Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 44

October 27, 2014

Volume 53, Issue 44

Pages 11667–11983

  1. Cover Pictures

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    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Gas-Phase Preparation of Carbonic Acid and Its Monomethyl Ester (Angew. Chem. Int. Ed. 44/2014) (page 11667)

      Dr. Hans Peter Reisenauer, M. Sc. J. Philipp Wagner and Prof. Dr. Peter R. Schreiner

      Article first published online: 5 SEP 2014 | DOI: 10.1002/anie.201408177

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      Carbonic acid (“Kohlensäure”) and its monomethyl ester can be readily prepared through the gas-phase pyrolysis of Boc2O (Boc=tert-butyloxycarbonyl) and MeOC(O)OtBu, respectively, as described by P. R. Schreiner et al. in their Communication on page 11766 ff. This novel, independent preparation of the two structures and their unequivocal identification through IR spectroscopy show that the gas phase above the so-called α-polymorph of H2CO3 is actually the monomethyl ester, whereas only the β-polymorph is truly carbonic acid.

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      Inside Cover: An Organotrifluoroborate for Broadly Applicable One-Step 18F-Labeling (Angew. Chem. Int. Ed. 44/2014) (page 11668)

      Zhibo Liu, Maral Pourghiasian, Mark Alex Radtke, Joseph Lau, Dr. Jinhe Pan, Gemma M. Dias, Dr. Donald Yapp, Dr. Kuo-Shyan Lin, Prof. Dr. Francois Bénard and Prof. Dr. David M. Perrin

      Article first published online: 5 SEP 2014 | DOI: 10.1002/anie.201408269

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      Time is the essence for 18F labeling. The poor reactivity of aqueous fluoride ions has long been a challenge in 18F labeling. In their Communication on page 11876 ff., D. M. Perrin et al. present trifluoroborate–peptide conjugates that are labeled by isotopic exchange in water within 15 minutes to provide 18F tracers with high specific activity. Time-consuming HPLC can be avoided. Several bioactive ligands enable PET imaging of in vivo targets.

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      Inside Back Cover: An Organotrifluoroborate for Broadly Applicable One-Step 18F-Labeling (Angew. Chem. Int. Ed. 44/2014) (page 11985)

      Zhibo Liu, Maral Pourghiasian, Mark Alex Radtke, Joseph Lau, Dr. Jinhe Pan, Gemma M. Dias, Dr. Donald Yapp, Dr. Kuo-Shyan Lin, Prof. Dr. Francois Bénard and Prof. Dr. David M. Perrin

      Article first published online: 22 SEP 2014 | DOI: 10.1002/anie.201408834

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      Olfactory receptors are protein-based sensors that can detect various vaporous chemical compounds. In their Communication on page 11798 ff., K. Sato and S. Takeuchi report an electrophysiological technique to record the response to vapor odorants through the reconstituted insect olfactory receptors in mammalian cell lines. Their approach integrates a micro-electromechanical system and a functional gene expression system.

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      Back Cover: Fluxionally Chiral DMAP Catalysts: Kinetic Resolution of Axially Chiral Biaryl Compounds (Angew. Chem. Int. Ed. 44/2014) (page 11986)

      Gaoyuan Ma, Dr. Jun Deng and Prof. Dr. Mukund P. Sibi

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408268

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      Place a pair of enantiomers in a box, wave a magic wand (a chiral catalyst), and two enantioenriched compounds pop out because of their differential interaction with the catalyst. In their Communication on page 11818 ff., M. P. Sibi et al. demonstrate that a novel 4-dimethylaminopyridine catalyst with fluxional chirality is efficient in promoting acylative kinetic resolution of axially chiral biaryl compounds with selectivities of up to 51:1.

  2. Frontispiece

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      Frontispiece: A “Schizophotonic” All-In-One Nanoparticle Coating for Multiplexed SE(R)RS Biomedical Imaging

      Dr. Pasquale Iacono, Dr. Hazem Karabeber and Prof. Dr. Moritz F. Kircher

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201484461

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      Imaging Agents In their Communication on page 11756, M. F. Kircher and co-workers employed a biocompatible polymeric surface coating for gold nanoparticles. The resulting nanoprobes were shown to be capable of multiplexed lymph-node imaging.

  3. Graphical Abstract

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    1. Graphical Abstract: Angew. Chem. Int. Ed. 44/2014 (pages 11671–11685)

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201490042

  4. Flashback

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    1. 50 Years Ago ... (page 11683)

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201484414

  5. News

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  6. Author Profile

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    1. Hiroshi Sugiyama (page 11692)

      Article first published online: 2 JUL 2014 | DOI: 10.1002/anie.201403997

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      “My favorite theorem is Koopman's theorem. My favorite painter is Salvador Dalí …” This and more about Hiroshi Sugiyama can be found on page 11692.

