Chemistry - A European Journal

Cover image for Vol. 19 Issue 27

July 1, 2013

Volume 19, Issue 27

Pages 8689–9071

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Cetylpyridinium Chloride Activated Trinitrotoluene Explosive Lights Up Robust and Ultrahigh Surface-Enhanced Resonance Raman Scattering in a Silver Sol (Chem. Eur. J. 27/2013) (page 8689)

      Dr. Honglin Liu, Dongyue Lin, Yudie Sun, Dr. Liangbao Yang and Prof. Jinhuai Liu

      Version of Record online: 21 JUN 2013 | DOI: 10.1002/chem.201390097

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      Difficult, but excellent surface-enhanced resonance Raman scattering (SERRS) provides a fast and accurate method for the detection of ultra-small traces of trinitrotoluene (TNT) under low laser power and in a short integration time. In their Full Paper on page 8789 ff., H. L. Liu, L. B. Yang, J. H. Liu et al. describe how cetylpyridinium chloride modified on Ag sols not only acts as the surface-seeking species to trap sulfite-sulfonated TNT, but also undergoes complexation with the sulfonated TNT, resulting in the appearance of two charge-transfer bands at 467 and 530 nm.

    2. You have free access to this content
      Inside Cover: Ternary Rare-Earth Transition-Metal Polyhydride Cluster Compounds (Chem. Eur. J. 27/2013) (page 8690)

      Tobias Bauer, Dr. Frank R. Wagner and Prof. Dr. Rhett Kempe

      Version of Record online: 21 JUN 2013 | DOI: 10.1002/chem.201390098

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      The first examples of ternary rare-earth transition-metal polyhydride clusters (such as depicted) are reported by F. R. Wagner, R. Kempe, and T. Bauer in their Communication on page 8732 ff. Cluster formation proceeds through C[BOND]H bond activation of the Cp ligands that stabilize the transition-metal-containing starting material. Analysis of the electronic structure of the polyhydride cluster compounds revealed covalent Re[BOND]Lu bonding and ionic transition metal hydride–Lu interactions.

  2. Graphical Abstract

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

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

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

      Biomimetic Synthesis of Materials for Technology (pages 8710–8725)

      Dr. Johanna M. Galloway, Dr. Jonathan P. Bramble and Dr. Sarah S. Staniland

      Version of Record online: 12 JUN 2013 | DOI: 10.1002/chem.201300721

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      Biomineralization for technology: Bioinspired, biokleptic and biomimetic materials can be used to form a wide range of technologically relevant materials under environmentally friendly conditions (see figure). A range of biotemplated and bioinspired materials have been described that can be used to develop components for devices, such as optics, photonics, photovoltaics, circuits and data storage.

  5. Communications

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

      Metal-Free Oxidative para Cross-Coupling of Phenols (pages 8726–8731)

      Dr. Koji Morimoto, Kazuma Sakamoto, Yusuke Ohnishi, Takeshi Miyamoto, Dr. Motoki Ito, Dr. Toshifumi Dohi and Prof. Dr. Yasuyuki Kita

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201301028

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      C[BOND]C coupling: Direct oxidative coupling reactions are an attractive tool for environmentally benign chemistry. The oxidative biaryl coupling reaction of phenols with various arenes at the para positions with hypervalent iodine reagents may also be included in this category. The reaction proceeds under very mild conditions without metal catalysts in a very short time under ambient conditions (see scheme; HFIP=hexafluoroisopropanol).

    2. Metal–Metal Interactions

      Ternary Rare-Earth Transition-Metal Polyhydride Cluster Compounds (pages 8732–8735)

      Tobias Bauer, Dr. Frank R. Wagner and Prof. Dr. Rhett Kempe

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/chem.201301290

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      Combining three: The first examples of ternary rare-earth transition-metal polyhydride clusters (see figure) are reported. Cluster formation proceeds through C[BOND]H bond activation of the Cp ligands that stabilize the transition-metal-containing starting material. Analysis of the electronic structure of the polyhydride cluster compounds revealed covalent Re[BOND]Lu bonding and ionic transition metal hydride–Lu interactions.

