Chemistry - A European Journal

Cover image for Vol. 16 Issue 29

August 2, 2010

Volume 16, Issue 29

Pages 8565–8927

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
    9. Full Papers
    10. Preview
    1. Cover Picture: Cyclopolymerization and Copolymerization of Functionalized 1,6-Heptadienes Catalyzed by Pd Complexes: Mechanism and Application to Physical-Gel Formation (Chem. Eur. J. 29/2010) (page 8565)

      Sehoon Park, Takeshi Okada, Daisuke Takeuchi and Kohtaro Osakada

      Version of Record online: 29 JUL 2010 | DOI: 10.1002/chem.201090140

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      Cyclo- and copolymerization of functionalized 1,6-heptadienes catalyzed by Pd complexes is presented in the Full Paper by K. Osakada et al. on page 8662 ff. The polymer growth involves selective chain-walking isomerization and inter- and intramolecular insertion reactions of the vinyl groups into the Pd–polymer bond.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
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    1. Inside Cover: Photochemistry and Reactivity of the Phenyl Radical–Water System: A Matrix Isolation and Computational Study (Chem. Eur. J. 29/2010) (page 8566)

      Artur Mardyukov, Rachel Crespo-Otero, Elsa Sanchez-Garcia and Wolfram Sander

      Version of Record online: 29 JUL 2010 | DOI: 10.1002/chem.201090141

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      A mechanism for the hydrogen transfer from water to the phenyl radical under formation of the hydroxyl radical and benzene, which subsequently reacts under complete decomposition, is proposed by W. Sander et al. in their Full Paper on page 8679 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
    9. Full Papers
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  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
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    1. You have free access to this content
      Corrigendum: Preorganized, Macromolecular, Gene-Delivery Systems (page 8579)

      Carmen Ortiz Mellet, Juan M. Benito and José M. García Fernández

      Version of Record online: 29 JUL 2010 | DOI: 10.1002/chem.201090143

      This article corrects:

      Preorganized, Macromolecular, Gene-Delivery Systems

      Vol. 16, Issue 23, 6728–6742, Version of Record online: 28 MAY 2010

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
    9. Full Papers
    10. Preview
  6. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
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    1. Total Synthesis

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      Synthetic Studies Inspired by Vinigrol (pages 8586–8595)

      Alexander D. Huters and Neil K. Garg

      Version of Record online: 2 JUL 2010 | DOI: 10.1002/chem.201000916

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      Vinigrol, a diterpene natural product, has been a fascinating target for total synthesis for over two decades. Recent synthetic studies that have ultimately allowed access to the coveted vinigrol scaffold, including the approaches reported by Barriault, Njarđarson, and Hanna, as well as the first total synthesis of vinigrol, reported by Baran in 2009, are described.

  7. Communications

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
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    8. Communications
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    1. Reaction Mechanisms

      Palladium Round Trip in the Negishi Coupling of trans-[PdMeCl(PMePh2)2] with ZnMeCl: An Experimental and DFT Study of the Transmetalation Step (pages 8596–8599)

      Beatriz Fuentes, Max García-Melchor, Agustí Lledós, Feliu Maseras, Juan A. Casares, Gregori Ujaque and Pablo Espinet

      Version of Record online: 7 JUL 2010 | DOI: 10.1002/chem.201001332

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      Gets there in the end: The large rate difference of the slow reductive elimination and the fast transmetalation–retrotransmetalation steps allows Pd to visit complexes 3, 2, and 1 many times before coupling from 2 takes place. This fast recurrence of transformations offers many opportunities for the formation of undesired homocoupling products in Negishi reactions by statistically accessible “mistaken” retrotransmetalation events in the multitude of processes preceding the slower irreversible reductive elimination of the coupling product.

