Chemistry - A European Journal

Cover image for Vol. 20 Issue 11

March 10, 2014

Volume 20, Issue 11

Pages 2969–3233

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Cover Picture: Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of Fc[BOND]C[TRIPLE BOND]N and Fc[BOND]C[TRIPLE BOND]C[BOND]C[TRIPLE BOND]N (Chem. Eur. J. 11/2014) (page 2969)

      Lisanne Becker, Frank Strehler, Marcus Korb, Dr. Perdita Arndt, Dr. Anke Spannenberg, Dr. Wolfgang Baumann, Prof. Dr. Heinrich Lang and Prof. Dr. Uwe Rosenthal

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201490042

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      Group 4 Metallocene alkyne complexes react with ferrocenyl (Fc) nitriles. In their Full Paper on page 3061ff., H. Lang, U. Rosenthal, et al. show that in the case of Fc[BOND]C[TRIPLE BOND]N, an unusual nitrile–nitrile C[BOND]C homocoupling was observed, whereas with Fc[BOND]C[TRIPLE BOND]C[BOND] C[TRIPLE BOND]N, products derived from alkyne– nitrile C[BOND]C coupling of two nitrile substrates were isolated.

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      Back Cover: Amphiphilic Inclusion Spaces for Various Guests and Regulation of Fluorescence Intensity of 1,8-Bis(4-aminophenyl)anthracene Crystals (Chem. Eur. J. 11/2014) (page 3236)

      Misa Sugino, Keisuke Hatanaka, Yusuke Araki, Dr. Ichiro Hisaki, Prof. Dr. Mikiji Miyata and Dr. Norimitsu Tohnai

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201490045

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      Amphiphilic inclusion spaces  were constructed by crystallization of 1,8-bis(4-aminophenyl)anthracene with various guests. The solid-state fluorescence efficiencies changed depending on the guests. N. Tohnai et al. in the Full Paper on page 3069 ff. elucidated that guest molecules immobilize the host framework from within to suppress the non-radiation processes. Therefore, the fluorescence efficiencies were efficiently regulated by the host–guest interactions and the guest occupancy in the inclusion spaces.

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of Fc[BOND]C[TRIPLE BOND]N and Fc[BOND]C[TRIPLE BOND]C[BOND]C[TRIPLE BOND]N (page 2972)

      Lisanne Becker, Frank Strehler, Marcus Korb, Dr. Perdita Arndt, Dr. Anke Spannenberg, Dr. Wolfgang Baumann, Prof. Dr. Heinrich Lang and Prof. Dr. Uwe Rosenthal

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201400193

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      The fact that these reactions are highly selective is therefore very surprising and interesting.” Read more about the story behind the cover in the Cover Profile and about the research itself on page 3061 ff. (DOI: 10.1002/chem.201304478)

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Graphical Abstract: Chem. Eur. J. 11/2014 (pages 2973–2983)

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201490043

  4. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Corrigendum: Exocyclic Control of Turn Induction in Macrocyclic Peptide Scaffolds (page 2983)

      Serge Zaretsky, Dr. Conor C. G. Scully, Dr. Alan J. Lough and Prof. Dr. Andrei K. Yudin

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201400422

      This article corrects:

      Exocyclic Control of Turn Induction in Macrocyclic Peptide Scaffolds

      Vol. 19, Issue 52, 17668–17672, Article first published online: 20 NOV 2013

    2. You have free access to this content
      Corrigendum: Highly Luminescent N-Doped Carbon Quantum Dots as an Effective Multifunctional Fluorescence Sensing Platform (page 2983)

      Dr. Zhaosheng Qian, Juanjuan Ma, Xiaoyue Shan, Dr. Hui Feng, Prof. Linxiang Shao and Prof. Jianrong Chen

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201400424

      This article corrects:

      Highly Luminescent N-Doped Carbon Quantum Dots as an Effective Multifunctional Fluorescence Sensing Platform

      Vol. 20, Issue 8, 2254–2263, Article first published online: 21 JAN 2014

  5. News

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

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

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      Transition-Metal-Free Catalytic Reduction of Carbon Dioxide (pages 2990–2996)

      Prof. Frédéric-Georges Fontaine, Marc-André Courtemanche and Marc-André Légaré

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304376

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      Less is more: Metal-free systems, including frustrated Lewis pairs (FLPs), have been shown to bind CO2. By reducing the Lewis acidity and basicity of the ambiphilic system, it is possible to generate active catalysts for the deoxygenative hydroboration of carbon dioxide to methanol derivatives with conversion rates comparable to those of transition-metal-based catalysts (see scheme).

