Chemistry - A European Journal

Cover image for Chemistry - A European Journal

September 8, 2008

Volume 14, Issue 26

Pages 7723–8039

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    8. Preview
    1. Cover Picture: 1,4-Dicyanobenzene as a Scaffold for the Preparation of Bimetallic Actinide Complexes Exhibiting Metal–Metal Communication (Chem. Eur. J. 26/2008) (page 7723)

      Eric J. Schelter, Jacqueline M. Veauthier, Christopher R. Graves, Kevin D. John, Brian L. Scott, Joe D. Thompson, Jaime A. Pool-Davis-Tournear, David E. Morris and Jaqueline L. Kiplinger

      Version of Record online: 1 SEP 2008 | DOI: 10.1002/chem.200890101

      Thumbnail image of graphical abstract

      An organometallic uranium bimetallic complex exhibits signatures of electronic delocalization. In their Full Paper on page 7782 ff., J. L. Kiplinger, D. E. Morris et al. have shown that multimetallic uranium and thorium architectures can be easily assembled by using nitrile insertion chemistry into actinide–carbon bonds. With its covalent metal–ligand bonds, the resulting 1,4-phenylenediketimide bridging ligand provides a useful platform for the study of metal–metal interactions. Electrochemistry of the thorium analogue affords definition of metal-based processes in the uranium bimetallic system.

  2. Graphical Abstract

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    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
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  3. News

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
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  4. Concept

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
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    1. Polyvalent Ligands

      The Design of Polyvalent Therapeutics (pages 7738–7747)

      Amit Joshi, David Vance, Prakash Rai, Aditya Thiyagarajan and Ravi S. Kane

      Version of Record online: 13 JUN 2008 | DOI: 10.1002/chem.200800278

      Thumbnail image of graphical abstract

      One concept, numerous applications: Polyvalency—the principle of multiple simultaneous interactions—finds numerous applications ranging from targeted drug delivery and imaging to enhancing or suppressing immune responses and the design of inhibitors of toxins and pathogens (see graphic).

  5. Communications

    1. Top of page
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    1. PEGylated Liposomes

      Stable and Potent Polyvalent Anthrax Toxin Inhibitors: Raft-Inspired Domain Formation in Liposomes that Contain PEGylated Lipids (pages 7748–7751)

      Prakash Rai, David Vance, Vincent Poon, Jeremy Mogridge and Ravi S. Kane

      Version of Record online: 30 JUL 2008 | DOI: 10.1002/chem.200801097

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      A raft of inspiration: We report the synthesis of highly active and stable polyvalent anthrax toxin inhibitors based on laterally phase-separated PEGylated liposomes (see figure). Heterogeneous domain-containing PEGylated liposomes are considerably more active than their homogeneous counterparts.

    2. Self–Assembly

      Self-Assembly of L-Cysteinato Trinuclear Cations into Metallosupramolecular Architectures Controlled by Protons, Metal Ions, and Chirality (pages 7752–7755)

      Takashi Aridomi, Keiichi Takamura, Asako Igashira-Kamiyama, Tatsuya Kawamoto and Takumi Konno

      Version of Record online: 9 JUL 2008 | DOI: 10.1002/chem.200800887

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      Complete control: Versatile self-assembly of the L-cysteinato CoIIIHgIICoIII trinuclear complex into dimeric, metallohelix, and metallocage structures, which is induced by deprotonation of L-cysteine carboxyl groups, is reported. Remarkably, the homochiral (ΛLΛL-CoIIIHgIICoIII)6 metallocage, which encapsulates an aqua metal ion, was formed from the meso-like ΔLΛL isomer of this trinuclear complex, as well as from its ΛLΛL isomer (see scheme).

    3. Allenes

      Chemodivergence in Alkene/Allene Cycloetherification of Enallenols: Iron versus Noble Metal Catalysis (pages 7756–7759)

      Benito Alcaide, Pedro Almendros and Teresa Martínez del Campo

      Version of Record online: 18 JUL 2008 | DOI: 10.1002/chem.200801166

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      Chemodivergent metal-catalyzed oxycyclization of enallenols, such as those depicted, may occur by judicious choice of the catalyst, namely iron trichloride versus precious metal salts, owing to their potential ability to discriminate both reactive sites.