    2. Heterocycles

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      Sodium-Mediated Magnesiation of Thiophene and Tetrahydrothiophene: Structural Contrasts with Furan and Tetrahydrofuran (pages 8600–8604)

      Victoria L. Blair, Alan R. Kennedy, Robert E. Mulvey and Charles T. O'Hara

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201001139

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      Metallation of sulfur heterocycles: Alkali-metal-mediated magnesiation has been employed to regioselectively metallate the S-heterocycles thiophene and tetrahydrothiophene at ambient temperature. The structural chemistry of the metallo-compounds is remarkably different from that previously observed for the corresponding O-heterocycles (see figure).

    3. Asymmetric Synthesis

      Concise Asymmetric Synthesis of Fully Substituted Isoxazoline-N-Oxide through Lewis Base Catalyzed Nitroalkene Activation (pages 8605–8609)

      Cheng Zhong, Lekh Nath S. Gautam, Jeffrey L. Petersen, Novruz G. Akhmedov and Xiaodong Shi

      Version of Record online: 6 JUL 2010 | DOI: 10.1002/chem.201001237

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      Transforming isoxazoline-N-oxides: A concise asymmetric synthesis of isoxazoline-N-oxides is reported through secondary amine Lewis base catalyzed nitroalkene activation and sequential intermolecular condensation with aldehydes and ylides. Application of camphor-derived chiral sulfur ylides gave the enantiomeric-enriched isoxazoline-N-oxides in excellent yields and stereoselectivity. Simple transformations of isoxazoline-N-oxide led to the gram-scale synthesis of a (−)-clausenamide analogue in four steps, with excellent stereochemistry control (see scheme).

    4. Ylides

      Nucleophilic Reactivities of Sulfur Ylides and Related Carbanions: Comparison with Structurally Related Organophosphorus Compounds (pages 8610–8614)

      Roland Appel and Herbert Mayr

      Version of Record online: 30 JUN 2010 | DOI: 10.1002/chem.201001455

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      The nucleophilicity parameters of stabilized sulfur ylides, methylsulfonyl-, and methylsulfinyl stabilized carbanions have been determined from the rates of their reactions with benzhydrylium ions and quinone methides. Direct comparisons of the nucleophilic reactivities of sulfur and phosphorus ylides as well as their related carbanions have now become possible.

    5. Coordination Complexes

      Straightforward Generation of Helical Chirality Driven by a Versatile Heteroscorpionate Ligand: Self-Assembly of a Metal Helicate by Using CH[BOND]π Interactions (pages 8615–8619)

      Antonio Otero, Agustín Lara-Sánchez, Juan Fernández-Baeza, Carlos Alonso-Moreno, Juan Tejeda, José A. Castro-Osma, Isabel Márquez-Segovia, Luis F. Sánchez-Barba, Ana M. Rodríguez and M. Victoria Gómez

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000694

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      In a twist: The synthesis of novel architectures, through the use of versatile heteroscorpionate ligands, was developed that allows helical chirality in aluminium complexes (see figure).

    6. Solar Cells

      Hierarchical Tin Oxide Octahedra for Highly Efficient Dye-Sensitized Solar Cells (pages 8620–8625)

      Yu-Fen Wang, Jian-Wen Li, Yuan-Fang Hou, Xiao-Yun Yu, Cheng-Yong Su and Dai-Bin Kuang

      Version of Record online: 30 JUN 2010 | DOI: 10.1002/chem.201001333

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      Hierarchical SnO2octahedra consisting of SnO2 nanoparticles (≈30 nm in diameter) can be successfully fabricated by a fast sonochemical process followed by heat treatment (see figure). The dye-sensitized solar cell based on the photoelectrodes consisting of the bifunctional hierarchical octahedral SnO2 shows a power conversion efficiency of 6.40 %.

