Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 18

April 27, 2015

Volume 54, Issue 18

Pages 5263–5526

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Cover Picture: Intracellular Modulation of Excited-State Dynamics in a Chromophore Dyad: Differential Enhancement of Photocytotoxicity Targeting Cancer Cells (Angew. Chem. Int. Ed. 18/2015) (page 5263)

      Dr. Safacan Kolemen, Dr. Murat Işık, Gyoung Mi Kim, Dabin Kim, Hao Geng, Muhammed Buyuktemiz, Tugce Karatas, Prof. Xian-Fu Zhang, Prof. Yavuz Dede, Prof. Juyoung Yoon and Prof. Engin U. Akkaya

      Article first published online: 27 MAR 2015 | DOI: 10.1002/anie.201502270

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      Orthogonal BODIPY dimers offer exciting potential as activatable photosensitizers for photodynamic therapy. In their Communication on page 5340 ff., J. Yoon, E. U. Akkaya et al. report a photosensitizer that is switched on by a reaction with glutathione (GSH). Comparative cell culture data show that the agent is preferentially activated in cancer cells as they feature a higher glutathione level than normal cells.

    2. You have free access to this content
      Inside Cover: Reversible 1,1-Hydroboration: Boryl Insertion into a C[BOND]N Bond and Competitive Elimination of HBR2 or R[BOND]H (Angew. Chem. Int. Ed. 18/2015) (page 5264)

      Deng-Tao Yang, Soren K. Mellerup, Xiang Wang, Dr. Jia-Sheng Lu and Prof. Dr. Suning Wang

      Article first published online: 8 APR 2015 | DOI: 10.1002/anie.201502753

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      N-heterocyclic molecules undergo an unprecedented 1,1-hydroboration with a variety of boranes (HBR2) to form new BN heterocycles that undergo two competitive thermal-elimination pathways: retro-1,1-hydroboration or R[BOND]H elimination. As S. Wang et al. show in their Communication on page 5498 ff., the elimination pathway is an efficient method for providing highly emissive BN-doped arenes. The cover art was designed and painted by Yufei Li, a Ph.D. student at Queen′s University.

    3. You have free access to this content
      Inside Back Cover: Formation of Tri- and Tetranuclear Titanacycles through Decamethyltitanocene-Mediated Intermolecular C–C Coupling of Dinitriles (Angew. Chem. Int. Ed. 18/2015) (page 5527)

      Dr. Lisanne Becker, Dr. Perdita Arndt, Dr. Anke Spannenberg, Dr. Haijun Jiao and Prof. Dr. Uwe Rosenthal

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201502909

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      Reactions of dinitriles with titanocenes lead to the formation of macrocycles through nitrile–nitrile C[BOND]C couplings. In their Communication on page 5523 ff., U. Rosenthal and co-workers also show, that these macrocycles are sometimes not stable and very difficult to characterize ("pain and pleasure” of conducting research symbolized by the titan Atlas, who is holding a macrocycle). The sky in the background shows the logo of the Leibniz Institute for Catalysis, which supported this work.

    4. You have free access to this content
      Back Cover: A Facile and Versatile Approach to Double N-Heterohelicenes: Tandem Oxidative C[BOND]N Couplings of N-Heteroacenes via Cruciform Dimers (Angew. Chem. Int. Ed. 18/2015) (page 5528)

      Dr. Daisuke Sakamaki, Daisuke Kumano, Prof. Dr. Eiji Yashima and Prof. Dr. Shu Seki

      Article first published online: 18 MAR 2015 | DOI: 10.1002/anie.201502273

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      Double N-hetero[5]helicenes that consist of two nitrogen-substituted heteropentacenes were synthesized by tandem oxidative C[BOND]N couplings via the cruciform dimers. In their Communication on page 5404 ff., D. Sakamaki, S. Seki, and co-workers describe the synthesis, structures, and electronic properties of these novel compounds, which are remarkably stable toward racemization.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Frontispiece: Origin of Extraordinary Stability of Square-Planar Carbon Atoms in Surface Carbides of Cobalt and Nickel

      Anjan Nandula, Quang Thang Trinh, Prof. Mark Saeys and Prof. Anastassia N. Alexandrova

      Article first published online: 20 APR 2015 | DOI: 10.1002/anie.201581861

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      Alloys In their Communication on page 5312 ff., M. Saeys,. A. N. Alexandrova, et al. present a chemical bonding model to explain the special stability and the reconstruction of surface cobalt and nickel carbides containing square-planar carbon atoms.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Corrigendum: Selective Formation of Metastable Ferrihydrite in the Chiton Tooth (page 5281)

      Dr. Lyle M. Gordon, Jessica K. Román, Dr. R. Michael Everly, Michael J. Cohen, Dr. Jonathan J. Wilker and Dr. Derk Joester

      Article first published online: 20 APR 2015 | DOI: 10.1002/anie.201501166

      This article corrects:

      Selective Formation of Metastable Ferrihydrite in the Chiton Tooth1

      Vol. 53, Issue 43, 11506–11509, Article first published online: 4 SEP 2014

  5. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. Otto Dopfer (page 5288)

      Article first published online: 25 NOV 2014 | DOI: 10.1002/anie.201411127

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      “If I could be anyone for a day, I would be an astronaut. My favorite book is ‘1984’ by George Orwell …” This and more about Otto Dopfer can be found on page 5288.