    3. Fluorescent Probes

      9-(4-Dimethylaminophenyl)benzo[b]quinolizinium: A Near-Infrared Fluorophore for the Multicolor Analysis of Proteins and Nucleic Acids in Living Cells (pages 8736–8741)

      Dr. Roberta Bortolozzi, Prof. Dr. Heiko Ihmels, Laura Thomas, Dr. Maoqun Tian and Dr. Giampietro Viola

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201301164

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      All lit up: The title compound operates as a fluorescent light-up probe that enables the detection of different biologically relevant hosts at different fluorescence maxima. It is demonstrated that this chemosensor also allows the fluorimetric multicolor analysis of different components in living cells (see figure).

    4. Light-Emitting Diodes

      Synthesis of Highly Fluorescent Diquinaldinatoalumino Silole Derivatives (pages 8742–8745)

      Erika Pusztai, Dr. Seunghyun Jang, Dr. Irina S. Toulokhonova, Dr. Ilia A. Guzei, Prof. Robert West, Dr. Rongrong Hu and Prof. Ben Zhong Tang

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300728

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      Two-in-one fluorescent compounds: Blending the strong emitter, diquinaldinato aluminum, and the good electron transporter, tetraphenyl silole, resulted in highly fluorescent compounds that are promising candidates for light-emitting devices without the need of dopants (see figure).

    5. Metalated Nitriles

      Metalated Nitriles: SNi and SNi′ Installation of Contiguous Quaternary–Tertiary and Quaternary–Quaternary Centers (pages 8746–8750)

      Dr. Jesus A. Lujan-Montelongo, Ping Lu, Dr. Wang Liu and Prof. Fraser F. Fleming

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/chem.201301046

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      “Black belt” SNi and SNi′: Deuterium labeling revealed an inherent preference of N- and C-metalated nitriles for SNi, rather than SNi′ displacement. The fundamental reactivity preferences are harnessed in a series of cyclizations to cis- and trans-decalins that install contiguous quaternary–tertiary and quaternary–quaternary stereocenters (see scheme).

    6. Alkylation

      TaMe3Cl2-Catalyzed Intermolecular Hydroaminoalkylation: A Simple Complex for Enhanced Reactivity and Expanded Substrate Scope (pages 8751–8754)

      Dr. Zhengxing Zhang, Jean-Denys Hamel and Prof. Dr. Laurel L. Schafer

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/chem.201300992

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      Tantalizingly simple: The common organometallic starting material TaMe3Cl2 can be used for the catalytic C[BOND]H functionalization reaction, hydroaminoalkylation. The substrate scope for this readily accessed compound includes unactivated terminal and internal alkenes, styrene derivatives, and both alkylaryl- and dialkyl secondary amines (see scheme).

    7. Enzyme Assays

      Specifically Monitoring Butyrylcholinesterase by Supramolecular Tandem Assay (pages 8755–8759)

      Dr. Dong-Sheng Guo, Jing Yang and Prof. Yu Liu

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/chem.201300980

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      Heart AChE: Two cholinesterases can be readily differentiated by applying the tandem-assay principle, in which the activity of butyrylcholinesterase (BChE) can be directly and specifically monitored, even with excess acetylcholinesterase (AChE; see scheme).

    8. Hydrophosphination

      Iron-Salt-Promoted Highly Regioselective α and β Hydrophosphination of Alkenyl Arenes (pages 8760–8764)

      Dr. Lucie Routaboul, Dr. Fabien Toulgoat, Jérémie Gatignol, Jean-François Lohier, Dr. Brigitte Norah, Dr. Olivier Delacroix, Dr. Carole Alayrac, Dr. Marc Taillefer and Prof. Dr. Annie-Claude Gaumont

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201301417

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      Iron(ic) phosphination: The iron-promoted hydrophosphination of alkenyl arenes with diphenylphosphine as the phosphinating agent has been established. This method provides efficient access to diarylalkylphosphines. The regioselectivity of the reaction can be fine-tuned by the choice of the iron salts, offering highly selective access to both the β and the α adducts (see scheme).

