim Graham, Elwy H. Abdelkader, Dr. Kellie L. Tuck and Prof. Gottfried Otting

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406274

      Thumbnail image of graphical abstract

      Stable and versatile: Three different lanthanide-binding tags have been explored that can be attached to p-azidophenyl-L-alanine in a click reaction. Loaded with lanthanides, the tags reliably induced pseudocontact shifts in proteins and the data were readily fitted by a single magnetic susceptibility anisotropy tensor (see figure). They present widely applicable tools for protein structure analysis by paramagnetic NMR spectroscopy.

    2. Organocatalysis

      One-Pot Synthesis of O-Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]-Meisenheimer Rearrangement

      Alexis Theodorou, Dr. Dimitris Limnios and Prof. Dr. Christoforos G. Kokotos

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406173

      Thumbnail image of graphical abstract

      All in one pot: The organocatalytic oxidation of tertiary allylic amines followed by a Meisenheimer rearrangement leads to protected hydroxylamines (see scheme).

  41. Communications

    1. Magnetism

      A Single-Ion Magnet Based on a Heterometallic CoIII2DyIII Complex

      Dr. Joydeb Goura, Jamie Brambleby, Dr. Paul Goddard and Prof. Dr. Vadapalli Chandrasekhar

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406021

      Thumbnail image of graphical abstract

      A zero-field SIM: A diamagnetic CoIII-containing CoIII2Dy single-ion magnet has been synthesised and characterised (see figure).

  42. Full Papers

    1. Ion Sorbents

      Highly Efficient Copper(II) Ion Sorbents Obtained by Calcium Carbonate Mineralization on Functionalized Cross-Linked Copolymers

      Dr. Marcela Mihai, Dr. Ion Bunia, Florica Doroftei, Dr. Cristian-Dragos Varganici and Prof. Bogdan C. Simionescu

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201406011

      Thumbnail image of graphical abstract

      Copper(II) ion sorbents were obtained by CaCO3 mineralization on polymeric beads as insoluble templates. A copolymer functionalized with weakly acidic, basic, or amphoteric functional groups was used. The beads were tested for CuII ion sorbtion before and after mineralization, and the morphology was investigated by scanning electron microscopy. Sorption capacity increased significantly after CaCO3 crystal growth on the weakly anionic bead surface compared to unmodified beads.

    2. Photoelectrochemical Cytosensor

      Long-Lived Charge Carriers in Mn-Doped CdS Quantum Dots for Photoelectrochemical Cytosensing

      Dr. Peng Wu, Dr. Jian-Bing Pan, Xiang-Ling Li, Prof. Xiandeng Hou, Prof. Jing-Juan Xu and Prof. Hong-Yuan Chen

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201405798

      Thumbnail image of graphical abstract

      Impeded recombination for enhanced separation: Long-lived charge carriers elicited by Mn2+ doping of CdS quantum dots (QDs) boost photocurrent generation therein (see figure). This enhancement has been exploited for photoelectrochemical cytosensing.

    3. Dynamic Behavior

      A Ferrocenyl Kaleidoscope: Slow Interconversion of Six Diastereo-atropisomers of 2,6-Di-tert-butyl-9,10-diferrocenyltriptycene

      Dr. Kirill Nikitin, Dr. Jimmy Muldoon, Dr. Helge Müller-Bunz and Prof. Dr. Michael J. McGlinchey

      Article first published online: 12 FEB 2015 | DOI: 10.1002/chem.201405968

      Thumbnail image of graphical abstract

      Rotational dynamics: Six interconverting rotamers that are almost equivalent in energy are obtained for 2,6-di-tert-butyl-9,10-diferrocenyltriptycene. Application of one- and two-dimensional NMR techniques over a range of temperatures together, with a detailed analysis of the homo- and heteronuclear correlations, resulted in the unequivocal mapping of the 99 1H and 162 13C positions in the six interconverting systems.

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