  7. Highlight

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. Azidation

      Cyclic Hypervalent Iodine Reagents and Iron Catalysts: The Winning Team for Late-Stage C[BOND]H Azidation (pages 5290–5292)

      Maria Victoria Vita and Prof. Dr. Jerome Waser

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501666

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      1+1=3: By combining the exceptional reactivities of cyclic hypervalent iodine reagents and iron catalysts, Sharma and Hartwig achieved the azidation of C[BOND]H bonds with unprecedented efficiency and selectivity. The late-stage introduction of azides into complex bioactive molecules will greatly facilitate the synthesis of analogues and accelerate the discovery of new chemical entities.

  8. Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. Paper-Based Microfluidics

      Paper-Based Inkjet-Printed Microfluidic Analytical Devices (pages 5294–5310)

      Kentaro Yamada, Prof. Dr. Terence G. Henares, Prof. Dr. Koji Suzuki and Prof. Dr. Daniel Citterio

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201411508

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      Just inkjet it: Inkjet printing plays an important role as a process technology in the fast-growing field of microfluidic devices made of paper. This Review introduces the basics, strengths, and weaknesses related to the inkjet printing of functional materials essential for paper-based analytical devices. The discussion includes fundamental aspects as well as examples of analytical applications.

  9. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlight
    9. Review
    10. Communications
    1. Alloys | Very Important Paper

      Origin of Extraordinary Stability of Square-Planar Carbon Atoms in Surface Carbides of Cobalt and Nickel (pages 5312–5316)

      Anjan Nandula, Quang Thang Trinh, Prof. Mark Saeys and Prof. Anastassia N. Alexandrova

      Article first published online: 24 MAR 2015 | DOI: 10.1002/anie.201501049

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      Out for the count: The unusual stability and reconstruction of surface cobalt and nickel carbides containing square-planar carbon atoms is explained by local aromaticity and electron count. A chemical bonding model for these systems is presented and explains the unusual structure, special stability, and the reconstruction. Several new aromatic and stable two-dimensional alloys are predicted.

    2. Polymersomes | Hot Paper

      Polymersomes Prepared from Thermoresponsive Fluorescent Protein–Polymer Bioconjugates: Capture of and Report on Drug and Protein Payloads (pages 5317–5322)

      Chin Ken Wong, Alistair J. Laos, Dr. Alexander H. Soeriyadi, Prof. Jörg Wiedenmann, Prof. Paul M. G. Curmi, Prof.  J. Justin Gooding, Dr. Christopher P. Marquis, Prof. Martina H. Stenzel and Assoc. Prof. Pall Thordarson

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412406

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      Temperature-induced self-assembly: A temperature-sensitive green fluorescent (amilFP497) protein–polymer bioconjugate forms polymersomes above 37 °C which encapsulate a mixture of pink fluorescent protein (PE545) and a red drug molecule (DOX). The spatial location of the payload is revealed by fluorescence lifetime microscopy.

    3. Biological Probes

      Construction of an Upconversion Nanoprobe with Few-Atom Silver Nanoclusters as the Energy Acceptor (pages 5323–5327)

      Yan Xiao, Lingyu Zeng, Tian Xia, Zhengjun Wu and Dr. Zhihong Liu

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201500008

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      Few but fine: A luminescence resonance energy transfer (LRET) probe for biothiols was constructed by decorating upconversion phosphors (UCPs) with dithiol-stabilized silver nanoclusters as energy acceptors. The probe was uploaded into living cells and used to detect intracellular biothiol levels with high discrimination. It was also found to be suitable for tissue imaging in vivo (see picture).

    4. In-Cell NMR Spectroscopy | Very Important Paper

      Direct Observation of Ca2+-Induced Calmodulin Conformational Transitions in Intact Xenopus laevis Oocytes by 19F NMR Spectroscopy (pages 5328–5330)

      Yansheng Ye, Xiaoli Liu, Dr. Guohua Xu, Prof. Dr. Maili Liu and Prof. Dr. Conggang Li

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201500261

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      Confined in a cell: 19F NMR spectroscopy has been used to directly observe transition between the free and Ca2+-bound form of 19F-labeled calmodulin (CaM) in intact Xenopus oocytes. Under physiological conditions, most CaM is in the apo form, and Ca-CaM only appears at high Ca2+ levels. The affinity of Ca2+ for CaM is enhanced by MLCK in cells. Paramagnetic NMR spectroscopy was also used to obtain long-range structural constraints.

    5. Nanostructures

      Formation of Nickel Sulfide Nanoframes from Metal–Organic Frameworks with Enhanced Pseudocapacitive and Electrocatalytic Properties (pages 5331–5335)

      Dr. Xin-Yao Yu, Le Yu, Hao Bin Wu and Prof. Xiong Wen (David) Lou

      Article first published online: 20 FEB 2015 | DOI: 10.1002/anie.201500267

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      From frameworks to frames: Nickel sulfide nanoframes are synthesized through the reaction between Ni-Co Prussian blue analogue nanocubes and S2− ions (see scheme). Benefitting from their structural merits including open structure and high porosity, these NiS nanoframes exhibit enhanced electrochemical properties for both supercapacitors and hydrogen evolution reaction.