    9. Cross-Coupling

      Vinyl Nosylates: An Ideal Partner for Palladium-Catalyzed Cross-Coupling Reactions (pages 8765–8768)

      Nicolas P. Cheval, Anna Dikova, Dr. Aurélien Blanc, Prof. Jean-Marc Weibel and Prof. Patrick Pale

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201300127

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      In a hurry to leave! Nosylates act as an excellent leaving group in various palladium-catalyzed cross-couplings, such as Suzuki, Stille, Heck, and Sonogashira reactions (see scheme). Crystalline, stable, and cheap vinyl and aryl nosylates proved better than classical halides and triflates, consistently giving higher yields of coupling products. Their usefulness in C[BOND]C bond formation was also demonstrated by the rapid synthesis of the alkaloid dubamine.

    10. Ferroelectric Materials

      Multifunctional DyIII4 Cluster Exhibiting White-Emitting, Ferroelectric and Single-Molecule Magnet Behavior (pages 8769–8773)

      Peng-Hu Guo, Jun-Liang Liu, Dr. Jian-Hua Jia, Dr. Jing Wang, Fu-Sheng Guo, Yan-Cong Chen, Wei-Quan Lin, Ji-Dong Leng, Prof. Dr. Ding-Hua Bao, Dr. Xu-Dong Zhang, Prof. Dr. Jun-Hua Luo and Prof. Dr. Ming-Liang Tong

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/chem.201300299

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      Multifunctional material: A remarkable case of a single-molecule magnet that demonstrates white-light emission and ferroelectricity was observed in a butterfly-shaped chiral DyIII4 cluster, [Dy4(μ-bpt)43-OH)2(μ-OMe)2(NO3)4]3 MeOH (bpt=3,5-bis(pyridin-2-yl)-1,2,4-trizolate, see figure).

  6. Full Papers

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

      Experimental and Computational Probes of the Nature of Halogen Bonding: Complexes of Bromine-Containing Molecules with Bromide Anions (pages 8774–8788)

      Prof. Sergiy V. Rosokha, Charlotte L. Stern and Jeremy T. Ritzert

      Version of Record online: 11 JUN 2013 | DOI: 10.1002/chem.201300577

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      Charge transfer or electrostatics: Experimental and computational characterization of the complexes between bromocarbons and Br ions, [R[BOND]Br, Br] revealed that their structural (inter- and intramolecular bond lengths) and spectral features are directly related to the Br[RIGHTWARDS ARROW]R[BOND]Br charge transfer, and their energetics are accounted for by the combination of the charge-transfer and electrostatic interactions. The results indicate that orbital (charge-transfer) interactions play a vital role in the R[BOND]Br⋅⋅⋅Br halogen bonding (see figure).

    2. Sensors

      Cetylpyridinium Chloride Activated Trinitrotoluene Explosive Lights Up Robust and Ultrahigh Surface-Enhanced Resonance Raman Scattering in a Silver Sol (pages 8789–8796)

      Dr. Honglin Liu, Dongyue Lin, Yudie Sun, Dr. Liangbao Yang and Prof. Jinhuai Liu

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/chem.201300815

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      Hits the (hot) spot: Double resonance (molecular electronic resonance and plasmon resonance) is first realized for trinitrotoluene (TNT; see figure). Cetylpyridinium chloride modified on Ag sols not only acts as the surface-seeking species to trap sulfite-sulfonated TNT, but also undergoes complexation with the sulfonated TNT, resulting in the appearance of two charge-transfer bands at 467 and 530 nm.