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Drug Delivery

      Acetylcholine-Triggered Cargo Release from Supramolecular Nanovalves Based on Different Macrocyclic Receptors (pages 2998–3004)

      Yue Zhou, Li-Li Tan, Qing-Lan Li, Xi-Long Qiu, Prof. Ai-Di Qi, Yanchun Tao and Prof. Ying-Wei Yang

      Article first published online: 1 MAR 2014 | DOI: 10.1002/chem.201304864

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      Supramolecular nanovalves: Mesoporous silica nanoparticles (MSNs) equipped with calixarene- or pillarene-based nanovalves were prepared and characterized (see scheme). Acetylcholine (ACh), a neurotransmitter, successfully triggered cargo release from the nanocontainers, which could be useful for Parkinson's disease (PD) treatment.

    2. Cascade Reactions

      Phase-Transfer-Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen-Bond-Assisted Isocyanide Cyclization Cascade (pages 3005–3009)

      Dr. Peter C. Knipe, Dr. Matija Gredičak, Artiom Cernijenko, Dr. Robert S. Paton and Dr. Martin D. Smith

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201400192

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      Generating complexity: A cascade reaction that generates pyrrolo- and pyridoindoline motifs from isocyanide precursors under phase-transfer conditions is described. Quantum chemical calculations demonstrated that intramolecular general-acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5-endo-dig cyclization, rather than an anionic 6π electrocyclization (see scheme).

    3. Magnetic Wheels

      Combining Complementary Ligands into one Framework for the Construction of a Ferromagnetically Coupled [MnIII12] Wheel (pages 3010–3013)

      Dr. Sergio Sanz, Jamie M. Frost, Thayalan Rajeshkumar, Dr. Scott J. Dalgarno, Dr. Gopalan Rajaraman, Dr. Wolfgang Wernsdorfer, Prof. Jürgen Schnack, Dr. Paul. J. Lusby and Prof. Euan K. Brechin

      Article first published online: 27 JAN 2014 | DOI: 10.1002/chem.201304740

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      Manganic roundabout: A ligand comprising both phenolic oxime and diethanolamine moieties assembles a [MnIII12] wheel, in which nearest neighbours are coupled ferromagnetically (see figure).

    4. Li-ion Batteries

      Using Simple Spray Pyrolysis to Prepare Yolk–Shell-Structured ZnO–Mn3O4 Systems with the Optimum Composition for Superior Electrochemical Properties (pages 3014–3018)

      Seung Ho Choi and Prof. Yun Chan Kang

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201304118

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      Powdered eggs: A spray-pyrolysis process is introduced as an effective tool for the preparation of yolk–shell-structured materials. Yolk–shell-structured ZnO–Mn3O4 powders with various molar ratios of Zn and Mn were prepared (see figure), and a 1:1 ratio is shown to have the high capacities and good cycling performances that are needed for anode materials in Li-ion batteries.

    5. Light Harvesting

      Light Harvesting and Amplification of Emission of Donor Perylene–Acceptor Perylene Aggregates in Aqueous Medium (pages 3019–3022)

      Pradip K. Sukul, Dr. Ayan Datta and Dr. Sudip Malik

      Article first published online: 23 FEB 2014 | DOI: 10.1002/chem.201304431

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      Light harvesting: Through the use of rational design, a pair of water-soluble donor- and acceptor-type twisted perylene bisimide units have been synthesized. Together, these form aggregates when the pH of the medium is lowered, emitting bright yellow fluorescence. The light-harvesting efficiency of the co-assembled system can be tuned by controlling the ratio of donor to acceptor and over 98 % efficiency has been achieved.

    6. Self-Assembled Nanochannels

      Triazole-Tailored Guanosine Dinucleosides as Biomimetic Ion Channels to Modulate Transmembrane Potential (pages 3023–3028)

      Y. Pavan Kumar, Rabindra Nath Das, Sonu Kumar, Ole Mathis Schütte, Prof. Dr. Claudia Steinem and Prof. Dr. Jyotirmayee Dash

      Article first published online: 20 FEB 2014 | DOI: 10.1002/chem.201304530

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      Coming through: A “click” ion-channel platform was established by employing a clickable guanosine azide or alkyne with covalent spacers. The guanosine derivatives modulated the traffic of ions across the phospholipid bilayer. FRET studies of the dansyl fluorophore with the membrane-binding fluorophore Nile red revealed that the dansyl fluorophore is deeply embedded in the phospholipid bilayer (see figure).