    6. Protein-Structure Elucidation

      Dependence of Distance Distributions Derived from Double Electron–Electron Resonance Pulsed EPR Spectroscopy on Pulse-Sequence Time (pages 5336–5339)

      Dr. James L. Baber, Dr. John M. Louis and Dr. G. Marius Clore

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500640

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      Feel the pulse of the times: Pulsed double electron–electron resonance (DEER) is a powerful method in structural biology for obtaining P(r) distance distributions between pairs of site-specific spin labels. However, the length of the second echo period can have a profound effect on DEER-derived P(r) distributions (see graphs) owing to local environmental effects on spin-label phase memory relaxation times. It is shown how these effects can be minimized and circumvented.

    7. Photodynamic Therapy | Hot Paper

      Intracellular Modulation of Excited-State Dynamics in a Chromophore Dyad: Differential Enhancement of Photocytotoxicity Targeting Cancer Cells (pages 5340–5344)

      Dr. Safacan Kolemen, Dr. Murat Işık, Gyoung Mi Kim, Dabin Kim, Hao Geng, Muhammed Buyuktemiz, Tugce Karatas, Prof. Xian-Fu Zhang, Prof. Yavuz Dede, Prof. Juyoung Yoon and Prof. Engin U. Akkaya

      Article first published online: 24 MAR 2015 | DOI: 10.1002/anie.201411962

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      Selective switch: A dimeric BODIPY dye with reduced symmetry is ineffective as a photosensitizer unless it is activated by a reaction with intracellular glutathione (GSH). Staining with red-fluorescent Annexin V shows that the photosensitizer is preferentially switched on in cancer cells, which feature a higher GSH level than normal cells.

    8. Lithium-Ion Batteries | Very Important Paper

      Solvated Graphene Frameworks as High-Performance Anodes for Lithium-Ion Batteries (pages 5345–5350)

      Dr. Yuxi Xu, Zhaoyang Lin, Dr. Xing Zhong, Ben Papandrea, Prof. Yu Huang and Xiangfeng Duan

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500677

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      Solvated graphene frameworks (SGFs) that were prepared through a convenient solvent-exchange approach are binder-free anodes for lithium-ion batteries with significantly improved properties compared to unsolvated graphene frameworks. They exhibit ultrahigh reversible capacities, excellent rate capabilities, and superior cycling stabilities. GA=graphene aerogel.

    9. Corannulenes | Hot Paper

      Iridium-Catalyzed Reductive Carbon–Carbon Bond Cleavage Reaction on a Curved Pyridylcorannulene Skeleton (pages 5351–5354)

      Dr. Shohei Tashiro, Dr. Mihoko Yamada and Prof. Dr. Mitsuhiko Shionoya

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500819

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      Iridium scissors: In the presence of a catalytic amount of IrCl3n H2O in ethylene glycol at 250 °C, 2-pyridylcorannulene undergoes a site-selective C[BOND]C bond cleavage reaction, which leads to a strain-free flat benzo[ghi]fluoranthene. This process is driven both by the coordination of the 2-pyridyl moiety to the iridium center and by strain relief of the curved corannulene skeleton.

    10. Molecular Gear | Very Important Paper

      You have full text access to this OnlineOpen article
      Caterpillar Track Complexes in Template-Directed Synthesis and Correlated Molecular Motion (pages 5355–5359)

      Shiqi Liu, Dr. Dmitry V. Kondratuk, Dr. Sophie A. L. Rousseaux, Dr. Guzmán Gil-Ramírez, Dr. Melanie C. O'Sullivan, Jonathan Cremers, Prof. Tim D. W. Claridge and Prof. Harry L. Anderson

      Article first published online: 12 FEB 2015 | DOI: 10.1002/anie.201412293

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      Turning in unison: Two wheel-like templates work together to direct the synthesis of a nanoring. Their rotation is synchronized in the resulting 2:1 caterpillar track complex.

    11. Carbon Dots | Hot Paper

      Red, Green, and Blue Luminescence by Carbon Dots: Full-Color Emission Tuning and Multicolor Cellular Imaging (pages 5360–5363)

      Kai Jiang, Shan Sun, Dr. Ling Zhang, Yue Lu, Prof. Aiguo Wu, Prof. Congzhong Cai and Prof. Hengwei Lin

      Article first published online: 31 MAR 2015 | DOI: 10.1002/anie.201501193

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      On the dot: A facile approach to photoluminescent carbon dots (CDs) that can be excited by a single wavelength and demonstrate emission of the three primary colors (red, green, and blue) is reported. The resulting CDs can be potentially used in the fabrication of flexible full-color emission films and in multicolor cellular imaging.

    12. Chemical Decaging

      Chemical Remodeling of Cell-Surface Sialic Acids through a Palladium-Triggered Bioorthogonal Elimination Reaction (pages 5364–5368)

      Jie Wang, Bo Cheng, Jie Li, Zhaoyue Zhang, Weiyao Hong, Prof. Dr. Xing Chen and Prof. Dr. Peng R. Chen

      Article first published online: 12 MAR 2015 | DOI: 10.1002/anie.201409145

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      Chemical decaging: Palladium-mediated depropargylation (see scheme) was coupled with metabolic glycan labeling to mimic the enzymatic de-N-acetylation of Neu5Ac: a proposed mechanism for the natural occurrence of neuramic acid (Neu) on cell-surface glycans (Neu5Ac is N-acetylated Neu). Unmasking of the C5 amine by this strategy was used to manipulate cell-surface charge and neutralize the negatively charged carboxyl group of sialic acids.

