Chemistry - A European Journal

Cover image for Vol. 15 Issue 8

February 9, 2009

Volume 15, Issue 8

Pages 1791–2003

  1. Cover Picture

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Minireview
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    1. Cover Picture: Gated and Differently Functionalized (New) Porous Capsules Direct Encapsulates' Structures: Higher and Lower Density Water (Chem. Eur. J. 8/2009) (page 1791)

      Tamoghna Mitra, Pere Miró, Adrian-Raul Tomsa, Alice Merca, Hartmut Bögge, Josep Bonet Ávalos, Josep Maria Poblet, Carles Bo and Achim Müller

      Version of Record online: 2 FEB 2009 | DOI: 10.1002/chem.200990018

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      Ubiquitous water is apart from its anomalies, for several reasons the most mysterious compound. According to its basic role in life processes it has even been considered as a biomolecule especially in context of the important role of confined “high and low density water”. C. Bo, A. Müller et al. report on page 1844 ff., confined higher and lower density water assemblies encapsulated in the same type of porous capsule that exhibit differently functionalized internal shells (see picture).

  2. Graphical Abstract

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

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    6. Communications
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  4. Minireview

    1. Top of page
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    1. Ionic Liquids

      Do We Understand the Recyclability of Ionic Liquids? (pages 1804–1810)

      Bo Wu, WeiWei Liu, YuMei Zhang and HuaPing Wang

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801509

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      Recycling of “green” solvents: Recycling of ionic liquids with high efficiency is of key importance on going from the laboratory-scale to large-scale industrial application of these solvents.

  5. Communications

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    1. Fullerenes

      C80Cl12: A Chlorine Derivative of the Chiral D2-C80 Isomer—Empirical Rationale of Halogen-Atom Addition Pattern (pages 1812–1815)

      Kalin S. Simeonov, Konstantin Yu Amsharov and Martin Jansen

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802198

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      Welcome to the family! The constitution of the chiral D2-C80 fullerene has been confirmed through single-crystal X-ray analysis of the chlorinated C80Cl12. The addition pattern of the chlorine atoms in the structure of C80Cl12 together with other structures of halogenated higher fullerenes is discussed. A stepwise principle of higher fullerene reactivity is proposed. Unusual short intermolecular chlorine–chlorine contacts are reported.

    2. Heparin Chemosensor

      Selective Chromofluorogenic Sensing of Heparin by using Functionalised Silica Nanoparticles Containing Binding Sites and a Signalling Reporter (pages 1816–1820)

      Estela Climent, Pilar Calero, M. Dolores Marcos, Ramón Martínez-Máñez, Félix Sancenón and Juan Soto

      Version of Record online: 9 JAN 2009 | DOI: 10.1002/chem.200802074

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      Heparin detective: Silica nanoparticles functionalised with ion-channel scaffolds were prepared and used for the chromofluorogenic sensing of heparin in aqueous environments (see figure). The surface of the nanoparticles was functionalised with polyamines (binding sites) and thiols. The reaction of a dye (squaraine) with the surface thiol groups was selectively inhibited by the coordination of heparin with the partly protonated polyamines.

    3. Heterogeneous Catalysis

      Highly Efficient Visible-Light Plasmonic Photocatalyst Ag@AgBr (pages 1821–1824)

      Peng Wang, Baibiao Huang, Xiaoyang Zhang, Xiaoyan Qin, Hao Jin, Ying Dai, Zeyan Wang, Jiyong Wei, Jie Zhan, Shaoying Wang, Junpeng Wang and Myung-Hwan Whangbo

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200802327

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      Visible improvements: Owing to the plasmon resonance of silver nanoparticles deposited on the surface of AgBr, the newly-prepared plasmonic photocatalyst Ag§AgBr has a strong absorption in the visible region (see picture) and shows high efficiency in the photodegradation of organic pollutants under visible light.

    4. Reaction Mechanisms

      On the Possibility of Conversion of Alcohols to Ketones and Aldehydes by Phosphinoboranes R2PBR′R′′: A Computational Study (pages 1825–1829)

      Timofei Privalov

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802320

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      Can phosphinoboranes promote hydrogenation of carbonyl moieties? By means of B3LYP and MPW1K density functional calculations the likelihood of the oxidation of alcohols by phosphinoboranes R2PBR′2 (1) was explored. As a proof-of-principle, a theoretical study that tests the reversibility of the alcohol oxidation is reported. The potential of 1 as a metal-free hydrogenation mediator is discussed for a series of hydrogen sources such as primary and secondary alcohols.