    7. Helical Superstructures

      Hierarchical Crystalline Superstructures of Conducting Polymers with Homohelicity (pages 8626–8630)

      Yong Yan, Yajie Zhang, Wenping Hu and Zhixiang Wei

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000999

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      Tuning hierarchical superstructures of helical nanofibers: Helical conducting polyaniline (PANI) nanofibers can self-assemble into linear nanofibers, branched nanofibers, and microribbons by controlling their aggregation processes. Structural studies indicated that helical PANI molecules are arranged normal to the long axis of nanofibers, which is very similar to the arrangement of peptides in β sheets (see figure).

    8. Polyoxometalates

      Borate Accelerates Rates of Steady Oxygen-Isotope Exchange for Polyoxoniobate Ions in Water (pages 8631–8634)

      Eric M. Villa, C. André Ohlin and William H. Casey

      Version of Record online: 2 JUL 2010 | DOI: 10.1002/chem.201000946

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      Borate: guilty and charged! The borate ion, and possibly carbonate, enhances rates of steady oxygen-isotope exchanges at some, but not all, structural sites in polyoxometalate ions. Addition of an oxygen atom to an incoming neutral boric acid molecule (blue=boron) from a bridging oxygen atom on a decametalate ion is shown here.

    9. Nucleotide Binding

      The Unusual Nucleotide Recognition Properties of the Resistance Enzyme ANT(4′): Inorganic Tri/Polyphosphate as a Substrate for Aminoglycoside Inactivation (pages 8635–8640)

      Julia Revuelta, Francisco Corzana, Agatha Bastida and Juan Luis Asensio

      Version of Record online: 28 MAY 2010 | DOI: 10.1002/chem.201000641

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      A pocket of resistance: We have analysed the molecular determinants for nucleotide recognition by the resistance enzyme ANT(4′). Our results demonstrate that its binding epitope is restricted to the inorganic triphosphate fragment. Strikingly, this, together with longer polyphosphate oligomers, can be employed as cosubstrates in aminoglycoside inactivation (see figure), implying a change in the normal activity of the enzyme. These results have implications in the design of specific enzymatic inhibitors.

    10. Supramolecular Chemistry

      A General pH-Responsive Supramolecular Nanovalve Based on Mesoporous Organosilica Hollow Nanospheres (pages 8641–8646)

      Wanping Guo, Jing Wang, Sang-Joon Lee, Fuping Dong, Sung Soo Park and Chang-Sik Ha

      Version of Record online: 30 JUN 2010 | DOI: 10.1002/chem.201000980

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      Smart release on demand: A general pH-responsive supramolecular nanovalve operating in aqueous media has been designed by using mesoporous organosilica hollow nanospheres as nanocontainers (see picture). The nanovalve is capable of storing guest molecules within the hollow core and mesopore shell and releasing them on demand by acid/base triggering of the capping molecule, demonstrating a delicate vehicle for controlled release.

    11. Imaging Agents

      Bionanoprobes with Excellent Two-Photon-Sensitized Eu3+ Luminescence Properties for Live Cell Imaging (pages 8647–8651)

      Guangsheng Shao, Rongcheng Han, Yan Ma, Minxian Tang, Fumin Xue, Yinlin Sha and Yuan Wang

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201001367

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      Bionanoprobes with high dispersion stability in water, excellent photostability, and biocompatibility were prepared by encapsulating [Eu(tta)3dpbt] (tta=thenoyltrifluoroacetonato, dpbt=2-(N,N-diethylanilin-4-yl)-4,6-bis-(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) in water-dispersible poly(methyl methacrylate-co-methacrylic acid) nanospheres and modifying the nanosphere surfaces with a monoclonal antibody (see scheme). The bionanoprobes exhibited excellent performance in the target-specific imaging of live cancer cells.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Communications
    9. Full Papers
    10. Preview
    1. Supramolecular Assembly

      Rational Design of Nanofibers and Nanorings through Complementary Hydrogen-Bonding Interactions of Functional π Systems (pages 8652–8661)

      Shiki Yagai, Hiroaki Aonuma, Yoshihiro Kikkawa, Shun Kubota, Takashi Karatsu, Akihide Kitamura, Sankarapillai Mahesh and Ayyappanpillai Ajayaghosh

      Version of Record online: 7 JUL 2010 | DOI: 10.1002/chem.201000839

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      Line up! Oligo(p-phenylenevinylene)s capped on one end by a monotopic melamine hydrogen-bonding module can self- and co-aggregate with cyanuric acid to produce various self-assembled architectures (see figure).