    13. Neurosciences

      Selective Aptamer-Based Control of Intraneuronal Signaling (pages 5369–5373)

      Dr. Sabine Lennarz, MSc Therese Christine Alich, Dr. Tony Kelly, Dr. Michael Blind, Prof. Dr. Heinz Beck and Prof. Dr. Günter Mayer

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201409597

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      Clamp-it: Intracellular availability of functional aptamers is achievable through the patch-clamp pipette. The delivery of a specific aptamer in such a way leads to efficient inhibition of mitogen-activated kinase-dependent synaptic plasticity. This approach introduces synthetic aptamers as generic tools, readily applicable to study single components of intracellular signaling networks.

    14. NMR Spectroscopy

      Real-Time Monitoring of Cancer Cell Metabolism and Effects of an Anticancer Agent using 2D In-Cell NMR Spectroscopy (pages 5374–5377)

      Dr. He Wen, Yong Jin An, Wen Jun Xu, Prof. Keon Wook Kang and Prof. Sunghyouk Park

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201410380

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      Monitoring metabolism: For “In-cell NMR metabolomics”, live cells were harvested and centrifuged into an NMR tube. Using 13C6-glucose and heteronuclear NMR spectroscopy, real-time metabolic flux differences between cancer and normal cells were obtained. The method also detected live metabolic alteration by an anticancer agent, leading to the identification of new functional targets.

    15. Conformational Analysis

      Evidence for a Boat Conformation at the Transition State of GH76 α-1,6-Mannanases—Key Enzymes in Bacterial and Fungal Mannoprotein Metabolism (pages 5378–5382)

      Dr. Andrew J. Thompson, Gaetano Speciale, Javier Iglesias-Fernández, Zalihe Hakki, Tyson Belz, Dr. Alan Cartmell, Richard J. Spears, Emily Chandler, Max J. Temple, Dr. Judith Stepper, Prof. Harry J. Gilbert, Prof. Carme Rovira, Prof. Spencer J. Williams and Prof. Gideon J. Davies

      Article first published online: 13 MAR 2015 | DOI: 10.1002/anie.201410502

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      Family GH76­ endo-α-mannanases participate in construction and breakdown of fungal cell wall mannoprotein. A combined synthetic, structural, and theoretical study discloses the first inhibitors of this family of enzymes and quantifies how the enzyme distorts an azasugar inhibitor into a transition-state-mimicking boat conformation.

    16. Hydrogels

      Hybrid Supramolecular and Colloidal Hydrogels that Bridge Multiple Length Scales (pages 5383–5388)

      Emma-Rose Janeček, Dr. Jason R. McKee, Cindy S. Y. Tan, Dr. Antti Nykänen, Dr. Marjo Kettunen, Prof. Janne Laine, Prof. Olli Ikkala and Prof. Oren A. Scherman

      Article first published online: 13 MAR 2015 | DOI: 10.1002/anie.201410570

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      The combination of a colloidal hydrogel consisting of nanofibrillated cellulose with an interpenetrating supramolecular hydrogel based on hydroxyethyl cellulose leads to a hybrid nanocomposite hydrogel. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces, resulting in an enhanced rheological yield strain and storage modulus.

    17. Fluorescent Probes | Hot Paper

      A FRET Probe for Cell-Based Imaging of Ganglioside-Processing Enzyme Activity and High-Throughput Screening (pages 5389–5393)

      Dr. Guang-Yu Yang, Dr. Caishun Li, Dr. Michael Fischer, Prof. Christopher W. Cairo, Prof. Yan Feng and Prof. Stephen G. Withers

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201411747

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      Clear-cut: A small-molecule FRET probe was designed and synthesized for monitoring at least three key enzymatic activities involved in ganglioside degradation. The substrate, which contains BODIPY (Fluor) and Coumarin (Coum) fluorophores at opposite termini, enables sensitive fluorogenic assay in both cell lysates and living cells and should be useful for dissecting the mechanisms of these enzymes, as well as for protein engineering and inhibitor development.

    18. Para-Selective Liquid Sorption

      Separation of p-Divinylbenzene by Selective Room-Temperature Adsorption Inside Mg-CUK-1 Prepared by Aqueous Microwave Synthesis (pages 5394–5398)

      Beau Saccoccia, Alisha M. Bohnsack, Nolan W. Waggoner, Kyung Ho Cho, Ji Sun Lee, Dr. Do-Young Hong, Dr. Vincent M. Lynch, Dr. Jong-San Chang and Prof. Simon M. Humphrey

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411862

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      From complex to simple: The porous material Mg-CUK-1 has been prepared using an aqueous microwave-assisted synthetic method. This material contains infinite one-dimensional pores that show highly selective, room-temperature adsorption of p-divinylbenzene (p-DVB) and other organic compounds from complex mixtures of isomers.