    5. Domino Reactions

      Highly Efficient Access to Bi- and Tricyclic Ketals through Gold-Catalyzed Tandem Reactions of 4-Acyl-1,6-diynes (pages 1830–1834)

      Jia Meng, Yu-Long Zhao, Chuan-Qing Ren, You Li, Zhu Li and Qun Liu

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802304

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      Single step: Fused bicyclic and bridged tricyclic ketals were synthesized in a single step from the reactions of easily available 4-acyl-1,6-diynes with H2O and alkanols (see scheme). The highly efficient AuCl3-catalyzed multicomponent domino reactions, involving five C[BOND]O bond formations, can proceed in a highly regio- and diastereoselective manner at room temperature under air and lead to structures of high molecular complexity from simple starting materials in an atom economic way.

  6. Full Papers

    1. Top of page
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    3. Graphical Abstract
    4. News
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    6. Communications
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    1. Organometallic Latch

      A Molecular Paddlewheel with a Sliding Organometallic Latch: Syntheses, X-Ray Crystal Structures and Dynamic Behaviour of [Cr(CO)36-2-(9-triptycyl)indene}], and of [M(CO)35-2-(9-triptycyl)indenyl}] (M=Mn, Re) (pages 1836–1843)

      Kirill Nikitin, Helge Müller-Bunz, Yannick Ortin and Michael J. McGlinchey

      Version of Record online: 16 JAN 2009 | DOI: 10.1002/chem.200801940

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      Metal clamping in operation! Deprotonation of [η6-2-(9-triptycyl)indene]tricarbonylchromium induces a haptotropic shift of the organometallic fragment from the six-membered to the five-membered ring, as in a[RIGHTWARDS ARROW]b. In the anion, rotation of the molecular paddlewheel is blocked by the bulky tripod. X-ray crystal structures provide pictures of the system in both its “ON” and “OFF” states.

    2. Polyoxometalates

      Gated and Differently Functionalized (New) Porous Capsules Direct Encapsulates' Structures: Higher and Lower Density Water (pages 1844–1852)

      Tamoghna Mitra, Pere Miró, Adrian-Raul Tomsa, Alice Merca, Hartmut Bögge, Josep Bonet Ávalos, Josep Maria Poblet, Carles Bo and Achim Müller

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801602

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      Either more or less neighbors favored? By deliberate choice of the internal ligands of the porous nanocapsules [{(Mo)Mo5}12{Mo2(ligand)}30]n, the respective cavities can be differently sized/functionalized. This allows one to trap, in two different corresponding capsules, 100 water molecules arranged in shells that exhibit more and less dense packing, respectively—the latter type in a capsule with smaller internal ligands; the picture shows the related 100 O atoms at the vertices of the four polyhedra, while two dodecahedra (shown in pale green and red) have only 10 H2O molecules instead of 20.

    3. Sol–Gel Chemistry

      Efficient Air-Stable Organometallic Low-Molecular-Mass Gelators for Ionic Liquids: Synthesis, Aggregation and Application of Pyridine-Bridged Bis(benzimidazolylidene)–Palladium Complexes (pages 1853–1861)

      Tao Tu, Xiaoling Bao, Wilfried Assenmacher, Herwig Peterlik, Jörg Daniels and Karl Heinz Dötz

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802116

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      Beyond catalysis: Novel pincer-type pyridine-bridged bis(benzimidazolylidene)–palladium complexes have been synthesised and shown to efficiently gelate a variety of solvents and customary ionic liquids. π-Stacking, van der Waals interactions, hydrogen and metal–metal bonding are responsible for 3D gel networks formed by the metallogelators.

    4. Reaction Mechanisms

      Oxidation of Ethers, Alcohols, and Unfunctionalized Hydrocarbons by the Methyltrioxorhenium/H2O2 System: A Computational Study on Catalytic C[BOND]H Bond Activation (pages 1862–1869)

      Erik A. Karlsson and Timofei Privalov

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200801493

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      A concerted mechanism that does not involve an ionic intermediate was revealed by a DFT study on oxidation of ethers, alcohols, and unfunctionalized hydrocarbons by methyltrioxorhenium/H2O2. Instead, C[BOND]H insertion occurs through hydride transfer and then turns into a hydroxide transfer/rebound in a concerted fashion. The picture shows selected frames from an intrinsic reaction coordinate scan from the transition state to the product for the oxidation of cis-1,2-dimethylcyclohexane.