    7. Magnetocaloric Effect

      Switching of the Magnetocaloric Effect of MnII Glycolate by Water Molecules (pages 3029–3035)

      Yan-Cong Chen, Fu-Sheng Guo, Jun-Liang Liu, Ji-Dong Leng, Dr. Peter Vrábel, Prof. Dr. Martin Orendáč, Dr. Jan Prokleška, Prof. Dr. Vladimír Sechovský and Prof. Dr. Ming-Liang Tong

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201304423

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      Magnetocaloric effect: The transformation of MnII glycolates (glc) between the three-dimensional coordination polymer [Mn(glc)2]n (1) and discrete mononuclear phase [Mn(glc)2(H2O)2] (2) can be reversibly switched by water molecules, which dramatically change the magnetocaloric effect of MnII glycolates from the maximum of 6.9 J kg−1 K−1 in 1 to 60.3 J kg−1 K−1 in 2.

    8. Carbenes

      Carbene-9-BBN Ring Expansions as a Route to Intramolecular Frustrated Lewis Pairs for CO2 Reduction (pages 3036–3039)

      Dr. Tongen Wang and Prof. Dr. Douglas W. Stephan

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201304870

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      A BOB well done: Reactions of phosphine-derived carbenes with 9-borabicyclo[3.3.1]nonane (9-BBN) result in ring-expansion reactions to generate novel intramolecular frustrated Lewis pairs (FLPs). These FLPs effect the catalytic reduction of CO2 in the presence of boranes to give BOB and methoxy-borate species (see scheme).

    9. Synthetic Methods

      Regio- and Enantioselective Synthesis of N-Allylindoles by Iridium-Catalyzed Allylic Amination/Transition-Metal-Catalyzed Cyclization Reactions (pages 3040–3044)

      Ke-Yin Ye, Prof. Li-Xin Dai and Prof. Shu-Li You

      Article first published online: 20 FEB 2014 | DOI: 10.1002/chem.201400026

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      Regio- and enantioselective synthesis of N-allylindoles was realized through an iridium-catalyzed asymmetric allylic amination reaction with 2-alkynylanilines and subsequent transition-metal-catalyzed cyclization reactions (see scheme). The highly enantioenriched allylic amines prepared from Ir catalysis were treated with catalytic amount of NaAuCl42 H2O or PdCl2 providing various substituted N-allylindoles in excellent yields and enantioselectivities (dbcot=dibenzo[a,e]cyclooctatetraene).

    10. Photoredox Catalysis

      Visible-Light-Induced C[BOND]S Bond Activation: Facile Access to 1,4-Diketones from β-Ketosulfones (pages 3045–3049)

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

      Article first published online: 20 FEB 2014 | DOI: 10.1002/chem.201304898

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      A new and efficient method for the synthesis of 1,4-diketones from β-ketosulfones was developed by means of a visible-light-induced C[BOND]S bond activation process (see scheme). Symmetrical and unsymmetrical 1,4-diketones can be easily prepared in moderate to good yields.

  8. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Sustainable Catalysis

      Urea-Based Porous Organic Frameworks: Effective Supports for Catalysis in Neat Water (pages 3050–3060)

      Dr. Liuyi Li, Dr. Zhilin Chen, Dr. Hong Zhong and Prof. Dr. Ruihu Wang

      Article first published online: 20 FEB 2014 | DOI: 10.1002/chem.201304046

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      Feeling supportive? Two urea-based porous organic frameworks were prepared by a facile urea-forming condensation and can serve as effective supports in palladium-catalyzed Suzuki–Miyaura cross-coupling reactions and reduction of nitroarenes in water. The reactions can even be efficiently performed at room temperature. The original morphology of the urea-based frameworks was maintained after the catalytic reactions.