    2. Polymerization

      Cyclopolymerization and Copolymerization of Functionalized 1,6-Heptadienes Catalyzed by Pd Complexes: Mechanism and Application to Physical-Gel Formation (pages 8662–8678)

      Sehoon Park, Takeshi Okada, Daisuke Takeuchi and Kohtaro Osakada

      Version of Record online: 14 JUL 2010 | DOI: 10.1002/chem.201000604

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      Pd complexes with diimine ligands catalyze the cyclopolymerization of functionalized 1,6-heptadienes (see scheme), as well as their copolymerization with ethylene and 1-hexene. The resultant polymers contain 1,2-trans-fused cyclopentane rings along the polymer chain.

    3. Radical Reactions

      Photochemistry and Reactivity of the Phenyl Radical–Water System: A Matrix Isolation and Computational Study (pages 8679–8689)

      Artur Mardyukov, Rachel Crespo-Otero, Elsa Sanchez-Garcia and Wolfram Sander

      Version of Record online: 14 JUL 2010 | DOI: 10.1002/chem.200903362

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      The phenyl radical forms a hydrogen-bonded complex with water that could be isolated in solid argon at 10 K. Visible-light irradiation results in the transfer of a hydrogen atom from water to the phenyl radical under formation of a complex between OH and benzene. Prolonged irradiation results in the complete destruction of the benzene molecule and formation of a ring-opened ketene (see scheme).

    4. Organogels

      Thermo- and Acid-Responsive Photochromic Spironaphthoxazine-Containing Organogelators (pages 8690–8698)

      Yongguang Li, Keith Man-Chung Wong, Anthony Yiu-Yan Tam, Lixin Wu and Vivian Wing-Wah Yam

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000150

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      I like the way you move: A series of photochromic spironaphthoxazine derivatives has been designed, synthesized, and characterized by using 1H NMR spectroscopy, FAB mass spectrometry, and elemental analysis. The photophysical and photochromic behavior has also been investigated. Two of the compounds have been shown to be capable of forming stable thermoreversible organogels in organic solvents (see figure).

    5. Nanoparticle Fluorescence

      Polyelectrolyte-Assisted Formation of Molecular Nanoparticles Exhibiting Strongly Enhanced Fluorescence (pages 8699–8706)

      Ch. G. Chandaluri, A. Patra and T. P. Radhakrishnan

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.201000502

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      In a new light: Polyelectrolyte (sodium poly(styrenesulfonate) (NaPSS)) complexation followed by polyelectrolyte-assisted nanoparticle formation induces fluorescence enhancement by nearly two orders of magnitude (see picture) in a quinodimethane-based molecule (7,7-bis(piperazinium)-8,8-dicyanoquinodimethane bis(p-toluenesulfonate) (BT2)).

    6. Powder Diffraction

      Al3Li4(BH4)13: A Complex Double-Cation Borohydride with a New Structure (pages 8707–8712)

      Inge Lindemann, Roger Domènech Ferrer, Lothar Dunsch, Yaroslav Filinchuk, Radovan Černý, Hans Hagemann, Vincenza D'Anna, Latévi Max Lawson Daku, Ludwig Schultz and Oliver Gutfleisch

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000831

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      Mixed borohydrides: The synthesis, structure determination and decomposition pathway of a new complex double-cation borohydride with a very high hydrogen density are presented. The unique 3D-framework structure (see figure) contains complex anions [Al(BH4)4] and cations [Li4(BH4)]3+, which rationalise the unexpected stoichiometry Al3Li4(BH4)13.