      Corrected by:

      Corrigendum: Corrigendum: Chemodivergence in Alkene/Allene Cycloetherification of Enallenols: Iron versus Noble Metal Catalysis

      Vol. 17, Issue 4, 1074, Version of Record online: 18 JAN 2011

    4. Semiconducting Materials

      Isomeric Effect on Microscale Self-Assembly: Interplay between Molecular Property and Solvent Polarity in the Formation of 1 D n-Type Microbelts (pages 7760–7764)

      Jie-Yu Wang, Jing Yan, Zhendong Li, Ji-Min Han, Yuguo Ma, Jiang Bian and Jian Pei

      Version of Record online: 15 JUL 2008 | DOI: 10.1002/chem.200800396

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      The number of substituents and the different substitution patterns in a series of truxenone derivatives (see picture) greatly affected their molecular properties; this is clearly manifested in their different behaviors in self-assembly and the resulting 1D microstructures. This series of molecules represents a new family of one-dimensional organic n-type semiconductors.

    5. Peptide Dissociation Mechanisms

      Infrared Multiple-Photon Dissociation Mechanisms of Peptides of Glycine (pages 7765–7770)

      Ronghu Wu and Terry B. McMahon

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200800594

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      Peptide patterns: The current experimental results indicate that infrared multiple-photon dissociation (IRMPD) of peptides forms more structurally informative sequence b and y ions, and fewer less useful nonsequence ions. Also the dissociation pathways are the same through excitation of different modes of the peptide. For the first time, it has been confirmed that the peptide dissociation pathway is not related to the initial protonation site or the conformation (e.g., cyclic or linear, see graphic) of the peptide.

    6. Zeolites

      A New Zeolitic Topology with Sixteen-Membered Ring and Multidimensional Large Pore Channels (pages 7771–7773)

      Tao Wu, Xianhui Bu, Rui Liu, Zhien Lin, Jian Zhang and Pingyun Feng

      Version of Record online: 15 JUL 2008 | DOI: 10.1002/chem.200800736

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      Two new four-connected metal imidazolates with an unprecedented four-connected topology have been synthesized and structurally characterized. TIF-1Zn (see figure) exhibits permanent microporosity and has high thermal stability. It features unusual topological features, such as 3- and 16-rings and multidimensional large pore channels, which underlines the rich synthetic and structural chemistry of imidazolate-based porous frameworks that are yet to be explored.

  6. Full Papers

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

      Probing Kinase Activities by Electrochemistry, Contact-Angle Measurements, and Molecular-Force Interactions (pages 7774–7781)

      Ofer I. Wilner, Claudio Guidotti, Agnieszka Wieckowska, Ron Gill and Itamar Willner

      Version of Record online: 12 AUG 2008 | DOI: 10.1002/chem.200800765

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      Versatile sensors: Different methods, such as impedance spectroscopy, molecular-force interactions, or contact-angle measurements proved to be effective tools to probe CK2 protein kinase (see graphic). This enzyme is active in intracellular signal transduction, cell division, and cell proliferation.

    2. Actinide Complexes

      1,4-Dicyanobenzene as a Scaffold for the Preparation of Bimetallic Actinide Complexes Exhibiting Metal–Metal Communication (pages 7782–7790)

      Eric J. Schelter, Jacqueline M. Veauthier, Christopher R. Graves, Kevin D. John, Brian L. Scott, Joe D. Thompson, Jaime A. Pool-Davis-Tournear, David E. Morris and Jaqueline L. Kiplinger

      Version of Record online: 7 AUG 2008 | DOI: 10.1002/chem.200800585

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      Bridging the gap: Nitrile insertion chemistry with 1,4-dicyanobenzene has been used to prepare discrete dinuclear ThIV/ThIV (5f0–5f0) and UIV/UIV (5f2–5f2) organometallic complexes in which the two metal centers are covalently connected by a 1,4-phenylenediketimide bridging ligand (see picture). The uranium system displays appreciable electronic communication between the UIV centers through the π system of the dianionic diketimide bridging ligand.

    3. Dyes/Pigments

      Structure–Property Relationships for Self-Assembled Zinc Chlorin Light-Harvesting Dye Aggregates (pages 7791–7807)

      Valerie Huber, Sanchita Sengupta and Frank Würthner

      Version of Record online: 18 JUL 2008 | DOI: 10.1002/chem.200800764

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      Stuck together: Semisynthetic zinc chlorins derived from chlorophyll a self-assemble in aliphatic and aqueous solutions by noncovalent interactions into extended light-harvesting rods or smaller aggregates, depending on their structural features (see graphic).