    3. Acid–Base Interactions

      Reactivity of Lewis Basic Platinum Complexes Towards Fluoroboranes (pages 8797–8805)

      Dr. Jürgen Bauer, Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst and Dr. Krzysztof Radacki

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201301056

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      Still elusive: Several attempts to yield the elusive, unsupported Lewis adduct between a Lewis basic transition-metal complex and a Lewis acidic borane are presented, including NMR spectroscopic characterization at low temperatures, isolation of secondary products and detailed DFT calculations (see figure).

    4. Ionic Liquids

      Changes in the Structural Dimensionality of Selenidostannates in Ionic Liquids: Formation, Structures, Stability, and Photoconductivity (pages 8806–8813)

      Dr. Yumei Lin, Dewang Xie, Prof. Dr. Werner Massa, Dr. Leonhard Mayrhofer, Sina Lippert, Benjamin Ewers, Dr. Alexey Chernikov, Prof. Dr. Martin Koch and Prof. Dr. Stefanie Dehnen

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201300807

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      New dimensions: Three selenidostannate phases yielded from complex transformation pathways in ionic liquids include (in part reversible) dimensionality changes of the anionic Sn/Se substructures (see figure). As rationalized by DFT investigations, the transformations are provoked by competing influences of temperature and amine addition (DMMP=2,6-dimethylmorpholine, en=ethane-1,2-diamine).

    5. Supramolecular Chemistry

      The Tris-Urea Motif and Its Incorporation into Polydimethylsiloxane-Based Supramolecular Materials Presenting Self-Healing Features (pages 8814–8820)

      Dr. Nabarun Roy, Prof. Eric Buhler and Prof. Jean-Marie Lehn

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201203518

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      Healing power: Easy access to a tris-urea motif, with the possibility of forming six H-bonds, has been demonstrated. This concept was further extended to the formation of soft functional materials based on polydimethylsiloxane moieties amenable to self-repair (see figure).

    6. Molecular Assemblies

      Coordination-Based Molecular Assemblies of Oligofurans and Oligothiophenes (pages 8821–8831)

      Adva Hayoun Barak, Graham de Ruiter, Dr. Michal Lahav, Dr. Sagar Sharma, Dr. Ori Gidron, Dr. Guennadi Evmenenko, Prof. Pulak Dutta, Prof. Michael Bendikov and Prof. Milko E. van der Boom

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300034

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      Coming to the surface: Surface-bound molecular assemblies (MA-1 to MA-3) were constructed by an iterative solution deposition approach. The formed MAs consist of either oligofuran or oligothiophene chromophores coordinated to a palladium salt.

    7. Density Functional Calculations

      Quantum Chemical Study of the Reactions between Pd+/Pt+ and H2O/H2S (pages 8832–8838)

      Dr. Oier Lakuntza, Dr. Jon M. Matxain, Dr. Fernando Ruipérez, Prof. Dr. Jesus M. Ugalde and Prof. Peter B. Armentrout

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201300222

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      Reactivity uncovered! The reactions of water and hydrogen sulfide with palladium and platinum cations have been studied in both low- and high-spin states (see figure; Q=quartet, D=doublet states). The results of these calculations predict that only the formation of platinum sulfide is exothermic (in both spin states), whereas for the remaining species the oxides and sulfides are found to be more reactive than their corresponding bare metal cations.

    8. Chelates

      Bispidine Platform Grants Full Control over Magnetic State of Ferrous Chelates in Water (pages 8839–8849)

      Jacek Lukasz Kolanowski, Dr. Erwann Jeanneau, Robert Steinhoff and Prof. Dr. Jens Hasserodt

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201300604

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      All under control: Structural variation of bispidines allows for the preparation of ferrous complexes that adopt magnetic properties of choice under environmentally benign conditions in water at room temperature. Pairs of constitutionally similar, robust chelates with a binary off–on magnetic relationship are obtained (see figure).