    19. Ionic Liquids

      Transformation of Atmospheric CO2 Catalyzed by Protic Ionic Liquids: Efficient Synthesis of 2-Oxazolidinones (pages 5399–5403)

      Jiayin Hu, Jun Ma, Qinggong Zhu, Zhaofu Zhang, Congyi Wu and Prof. Buxing Han

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411969

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      CO2 capture: Under mild, metal-free conditions, protic ionic liquids, such as 1,8-diazabicyclo[5.4.0]-7-undecenium 2-methylimidazolide [DBUH][MIm], can catalyze the reaction between CO2 and propargylic amines to form 2-oxazolidinones. Both the cation and anion of the ionic liquids play key roles in accelerating the reaction.

    20. Helicenes

      A Facile and Versatile Approach to Double N-Heterohelicenes: Tandem Oxidative C[BOND]N Couplings of N-Heteroacenes via Cruciform Dimers (pages 5404–5407)

      Dr. Daisuke Sakamaki, Daisuke Kumano, Prof. Dr. Eiji Yashima and Prof. Dr. Shu Seki

      Article first published online: 13 MAR 2015 | DOI: 10.1002/anie.201500684

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      Double N-hetero[5]helicenes that are composed of two nitrogen-substituted heteropentacenes were synthesized by tandem oxidative C[BOND]N couplings via the cruciform dimers in only two steps from commercially available naphthalene derivatives. These compounds are remarkably stable towards racemization, and the two heteroacenes moieties were shown to be strongly electronically coupled.

    21. Hydrogels

      Fibrillar Networks of Glycyrrhizic Acid for Hybrid Nanomaterials with Catalytic Features (pages 5408–5412)

      Dr. Abhijit Saha, Dr. Jozef Adamcik, Dr. Sreenath Bolisetty, Stephan Handschin and Prof. Dr. Raffaele Mezzenga

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201411875

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      Hybrid nanomaterials: Self-assembled fibrillar networks of glycyrrhizic acid (GA) in water are used as scaffolds for the precision design of hybrid nanomaterials for use in catalysis. By incorporating graphene oxide and in situ synthesized gold nanoparticles, an enhanced catalytic efficiency is obtained as a result of the high affinity of the substrate to the graphene oxide.

    22. Plasmonic Photocatalysis

      Probing Long-Lived Plasmonic-Generated Charges in TiO2/Au by High-Resolution X-ray Absorption Spectroscopy (pages 5413–5416)

      Dr. Lucia Amidani, Dr. Alberto Naldoni, Dr. Marco Malvestuto, Dr. Marcello Marelli, Dr. Pieter Glatzel, Dr. Vladimiro Dal Santo and Prof. Federico Boscherini

      Article first published online: 6 MAR 2015 | DOI: 10.1002/anie.201412030

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      Hot electrons: An atomistic description of the electronic and structural changes of TiO2 resulting from the injection of hot electrons is presented. High resolution X-ray spectroscopy shows that plasmonic charges are trapped on Ti states at the semiconductor surface, giving rise to transient low-coordinate Ti sites which have long-enough lifetimes to play a major role in catalytic processes (LSPR=localized surface plasmon resonance).

    23. Coordination Geometry

      Na4IrO4: Square-Planar Coordination of a Transition Metal in d5 Configuration due to Weak On-Site Coulomb Interactions (pages 5417–5420)

      Dr. Sudipta Kanungo, Dr. Binghai Yan, Patrick Merz, Prof. Dr. Claudia Felser and Prof. Dr. Martin Jansen

      Article first published online: 13 MAR 2015 | DOI: 10.1002/anie.201411959

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      Bending the rules: A square-planar coordination mode in transition-metal (TM) complexes is typically assumed to require a d8 or d9 TM electronic configuration. A square-planar structure for the IrO4 moiety in Na4IrO4 is reported where IrIV has a d5 electronic configuration. The weak Coulomb interactions of Ir-5d states stabilize this unconventional square-planar structure.

    24. Gas-Phase Chemistry

      Unexpected Chemistry from the Reaction of Naphthyl and Acetylene at Combustion-Like Temperatures (pages 5421–5424)

      Dr. Dorian S. N. Parker, Prof. Dr. Ralf. I. Kaiser, Dr. Biswajit Bandyopadhyay, Dr. Oleg Kostko, Dr. Tyler P. Troy and Dr. Musahid Ahmed

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201411987

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      Photoionization mass spectrometry was used to investigate the reaction of 1- and 2-naphthyl radicals in excess acetylene under combustion-like conditions. The reaction produces 1- and 2-ethynylnaphthalenes (C12H8), acenaphthylene (C12H8); and diethynylnaphthalenes (C14H8). Neither phenanthrene nor anthracene (C14H10) was found, which indicates that a hydrogen abstraction/acetylene addition mechanism does not lead to aromatic-ring formation.

    25. Nanostructures | Very Important Paper

      A Facile and Universal Top-Down Method for Preparation of Monodisperse Transition-Metal Dichalcogenide Nanodots (pages 5425–5428)

      Xiao Zhang, Zhuangchai Lai, Zhengdong Liu, Chaoliang Tan, Ying Huang, Dr. Bing Li, Dr. Meiting Zhao, Prof. Linghai Xie, Prof. Wei Huang and Prof. Hua Zhang

      Article first published online: 11 MAR 2015 | DOI: 10.1002/anie.201501071

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      On the dot: The title nanodots (NDs), including MoS2, WS2, ReS2, TaS2, MoSe2, WSe2, and NbSe2, are prepared from their bulk crystals by using a combination of grinding and sonication techniques. The synthesized nanodots, mixed with polyvinylpyrrolidone, are used as active layers for fabrication of memory devices having a nonvolatile memory effect. TMD=transition-metal dichalcogenides.