  7. News

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  8. Highlights

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    1. Bacterial Resistance

      Aspergillomarasmine A, an Inhibitor of Bacterial Metallo-β-Lactamases Conferring blaNDM and blaVIM Resistance (pages 11696–11698)

      Dr. Franz von Nussbaum and Dr. Guido Schiffer

      Article first published online: 24 SEP 2014 | DOI: 10.1002/anie.201407921

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      Silencing the deadly “bla-bla” of superbugs: The natural product aspergillomarasmine A (AMA) showed in vivo efficacy against Enterobacteriaceae, conferring broad β-lactam resistance blaNDM-1 (NDM-1: New Delhi Metallo-β-lactamase 1). In rodents, the natural product restored efficacy of the gold standard meropenem by inhibition of the Zn-containing active site in NDM-1.

    2. Water

      Advancing into Water’s “No Man’s Land”: Two Liquid States? (pages 11699–11701)

      Dr. Dietmar Paschek and Prof. Ralf Ludwig

      Article first published online: 22 SEP 2014 | DOI: 10.1002/anie.201408057

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      A tale of two liquids? Liquid water exhibits many anomalous properties which are strongly amplified in the supercooled state. A possible explanation for the unusual behavior is a phase transition between two distinct metastable forms of liquid water at deeply supercooled conditions. A recent theoretical study has confirmed the existence of this liquid–liquid phase transition.

  9. Minireview

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    1. Upconversion

      Enhancing Luminescence in Lanthanide-Doped Upconversion Nanoparticles (pages 11702–11715)

      Sanyang Han, Dr. Renren Deng, Dr. Xiaoji Xie and Prof. Xiaogang Liu

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201403408

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      Lighten up: Light trapping by upconversion nanoparticles often suffers from low conversion efficiency because of the small absorption cross-section and surface quenching effects of the nanoparticles. To this end, effective strategies have been developed to enhance upconversion luminescence, thus paving the way for new biological approaches and inexpensive energy conversion methods.

  10. Review

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    1. Supramolecular Chemistry of Anions

      Advances in Anion Supramolecular Chemistry: From Recognition to Chemical Applications (pages 11716–11754)

      Dr. Nicholas H. Evans and Prof. Paul D. Beer

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201309937

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      Since the start of this millennium, anion supramolecular chemistry has evolved substantially beyond the chemistry of anion receptors. Alongside the research that continues on the binding and sensing of anions, large strides have been made in areas that have previously been underdeveloped, such as the use of anions as templates and for membrane transportation, and importantly in chemical applications including catalysis, ion extraction, and responsive molecular systems.

  11. Communications

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    1. Nanoparticle Imaging Agents

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      A “Schizophotonic” All-In-One Nanoparticle Coating for Multiplexed SE(R)RS Biomedical Imaging (pages 11756–11761)

      Dr. Pasquale Iacono, Dr. Hazem Karabeber and Prof. Dr. Moritz F. Kircher

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201403835

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      Split personality: A biocompatible polymeric surface coating gives rise to dual emissive SERS/NIRF behavior when bound to gold nanoparticles of varying sizes. These polymers allow the first synthesis of SERS nanoprobes with gold cores smaller than 20 nm. These nanoprobes are shown to be capable of multiplexed lymph-node imaging.

    2. Ionic Liquids

      On the Formation of a Protic Ionic Liquid in Nature (pages 11762–11765)

      Prof. Li Chen, Genevieve E. Mullen, Myriam Le Roch, Cody G. Cassity, Prof. Nicolas Gouault, Prof. Henry Y. Fadamiro, Prof. Robert E. Barletta, Prof. Richard A. O'Brien, Prof. Richard E. Sykora, Prof. Alexandra C. Stenson, Prof. Kevin N. West, Howard E. Horne, Jeffrey M. Hendrich, Kang Rui Xiang and Prof. James H. Davis Jr.

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404402

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      Crazy about ionic liquids: Throughout the southern United States, the invasive ant species S. invicta (fire ants) and N. fulva (tawny crazy ants) vie for resources. During confrontations, N. fulva is sprayed by S. invicta with a lipophilic, piperidine-based venom. The former defeats this chemical attack by grooming with its own venom, formic acid. The combination forms a protic ionic liquid, which is the first naturally occurring ionic liquid to be reported.

    3. Carbonic Acid | Hot Paper

      Gas-Phase Preparation of Carbonic Acid and Its Monomethyl Ester (pages 11766–11771)

      Dr. Hans Peter Reisenauer, M. Sc. J. Philipp Wagner and Prof. Dr. Peter R. Schreiner

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406969

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      The matrix-isolation IR spectrum of carbonic acid generated through gas-phase pyrolysis of Boc2O (Boc=tert-butoxycarbonyl) or (tBuO)2CO unequivocally shows that the long-claimed identity of the gas phase above its α-polymorph is not carbonic acid, but rather the monomethyl ester, which was analogously prepared from MeOC(O)OtBu and identified in the gas phase for the first time.