    9. Rotaxanes

      Using “Threading Followed by Shrinking” to Synthesize Highly Stable Dialkylammonium-Ion-Based Rotaxanes (pages 8850–8860)

      Liang-Yun Wang, Jia-Ling Ko, Prof. Chien-Chen Lai, Yi-Hung Liu, Prof. Shie-Ming Peng and Prof. Sheng-Hsien Chiu

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201300049

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      Shrink wrap: A “threading followed by shrinking” method, which was used to extrude both arylmethyl sulfone motifs from the macrocyclic components of dialkylammonium-ion-based [2]pseudorotaxanes, afforded robust [2]rotaxanes that were sufficiently stable to maintain their molecular integrity in CD3SOCD3 at 393 K for at least 5 h (see figure).

    10. Gels

      Multistimuli-Responsive Supramolecular Organogels Formed by Low-Molecular-Weight Peptides Bearing Side-Chain Azobenzene Moieties (pages 8861–8874)

      Paola Fatás, Jürgen Bachl, Stefan Oehm, Dr. Ana I. Jiménez, Prof. Carlos Cativiela and Prof. David Díaz Díaz

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201300796

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      Intelligent response: The incorporation of the azobenzene moiety into the side chain of low-molecular-weight peptides allows for the preparation of multistimuli-responsive supramolecular organogels. The presence and position of the azobenzene residue act as a versatile regulator to reduce the minimum gelation concentration and enhance both the thermal stability and mechanical strength of the materials (see figure).

    11. Total Synthesis

      Convergent Synthesis of (−)-Quinocarcin Based on the Combination of Sonogashira Coupling and Gold(I)-Catalyzed 6-endo-dig Hydroamination (pages 8875–8883)

      Hiroaki Chiba, Yuki Sakai, Ayako Ohara, Dr. Shinya Oishi, Prof. Dr. Nobutaka Fujii and Prof. Dr. Hiroaki Ohno

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300687

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      Golden(I): A convergent asymmetric total synthesis of quinocarcin employed Sonogashira and Au-catalyzed hydroamination reactions (see scheme). The regioselectivity of the intramolecular hydroamination of an unsymmetrical alkyne was switched by substrate control.

    12. Polymerisation

      Highly Active, Thermally Stable, Ethylene-Polymerisation Pre-Catalysts Based on Niobium/Tantalum[BOND]Imine Systems (pages 8884–8899)

      Prof. Carl Redshaw, Mark Walton, Dr. Lucy Clowes, Dr. David L. Hughes, Dr. Anna-Marie Fuller, Dr. Yimin Chao, Dr. Alex Walton, Dr. Victor Sumerin, Dr. Pertti Elo, Dr. Igor Soshnikov, Dr. Weizhen Zhao and Prof. Wen-Hua Sun

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300453

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      Ta very much: The combination of a niobium or tantalum pre-catalyst that contains an imine-based ligand set and a MeAlCl2 (MADC) co-catalyst is capable, in the presence of ethyl trichloroacetate (ETA), of polymerising ethylene with activities in excess of 11 000 g mmol−1 h−1 bar−1 for niobium and 20 000 g mmol−1 h−1 bar−1 for tantalum. These systems produced essentially linear, high-molecular-weight polyethylene.

    13. Bodipy Dyes

      Ultrafast Energy Transfer in Triptycene-Grafted Bodipy Scaffoldings (pages 8900–8912)

      Thomas Bura, Dr. Francesco Nastasi, Dr. Fausto Puntoriero, Dr. Sebastiano Campagna and Dr. Raymond Ziessel

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201300413

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      Fast, faster, ultrafast: Grafting three identical Bodipy units on a triptycene core allowed regioselective transformation of a single Bodipy through a Knovenagel reaction. The use of two different aromatic aldehydes produced a triptycene platform modified by three different Bodipy dyes. Luminescence properties and transient absorption spectroscopy indicate a fast (ps) stepwise energy transfer from higher- to lower-energy Bodipy units (see figure).