    7. Synthetic Methods

      Imination of Sulfides and Sulfoxides with Sulfonylimino-λ3-Bromane under Mild, Metal-Free Conditions (pages 8713–8718)

      Masahito Ochiai, Masao Naito, Kazunori Miyamoto, Satoko Hayashi and Waro Nakanishi

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000759

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      Metal-free imination: Exposure of sulfides and sulfoxides to triflylimino-λ3-bromane in CH2Cl2 at 0 °C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields, under transition-metal-free conditions (see scheme).

    8. Photocatalysts

      Synthesis of Hierarchical Macro-/Mesoporous Solid-Solution Photocatalysts by a Polymerization–Carbonization–Oxidation Route: The Case of Ce0.49Zr0.37Bi0.14O1.93 (pages 8719–8725)

      Guangcheng Xi and Jinhua Ye

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.200903380

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      Solid-solution photocatalyst: A hierarchical macro-/mesoporous (HMM) Ce0.49Zr0.37Bi0.14O1.93 solid-solution network (see picture) has been fabricated by a polymerization–carbonization–oxidation route. The obtained material combines high specific surface area, HMM structure, and high crystallinity, and as a result shows a strong structure-induced enhancement of visible-light harvest and enhanced visible-light photocatalytic activity in the photodegradation of methyl orange.

    9. Metathesis

      Studies on Electronic Effects in O-, N- and S-Chelated Ruthenium Olefin-Metathesis Catalysts (pages 8726–8737)

      Eyal Tzur, Anna Szadkowska, Amos Ben-Asuly , Anna Makal, Israel Goldberg, Krzysztof Woźniak, Karol Grela  and N. Gabriel Lemcoff

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.200903457

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      Latent catalysts: New ruthenium bidentate benzylidene catalysts based on sulfur and nitrogen chelation are presented (see figure). The catalysts were thoroughly characterised and studied by spectroscopic and crystallographic techniques, and their reactivity in several metathesis reactions is described and analysed.

    10. Nucleophilic Addition

      The Wacker Process: Inner- or Outer-Sphere Nucleophilic Addition? New Insights from Ab Initio Molecular Dynamics (pages 8738–8747)

      Aleix Comas-Vives, András Stirling, Agustí Lledós and Gregori Ujaque

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.200903522

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      Wacker job: Does the nucleophilic addition step of the Wacker process proceed through an inner- or an outer-sphere mechanism (see image)? Ab initio molecular dynamics indicate that the outer-sphere mechanism is the less-energy-demanding pathway.

    11. Supramolecular Chemistry

      Unusual Photoinduced Electron Transfer from a Zinc Porphyrin to a Tetrapyridyl Free-Base Porphyrin in a Noncovalent Multiporphyrin Array (pages 8748–8756)

      Barbara Ventura, Lucia Flamigni, Maryline Beyler, Valérie Heitz and Jean-Pierre Sauvage

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/chem.201000375

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      Something a little unusual: A surprising electron transfer from a zinc porphyrin to a free-base porphyrin is detected in a noncovalent pentaporphyrin array (see figure).

    12. Zinc Oxide

      Sonochemical Preparation of Hierarchical ZnO Hollow Spheres for Efficient Dye-Sensitized Solar Cells (pages 8757–8761)

      Chun-Xiu He, Bing-Xin Lei, Yu-Fen Wang, Cheng-Yong Su, Yue-Ping Fang and Dai-Bin Kuang

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000264

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      More efficient power conversion: Hierarchical ZnO hollow spheres (400–500 nm in diameter) consisting of ZnO nanoparticles with a diameter of approximately 15 nm have been successfully prepared by a facile and rapid sonochemical process. The power conversion efficiency of the dye-sensitized solar cells based on hierarchical ZnO hollow spheres is 4.33 %, which represents a 38.8 % increase compared to that of a ZnO nanoparticle photoelectrode (3.12 %).