    4. Spin–Spin Coupling

      BINOL-3,3′-Triflone N,N-Dimethyl Phosphoramidites: Through-Space 19F,31P Spin–Spin Coupling with a Remarkable Dependency on Temperature and Solvent Internal Pressure (pages 7808–7812)

      Matthias Kruck, M. Paz Munoz, Hannah L. Bishop, Christopher G. Frost, Christopher J. Chapman, Gabriele Kociok-Köhn, Craig P. Butts and Guy C. Lloyd-Jones

      Version of Record online: 18 JUL 2008 | DOI: 10.1002/chem.200800825

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      Coupling under pressure: A complex interplay (see graphic) of stereochemistry, solvent internal pressure, molecular volume and thermal access to a wider conformational space, modulate through-space coupling between 31P and 19F nuclei that are six-bonds apart in a BINOL-derived phosphoramidite.

    5. Platinum Complexes

      Mono- and Diprotonation of the Superbasic Bisguanidine 1,2-Bis(N,N,N′,N′-tetramethylguanidino)benzene (btmgb) and PtII and PtIV Complexes of Chelating Bisguanidines and Guanidinates (pages 7813–7821)

      Anastasia Peters, Ute Wild, Olaf Hübner, Elisabeth Kaifer and Hans-Jörg Himmel

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200800244

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      The superbasic bisguanidine 1,2-bis(N,N,N′,N′-tetramethylguanidino) benzene (btmgb) was mono- and diprotonated and used as a chelating ligand in new PtII complexes (see figure for example). In addition, the structure of a new PtIV complex with a chelating guanidinate ligand is presented.

    6. Anion Binding

      Cooperative Binding of Calix[4]pyrrole–Anion Complexes and Alkylammonium Cations in Halogenated Solvents (pages 7822–7827)

      Dustin E. Gross, Franz P. Schmidtchen, Wiebke Antonius, Philip A. Gale, Vincent M. Lynch and Jonathan L. Sessler

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200800899

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      Smaller is better: Solution, solid-state, and molecular-dynamics evidence of calix[4]pyrrole–anion complexes interacting with cations (see scheme) is described herein. These interactions favor smaller N-methyl-substituted ammonium cations over larger-substituted alkylammonium cations in halogenated solvents.

    7. Stacking Interactions

      Experimental Measurement of Carbohydrate–Aromatic Stacking in Water by Using a Dangling-Ended DNA Model System (pages 7828–7835)

      Juan C. Morales, José J. Reina, Irene Díaz, Anna Aviñó, Pedro M. Nieto and Ramón Eritja

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200800335

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      With the help of DNA: Carbohydrate–aromatic stacking is a widespread, but poorly understood, structural motif found in protein–carbohydrate recognition processes. The measurement of carbohydrate–aromatic interactions from their contribution to the stability of a dangling-ended DNA model system (see scheme) has been carried out.

    8. Peptide Engineering

      Molecular Design of Specific Metal-Binding Peptide Sequences from Protein Fragments: Theory and Experiment (pages 7836–7846)

      Milan Kožíšek, Aleš Svatoš, Miloš Buděšínský, Alexander Muck, Mikael C. Bauer, Pavel Kotrba, Tomáš Ruml, Zdeněk Havlas, Sara Linse and Lubomír Rulíšek

      Version of Record online: 16 JUL 2008 | DOI: 10.1002/chem.200800178

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      Ab initio peptide design: A novel strategy is presented for designing peptides with specific metal-ion chelation sites, based on computationally predicted combinations of amino acid side chains coordinated around the desired coordination polyhedron and linked into a single polypeptide chain (see scheme). The gas-phase association constants of the metal ions with the designed peptides and the thermodynamic parameters of the metal-ion coordination in the condensed phase were experimentally determined.