    4. Molecular Recognition

      Amine-Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition (pages 11772–11777)

      Ritesh Haldar, Prof. Ryotaro Matsuda, Prof. Susumu Kitagawa, Prof. Subi J. George and Prof. Tapas Kumar Maji

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405619

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      It all stacks up: A supramolecular host with a nano-coordination space built up by the assembly of a 1D coordination polymer has been synthesized for encapsulation and recognition of various aromatic amine guest molecules through an emission-readout process. In some cases, the charge-transfer emission is enhanced by energy transfer from the chromophoric naphthalene linker unit.

    5. Molecular Diversity

      Synthesis of a Natural Product-Like Compound Collection through Oxidative Cleavage and Cyclization of Linear Peptides (pages 11778–11782)

      Dr. Rico Petersen, Dr. Sebastian T. Le Quement and Prof. Dr. Thomas E. Nielsen

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405747

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      Complexity made simple: By harnessing the power of solid-phase peptide synthesis, readily available amino acid building blocks (monomers) were assembled into peptide sequences (oligomers) designed to undergo cascade reactions. Using simple reagents and reaction conditions, a collection of natural product-like compounds was synthesized, with excellent control of embedded scaffold stereocenters.

    6. Bioconjugation

      Site-Selective Labeling of a Lysine Residue in Human Serum Albumin (pages 11783–11786)

      Dr. Shigehiro Asano, Dr. James T. Patterson, Dr. Thomas Gaj and Prof. Dr. Carlos F. Barbas III

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201405924

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      Analogues of TAK-242, a small molecule inhibitor of Toll-like receptor 4, were synthesized and conjugated to human serum albumin (HSA). These TAK-242-based cyclohexene compounds demonstrated high reactivity, and Lys64 was identified as the primary conjugation site. A bivalent HSA conjugate was also prepared in a site-specific manner.

    7. Chemical Imaging

      Imaging Lipid Metabolism in Live Caenorhabditis elegans Using Fingerprint Vibrations (pages 11787–11792)

      Dr. Ping Wang, Bin Liu, Delong Zhang, Micah Y. Belew, Prof. Heidi A. Tissenbaum and Prof. Ji-Xin Cheng

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406029

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      Fingerprinting cell metabolism: Hyperspectral stimulated Raman scattering (SRS) imaging of live worms in the fingerprint vibration region and multivariate analysis allowed the compositional analysis of subcellular compartments. The method led to concentration maps of fat storage, degree of fat unsaturation, and lipid oxidation and showed that lysosome-related organelles are sites for the storage of cholesterol in C. elegans.

    8. Microfluidics

      Tailoring of High-Order Multiple Emulsions by the Liquid–Liquid Phase Separation of Ternary Mixtures (pages 11793–11797)

      Martin F. Haase and Jasna Brujic

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406040

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      Multiple droplets within droplets: Mapping of the phase diagram revealed a linear relationship between the diameters of concentric layers of multiple emulsions with an “onion” topology. The slope of the line depended on the initial composition of the ternary mixture and the molecular weight of the surfactant. This general rule quantitatively predicted the number of droplet layers and enabled the self-assembly of polymer capsules and liposomes.

    9. Biosensors | Hot Paper

      Chemical Vapor Detection Using a Reconstituted Insect Olfactory Receptor Complex (pages 11798–11802)

      Dr. Koji Sato and Prof. Shoji Takeuchi

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201404720

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      Gas sensing by ion channels: Insect olfactory receptors consist of ligand-gated ion channels. Using cell assembly and extracellular field potential recording techniques, olfactory receptor-expressing cell spheroids were formed (see picture). The spheroids electrically responded to chemical vapors at biologically relevant concentrations.

    10. Membrane Nanodiscs

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      Bacterial Reaction Centers Purified with Styrene Maleic Acid Copolymer Retain Native Membrane Functional Properties and Display Enhanced Stability (pages 11803–11807)

      Dr. David J. K. Swainsbury, Stefan Scheidelaar, Prof. Rienk van Grondelle, Prof. J. Antoinette Killian and Dr. Michael R. Jones

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406412

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      Best of both worlds: Reaction centers purified from bilayer membranes using an amphipathic copolymer offer the experimental advantages of a detergent-solubilized membrane protein, but retain functional properties of the protein in the native bilayer. Under stress, reaction centers in copolymer–lipid nanodiscs are more robust than when housed in a detergent micelle or even the native membrane.

    11. Photoelectrochemistry

      Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method (pages 11808–11812)

      Dr. Jiao Zhao, Dr. Tsutomu Minegishi, Li Zhang, Dr. Miao Zhong, Gunawan, Dr. Mamiko Nakabayashi, Dr. Guijun Ma, Dr. Takashi Hisatomi, Dr. Masao Katayama, Prof. Dr. Shigeru Ikeda, Prof. Dr. Naoya Shibata, Prof. Dr. Taro Yamada and Prof. Dr. Kazunari Domen

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201406483

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      Porous photocathodes: CuInS2 porous films, prepared by sulfurization of electrodeposited metals and modified with thin layers of CdS and TiO2, evolved H2 from photoelectrochemical water reduction under simulated sunlight (see picture). The modified photocathodes showed a relatively high efficiency and stable H2 production under the reaction conditions by surface modification.