    14. Dendrimers

      Synthesis, Redox Activity of Rigid Ferrocenyl Dendrimers, and Isolation of Robust Ferricinium and Class-II Mixed-Valence Dendrimers (pages 8913–8921)

      Dr. Abdou K. Diallo, Dr. Jaime Ruiz and Prof. Dr. Didier Astruc

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201300560

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      Win or robust: Selective Sonogashira reactions with 1,3,5-tribromobenzene allowed the introduction of both ferrocenylethynyl and pentamethylferrocenylethynyl redox groups around stiff dendrimers, which led to the synthesis of both fully oxidized (ferricinium) dendrimers with 6 or 12 redox groups and a class-II mixed-valence dendrimer (see figure).

    15. Enzyme Catalysis

      Substrate-Dependent Stereospecificity of Tyl-KR1: An Isolated Polyketide Synthase Ketoreductase Domain from Streptomyces fradiae (pages 8922–8928)

      Matthias Häckh, Prof. Dr. Michael Müller and Dr. Steffen Lüdeke

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300554

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      Substrate dependence: The stereospecificity of an enzymatic reduction depends on the way a substrate binds to the active site. By using vibrational circular dichroism, it was shown that the stereospecificity and stereoselectivity of the ketoreductase Tyl-KR1 from a polyketide synthase complex in Streptomyces fradiae are inverted for different surrogates of polyketide-like substrates (see figure).

    16. Explosives

      Nitramines with Varying Sensitivities: Functionalized Dipyrazolyl- N-nitromethanamines as Energetic Materials (pages 8929–8936)

      Jiaheng Zhang, Dr. Chunlin He, Dr. Damon A. Parrish and Prof. Dr. Jean'ne M. Shreeve

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300747

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      Energize your chemistry! 1,3-Dichloro-2-nitro-2-azapropane is the precursor to energetic dense functionalized dipyrazolyl-N-nitromethanamines (see figure, blue: Nitrogen, red: oxygen). The new compounds exhibit high thermal stability, high performance, and moderate to low sensitivities.

    17. Supramolecular Chemistry

      Shape-Persistent (Pt-salphen)2 Phosphorescent Coordination Frameworks: Structural Insights and Selective Perturbations (pages 8937–8947)

      Dr. Zhengqing Guo, Dr. Shek-Man Yiu and Dr. Michael C. W. Chan

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300421

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      To π or not to π? The ratiometric phosphorescent ion-selective responses of axially rotating binuclear assemblies have been investigated by using X-ray crystallography, DFT calculations, and various spectroscopic techniques to provide an insight into the binding mechanism (see figure). These results may carry important implications for stimuli-responsive luminescent host complexes that engage in intramolecular interactions.

    18. Energetic Materials

      The Chemistry of 5-(Tetrazol-1-yl)-2H-tetrazole: An Extensive Study of Structural and Energetic Properties (pages 8948–8957)

      Dr. Niko Fischer, Dániel Izsák, Prof. Dr. Thomas M. Klapötke and Dr. Jörg Stierstorfer

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201300691

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      A bigger bang! 5-(Tetrazol-1-yl)-2H-tetrazole (1,5′-bistetrazole) was prepared according to a modified literature procedure and its chemistry was investigated by the preparation of several new salts with various metal and nitrogen-rich cations, as well as complexes with copper(II). The compounds were characterized and investigated as potential new energetic materials for various applications like primary and secondary explosives or pyrotechnic colorants.

    19. Guanidine Ligands

      Bisguanidines with Biphenyl, Binaphthyl, and Bipyridyl Cores: Proton-Sponge Properties and Coordination Chemistry (pages 8958–8977)

      Dr. Astrid Maronna, Dr. Olaf Hübner, Prof. Dr. Markus Enders, Dr. Elisabeth Kaifer and Prof. Dr. Hans-Jörg Himmel

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201204294

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      Showing some backbone: Bisguanidines with flexible biaryl backbones are proton sponges and ligands in a series of new mono- and dinuclear Group 10 metal complexes (see figure). The spin-density distribution in paramagnetic NiII complexes was studied by using NMR spectroscopy and quantum-chemical calculations.