    9. Asymmetric Catalysis

      Modular Chiral Bidentate Phosphonites: Design, Synthesis, and Application in Catalytic Asymmetric Hydroformylation Reactions (pages 7847–7857)

      Baoguo Zhao, Xingao Peng, Zheng Wang, Chungu Xia and Kuiling Ding

      Version of Record online: 15 JUL 2008 | DOI: 10.1002/chem.200800388

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      Fine-tuning of the selectivities in RhI-catalyzed asymmetric hydroformylation of styrene derivatives, vinyl acetate, and allyl cyanide can be achieved by judicious modifications of the substituents of air-stable modular chiral bidentate phosphonite ligands (see picture), affording the corresponding optically active aldehydes in high regio- and enantioselectivities with excellent activity.

    10. Boryl Complexes

      T-Shaped Platinum Boryl Complexes: Synthesis and Structure (pages 7858–7866)

      Holger Braunschweig, Krzysztof Radacki and Katharina Uttinger

      Version of Record online: 28 JUL 2008 | DOI: 10.1002/chem.200800879

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      Suited to a T: A series of unusual cationic T-shaped platinum(II) boryl complexes of the type trans-[(Cy3P)2Pt{B(X)Br}]+ (Cy=cyclohexyl) were synthesized by halide abstraction of corresponding bromo(boryl) compounds (see figure). The reactivity of trans-[(Cy3P)2Pt(BCat)]+ (Cat=catecholato) towards Lewis bases was also investigated.

    11. Asymmetric Catalysis

      One-Pot Organocatalytic Domino Michael/α-Alkylation Reactions: Direct Catalytic Enantioselective Cyclopropanation and Cyclopentanation Reactions (pages 7867–7879)

      Ismail Ibrahem, Gui-Ling Zhao, Ramon Rios, Jan Vesely, Henrik Sundén, Pawel Dziedzic and Armando Córdova

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200800442

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      One pot—many dishes: In the presence of a chiral amine, one-pot domino Michael/α-alkylation reactions between bromomalonates and bromoacetate esters give functionalized cyclopropanes and cylopentanes, respectively, with 93–99% ee (see scheme). Furthermore, one-pot combinations of amine and heterocyclic carbene catalysts enabled the highly enantioselective synthesis of β-malonate esters from bromomalonates and enals.

    12. π Basicity

      The Basicity of Unsaturated Hydrocarbons as Probed by Hydrogen-Bond-Acceptor Ability: Bifurcated N[BOND]H+⋅⋅⋅π Hydrogen Bonding (pages 7880–7891)

      Evgenii S. Stoyanov, Irina V. Stoyanova and Christopher A. Reed

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200800337

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      Join the ranks! A new scale for ranking π basicity in unsaturated hydrocarbons has been developed by using N[BOND]H stretching frequencies. Bifurcated hydrogen bonds to unsaturated hydrocarbons have been discovered (see scheme).

    13. Nitridosilicates

      HP-Ca2Si5N8—A New High-Pressure Nitridosilicate: Synthesis, Structure, Luminescence, and DFT Calculations (pages 7892–7902)

      S. Rebecca Römer, Cordula Braun, Oliver Oeckler, Peter J. Schmidt, Peter Kroll and Wolfgang Schnick

      Version of Record online: 15 JUL 2008 | DOI: 10.1002/chem.200800602

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      Turn up the pressure: The synthesis of HP-Ca2Si5N8 demonstrates that denser ternary nitridosilicates are accessible by high-pressure methods (see picture). The experiments were paralleled by DFT calculations and the material properties of the new HP-Ca2Si5N8 were examined.

    14. Copper Catalysis

      Synthesis of 4,5-Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System (pages 7903–7912)

      Luca Cecchi, Francesco De Sarlo and Fabrizio Machetti

      Version of Record online: 18 JUL 2008 | DOI: 10.1002/chem.200800554

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      Copper at work: The catalytic effect of CuII salts on the condensation of primary nitro compounds with dipolarophiles to give isoxazole derivatives is evidenced by plotting the reaction progress versus time under catalysis by a tertiary amine (blue) and CuII (brown; see figure). Nitroalkanes react only under CuII catalysis. The observed occurrence of induction periods in most reactions is ascribed to equilibria preceding the rate-determining step, and provides a hint as to the proposed reaction mechanism.