    5. Nanostructures

      A Synthetic Method for Transition-Metal Chalcogenide Nanocrystals (pages 1870–1875)

      Ding-Sheng Wang, Wen Zheng, Chen-Hui Hao, Qing Peng and Ya-Dong Li

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801815

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      A facile wet route was applied to prepare a series of chalcogenide semiconductor nanocrystals (see figure) in controllable shapes and sizes, while a general bottom-up approach was adopted to transform these cyclohexane-soluble monodisperse nanocrystals into water-soluble colloidal spheres.

    6. Oligonucleotides

      Self-Organization, Optical, and Electrical Properties of α-Quinquethiophene–Dinucleotide Conjugates (pages 1876–1885)

      Silvia Alesi, Giorgia Brancolini, Ilenia Viola, Massimo Luigi Capobianco, Alessandro Venturini, Nadia Camaioni, Giuseppe Gigli, Manuela Melucci and Giovanna Barbarella

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200801684

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      Biodriven self-organization of α-quinquethiophene (t5): Cast films of 5′TA3′-t5 are electroactive, photoluminescent, and chiral. Their growth is not directed by intermolecular Watson–Crick hydrogen bonding between the A⋅⋅⋅T moieties of interacting molecules, but is governed by intra- and intermolecular thiophene–nucleobase stacking interactions.

    7. Nanostructures

      Morphological Transformation of Co(OH)2 Microspheres from Solid to Flowerlike Hollow Core–Shell Structures (pages 1886–1892)

      Ru Qiao, Xiao Li Zhang, Ri Qiu, Ju Chang Kim and Young Soo Kang

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200800803

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      Co(OH)2that blooms: Flowerlike hollow spherical architectures of cobalt hydroxide obtained through a facile solvothermal process are reported for the first time (see picture). Their growth process involves aggregation of cobalt hydroxide nanoparticles into solid spheres and a hollowing effect through subsequent dissolution-diffusion-redeposition of the smaller crystallites under the surface layer.

    8. Dynamic Polymers

      Room Temperature Dynamic Polymers Based on Diels–Alder Chemistry (pages 1893–1900)

      P. Reutenauer, E. Buhler, P. J. Boul, S. J. Candau and J.-M. Lehn

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802145

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      Polymer, heal thyself! Dynamic polymers formed by a reversible Diels–Alder reaction were formed and studied by using neutron scattering at room temperature. They were used to obtain thin films that displayed self-healing at room temperature (see figure).

    9. Allenes

      Regioselectivity Control in the Metal-Catalyzed O[BOND]C Functionalization of γ-Allenols, Part 1: Experimental Study (pages 1901–1908)

      Benito Alcaide, Pedro Almendros, Teresa Martínez del Campo, Elena Soriano and José L. Marco-Contelles

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802034

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      Guiding cyclization: The 5-exo-trig cyclization pathway of γ-allenols can be completely reversed either by changing the metal (Pd instead of Au) or by using a methoxymethyl protecting group, with 7-endo-trig alkoxycyclization then dominating instead (see scheme). In addition, the regioselectivity of the La-catalyzed cycloetherification can be modulated (5-exo versus 6-endo versus 7-endo) simply through subtle variation in the functionalization of the allene component.

    10. Regioselectivity Control in the Metal-Catalyzed Functionalization of γ-Allenols, Part 2: Theoretical Study (pages 1909–1928)

      Benito Alcaide, Pedro Almendros, Teresa Martínez del Campo, Elena Soriano and José L. Marco-Contelles

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802035

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      Calculating cyclization: Theoretical work directed towards the elucidation of the mechanisms of the gold-, palladium-, and lanthanum-catalyzed oxycyclizations (5-exo versus 6-endo versus 7-endo) of γ-allenols has been pursued in close relationship with the experimental study (Part 1, accompanying paper) and has corroborated the bench results to provide a complete study of the reactivity of γ-allenols under different metal-catalyzed conditions.

    11. RNS Inhibitors

      Synthesis of Stable Aminoacyl-tRNA Analogues Containing Triazole as a Bioisoster of Esters (pages 1929–1938)

      Maryline Chemama, Matthieu Fonvielle, Michel Arthur, Jean-Marc Valéry and Mélanie Etheve-Quelquejeu

      Version of Record online: 26 NOV 2008 | DOI: 10.1002/chem.200801563

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      Stable analogues: An effective synthetic route involving cycloaddition between alkynes and azidonucleosides to afford a new class of stable aminoacyl-tRNA analogues such as depicted is presented. Biological evaluation showed that theses new compounds act as potent inhibitors of FemXWv aminoacyl transferase, a novel drug target.