    20. Photochromism

      Complete Photochromic Structural Changes in Ruthenium(II)[BOND]Diimine Complexes, Based on Control of the Excited States by Metalation (pages 8978–8990)

      Takuya Sawaki, Dr. Tomoya Ishizuka, Prof. Dr. Masaki Kawano, Dr. Yoshihito Shiota, Prof. Dr. Kazunari Yoshizawa and Prof. Dr. Takahiko Kojima

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/chem.201300437

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      Ru being served? Photochromic structural changes of RuII/TPA (TPA=tris(2-pyridylmethyl)amine) complexes that contain a diimine ligand are reported. Further metal coordination to the diimine ligand allows interconversion between its open/closed forms (see scheme).

    21. Homogeneous Catalysis

      Bulky Phosphinines: From a Molecular Design to an Application in Homogeneous Catalysis (pages 8991–9004)

      Jarno J. M. Weemers, Willem N. P. van der Graaff, Dr. Evgeny A. Pidko, Dr. Martin Lutz and Prof. Dr. Christian Müller

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201300557

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      Bulky phosphinines: An asymmetrically substituted, bulky, and atropisomeric phosphinine has been prepared and characterized (see figure). Rapid C[BOND]H activation on the 2-aryl substituent of the phosphorus heterocycle was achieved with [{Cp*IrCl2}2] (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of the phosphinine acted as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of 2-octene.

    22. Brønsted Acids

      H(OEt2)2[P(1,2-O2C6Cl4)3]: Synthesis, Characterization, and Application as a Single-Component Initiator for the Carbocationic Polymerization of Olefins (pages 9005–9014)

      Paul W. Siu, Khatera Hazin and Prof. Dr. Derek P. Gates

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201204288

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      Lining 'em up: Strong Brønsted acids, H(OEt2)[1] and H(OEt2)(NCMe)[1] ([1]=[TRISPHAT]=P(1,2-O2C6Cl4)3]), were prepared and characterized. It is shown that H(OEt2)2[1] is a very effective weighable single-component initiator for the cationic polymerization of vinyl ether, α-methylstyrene, styrene, and isoprene at reduced temperatures (<−50 °C) to afford moderate- to high-molecular weight polymers (see figure).

    23. Enantiodivergence

      Solvent-Dependent Enantiodivergence in the Chlorocyclization of Unsaturated Carbamates (pages 9015–9021)

      Dr. Atefeh Garzan, Arvind Jaganathan, Nastaran Salehi Marzijarani, Dr. Roozbeh Yousefi, Daniel C. Whitehead, Prof. James E. Jackson and Prof. Babak Borhan

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201300189

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      Two solvents, two enantiomers: Enantiodivergent hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates, controlled solely by the choice of solvent, yields oxazolidinones in high enantioselectivity (see scheme; DCDMH=1,3-dichloro-5,5-dimethyl hydantoin). The origin of the observed enantiodivergence is traced back to a solvent-selected entropy–enthalpy balance between pro-R and pro-S pathways that dictates the course of the reaction.

    24. Gas-Phase Reactions

      Experimental and Computational Studies on the Formation of Three para-Benzyne Analogues in the Gas Phase (pages 9022–9033)

      Dr. Lindsey M. Kirkpatrick, Dr. Nelson R. Vinueza, Dr. Bartłomiej J. Jankiewicz, Vanessa A. Gallardo, Dr. Enada F. Archibold, Dr. John J. Nash and Prof. Hilkka I. Kenttämaa

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/chem.201203264

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      Pick the right isomer! The generation of three positively charged para-benzyne analogues was attempted in an FT-ICR mass spectrometer. The experimental and quantum chemical findings indicate that the monoradical precursors for the para-benzynes undergo ring-opening faster than formation of the para-benzyne by iodine atom elimination, thus generating enediyne isomers of the para-benzynes (see scheme).