    13. Molecular Magnetism

      Theoretical Design of High-Spin Polycyclic Hydrocarbons (pages 8762–8772)

      Georges Trinquier, Nicolas Suaud and Jean-Paul Malrieu

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000044

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      Smart saturation: Saturating properly chosen vertices of polycyclic conjugated hydrocarbons may lead to high-spin organic units (see figure).

    14. Electron Transitions

      Studies of 2-Azaazulenium Derivatives: Unsymmetrical Trimethine Cyanine Dyes Bearing a 2-Azaazulenium Moiety as One of the Terminal Groups (pages 8773–8784)

      Julia Bricks, Aleksey Ryabitskii and Alexei Kachkovskii

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000366

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      Dye classification: Based on the results of quantum-chemical and spectral investigations of trimethine cyanine dye derivatives of 2-azaazulene, we propose a new classification of the terminal heterocycles (traditional Brooker's type and Azaazulene-like residues), and thus three types of cyanine dyes: Brooker's cyanines (BC), azaazulene-like (AAz) cyanines, and mixed AAz-BC dyes bearing the terminal groups of both types (see figure).

    15. Spin-Crossover Compounds

      Two-Step Thermal Spin Transition and LIESST Relaxation of the Polymeric Spin-Crossover Compounds Fe(X-py)2[Ag(CN)2]2 (X=H, 3-methyl, 4-methyl, 3,4-dimethyl, 3-Cl) (pages 8785–8796)

      J. Alberto Rodríguez-Velamazán, Chiara Carbonera, Miguel Castro, Elías Palacios, Takafumi Kitazawa, Jean-François Létard and Ramón Burriel

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000433

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      Three out of five members of the Fe(X-py)2[Ag(CN)2)]2 (py=pyridine; X=H, 3-Cl, 3-Me, 4-Me, 3,4-Me2) family of 2D polymeric spin-crossover (SCO) compounds (see picture) are among the rare examples of non-binuclear SCO compounds that show two-step behaviour not only in the thermal spin transition, but also in the relaxation of the photoinduced high-spin metastable state, as revealed by magnetic and calorimetric measurements.

    16. Self-Assembly

      Magnetic Coupling in Enantiomerically Pure Trinuclear Helicate-Type Complexes Formed by Hierarchical Self-Assembly (pages 8797–8804)

      Markus Albrecht, Marcel Fiege, Paul Kögerler, Manfred Speldrich, Roland Fröhlich and Marianne Engeser

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.200903108

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      Magnetic helicates: Enantiomerically pure trinuclear helicate-type complexes are self-assembled in a hierarchical process. With paramagnetic metal ions they show some interesting magnetic behavior (see figure).

    17. Antibiotics

      The Cobalt Way to Angucyclinones: Asymmetric Total Synthesis of the Antibiotics (+)-Rubiginone B2, (−)-Tetrangomycin, and (−)-8-O-Methyltetrangomycin (pages 8805–8821)

      Christian Kesenheimer, Aris Kalogerakis, Anja Meißner and Ulrich Groth

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.201000804

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      Like, totally: A convergent and asymmetric total synthesis of naturally occurring angucyclinone antibiotics (+)-rubiginone B2, (−)-tetrangomycin, and (−)-8-O-methyltetrangomycin by means of intramolecular cobalt-mediated [2+2+2] cycloaddition was established (see scheme).

    18. Azo Compounds

      2-Hydroxyazobenzenes to Tailor pH Pulses and Oscillations with Light (pages 8822–8831)

      Matthieu Emond, Thomas Le Saux, Sylvie Maurin, Jean-Bernard Baudin, Raphael Plasson and Ludovic Jullien

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000541

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      Sink or swing: The trans-to-cis isomerization of 2-hydroxyazobenzenes under UV light results in a tunable transient change of the protonation constant. Up to 2 pH units of fast, reversible pH drops and pH oscillations have been generated by shaping single-wavelength illumination (see picture).