    12. Photochemical CO2 Reduction

      Selective Generation of Formamides through Photocatalytic CO2 Reduction Catalyzed by Ruthenium Carbonyl Compounds (pages 11813–11817)

      Dr. Katsuaki Kobayashi, Dr. Takashi Kikuchi, Prof. Susumu Kitagawa and Prof. Koji Tanaka

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406553

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      Formamide generation: Photochemical CO2 reduction in the presence of a dialkyl amine and its ammonium salt affords a dialkyl formamide when a ruthenium carbonyl compound, [Ru(bpy)2(CO)2]2+, is used as a catalyst. Fast nucleophilic attack of the dialkyl amine on the Ru[BOND]CO scaffold with resulting formamide generation takes priority over the competing formation of formic acid.

    13. Asymmetric Organocatalysis

      Fluxionally Chiral DMAP Catalysts: Kinetic Resolution of Axially Chiral Biaryl Compounds (pages 11818–11821)

      Gaoyuan Ma, Dr. Jun Deng and Prof. Dr. Mukund P. Sibi

      Article first published online: 14 AUG 2014 | DOI: 10.1002/anie.201406684

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      A catalyst for kinetic resolution: Chiral 4-dimethylaminopyridine catalysts with a fluxional group to relay stereochemical information from a fixed stereogenic center to the catalytic center promoted the acylative kinetic resolution of secondary alcohols and axially chiral biaryl compounds with high enantioselectivity (see scheme). The highly modular design of the chiral DMAP catalysts enables significant variation of their structure.

    14. Adaptive Supramolecular Assemblies

      Adaptive Amphiphilic Dendrimer-Based Nanoassemblies as Robust and Versatile siRNA Delivery Systems (pages 11822–11827)

      Xiaoxuan Liu, Jiehua Zhou, Tianzhu Yu, Chao Chen, Qiang Cheng, Kheya Sengupta, Yuanyu Huang, Haitang Li, Cheng Liu, Yang Wang, Paola Posocco, Menghua Wang, Qi Cui, Suzanne Giorgio, Maurizio Fermeglia, Fanqi Qu, Sabrina Pricl, Yanhong Shi, Zicai Liang, Palma Rocchi, John J. Rossi and Ling Peng

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406764

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      Vesicle-like dendrimersomes formed through the self-assembly of an amphiphilic dendrimer are able to undergo structural rearrangement into spherical micelles to entrap and condense siRNA into stable nanoparticles, which protect siRNA and promote siRNA delivery in various cells, including human primary and stem cells, as well as in vivo. This system combines the advantages of lipid and dendrimer vectors, hence constituting a novel and efficient siRNA delivery platform.

    15. Zeolite Catalysis

      Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13 (pages 11828–11833)

      Christopher Paolucci, Anuj A. Verma, Dr. Shane A. Bates, Dr. Vincent F. Kispersky, Jeffrey T. Miller, Dr. Rajamani Gounder, Dr. W. Nicholas Delgass, Dr. Fabio H. Ribeiro and Dr. William F. Schneider

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407030

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      Copper redox catalysis: Operando spectroscopy and density functional calculations isolate copper oxidation and reduction half-cycles during the selective reduction of NOx over a Cu-exchanged SSZ-13 zeolite catalyst containing only isolated CuII sites. NH3 and NO together reduce CuII to CuI ions, and each reduction event generates a CuI/H+ pair (see picture).

    16. Supramolecular Gels

      Two-Component Supramolecular Gels Derived from Amphiphilic Shape-Persistent Cyclo[6]aramides for Specific Recognition of Native Arginine (pages 11834–11839)

      Youzhou He, Min Xu, Rongzhao Gao, Xiaowei Li, Fengxue Li, Xuedan Wu, Prof. Dingguo Xu, Dr. Huaqiang Zeng and Prof. Lihua Yuan

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407092

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      Picking and choosing: A supramolecular two-component gelation system based on the amphiphilic cyclo[6]aramide macrocycle and diethylammonium chloride is reported. This system provides a modularly tunable approach for creating functional two-component gel systems for highly specific recognition of L-arginine (L-Arg) from 19 other amino acids by competitive host–guest interactions.

    17. Reaction Mechanisms

      Crystal Structure of Tryptophan Lyase (NosL): Evidence for Radical Formation at the Amino Group of Tryptophan (pages 11840–11844)

      Dr. Yvain Nicolet, Laura Zeppieri, Dr. Patricia Amara and Dr. Juan C. Fontecilla-Camps

      Article first published online: 5 SEP 2014 | DOI: 10.1002/anie.201407320

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      Radical control: The 3-methylindolic acid block of nosiheptide is synthesized from tryptophan by the radical S-adenosyl-L-methionine enzyme NosL. Its X-ray structure shows how the protein selects its substrate and how, starting from an amino nitrogen-centered radical species, it orients the radical-based reaction to selectively cleave the Cα[BOND]Cβ bond of tryptophan, thus avoiding the spontaneous decarboxylation.

