Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 14

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

Upcoming VIPs

The following papers are very important in the opinion of two referees.

You are invited to comment on published VIPs. Please use the link given at the end of each such abstract. Scientific comments may be forwarded to the authors by the editorial office and may be posted on this page. Kindly let us know if your comments are for the editorial office only, the author, or the public as well.

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Structural Transformation: Assembly of an Otherwise Inaccessible DNA Nanocage

Dr. Yulin Li, Dr. Cheng Tian, Zhiyu Liu, Prof. Wen Jiang and Prof. Chengde Mao

Structural Transformation: Assembly of an Otherwise Inaccessible DNA NanocageOne way or another: A strategy has been developed for the assembly of DNA nanocages that can not be assembled directly. In this approach a precursor DNA nanocage is assembled first and is then isothermally transformed into a desired, complicated nanocage. Dramatic changes in the 3D structures and topologies accompany the transformation, as shown by native polyacrylamide gel electrophoresis and cryogenic electron microscopy imaging.

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Secondary Crystal Nucleation: Nuclei Breeding Factory Uncovered

Prof. Jamshed Anwar, Dr. Shahzeb Khan and Prof. Dr. Lennart Lindfors

Secondary Crystal Nucleation: Nuclei Breeding Factory UncoveredCrystal clear: Molecular dynamics simulations uncover the nuclei breeding factory responsible for secondary nucleation in crystal growth. The question why a few crystal seeds give rise to a many-fold increase in new crystals is answered. This mechanistic insight will enable better control in engineering crystalline products to design.

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A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride Anions

Somenath Garai, Dr. Mirta Rubčić, Dr. Hartmut Bögge, Dr. Erhard T. K. Haupt, Prof. Dr. Pierre Gouzerh and Prof. Dr. Achim Müller

A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride AnionsOverloaded: Porous molecular nanocontainers of the {Mo132} Keplerate type can integrate a uniquely large number of fluorides. These F ions (see structure, green) are partly as coordinated ligands at both the {(MoVI)MoVI5O21(H2O)5(F)} pentagonal units (orange) and the linkers (blue), partly as a disordered water/fluoride assembly inside the cavity. The H2O ligands are shown as red spheres (larger red spheres are for H2O coordinated e.g. to the MoV centers of the linkers).

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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

Origin of Extraordinary Stability of Square-Planar Carbon Atoms in Surface Carbides of Cobalt and NickelOut 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.

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A Constellation of Deuterium-Labeled Silanes as a Simple Mechanistic Probe not Requiring Absolute Configuration Determination

Dr. Thomas Fallon and Prof. Dr. Martin Oestreich

A Constellation of Deuterium-Labeled Silanes as a Simple Mechanistic Probe not Requiring Absolute Configuration DeterminationSilicon stargazing: A new type of mechanistic probe is designed and evaluated. A cocktail of deuterium-labeled hydrosilanes provides a “silent” stereochemical relationship between the silicon atom and the probe’s backbone as the basis of the analysis. This technique does not suffer from the biases of traditional methods, nor does it require the determination of the absolute configuration.

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Direct C(sp2)[BOND]C(sp3) Cross-Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides

Dr. Jay J. Dunsford, Dr. Ewan R. Clark and Dr. Michael J. Ingleson

Direct C(sp2)<img src="http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif" alt="[BOND]" />C(sp3) Cross-Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl HalidesZinc and you’ll miss it! Direct C(sp2)[BOND]C(sp3) cross-coupling of diaryl zinc reagents with alkyl halides proceeded rapidly at ambient temperature without a coordinating ethereal solvent or an added catalyst (see scheme). This versatile, operationally simple approach to C(sp2)[BOND]C(sp3) bond formation enables the expedient construction of a diverse array of carbon-based structural motifs.

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Improving the Electrochemical Performance of the Li4Ti5O12 Electrode in a Rechargeable Magnesium Battery by Lithium–Magnesium Co-Intercalation

Na Wu, Zhen-Zhong Yang, Hu-Rong Yao, Dr. Ya-Xia Yin, Prof. Lin Gu and Prof. Yu-Guo Guo

Improving the Electrochemical Performance of the Li4Ti5O12 Electrode in a Rechargeable Magnesium Battery by Lithium–Magnesium Co-IntercalationSynergy between Mg2+ and Li+ ions: By controlling the collaborative electrochemistry of magnesium and lithium cations, Li4Ti5O12 electrodes (LTO; see picture) close to sub-micron size gain extraordinary electrochemical energy storage capability. The electrodes show improved kinetics in rechargeable magnesium batteries.

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High Ethene/Ethane Selectivity in 2,2′-Bipyridine-Based Silver(I) Complexes by Removal of Coordinated Solvent

Dr. Matthew G. Cowan, William M. McDanel, Prof. Hans H. Funke, Dr. Yuki Kohno, Prof. Douglas L. Gin and Prof. Richard D. Noble

High Ethene/Ethane Selectivity in 2,2′-Bipyridine-Based Silver(I) Complexes by Removal of Coordinated SolventSite unseen: The coordination complexes 1 and 2, having open silver(I) sites, were prepared and investigated for ethene/ethane binding. These complexes display ethene/ethane selectivity of up to 13 times higher than comparable solid sorbents, ethene loadings of up to 2.38 mmol g−1, and saturation of silver(I) sites of up to 0.96 molethene/molsilver(I). Tf=trifluoromethanesulfonyl.