    19. Energy Transfer

      Vectorial Photoinduced Energy Transfer Between Boron–Dipyrromethene (Bodipy) Chromophores Across a Fluorene Bridge (pages 8832–8845)

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

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.201000466

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      Energy exchange: Intercomponent photoinduced energy transfer takes place between different 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (Bodipy) subunits separated by a fluorene spacer (see figure). The efficiency and rate of such a process can be tuned by the presence of protons.

    20. Group 13 Elements

      First Dinuclear Copper/Gallium Complexes: Supporting Cu0 and CuI Centres by Low-Valent Organogallium Ligands (pages 8846–8853)

      Timo Bollermann, Ganesan Prabusankar, Christian Gemel, Rüdiger W. Seidel, Manuela Winter and Roland A. Fischer

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000465

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      Right system? Reactions of suitable copper precursors with gallium(I) species lead to three dinuclear copper complexes with direct Cu–Ga donor–acceptor interactions. Depending on the ligand system and the oxidation state, complexes with very short Cu⋅⋅⋅Cu distances and also the first complex of Cu0 are formed (see picture).

    21. Main Group Chemistry

      Formation and Rearrangement of SnII Phosphanediide Cages (pages 8854–8860)

      Mary McPartlin, Rebecca L. Melen, Vesal Naseri and Dominic S. Wright

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000656

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      Release me: Tin(II) phosphanediides are readily prepared by deprotonation of RPH2 with Sn(NMe2)2 at room temperature. These species exhibit interesting thermolysis reactions, giving rise to diphosphanes, diphosphenes and tin metal on heating (see scheme).

    22. Ferrocenylboranes

      Planar Chiral Organoborane Lewis Acids Derived from Naphthylferrocene (pages 8861–8867)

      Jiawei Chen, Krishnan Venkatasubbaiah, Thilagar Pakkirisamy, Ami Doshi, Andrej Yusupov, Yesha Patel, Roger A. Lalancette and Frieder Jäkle

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000372

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      Ferrocenylboranes go chiral: Enantiomerically pure naphthylferrocene derivatives NpFcM (NpFc=2-(1-naphthyl)ferrocene, M=SnMe3, HgCl) have been prepared by directed ortho-metalation and subsequent selective transmetalation procedures. NpFcHgCl was successfully used as a precursor for the preparation of highly Lewis acidic planar chiral organoboranes (see scheme).

    23. Molybdenum and Tungsten Catalysts

      Preparation of Imidazolin-2-iminato Molybdenum and Tungsten Benzylidyne Complexes: A New Pathway to Highly Active Alkyne Metathesis Catalysts (pages 8868–8877)

      Birte Haberlag, Xian Wu, Kai Brandhorst, Jörg Grunenberg, Constantin G. Daniliuc, Peter G. Jones and Matthias Tamm

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000597

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      Alkyne metathesis: A new synthetic route to imidazolin-2-iminato molybdenum and tungsten benzylidyne complexes from [Mo(CO)6] or [W(CO)6] has been established that affords highly active catalysts for alkyne cross metathesis and ring-closing alkyne metathesis (see figure). The tungsten complex tends to show a superior catalytic performance, which is in line with DFT studies predicting a higher barrier for the molybdenum-based catalyst system.

    24. Organophosphates

      Hydrolysis of Organophosphate Esters: Phosphotriesterase Activity of Metallo-β-lactamase and Its Functional Mimics (pages 8878–8886)

      A. Tamilselvi and Govindasamy Mugesh

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.201000282

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      Functional mimics: Binuclear zinc(II) complexes that exhibit good metallo-β-lactamase (mβl) activity are poor mimics of phosphotriesterase (PTE) and vice versa, indicating that the binding of β-lactam substrates at the binuclear zinc(II) center is different to that in phosphotriesters (see scheme). Furthermore, phosphodiesters, the products from the hydrolysis of phosphotriesters, inhibit the PTE activity of mβl and its functional mimics.