    15. Photochemistry

      Head-to-Tail Interactions in Tyrosine/Benzophenone Dyads in the Ground and the Excited State: NMR and Laser Flash Photolysis Studies (pages 7913–7929)

      Gerald Hörner, Gordon L. Hug, Dariusz Pogocki, Piotr Filipiak, Walter Bauer, Andreas Grohmann, Anica Lämmermann, Tomasz Pedzinski and Bronislaw Marciniak

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200800315

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      In the dark and in the light: Aromatic–aromatic interactions between ketone and phenol moieties in benzophenone/tyrosine dyads display substantial sensitivity towards the regio- and stereochemical properties of the linker. The extent of the π–π interactions in the ground state reflects the reactivity in excited-state hydrogen-atom transfer (see graphic).

    16. Hydron Transfer

      Construction of Titanasiloxanes by Incorporation of Silanols to the Metal Oxide Model [{Ti(η5-C5Me5)(μ-O)}33-CR)]: DFT Elucidation of the Reaction Mechanism (pages 7930–7938)

      Jorge J. Carbó, Octavio González-del Moral, Avelino Martín, Miguel Mena, Josep-M. Poblet and Cristina Santamaría

      Version of Record online: 9 JUL 2008 | DOI: 10.1002/chem.200800630

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      Hydron migration and ligand rotation: μ3-Alkylidyne fragments are transformed to μ-alkylidene, alkyl, or alkane groups by incorporation of silanols, silanediols, or silanetriols to the organometallic oxide [{Ti(η5-C5Me5)(μ-O)}33-CR)] (R=H, Me). DFT calculations suggest a reaction mechanism involving the oxygen atoms of the Ti3O3 ring and μ-alkylidene ligand rotation on the molecular model oxide (see graphic).

    17. Alkynes

      Synthesis and Optical Properties of all-trans-Oligodiacetylenes (pages 7939–7950)

      Gregor S. Pilzak, Barend van Lagen, Cindy C. J. Hendrikx, Ernst J. R. Sudhölter and Han Zuilhof

      Version of Record online: 9 JUL 2008 | DOI: 10.1002/chem.200800241

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      Organic nanorods: all-trans-Oligodiacetylenes (shown here) were synthesised by a Sonogashira reaction sequence and their optical properties were studied under steady-state and time-resolved conditions in solution and thin films. This allows clarification of solid-state effects.

    18. Cyclopropanes

      Stereoselective Synthesis of Cyclopropanes Based on a 1,2-Chirality Transfer (pages 7951–7960)

      Olaf Muehling and Pablo Wessig

      Version of Record online: 18 JUL 2008 | DOI: 10.1002/chem.200801002

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      A stereoselective photochemical route to enantiomerically enriched bicyclic cyclopropane derivatives (see scheme), based on a conceptually novel 1,2-chirality transfer approach, is described.

    19. Ferrofluids

      Synthesis, Surface Modifications, and Size-Sorting of Mixed Nickel–Zinc Ferrite Colloidal Magnetic Nanoparticles (pages 7961–7968)

      P. Majewski and P. Krysiński

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200800369

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      Nanoferrite functionalization: Surface modification of nanoferrites by means of acid chloride chemistry led to the formation of covalent bonds between the OH groups at the nanoparticle surfaces and the acid chloride molecules (see scheme). This provided the nanoferrites with functional carboxy groups capable of further modifications with, for example, drug molecules.

    20. C[BOND]C Coupling Reactions

      Rationally Designed Pincer-Type Heck Catalysts Bearing Aminophosphine Substituents: PdIV Intermediates and Palladium Nanoparticles (pages 7969–7977)

      Jeanne L. Bolliger, Olivier Blacque and Christian M. Frech

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200800441

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      Snappy reagents: Aminophosphine-based pincer complexes of palladium, which could promote both the formation of PdIV intermediates and palladium nanoparticles, are excellent Heck catalysts. Although palladium nanoparticles are the catalytically active form of these catalysts, the thermal accessibility of aminophosphine-based PdIV intermediates was experimentally and computationally demonstrated in a halide exchange reaction of [C6H3{XP(piperidinyl)2}2Pd(Cl)] (X=NH 1 or O 2) with bromobenzene at 100 °C in DMF (see scheme).