    2. C[BOND]C Coupling

      Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of Fc[BOND]C[TRIPLE BOND]N and Fc[BOND]C[TRIPLE BOND]C[BOND]C[TRIPLE BOND]N (pages 3061–3068)

      Lisanne Becker, Frank Strehler, Marcus Korb, Dr. Perdita Arndt, Dr. Anke Spannenberg, Dr. Wolfgang Baumann, Prof. Dr. Heinrich Lang and Prof. Dr. Uwe Rosenthal

      Article first published online: 24 FEB 2014 | DOI: 10.1002/chem.201304478

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      Unusual coupling: The treatment of Group 4 metallocene alkyne complexes with ferrocenyl (Fc)-substituted nitriles leads very selectively to unusual nitrile–nitrile and nitrile–alkyne coupling reactions. Fc[BOND]C[TRIPLE BOND]N and Fc[BOND]C[TRIPLE BOND]C[BOND]C[TRIPLE BOND]N were converted into 1-metalla-2,5-diaza-cyclopenta-2,4-dienes and 1-metalla-2-aza-cyclopenta-2,4-dienes, respectively, the electrochemical behavior of which was studied (see scheme).

    3. Inclusion Crystals

      Amphiphilic Inclusion Spaces for Various Guests and Regulation of Fluorescence Intensity of 1,8-Bis(4-aminophenyl)anthracene Crystals (pages 3069–3076)

      Misa Sugino, Keisuke Hatanaka, Yusuke Araki, Dr. Ichiro Hisaki, Prof. Dr. Mikiji Miyata and Dr. Norimitsu Tohnai

      Article first published online: 20 FEB 2014 | DOI: 10.1002/chem.201304541

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      Immobilisation by guests from within: Inclusion crystals of 1,8-bis(4-aminophenyl)anthracene (1,8-BAPA) constructed the same inclusion space for eight guest molecules including not only non-polar guests (benzene) but also polar guests (DMF; see scheme). Fluorescence efficiencies varied depending on guest molecule polarity. Strong host–guest interactions and filling of the inclusion space led to a high fluorescence intensity.

    4. Hydrogels

      A Dithienylethene-Based Rewritable Hydrogelator (pages 3077–3083)

      Dr. Jochem T. van Herpt, Dr. Marc C. A. Stuart, Prof. Dr. Wesley R. Browne and Prof. Dr. Ben L. Feringa

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201304064

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      Flicking the switch: Dithienylethene photochromic switching units have been incorporated into a hydrogelating system based on a tripeptide motif. The resulting hybrid system provides both a photochromic response (see figure) and the ability to gelate water under acidic and neutral conditions.

    5. Nanostructures

      Direct Growth of Cobalt Hydroxide Rods on Nickel Foam and Its Application for Energy Storage (pages 3084–3088)

      Dr. Rahul R. Salunkhe, Dr. Bishnu Prasad Bastakoti, Dr. Chun-Tsung Hsu, Dr. Norihiro Suzuki, Prof. Dr. Jung Ho Kim, Prof. Dr. Shi Xue Dou, Prof. Dr. Chi-Chang Hu and Prof. Dr. Yusuke Yamauchi

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201303652

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      Time for a bath! One-step, simple, and inexpensive synthesis of Co(OH)2 rods on Ni foam by the optimized chemical-bath-deposition method is described. The Ni-foam substrate can serve both as current collector and give nucleation sites for growth of Co(OH)2 rods, which eliminates the use of ancillary conducting material and binder (see figure).

    6. DNA Binding

      From Intercalation to Groove Binding: Switching the DNA-Binding Mode of Isostructural Transition-Metal Complexes (pages 3089–3096)

      Dr. Haslina Ahmad, Ashley Wragg, Will Cullen, Claire Wombwell, Dr. Anthony J. H. M. Meijer and Dr. Jim A. Thomas

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201304053

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      Bind the gap: Closely related d6-metal ion complexes (see figure) containing identical unfused polycyclic aromatic ligands can interact with DNA through either intercalation or groove binding. Experimental and computational studies show that the mode of interaction of individual complexes is strongly dependent not on their structure, but their stereoelectronic properties.