    25. Anion Receptors

      Stepwise Encapsulation of Sulfate Ions by Ferrocenyl-Functionalized Tripodal Hexaurea Receptors (pages 9034–9041)

      Xiaojuan Huang, Prof. Dr. Biao Wu, Dr. Chuandong Jia, Prof. Dr. Benjamin P. Hay, Dr. Minrui Li and Prof. Dr. Xiao-Juan Yang

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201300275

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      The time capsule: Three ferrocenyl-functionalized tripodal hexaurea anion receptors were designed for sulfate recognition. Owing to its trigonal-bipyramidal shape, a meta-phenylene-bridged ligand can encapsulate two SO42− ions in two distinct steps. CV studies showed two types of electrochemical response of the Fc/Fc+ redox couple upon anion binding, that is, a shift of the wave and the appearance of a new peak.

    26. NMR Spectroscopy

      Probing the Coordination Environment of the Human Copper Chaperone HAH1: Characterization of HgII-Bridged Homodimeric Species in Solution (pages 9042–9049)

      Dr. Marek Łuczkowski, Dr. Brian A. Zeider, Alia V. H. Hinz, Dr. Monika Stachura, Dr. Saumen Chakraborty, Prof. Lars Hemmingsen, Dr. David L. Huffman and Prof. Vincent L. Pecoraro

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/chem.201204184

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      HAH1, the HgII carrier? Trafficking of CuI in human cells is achieved through complexation by the metallochaperone, HAH1. In addition, HAH1 strongly binds HgII; the solution behavior of HgII–HAH1 complexation (see figure) has remained obscure, but is elucidated in this work. Structures are reported that may represent central intermediates in the processing of HgII ions.

    27. Substituent Effects

      Substituent Effects on Oxidation-Induced Formation of Quinone Methides from Arylboronic Ester Precursors (pages 9050–9058)

      Dr. Sheng Cao, Robin Christiansen and Prof. Xiaohua Peng

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/chem.201300539

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      Tunable quinone methide formation: Aromatic substituents and the benzylic leaving group strongly affect the H2O2-induced formation of quinone methides (QMs) from arylboronic esters (see scheme). The reactivity of arylboronic esters can be predictably adjusted by varying substituents.

    28. Lipid Bilayer Membranes

      Forming Lipid Bilayer Membrane Arrays on Micropatterned Polyelectrolyte Film Surfaces (pages 9059–9063)

      Ying Zhang, Lei Wang, Xuejing Wang, Guodong Qi and Prof. Xiaojun Han 

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201204419

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      Layer-by-layer assembly of polyelectrolyte films on modified glass substrates, followed by micropatterning by deep-UV photolysis though a mask and immersion of the patterned substrates in a solution of lipid vesicles, afforded lipid bilayer arrays (see figure). The migration behavior of charged lipids in the lipid bilayer arrays under an electric field suggests that these patterned supported bilayers may have applications in studies on the manipulation of charged species in the membrane.

    29. Nanostructures

      New Nanostructured Materials: Synthesis of Dodecanuclear NiII Complexes and Surface Deposition Studies (pages 9064–9071)

      Alba Pons-Balagué, Dr. Stergios Piligkos, Dr. Simon J. Teat, Dr. Jose Sánchez Costa, Muhandis Shiddiq, Dr. Stephen Hill, Dr. German R. Castro, Dr. Pilar Ferrer-Escorihuela and Dr. E. Carolina Sañudo

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/chem.201204081

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      Made in a microwave reactor: Nickel complexes templated around a NO3 or CO32− μ6 anion are prepared by microwave-assisted synthesis. The magnetic properties and nanostructuration of the Ni12 species on mica surfaces are studied by AFM and grazing-incidence X-ray diffraction. The formation of polycrystalline thin layers is revealed (see figure).

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