    21. RNA Recognition

      Steric Effects in RNA Interference: Probing the Influence of Nucleobase Size and Shape (pages 7978–7987)

      Alvaro Somoza, Adam P. Silverman, Rand M. Miller, Jijumon Chelliserrykattil and Eric T. Kool

      Version of Record online: 15 JUL 2008 | DOI: 10.1002/chem.200800837

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      RNAi and sterics: RNA nonpolar nucleobase analogues are substituted into short interfering RNAs to probe the origins of sequence selectivity in RNAi. Cellular gene suppression experiments show that analogues with the shape of natural bases exhibit the same (or better) selectivity for the correct Watson–Crick partner in an mRNA target (see graphic).

    22. Epoxidation

      A Simple and Effective Catalytic System for Epoxidation of Aliphatic Terminal Alkenes with Manganese(II) as the Catalyst (pages 7988–7996)

      Kam-Piu Ho, Wing-Leung Wong, Kin-Ming Lam, Cheuk-Piu Lai, Tak Hang Chan and Kwok-Yin Wong

      Version of Record online: 10 JUL 2008 | DOI: 10.1002/chem.200800759

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      Mn epoxidation: A simple catalytic system with Mn(ClO4)2 as the catalyst and peracetic acid as the oxidant has been developed to efficiently epoxidise aliphatic terminal alkenes with high product selectivity at ambient temperature. ESI-MS and EPR spectroscopic studies suggest that the active catalyst could be high-valent oligonuclear Mn–oxo clusters, which were first observed in the terminal alkene epoxidation.

    23. Active Polyisobutenes

      Solvent-Ligated Copper(II) Complexes for the Homopolymerization of 2-Methylpropene (pages 7997–8003)

      Yang Li, Lih Ting Voon, Hui Yee Yeong, Ahmed K. Hijazi, Narayanan Radhakrishnan, Klaus Köhler, Brigitte Voit, Oskar Nuyken and Fritz E. Kühn

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200701928

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      Very active polyisobutenes with a high proportion of terminal double bonds and a fairly low polydispersity index are obtained by using 2-methylpropene polymerization using CuII cations [CuII(NCR)6]2+ (R=CH3, Bn, C2H5) with weakly coordinating nitrile ligands and noncoordinating counterions [A] as catalysts (examples are shown here).

    24. Fluorescent Probes

      Novel Probes Showing Specific Fluorescence Enhancement on Binding to a Hexahistidine Tag (pages 8004–8012)

      Mie Kamoto, Naoki Umezawa, Nobuki Kato and Tsunehiko Higuchi

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200701896

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      Simple and specific: We have developed novel “turn-on” fluorescent probes that are intrinsically only weakly fluorescent (see scheme), but which show a dramatic increase in fluorescence in the presence of hexahistidine. The fluorescence response is specific; no fluorescence enhancement was observed with a control peptide containing nonadjacent histidine residues.

    25. Crystal-Packing-Induced Antiferromagnetic Interactions of Metallocenes: Cyanonickelocenes, -cobaltocenes, and -ferrocenes (pages 8013–8024)

      Sandra Altmannshofer, Eberhardt Herdtweck, Frank H. Köhler, Robert Miller, Rüdiger Mölle, Ernst-Wilhelm Scheidt, Wolfgang Scherer and Cyrille Train

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200701538

      Thumbnail image of graphical abstract

      Magnetic interaction: Metallocenes abandon their familiar orientation in the crystal and form stacks when substituted with nitrile ligands. This behavior entails magnetic interactions through intermolecular spin exchange, which is established by magic-angle spinning (MAS) NMR spectroscopic analysis and magnetic measurements (see picture). The redox potentials experience strong positive shifts.

    26. Coordination Chemistry

      A Structural and Computational Study of Synthetically Important Alkali-Metal/Tetramethylpiperidide (TMP) Amine Solvates (pages 8025–8034)

      David R. Armstrong, David V. Graham, Alan R. Kennedy, Robert E. Mulvey and Charles T. O'Hara

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200800158

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      Structural variations: Synthetic studies and DFT calculations have shown that N,N,N′,N′-tetramethylethylenediamine (TMEDA) adducts of sodium and potassium 2,2,6,6-tetramethylpiperidide (TMP) adopt very different structures to their previously known lithium analogue with the immense steric bulk of TMP playing a major role in this distinction. The structure of the potassium compound is shown here.

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      Preview: Chem. Eur. J. 27/2008 (page 8039)

      Version of Record online: 1 SEP 2008 | DOI: 10.1002/chem.200890104

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