    26. Silafulleranes | Very Important Paper

      One-Step Synthesis of a [20]Silafullerane with an Endohedral Chloride Ion (pages 5429–5433)

      Dipl.-Chem. Jan Tillmann, Dipl.-Chem. Josef Heinrich Wender, Dr. Ute Bahr, Dr. Michael Bolte, Dr. Hans-Wolfram Lerner, Prof. Dr. Max C. Holthausen and Prof. Dr. Matthias Wagner

      Article first published online: 4 MAR 2015 | DOI: 10.1002/anie.201412050

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      As simple as this: A stable, crystalline [20]silafullerane forms in preparatively useful yields through wet-chemical self-assembly from Si2Cl6 and chloride ions in the presence of an amine. Each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement.

    27. Soft Matter

      Photothermally Reprogrammable Buckling of Nanocomposite Gel Sheets (pages 5434–5437)

      Adam W. Hauser, Arthur A. Evans, Jun-Hee Na and Ryan C. Hayward

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201412160

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      Re-programmable morphing: Patterns of white light are used to dynamically reconfigure photothermal nanocomposite hydrogel sheets into numerous 3D shapes. Fast and reversible transformations are achieved on timescales tuneable down to several seconds. This concept for externally adaptable elastic hydrogel sheets may find applications in soft robotics, drug delivery, or microfluidics.

    28. Heterocycle Synthesis

      Platinum-Catalyzed Domino Reaction with Benziodoxole Reagents for Accessing Benzene-Alkynylated Indoles (pages 5438–5442)

      Yifan Li and Prof. Dr. Jerome Waser

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201412321

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      Pt and hyper-I: Indoles are omnipresent in natural products, bioactive molecules, and organic materials. To access benzene-ring-alkynylated indoles with an unsubstituted pyrrole ring is highly challenging. Reported here is the title reaction, which selectively leads to C5- or C6-alkynylated indoles starting from easily available pyrroles. The ethynylbenziodoxole hypervalent iodine reagent is key to the success of the reaction.

    29. Synthetic Methods

      Copper-Catalyzed Intermolecular Carboetherification of Unactivated Alkenes by Alkyl Nitriles and Alcohols (pages 5443–5446)

      Claire Chatalova-Sazepin, Dr. Qian Wang, Prof. Dr. Glenn M. Sammis and Prof. Dr. Jieping Zhu

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412357

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      Three-component coupling of alkenes, alcohols, and alkyl nitriles catalyzed by copper triflate afforded 4-alkoxyalkyl nitriles in good to excellent yields. The reaction forms a C[BOND]C and a C[BOND]O bond with concomitant creation of a quaternary carbon center. The involvement of a radical intermediate was proven by a radical clock experiment.

    30. Carbocycles

      Stereoselective Nickel-Catalyzed [2+2] Cycloadditions of Ene-Allenes (pages 5447–5450)

      Njamkou N. Noucti and Prof. Erik J. Alexanian

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201411737

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      Nicked! The title reaction encompasses a broad range of ene-allene substrates, thus providing efficient access to fused cyclobutanes from easily accessed π-components. An inexpensive catalytic system comprised of [Ni(cod)2] and dppf was used, thus constituting an attractive approach to challenging cyclobutane frameworks under mild reaction conditions. cod=1,5-cyclooctadiene, dppf=1,1′-bis(diphenylphosphino)ferrocene.

    31. Natural Product Synthesis | Hot Paper

      A Concise and Scalable Strategy for the Total Synthesis of Dictyodendrin B Based on Sequential C[BOND]H Functionalization (pages 5451–5455)

      Andrew K. Pitts, Dr. Fionn O'Hara, Dr. Robert H. Snell and Prof. Matthew J. Gaunt

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201500067

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      One by one: A sequential C[BOND]H functionalization strategy for the synthesis of the marine alkaloid dictyodendrin B is reported. The synthetic route begins from commercially available 4-bromoindole and involves six direct functionalizations around the heteroarene core as part of a gram-scale strategy towards the natural product.

    32. Porphyrinoids

      A Möbius Aromatic [28]Hexaphyrin Bearing a Diethylamine Group: A Rigid but Smooth Conjugation Circuit (pages 5456–5459)

      Tomohiro Higashino, Takanori Soya, Woojae Kim, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Article first published online: 4 FEB 2015 | DOI: 10.1002/anie.201500099

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      Möbius versus Hückel: An NEt2-group-bearing [28]hexaphyrin was prepared from a [26]hexaphyrin (see Scheme) and is a rare example of a Möbius aromatic metal-free expanded porphyrin. It displays the largest diatropic ring current among known [28]hexaphyrins. Reduction and oxidation of this molecule led to the production of a Hückel antiaromatic [28]hexaphyrin and a Hückel aromatic [26]hexaphyrin by a Möbius-to-Hückel topology switch.