    18. Luminescent Organic Radicals

      Luminescence, Stability, and Proton Response of an Open-Shell (3,5-Dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl Radical (pages 11845–11848)

      Yohei Hattori, Dr. Tetsuro Kusamoto and Prof. Dr. Hiroshi Nishihara

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407362

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      Enhanced photostability: A luminescent open-shell organic radical with high chemical stability was synthesized. The (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl (PyBTM) radical emits fluorescent light from the lowest doublet excited state and is up to 115 times more photostable than the previously reported luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radical.

    19. Organocatalysis

      Catalytic Enantioselective Alkylation of Sulfenate Anions to Chiral Heterocyclic Sulfoxides Using Halogenated Pentanidium Salts (pages 11849–11853)

      Lili Zong, Xu Ban, Choon Wee Kee and Prof. Dr. Choon-Hong Tan

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201407512

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      Phase transfer catalysis: Halogenated pentanidium salts are efficient phase-transfer catalysts for the enantioselective alkylation of sulfenate anions to sulfoxides with high enantioselectivity and high yield. Mechanistic studies indicate the ability of the catalysts to simultaneously activate/stabilize both nucleophile and electrophile through multiple noncovalent interactions (ion-pairing interaction, nonclassical hydrogen bonds, and halogen bonds).

    20. Halogen Bonding

      Iodide-Induced Shuttling of a Halogen- and Hydrogen-Bonding Two-Station Rotaxane (pages 11854–11858)

      Dr. Antonio Caballero, Laura Swan, Dr. Fabiola Zapata and Prof. Paul D. Beer

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407580

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      Set the wheel in motion: Halogen-bonding (XB) anion recognition is used to control the molecular motion of an interlocked structure. A novel XB–HB two-station rotaxane (HB=hydrogen bonding) is demonstrated to undergo shuttling of the macrocyclic wheel component from the HB to the XB station driven by iodide recognition, whereas chloride binding results in the macrocycle residing at the HB station.

    21. Electrochemistry

      Simultaneous Detection of Single Attoliter Droplet Collisions by Electrochemical and Electrogenerated Chemiluminescent Responses (pages 11859–11862)

      Jeffrey E. Dick, Dr. Christophe Renault, Dr. Byung-Kwon Kim and Prof. Dr. Allen J. Bard

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407937

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      Shedding light on current events: A clear correlation between electrochemical and electrogenerated chemiluminescent (ECL) responses has been observed for collisions of nano- and micro-sized oil droplets on an ultra-microelectrode surface. The droplets serve as attoliter electrolysis reactors that, upon oxidation of the constituents within the droplet, display simultaneous current and ECL spikes. PMT=photomultiplier tube, TPrA=tri-n-propylamine.

    22. Antitumor Agents | Hot Paper

      A CXCR4-Targeted Site-Specific Antibody–Drug Conjugate (pages 11863–11867)

      Dr. Sumith A. Kularatne, Dr. Vishal Deshmukh, Dr. Jennifer Ma, Dr. Virginie Tardif, Dr. Reyna K. V. Lim, Holly M. Pugh, Dr. Ying Sun, Anthony Manibusan, Aaron J. Sellers, Dr. Richard S. Barnett, Shailaja Srinagesh, Jane S. Forsyth, Dr. Wolf Hassenpflug, Dr. Feng Tian, Dr. Tsotne Javahishvili, Prof. Brunhilde Felding-Habermann, Prof. Brian R. Lawson, Dr. Stephanie A. Kazane and Prof. Peter G. Schultz

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408103

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      Hitting the mark(er): A chemically defined anti-CXCR4–auristatin antibody–drug conjugate (ADC) was produced that selectively targets and eliminates CXCR4+ metastatic cancer cells in vitro and in vivo with no significant overt toxicity. Because the CXCR4 receptor is highly expressed in the majority of metastatic cancers, a CXCR4–auristatin ADC may be useful for the treatment of a variety of metastatic malignancies.

    23. C[BOND]H Activation | Hot Paper

      Radical C[BOND]H Functionalization of Heteroarenes under Electrochemical Control (pages 11868–11871)

      Dr. Alexander G. O'Brien, Dr. Akinobu Maruyama, Dr. Yasuhide Inokuma, Prof. Makoto Fujita, Prof. Phil S. Baran and Prof. Donna G. Blackmond

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201407948

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      Electrochemical reactions are shown to be effective for the C[BOND]H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions and of interest in medicinal chemistry. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C[BOND]H functionalization process.

    24. Biomass Conversion

      Solvent Effects in Acid-Catalyzed Biomass Conversion Reactions (pages 11872–11875)

      Max A. Mellmer, Dr. Canan Sener, Dr. Jean Marcel R. Gallo, Dr. Jeremy S. Luterbacher, Dr. David Martin Alonso and Prof. James A. Dumesic

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408359

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      In acid-catalyzed biomass conversion (e.g., dehydration of xylose to furfural), the use of polar aprotic organic solvents, such as γ-valerolactone, affects the stabilization of the acidic proton relative to the protonated transition states. This leads to accelerated reaction rates and increased product selectivities compared to the transformations in aqueous media.