    7. Supramolecular Chemistry

      Tracking “Apolar” NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action (pages 3097–3105)

      Dr. Vladimir S. Korenev, Antoine G. Boulay, Dr. Mohamed Haouas, Dr. Fatma Bannani, Prof. Dr. Vladimir P. Fedin, Prof. Dr. Maxim N. Sokolov, Emmanuel Terazzi, Somenath Garai, Prof. Dr. Achim Müller, Dr. Francis Taulelle, Dr. Jérôme Marrot, Dr. Nathalie Leclerc, Dr. Sébastien Floquet and Prof. Dr. Emmanuel Cadot

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201303719

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      Please accept me: Two giant polyoxothiometalates were synthesized based on linking oxomolybdate building blocks with {Mo2O2S2}2+ groups (see figure). The much larger Mo132-type Keplerate exhibits 20 pores and the smaller Mo63 cluster only two; both can integrate apolar NMe4+ cations (shown for the smaller one). 1H NMR DOSY spectra allowed quantitative tracking of the interactions of the NMe4+ cations with the pores of the Keplerate.

    8. Electrocatalysts

      Nitrogen and Phosphorus Dual-Doped Hierarchical Porous Carbon Foams as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reactions (pages 3106–3112)

      Dr. Hongliang Jiang, Prof. Yihua Zhu, Dr. Qian Feng, Dr. Yunhe Su, Prof. Xiaoling Yang and Prof. Chunzhong Li

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304561

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      Foam sweet foam: N and P dual-doped carbon foams with hierarchical interconnected macro-/mesoporous structures have been synthesized by poly(vinyl alcohol) hydrogel-based composites as in situ templates (see figure), which can serve as efficient metal-free electrocatalysts with a four-electron reaction pathway for oxygen reduction reactions in basic, neutral, and acidic media.

    9. Homogeneous Catalysis

      Alkyne/Alkene/Allene-Induced Disproportionation of Cationic Gold(I) Catalyst (pages 3113–3119)

      Manish Kumar, Dr. Jacek Jasinski, Prof. Dr. Gerald B. Hammond and Prof. Dr. Bo Xu

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304271

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      The first detailed experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)-induced disproportionation of gold(I) may play a key role in the decay process (see scheme; TF = trifluoromethanesulfonyl).

    10. Heterometallic Complexes

      Structural and Photophysical Study on Heterobimetallic Complexes with d8–d10 Interactions Supported by Carborane Ligands: Theoretical Analysis of the Emissive Behaviour (pages 3120–3127)

      Dr. Olga Crespo, Prof. M. Concepción Gimeno, Prof. Antonio Laguna, Dr. Olli Lehtonen, Dr. Isaura Ospino, Prof. Pekka Pyykkö and Dr. M. Dolores Villacampa

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201303735

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      A family of red emitters of formula [M{(PPh2)2C2B9H10}(S2C2B10H10)M′(PPh3)] (M=Pd, Pt; M′=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] (see figure) was synthesised. Theoretical studies on [M{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to-“P2-M-S2” group (ML′) charge-transfer (LML′CT) transitions for M=Pt and to metal (M)-to-“P2-M-S2” group (ML′) charge-transfer (MML′CT) transitions for M=Ni, Pd.

    11. Isomerism

      You have full text access to this OnlineOpen article
      Steady-State and Pseudo-Steady-State Photocrystallographic Studies on Linkage Isomers of [Ni(Et4dien)(η2-O,ON)(η1-NO2)]: Identification of a New Linkage Isomer (pages 3128–3134)

      Lauren E. Hatcher, Dr. Jeppe Christensen, Dr. Michelle L. Hamilton, Dr. Jose Trincao, Dr. David R. Allan, Dr. Mark R. Warren, Dr. Ian P. Clarke, Prof. Dr. Michael Towrie, Dr Sara Fuertes, Prof. Dr. Charles C. Wilson, Dr. Christopher H. Woodall and Prof. Dr. Paul R. Raithby

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304172

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      Linkage isomers: Photocrystallographic studies of nitro–nitrito isomerism in a nickel complex show that both the type of photoactive species produced and its lifetime are highly temperature dependent. Below 150 K, 100 % conversion to a metastable endo-nitrito isomer is achieved. At 150–160 K, the reverse decay process occurs with activation energy of +48.6 kJ mol−1. At about 140–190 K, a new exo-nitrito isomer is also seen that is only detected under pseudo-steady-state conditions.

    12. Organic Chemistry

      Regioselective Ruthenium-Catalyzed Carbonylative Direct Arylation of Five-Membered and Condensed Heterocycles (pages 3135–3141)

      Jola Pospech, Dr. Anis Tlili, Dr. Anke Spannenberg, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304314

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      C[BOND]H bond functionalization: A ruthenium-catalyzed carbonylative C[BOND]H bond arylation process for the three-component synthesis of complex aryl–(hetero)aryl ketones in an aqueous solution has been developed (see scheme). By exploiting the ortho-activating effect of nitrogen-containing directing groups, a regioselective, successive twofold C(sp2)[BOND]C(sp2) bond formation has been achieved.