    33. Cycloaddition

      Catalytic Asymmetric Inverse-Electron-Demand Oxa-Diels–Alder Reaction of In Situ Generated ortho-Quinone Methides with 3-Methyl-2-Vinylindoles (pages 5460–5464)

      Jia-Jia Zhao, Si-Bing Sun, Sai-Huan He, Dr. Qiong Wu and Prof. Dr. Feng Shi

      Article first published online: 18 FEB 2015 | DOI: 10.1002/anie.201500215

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      Three in a row: The title reaction of ortho-quinone methides, generated in situ from ortho-hydroxybenzyl alcohols, has been established. By selecting 3-methyl-2-vinylindoles as a class of competent dienophiles, this approach provides an efficient strategy to construct enantioenriched chroman frameworks with three adjacent stereogenic centers in high yields and excellent stereoselectivities. CPA=chiral phosphoric acid.

    34. Allylic Compounds

      Ruthenium-Catalyzed C[BOND]C Coupling of Fluorinated Alcohols with Allenes: Dehydrogenation at the Energetic Limit of β-Hydride Elimination (pages 5465–5469)

      Brannon Sam, Tom Luong and Prof. Michael J. Krische

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500238

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      Alcohol is the answer! Ruthenium(II) complexes catalyze the C[BOND]C coupling of 1,1-disubstituted allenes and fluorinated alcohols to form homoallylic alcohols bearing all-carbon quaternary centers with good to complete levels of diastereoselectivity. Whereas fluorinated alcohols are relatively abundant and tractable, the corresponding aldehydes are often not commercially available because of their instability.

    35. Asymmetric Catalysis

      Phosphahelicenes in Asymmetric Organocatalysis: [3+2] Cyclizations of γ-Substituted Allenes and Electron-Poor Olefins (pages 5470–5473)

      Maxime Gicquel, Yang Zhang, Paul Aillard, Dr. Pascal Retailleau, Dr. Arnaud Voituriez and Dr. Angela Marinetti

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201500299

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      Helical P: Specially designed phosphahelicenes demonstrate high efficiency and enantioselectivity in organocatalytic cyclizations. These new helically chiral phosphines complement and outperform previous nucleophilic catalysts used in this field. Ipc*=(1R,2R,3R,5S)-2,6,6-trimethyl-bicyclo[3.1.1]-heptan-3-yl.

    36. Synthetic Methods

      Efficient Asymmetric Synthesis of Structurally Diverse P-Stereogenic Phosphinamides for Catalyst Design (pages 5474–5477)

      Dr. Zhengxu S. Han, Li Zhang, Yibo Xu, Dr. Joshua D. Sieber, Dr. Maurice A. Marsini, Dr. Zhibin Li, Dr. Jonathan T. Reeves, Dr. Keith R. Fandrick, Nitinchandra D. Patel, Dr. Jean-Nicolas Desrosiers, Dr. Bo Qu, Anji Chen, DiAndra M. Rudzinski, Dr. Lalith P. Samankumara, Dr. Shengli Ma, Dr. Nelu Grinberg, Dr. Frank Roschangar, Dr. Nathan K. Yee, Dr. Guijun Wang, Dr. Jinhua J. Song and Dr. Chris H. Senanayake

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500350

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      Making a ‘Phos’: A general, efficient, and highly enantioselective method for the synthesis of the title compounds relies on nucleophilic substitution of a chiral phosphinate. These chiral phosphinamides were utilized for the synthesis of readily tunable P-stereogenic Lewis base organocatalysts.

    37. C[BOND]H Activation

      Synthesis of Dibenzo[c,e]oxepin-5(7H)-ones from Benzyl Thioethers and Carboxylic Acids: Rhodium-Catalyzed Double C[BOND]H Activation Controlled by Different Directing Groups (pages 5478–5482)

      Xi-Sha Zhang, Yun-Fei Zhang, Zhao-Wei Li, Fei-Xian Luo and Prof. Dr. Zhang-Jie Shi

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500486

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      Double crossed! Reported is the rhodium(III)-catalyzed double C[BOND]H cross-coupling of benzyl thioethers and carboxylic acids. Two directing groups (DGs) are used to enhance the selectivity of the double C[BOND]H activation. One DG becomes part of the product and the other is removed in situ.

    38. Fused-Ring Systems

      Construction of a Hemifullerene Skeleton: A Regioselective Intramolecular Oxidative Cyclization (pages 5483–5487)

      Dr. Toru Amaya, Takanori Ito and Prof. Dr. Toshikazu Hirao

      Article first published online: 10 MAR 2015 | DOI: 10.1002/anie.201500548

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      Bowl full of π: The two-step synthesis of a strained π bowl, having a hemifullerene skeleton from sumanene, was achieved in a high yield. The reaction involved a regioselective intramolecular oxidative cyclization as the key reaction. This cyclization is regioselective and is likely to be under thermodynamic control.

    39. Alkylation

      Synthesis and Characterization of Tricarbastannatranes and Their Reactivity in B(C6F5)3-Promoted Conjugate Additions (pages 5488–5492)

      Azadeh Kavoosi and Prof. Eric Fillion

      Article first published online: 5 MAR 2015 | DOI: 10.1002/anie.201500983

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      Trane of thought: Spectroscopic investigation on the structure of tricarbastannatranes has been carried out. The B(C6F5)3-promoted conjugate addition of alkyl-tricarbastannatranes to benzylidene derivatives of Meldrum's acid and detailed mechanistic studies are presented.