    25. 18F-Labeling | Hot Paper

      An Organotrifluoroborate for Broadly Applicable One-Step 18F-Labeling (pages 11876–11880)

      Zhibo Liu, Maral Pourghiasian, Mark Alex Radtke, Joseph Lau, Dr. Jinhe Pan, Gemma M. Dias, Dr. Donald Yapp, Dr. Kuo-Shyan Lin, Prof. Dr. Francois Bénard and Prof. Dr. David M. Perrin

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406258

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      Like a postage stamp that neither alters a letter's weight nor changes its contents or destination, a new zwitterionic trifluoroborate radiosynthon transforms complex molecules into 18F-tracers that are labeled in a single aqueous-phase step in high yield and at high specific radioactivity without HPLC purification.

    26. Indole Chemistry

      Direct Oxidative Coupling of N-Acetyl Indoles and Phenols for the Synthesis of Benzofuroindolines Related to Phalarine (pages 11881–11885)

      Terry Tomakinian, Dr. Régis Guillot, Prof. Dr. Cyrille Kouklovsky and Dr. Guillaume Vincent

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201404055

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      Ironized! The unprecedented direct oxidative coupling between phenols and indole nuclei leading to the regioselective formation of the phalarine benzofuroindoline core is reported through the addition of phenoxy radicals to N-acetyl indoles mediated by FeCl3. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

    27. Heterogeneous Catalysis

      Cu–Al Spinel Oxide as an Efficient Catalyst for Methanol Steam Reforming (pages 11886–11889)

      Dr. Hongjuan Xi, Xiaoning Hou, Yajie Liu, Shaojun Qing and Prof. Dr. Zhixian Gao

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405213

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      Reforming reforming: Methanol steam reforming (MSR) was catalyzed by Cu–Al spinel oxide without prereduction. The catalysis is effectively initiated by the CuO phase present in CuAl2O4, which gradually releases active copper. Even the regenerated catalyst (CA2.5-900-R) was more active than the commercial Cu–Zn–Al (CZA) catalyst (see graph).

    28. C[BOND]H Activation

      Enantioselective C[BOND]H Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene (pages 11890–11894)

      Peng Yu, Jin-Shun Lin, Lei Li, Sheng-Cai Zheng, Ya-Ping Xiong, Li-Jiao Zhao, Prof. Dr. Bin Tan and Prof. Dr. Xin-Yuan Liu

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201405401

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      En route: The title redox-neutral reaction provides a convenient route to valuable enantioenriched trifluoromethylated N,O-aminals in good to excellent yields and with excellent regio-, chemo-, and enantioselectivity. The reaction features a CuI/Brønsted acid system and broad substrate scope.

    29. Heterocycle Synthesis

      Palladium-Catalyzed Annulation of Diarylamines with Olefins through C[BOND]H Activation: Direct Access to N-Arylindoles (pages 11895–11899)

      Dr. Upendra Sharma, Dr. Rajesh Kancherla, Togati Naveen, Soumitra Agasti and Prof. Debabrata Maiti

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406284

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      No group help needed: A palladium-catalyzed dehydrogenative coupling between diarylamines and olefins has been discovered for the synthesis of substituted indoles. This intermolecular annulation approach incorporates readily available olefins and obviates the need for any additional directing group. An ortho palladation, olefin coordination, and β-migratory insertion sequence has been proposed for the generation of an olefinated intermediate.

    30. Organopolymerization

      Proton-Transfer Polymerization (HTP): Converting Methacrylates to Polyesters by an N-Heterocyclic Carbene (pages 11900–11906)

      Dr. Miao Hong and Prof. Dr. Eugene Y.-X. Chen

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406630

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      Unsaturated polyesters are obtained specifically from dimethacrylates by a new step-growth polymerization catalyzed by an N-heterocyclic carbene.

    31. Carbohydrates

      Protecting-Group-Free One-Pot Synthesis of Glycoconjugates Directly from Reducing Sugars (pages 11907–11911)

      David Lim, Prof. Margaret A. Brimble, Dr. Renata Kowalczyk, Dr. Andrew J. A. Watson and Prof. Antony John Fairbanks

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406694

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      Sugars get sticky in water: The combined use of ADMP and the Cu-catalyzed Huisgen cycloaddition allows the synthesis of a range of glycoconjugates directly from the corresponding reducing sugar in one step under aqueous conditions. The reaction is stereoselective and may be applied to the convergent synthesis of triazole-linked glycosides, oligosaccharides, and glycopeptides.

    32. From Chitin to Bioactive Chitooligosaccharides and Conjugates: Access to Lipochitooligosaccharides and the TMG-chitotriomycin (pages 11912–11916)

      Guillaume Despras, Aurélien Alix, Dominique Urban, Boris Vauzeilles and Jean-Marie Beau

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406802

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      Short cuts from chitin: Deconstruction of chitin and selective reconstruction to give well-defined oligosaccharides provide an effective approach to bioactive glycoconjugates. This method was applied to the preparation of the important symbiotic glycolipids.