    13. Dye-Sensitized Solar Cells

      Molecular Dyads Comprising Metalloporphyrin and Alkynylplatinum(II) Polypyridine Terminal Groups for Use as a Sensitizer in Dye-Sensitized Solar Cells (pages 3142–3153)

      Eric Chi-Ho Kwok, Dr. Mei-Yee Chan, Dr. Keith Man-Chung Wong and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304051

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      A new class of molecular dyads comprising metalloporphyrin-linked alkynylplatinum(II) polypyridine complexes (see figure; TF = trifluoromethanesulfonyl) has been synthesized and characterized. The complexes can be applied as sensitizers for the fabrication of dye-sensitized solar cells (DSSCs), and they give satisfactory photovoltaic responses. Subtle changes in the alkynyl linker show significant improvements in the performance of the DSSCs.

    14. Organometallic Chemistry

      Halide-Free Diarylcalcium Complexes—Syntheses, Structures, and Stability (pages 3154–3161)

      Dr. Jens Langer, Mathias Köhler, Dr. Helmar Görls and Prof. Dr. Matthias Westerhausen

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304429

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      Calcium for your chemistry toolbox! A straightforward procedure allows the preparation of halide-free diarylcalcium complexes (see scheme; hmteta= N,N,N′,N′′,N′′′,N′′′-hexamethyltriethylenetetramine). Despite their enormous reactivity, leading to ether degradation reactions, the stability is sufficient for preparative organic and organometallic chemistry.

    15. Cross-Coupling Reactions

      Nickel-Catalyzed Csp2[BOND]Csp3 Bond Formation by Carbon[BOND]Fluorine Activation (pages 3162–3168)

      Dr. Alex D. Sun, Kaylyn Leung, Anita D. Restivo, Nicole A. LaBerge, Harumi Takasaki and Prof. Dr. Jennifer A. Love

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201303809

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      Gently does it! A general catalytic method for Csp2[BOND]Csp3 bond formation through C[BOND]F activation with an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms, is described (see scheme; DG = directing group). A variety of fluorine substitution patterns and functional groups (FGs) are readily tolerated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

    16. Bisphosphines

      New Functional Cyclic Aminomethylphosphine Ligands for the Construction of Catalysts for Electrochemical Hydrogen Transformations (pages 3169–3182)

      Dr. Elvira I. Musina, Vera V. Khrizanforova, Igor D. Strelnik, Murad I. Valitov, Yulia S. Spiridonova, Dr. Dmitry B. Krivolapov, Dr. Igor A. Litvinov, Dr. Marsil K. Kadirov, Dr. Peter Lönnecke, Prof. Dr. Evamarie Hey-Hawkins, Prof. Dr. Yulia H. Budnikova, Prof. Dr. Andrey A. Karasik and Prof. Dr. Oleg G. Sinyashin

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304234

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      1,5-Diaza-3,7-diphosphacyclooctanes with 2-pyridyl substituents on the phosphorus atoms have been synthesized by a Mannich-like condensation and readily form P,P-chelate complexes (see scheme). The catalytic activity of a cationic nickel(II) bis-P,P-chelate complex for electrochemical hydrogen evolution was studied.

    17. Natural Products

      Identification and Synthesis of Macrolide Pheromones of the Grain Beetle Oryzaephilus Surinamensis and the Frog Spinomantis Aglavei (pages 3183–3191)

      Susann Hötling, Dr. Birte Haberlag, Prof. Dr. Matthias Tamm, Dr. Jana Collatz, Patrick Mack, Prof. Dr. Johannes L. M. Steidle, Prof. Dr. Miguel Vences and Prof. Dr. Stefan Schulz

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304414

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      Attractive synthesis: Females of the sawtoothed grain beetle Oryzaephilus surinamensis are attracted to the new macrolide (5Z,8Z,12R)-tetradeca-5,8-dien-12-olide, cucujolide X, prepared by using a combination of Wittig reaction and ring-closing alkyne metathesis (RCAM; see scheme). The synthetic approach also allows the synthesis of the similar cucujolide V, used by both the beetle and the mantellid frog Spinomantis aglavei.