    40. Nanostructures

      Cobalt Phosphide Nanowires: Efficient Nanostructures for Fluorescence Sensing of Biomolecules and Photocatalytic Evolution of Dihydrogen from Water under Visible Light (pages 5493–5497)

      Dr. Jingqi Tian, Ningyan Cheng, Qian Liu, Prof. Wei Xing and Prof. Xuping Sun

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201501237

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      Quenched: The high fluorescence quenching ability of cobalt phosphide nanowires (CoP NWs) and their different affinity toward single-stranded and double-stranded DNA were used to develop a rapid fluorescence assay for nucleic acids and proteins. The attachment of dye-labelled oligonucleotide probes to the surface of the CoP semiconductor leads to greatly enhanced photocatalytic hydrogen evolution from H2O under visible light.

    41. B,N Heterocycles

      Reversible 1,1-Hydroboration: Boryl Insertion into a C[BOND]N Bond and Competitive Elimination of HBR2 or R[BOND]H (pages 5498–5501)

      Deng-Tao Yang, Soren K. Mellerup, Xiang Wang, Dr. Jia-Sheng Lu and Prof. Dr. Suning Wang

      Article first published online: 20 MAR 2015 | DOI: 10.1002/anie.201500487

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      NBC news: Boranes (HBR2) have been found to undergo facile and unprecedented 1,1-hydroboration with pyrido[1,2-a]isoindole (A) via an intermediate D, generating a variety of BN heterocycles (B) that can either undergo thermal retro-hydroboration or R[BOND]H elimination producing brightly fluorescent BN-phenanthrenes (C).

    42. Allyl Tin Complexes

      η3-Allyl Coordination at Tin(II)—Reactivity towards Alkynes and Benzonitrile (pages 5502–5506)

      Kilian M. Krebs, Jessica Wiederkehr, Julia Schneider, Dr. Hartmut Schubert, Dr. Klaus Eichele and Prof. Dr. Lars Wesemann

      Article first published online: 12 MAR 2015 | DOI: 10.1002/anie.201500386

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      3 to II: An example for the η3 coordination of an allyl group to a SnII center is presented. The allyl tin(II) compound undergoes allyl couplings in reactions with alkynes to yield tricyclic systems, and a sixteen-membered macrocycle is formed with benzonitrile (see Scheme).

    43. Nanostructures

      Synthesis of Nanostructured Carbon through Ionothermal Carbonization of Common Organic Solvents and Solutions (pages 5507–5512)

      Dr. Yuanqin Chang, Prof. Dr. Markus Antonietti and Dr. Tim-Patrick Fellinger

      Article first published online: 4 MAR 2015 | DOI: 10.1002/anie.201411685

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      Hot stuff: Hot-injection techniques were combined with ionothermal chemistry to transform common organic solvents into nanostructured porous carbons with high yields. The same method can be further applied to synthesize various carbon/inorganic composites, for example, for electrocatalytic applications.

    44. C[BOND]H Activation | Hot Paper

      Ruthenium(II)-Catalyzed C[BOND]H Activation/Alkyne Annulation by Weak Coordination with O2 as the Sole Oxidant (pages 5513–5517)

      M. Sc. Svenja Warratz, Dr. Christoph Kornhaaß, M. Sc. Ana Cajaraville, Benedikt Niepötter, Prof. Dr. Dietmar Stalke and Prof. Dr. Lutz Ackermann

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500600

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      Air and water: Ruthenium(II) biscarboxylates allow for the annulation of alkynes and alkenes by oxidative C[BOND]H functionalizations with molecular oxygen as the sole oxidant. The C[BOND]H/O[BOND]H functionalization process occurs with excellent selectivities under mild reaction conditions, with water produced as the only by-product.

    45. Reaction Mechanisms

      Electron Flow in Reaction Mechanisms—Revealed from First Principles (pages 5518–5522)

      Dr. Gerald Knizia and Dr. Johannes E. M. N. Klein

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201410637

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      Curly arrows from ab initio calculations: Curly arrows in reaction mechanisms are shown to correspond to changes in intrinsic bond orbitals (IBOs) along reaction paths. With this quantum chemical basis, even complex reaction mechanisms can be derived and visualized in a simple, direct, and intuitive form.

    46. Metallacycles

      Formation of Tri- and Tetranuclear Titanacycles through Decamethyltitanocene-Mediated Intermolecular C–C Coupling of Dinitriles (pages 5523–5526)

      Dr. Lisanne Becker, Dr. Perdita Arndt, Dr. Anke Spannenberg, Dr. Haijun Jiao and Prof. Dr. Uwe Rosenthal

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201500109

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      Big and beautiful: The reaction of [Cp*2Ti] with dicyano compounds led to macromolecules through nitrile–nitrile C[BOND]C couplings. Depending on the bridging unit X, the size and type of the macrocycle varies between three- and four-membered 1-metalla-2,5-diaza-cyclopenta-2,4-dienes (left) and a 1-metalla-2,5-diaza-cyclopent-3-ene (right). The structures of the products were investigated by X-ray crystallography and DFT analysis.

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