    33. Cancer Vaccines

      A Cancer Therapeutic Vaccine based on Clustered Tn-Antigen Mimetics Induces Strong Antibody-Mediated Protective Immunity (pages 11917–11920)

      Dr. Barbara Richichi, Baptiste Thomas, Dr. Michele Fiore, Dr. Rosa Bosco, Dr. Huma Qureshi, Prof. Dr. Cristina Nativi, Prof. Dr. Olivier Renaudet and Dr. Lbachir BenMohamed

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406897

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      Fantastic four: Four clustered mimetics of the tumor-associated carbohydrate antigen Tn (red) and a T-helper-cell peptide epitope (blue) conjugated to a cyclopeptide carrier (RAFT) are the chemical components of a new improved vaccine prototype. This fully synthetic vaccine elicits a robust and long-lasting IgG/IgM antibody response and induces tumor protection in mice through a B-cell-mediated mechanism.

    34. Synthetic Methods

      Palladium(0)-Catalyzed Cross-Coupling of 1,1-Diboronates with Vinyl Bromides and 1,1-Dibromoalkenes (pages 11921–11925)

      Huan Li, Zhikun Zhang, Xianghang Shangguan, Shan Huang, Dr. Jun Chen, Dr. Yan Zhang and Prof. Dr. Jianbo Wang

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407000

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      It takes two B: The title reactions afford 1,4-dienes and allenes. These reactions utilize the high reactivities of both 1,1-diboronates and allylboron intermediates generated in the initial coupling reaction.

    35. Photocatalysis

      Helical Graphitic Carbon Nitrides with Photocatalytic and Optical Activities (pages 11926–11930)

      Yun Zheng, Lihua Lin, Xiangju Ye, Fangsong Guo and Prof. Xinchen Wang

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407319

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      Helical nanorods: Graphitic carbon nitride with helical nanorod-like morphology similar to spiral vines is constructed for artificial photosynthesis. This helically conjugated polymer can also be fabricated with opposite chirality and shows photocatalytic activity for water splitting and CO2 conversion.

    36. Natural Product Synthesis

      Synthesis of Bis(indole) Alkaloids from Arundo donax: The Ynindole Diels–Alder Reaction, Conformational Chirality, and Absolute Stereochemistry (pages 11931–11934)

      Dr. Jingjin Chen, Andrew J. Ferreira and Prof. Dr. Christopher M. Beaudry

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201407336

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      Conformational chirality: Bis(indole) alkaloids from Arundo donax were synthesized using the first ynindole Diels–Alder reaction. The alkaloids are chiral, having stable enantiomeric conformations with half-lives of racemization of t1/2=4150–25100 seconds at room temperature. Their absolute stereochemistry was determined using the exciton chirality method.

    37. Electrochromic Supercapacitors | Hot Paper

      Large-Scale Fabrication of Pseudocapacitive Glass Windows that Combine Electrochromism and Energy Storage (pages 11935–11939)

      Peihua Yang, Peng Sun, Zhisheng Chai, Prof. Langhuan Huang, Dr. Xiang Cai, Prof. Shaozao Tan, Prof. Jinhui Song and Prof. Wenjie Mai

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407365

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      A pseudocapacitive glass window (15×15 cm2) is obtained by the deposition of WO3 on fluorine-doped tin oxide glass. Such smart pseudocapacitive glass windows show great potential in functioning as electrochromic windows and concurrently powering electronic devices, such as mobile phones or laptops.

    38. Cyclization

      Rhodium-Catalyzed Cyclization of Diynes with Nitrones: A Formal [2+2+5] Approach to Bridged Eight-Membered Heterocycles (pages 11940–11943)

      Dr. Chunxiang Wang, Dr. Dongping Wang, Hao Yan, Dr. Haolong Wang, Dr. Bin Pan, Dr. Xiaoyi Xin, Dr. Xincheng Li, Fan Wu and Prof. Dr. Boshun Wan

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407394

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      Five-atom building unit: N-aryl-substituted nitrones were employed as five-atom coupling partners in the rhodium-catalyzed cyclization with diynes. In this reaction, the nitrone moiety served as a directing group for the catalytic C[BOND]H activation of the N-aryl ring. This formal [2+2+5] approach allows rapid access to bridged eight-membered heterocycles with broad substrate scope.

    39. Biosynthesis | Very Important Paper

      You have full text access to this OnlineOpen article
      Chemical Probes for the Functionalization of Polyketide Intermediates (pages 11944–11949)

      Dr. Elena Riva, Dr. Ina Wilkening, Silvia Gazzola, W. M. Ariel Li, Dr. Luke Smith, Prof. Peter F. Leadlay and Dr. Manuela Tosin

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407448

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      Towards novel “unnatural” products: Fermentation of ACP mutants of S. lasaliensis in the presence of functionalized chemical probes with subsequent site-selective modifications generates a library of nonnatural lasalocid A precursors and derivatives.