    25. Enzyme Catalysis

      Cationic Reverse Micelles Create Water with Super Hydrogen-Bond-Donor Capacity for Enzymatic Catalysis: Hydrolysis of 2-Naphthyl Acetate by α-Chymotrypsin (pages 8887–8893)

      Fernando Moyano, R. Dario Falcone, J. C. Mejuto, Juana J. Silber and N. Mariano Correa 

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000437

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      Superwater: The hydrogen-bond-donor ability of water for the hydrolysis of 2-naphthyl acetate catalyzed by α-chymotrypsin in reverse micelles (RMs) depends dramatically on the kind of surfactant used to create the micellar system. Thus, catalyst activity in RMs formed from the cationic surfactant benzyl-n-hexadecyldimethylammonium chloride (BHDC) is much higher than in anionic sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) RMs or pure water, because interaction with the cationic interface (see picture) increases the hydrogen-bond-donor capacity of water.

    26. Cycloaddition and Cycloreversion

      [4+2] Cycloaddition Reactions Between 1,8-Disubstituted Cyclooctatetraenes and Diazo Dienophiles: Stereoelectronic Effects, Anticancer Properties and Application to the Synthesis of 7,8-Substituted Bicyclo[4.2.0]octa-2,4-dienes (pages 8894–8903)

      Rebecca L. Grange, Michael J. Gallen, Heiko Schill, Jenny P. Johns, Lin Dong, Peter G. Parsons, Paul W. Reddell, Victoria A. Gordon, Paul V. Bernhardt and Craig M. Williams

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.200903454

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      Toss diazo into the ring! [4+2] Cycloaddition reactions between 1,8-disubstituted cyclooctatetraenes and diazo compounds provide either 2,3- or 3,4-disubstituted adducts. Product distribution can be controlled by modulating the dienophile or the electron density of the cylooctatetraene. The adducts displayed selective action against various human tumour cell types, whilst also forming the basis of a new pathway to the synthetically challenging bicyclo[4.2.0]octa-2,4-diene family (see scheme).

    27. Trienol Ethers

      Cobalt-Mediated Linear 2:1 Co-oligomerization of Alkynes with Enol Ethers to Give 1-Alkoxy-1,3,5-Trienes: A Missing Mode of Reactivity (pages 8904–8913)

      David Lebœuf, Laura Iannazzo, Anaïs Geny, Max Malacria, K. Peter C. Vollhardt, Corinne Aubert and Vincent Gandon

      Version of Record online: 23 JUN 2010 | DOI: 10.1002/chem.201000486

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      Competing pathways: Trienol ethers, including diborylated derivatives, are constructed by cobalt-mediated linear co-oligomerization of alkynes with enol ethers. This formal alkyne coupling/C[BOND]H activation sequence proceeds in a highly regio- and diastereoselective fashion. Thermal electrocyclic ring closure, coupled with dehydroalkoxylation, leads to arene derivatives (see figure), the sequence constituting a formal [2+2+2] cycloaddition of alkynes to acetylene.

    28. Bioorganometallic Chemistry

      Ferrocene-Substituted Dithio-o-Carborane Isomers: Influence on the Native Conformation of Myoglobin Protein (pages 8914–8922)

      Chunhui Wu, Baohua Xu, Juan Zhao, Qibai Jiang, Fadong Wei, Hui Jiang, Xuemei Wang and Hong Yan

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000605

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      Go bio! Two ferrocene-substituted dithio-o-carborane isomers (FcSB1 and FcSB2) show a different binding affinity to myoglobin and affect the spin state of the heme iron center and the conformation of aromatic fluorophores in the protein matrix. The exploration of such biointeractions provides insights into the promising bioapplications of the relevant multifunctional organometallic complexes.

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      Preview: Chem. Eur. J. 30/2010 (page 8927)

      Version of Record online: 29 JUL 2010 | DOI: 10.1002/chem.201090145

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