    12. Conjugate Addition

      Copper-Catalyzed Enantioselective β-Boration of Acyclic Enones (pages 1939–1943)

      Hak-Suk Sim, Xinhui Feng and Jaesook Yun

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802150

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      Josi or Mandy? Asymmetric conjugate addition of diboron to acyclic enones catalyzed by copper affords chiral organoboronates that possess a boronate group at the β stereocenter with excellent chemical yields and enantioselectivities (see scheme). This method accommodates the structural variation of acyclic enones and provides access to highly functionalized chiral organoboronates in one step.

    13. Electrocyclizations

      Regio-, Peri-, and Torquoselectivity in Hydroxy Heptatrienyl Cation Electrocyclizations: The Iso/Homo-Nazarov Reaction (pages 1944–1956)

      Olalla Nieto Faza, Carlos Silva López, Rosana Álvarez and Ángel R. de Lera

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801133

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      Competition: The electrocyclizations of 1- and 3-hydroxyheptatrienyl cations (see scheme) have been computationally studied at the B3LYP/6-311G(d) level. The 1-hydroxy system clearly favors a 4e over a 6e process, while for the 3-hydroxy isomer these mechanisms compete.

    14. Supramolecular Chemistry

      Supramolecular Complexation of N-Alkyl- and N,N′-Dialkylpiperazines with Cucurbit[6]uril in Aqueous Solution and in the Solid State (pages 1957–1965)

      Mikhail V. Rekharsky, Hatsuo Yamamura, Tadashi Mori, Akihiro Sato, Motoo Shiro, Sergey V. Lindeman, Rajendra Rathore, Kouhei Shiba, Young Ho Ko, Narayanan Selvapalam, Kimoon Kim and Yoshihisa Inoue

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200800398

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      Water seeds: Complex stoichiometry/composition and degree of oligomerization (oligomeric supramolecular complex formation) of cucurbit[6]uril (CB[6]) with N-alkyl- and N,N′-dialkylpiperazine were investigated in aqueous solutions by means of isothermal titration calorimetry (ITC), ESI-MS, NMR and light scattering measurements.

    15. Ionic Liquids

      Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation (pages 1966–1976)

      Ines Raabe, Katrin Wagner, Kristin Guttsche, Mingkui Wang, Michael Grätzel, Gustavo Santiso-Quiñones and Ingo Krossing

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200800417

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      Weak and robust? Tetraalkylammonium salts of weakly coordinating fluorinated alkoxyaluminates are easily accessible, chemically robust materials that show interesting physico-chemical properties like low melting points, high electrochemical stability and electric conductivity in weakly polar solvents such as CH2Cl2, Ph-F and toluene.

    16. Solvatochromism

      Photo-, Solvent-, and Ion-Controlled Multichromism of Imidazolium-Substituted Diarylethenes (pages 1977–1984)

      Takuya Nakashima, Kentaro Miyamura, Toshiyuki Sakai and Tsuyoshi Kawai

      Version of Record online: 9 SEP 2008 | DOI: 10.1002/chem.200801192

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      Seeing red: Imidazolium-substituted diarylethenes show solvent- and ion-controlled chromisms in addition to reversible photochromic reactions. The shift of equilibrium between two closed-ring isomers with different π-conjugation length by interaction with nucleophilic species is responsible for the multichromic property (see scheme).

    17. Endohedral Complexes

      Influence of Endohedral Confinement on the Electronic Interaction between He atoms: A He2@C20H20 Case Study (pages 1985–1990)

      Erick Cerpa, Andreas Krapp, Roberto Flores-Moreno, Kelling J. Donald and Gabriel Merino

      Version of Record online: 19 NOV 2008 | DOI: 10.1002/chem.200801399

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      The shortest He–He distance!r(He–He)=1.265 Å. The electronic interaction between confined pairs of He atoms in the C20H20 dodecahedrane cage is analyzed (see figure). A key observation about bonding that emerges uniquely from endohedral complexes is that a short internuclear separation does not necessarily imply the existence of a chemical bond.

    18. Zeolites

      Zr–Zeolite Beta: A New Heterogeneous Catalyst System for the Highly Selective Cascade Transformation of Citral to (±)-Menthol (pages 1991–1999)

      Yuntong Nie, Stephan Jaenicke and Gaik-Khuan Chuah

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200801776

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      Minty green: Zr–zeolite beta (Zr-beta) directs the one-pot catalytic cascade transformation of citral to menthols with high diastereoselectivity. The solid catalyst, a bifunctional Ni/Zr-beta or a composite Zr-beta–Ni/MCM-41 system, is easily recovered and reused in this green synthetic method (see figure).

  7. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    8. Preview
    1. Preview: Chem. Eur. J. 9/2009 (page 2003)

      Version of Record online: 2 FEB 2009 | DOI: 10.1002/chem.200990021

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