    40. Amino Acids

      Sulfonamide-Promoted Palladium(II)-Catalyzed Alkylation of Unactivated Methylene C(sp3)[BOND]H Bonds with Alkyl Iodides (pages 11950–11954)

      Kai Chen and Prof. Dr. Bing-Feng Shi

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407848

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      Branching off: The title reaction of unactivated β-methylene C(sp3)[BOND]H bonds of α-amino acid substrates with alkyl iodides is described. The C(alkyl)–C(alkyl) bond-forming reaction proceeds in good yields, and β-branched amino acids can be obtained by using sequential reactions.

    41. Fluorescence Probes

      Protease Probes that Enable Excimer Signaling upon Scission (pages 11955–11959)

      Melanie Fischbach, Dr. Ute Resch-Genger and Prof. Dr. Oliver Seitz

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406909

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      Let there be excimer light: Large Stokes shifts and the long lifetime of excimer emission facilitate measurements in optically dense, autofluorescent media such as blood serum. However, proteolytic cleavage abolishes rather than installs proximity relationships required for excimer signaling. Herein, a new approach is introduced which enables on-switching of pyrene excimer emission upon proteolytic scission of hairpin-shaped PNA-peptide probe.

    42. Heterocycles

      Cascade Multicomponent Synthesis of Indoles, Pyrazoles, and Pyridazinones by Functionalization of Alkenes (pages 11960–11964)

      Dr. Kiran Matcha and Dr. Andrey P. Antonchick

      Article first published online: 6 OCT 2014 | DOI: 10.1002/anie.201406464

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      Fischer-man′s friend: A regioselective multicomponent route to indole synthesis by functionalization of simple alkenes has been developed and has a broad scope. The novel application of alkene trifluoromethylation provides entry into Fischer indole synthesis, and various trifluoromethylated nitrogen heterocycles can be conveniently obtained.

    43. Spin Isomers of Water | Very Important Paper

      Separating Para and Ortho Water (pages 11965–11968)

      Dr. Daniel A. Horke, Dr. Yuan-Pin Chang, Karol Długołęcki and Prof. Dr. Jochen Küpper

      Article first published online: 5 SEP 2014 | DOI: 10.1002/anie.201405986

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      Keep them separated: The two nuclear-spin isomers para and ortho water can be isolated in their absolute ground state in pure molecular beams. No pure para sample had previously been produced. This method for the separation of quantum states is generally applicable to all polar neutral molecules and allows the spatial separation of single quantum states and nuclear-spin isomers.

    44. Immunoproteasome Inhibition

      Selective Inhibition of the Immunoproteasome by Ligand-Induced Crosslinking of the Active Site (pages 11969–11973)

      Christian Dubiella, Haissi Cui, Dr. Malte Gersch, Arwin J. Brouwer, Prof. Dr. Stephan A. Sieber, Prof. Dr. Achim Krüger, Prof. Dr. Rob M. J. Liskamp and Prof. Dr. Michael Groll

      Article first published online: 22 SEP 2014 | DOI: 10.1002/anie.201406964

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      The current benchmark for proteasome inhibition, immunoproteasome inhibitors featuring α′,β′-epoxyketones, were compared to peptido sulfonyl fluorides (PSF) in terms of their mechanism of action, selectivity, and cytotoxicity. PSFs were found to remove the catalytically active nucleophile and then crosslink the active site. Cell-based activity and viability assays designate this warhead for selective immunoproteasome blockage.

    45. Noble Metalates

      Alkaline Earth Guests in Polyoxopalladate Chemistry: From Nanocube to Nanostar via an Open-Shell Structure (pages 11974–11978)

      Peng Yang, Yixian Xiang, Zhengguo Lin, Bassem S. Bassil, Prof. Jie Cao, Linyuan Fan, Yanxuan Fan, Prof. Ming-Xing Li, Pablo Jiménez-Lozano, Dr. Jorge J. Carbó, Prof. Josep M. Poblet and Prof. Ulrich Kortz

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407090

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      The noble template effect: The size of the alkaline earth metal ion guest (Ca2+, Sr2+, Ba2+) allows the shape and size of the resulting polyoxopalladate cluster to be tuned. The small Ca2+ ion leads to the 12-palladate nanocube, the large Ba2+ ion leads to the 15-palladate nanostar, and the intermediate-sized Sr2+ ion leads to an intermediary structure, an open-shell 12-palladate.

    46. Main-Group Chemistry

      Origin and Location of Electrons and Protons during the Formation of Intermetalloid Clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0, 1) (pages 11979–11983)

      Dipl.-Chem. Bastian Weinert, B.Sc. Fabian Müller, Dr. Klaus Harms, Dr. Rodolphe Clérac and Prof. Dr. Stefanie Dehnen

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407288

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      Desiring protons: The use of [GaBi3]2− in reactions with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0,1). By experimental and quantum chemical analyses, the presence of the Ga[BOND]H bonds was rationalized, and the transfer of electrons and protons during the formation process was elucidated.

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