    18. Mesoporous Materials

      Hierarchical Mesoporous SnO Microspheres as High Capacity Anode Materials for Sodium-Ion Batteries (pages 3192–3197)

      Dawei Su, Xiuqiang Xie and Prof. Guoxiu Wang

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201303702

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      Let it SnO: Hierarchical mesoporous SnO microspheres were synthesised by a hydrothermal method using NaSO4 as the morphology directing agent. When applied as anode materials for Na-ion batteries, they exhibited high reversible sodium storage capacity and excellent cyclability. The good electrochemical performance could be ascribed to the unique hierarchical mesoporous architecture of SnO microspheres (see graphic).

    19. Gold Catalysis

      Gold-Catalyzed Cycloisomerization of Yne-Vinylidenecyclopropanes: A Three-Carbon Synthon for [3+2] Cycloadditions (pages 3198–3204)

      Wei Yuan, Xiangying Tang, Yin Wei and Min Shi

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304579

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      Gold cats: A novel type of yne-vinylidenecyclopropanes (VDCPs) has been synthesized. These compounds can undergo an intramolecular cycloisomerization and perform as a three-carbon synthon for [3+2] cycloadditions under gold catalysis to give fused [4.3.0] and [5.3.0] bicyclic derivatives and VDCP-rearranged products in moderated to good yields under mild conditions (see scheme).

    20. Lactones

      Effect of Sodium Cation on Metallacycle β-Hydride Elimination in CO2–Ethylene Coupling to Acrylates (pages 3205–3211)

      Dong Jin, Prof. Paul G. Williard, Prof. Nilay Hazari and Prof. Wesley H. Bernskoetter

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304196

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      A sodium scramble: Sodium cations can be used to facilitate a β-hydride elimination reaction in CO2-derived nickelalactones, which is key to the production of acrylates. A related isomerization reaction can also occur without Lewis acid to produce rare unstabilized γ-nickelalactones, but with a higher activation energy and less favorable thermodynamics than the sodium-containing counterpart (see scheme).

    21. Nanocatalysts

      Manganese-Containing Periodic Mesoporous Organosilica with Ionic-Liquid Framework (Mn@PMO-IL): A Powerful, Durable, and Reusable Nanocatalyst for the Biginelli Reaction (pages 3212–3217)

      Dr. Dawood Elhamifar and Ahmad Shábani

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201304349

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      Heterogeneous Biginelli catalyst: A manganese-containing periodic mesoporous organosilica with ionic-liquid framework (Mn@PMO-IL) was prepared, characterized, and used as a nanocatalyst in the Biginelli reaction. This catalyst showed excellent reactivity and selectivity in the Biginelli condensation of various aldehydes with urea and alkyl acetoacetates. Moreover, the catalyst could be recovered and reused at least 14 times with no decrease in activity and selectivity (see scheme).

    22. Polymorphism

      Color Polymorphism: Understanding the Diverse Solid-State Packing and Color in Dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate (pages 3218–3224)

      Saied Md. Pratik, Abdulrahiman Nijamudheen, Sumantra Bhattacharya and Dr. Ayan Datta

      Article first published online: 13 FEB 2014 | DOI: 10.1002/chem.201303322

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      Multiple personality: A single chromophore exhibits three different colors depending on the nature of its packing in crystals (see figure) due to a tug-of-war among the intra- and intermolecular hydrogen bonds. Time-dependent DFT calculations reveal the role of the various types of hydrogen bonds in controlling the color of the polymorphs.

    23. Olefin Polymerization

      Design of Thermally Stable Amine–Imine Nickel Catalyst Precursors for Living Polymerization of Ethylene: Effect of Ligand Substituents on Catalytic Behavior and Polymer Properties (pages 3225–3233)

      Dr. Haibin Hu, Lei Zhang, Dr. Haiyang Gao, Prof. Fangming Zhu and Prof. Qing Wu

      Article first published online: 12 FEB 2014 | DOI: 10.1002/chem.201303813

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      Living at 65 °C: A bulky amine–imine nickel catalyst precursor with a tert-butyl group on the bridging carbon atom of the amine moiety was designed and synthesized. On activation with Et2AlCl, it catalyzes the living polymerization of ethylene even at 65 °C, which is the highest temperature of living polymerization of ethylene with late transition-metal catalysts. New di- and triblock PEs featuring different branched segments were precisely synthesized by tuning the reaction temperature (see figure).

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