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A Facile and Universal Top-Down Method for Preparation of Monodisperse Transition-Metal Dichalcogenide Nanodots

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

A Facile and Universal Top-Down Method for Preparation of Monodisperse Transition-Metal Dichalcogenide NanodotsOn 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.

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Solvated Graphene Frameworks as High-Performance Anodes for Lithium-Ion Batteries

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

Solvated Graphene Frameworks as High-Performance Anodes for Lithium-Ion BatteriesSolvated 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.

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Direct Observation of Ca2+-Induced Calmodulin Conformational Transitions in Intact Xenopus laevis Oocytes by 19F NMR Spectroscopy

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

Direct Observation of Ca2+-Induced Calmodulin Conformational Transitions in Intact Xenopus laevis Oocytes by 19F NMR SpectroscopyConfined 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.

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One-Step Synthesis of a [20]Silafullerane with an Endohedral Chloride Ion

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

One-Step Synthesis of a [20]Silafullerane with an Endohedral Chloride IonAs 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.

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On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect

Dr. Jilai Li, Dr. Xiao-Nan Wu, Dr. Maria Schlangen, Dr. Shaodong Zhou, Dr. Patricio González-Navarrete, Dr. Shiya Tang and Prof. Dr. Helmut Schwarz

On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping EffectBridging oxygen: A combination of mass spectrometry and quantum chemical calculations shows that [Ga2Mg2O5].+, bearing an unpaired electron at a bridging oxygen atom, is capable of activating the C[BOND]H bond of methane. The roles of spin density and charge distributions in hydrogen-atom transfer processes provide important guidance for the rational design of catalysts.

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Oxidative Addition of Carbon–Carbon Bonds to Gold

Dr. Maximilian Joost, Dr. Laura Estévez, Dr. Karinne Miqueu, Dr. Abderrahmane Amgoune and Dr. Didier Bourissou

Oxidative Addition of Carbon–Carbon Bonds to GoldGold(I) complexes ([(DPCb)Au]+) readily insert into the four-membered rings of biphenylene and benzocyclobutenone. These transformations afforded well-defined cationic organogold(III) complexes that were isolated and fully characterized. [(DPCb)Au]+ is the only complex to cleave selectively either the C(aryl)[BOND]C(O) or the C(alkyl)[BOND]C(O) bond of benzocyclobutenone under kinetic/thermodynamic control. DPCb=diphosphinocarborane.

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Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties

Jian Lin, Youzhen Dong, Qian Zhang, Dandan Hu, Prof. Dr. Na Li, Dr. Le Wang, Prof. Dr. Yang Liu and Prof. Dr. Tao Wu

Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical PropertiesZeolitic architecture: An interrupted chalcogenide-based zeolite-analog semiconductor with an entirely new boracite-related framework and specific sites at the interrupted section is reported. The specific indium sites serving as effective electrocatalytic active centers for the oxygen reduction reaction proved to be atomically precisely doped by trivalent bismuth ions.

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Well-Defined CuC2F5 Complexes and Pentafluoroethylation of Acid Chlorides

Liubov I. Panferova, Fedor M. Miloserdov, Dr. Anton Lishchynskyi, Dr. Marta Martínez Belmonte, Dr. Jordi Benet-Buchholz and Prof. Vladimir V. Grushin

Well-Defined CuC2F5 Complexes and Pentafluoroethylation of Acid ChloridesFour well-defined CuC2F5 complexes have been prepared and fully characterized, with [(phen)Cu(PPh3)C2F5] (phen=1,10-phenanthroline) proving to be a remarkably efficient fluoroalkylating agent for a broad variety of acid chlorides (see scheme). The developed procedure represents the first general method for the one-step conversion of RCOCl into valuable pentafluoroethyl ketones.

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Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC

Dr. Meng-Qiang Zhao, Morgane Sedran, Zheng Ling, Maria R. Lukatskaya, Olha Mashtalir, Michael Ghidiu, Boris Dyatkin, Darin J. Tallman, Prof. Thierry Djenizian, Prof. Michel W. Barsoum and Prof. Yury Gogotsi

Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SCCarbon/sulfur nanolaminates composed of multi-layered C/S flakes with predominantly amorphous, and some graphene-like, structures were synthesized by electrochemical extraction of Ti from a Ti2SC MAX phase. This approach provides a novel method for the room-temperature synthesis of “AX” layered structures by the selective extraction of “M” from the MAX phases.

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Organoaluminum-Mediated Direct Cross-Coupling Reactions

Hiroki Minami, Dr. Tatsuo Saito, Dr. Chao Wang and Prof. Dr. Masanobu Uchiyama

Organoaluminum-Mediated Direct Cross-Coupling ReactionsAll in Al: Simply heating an arylaluminum (ArAlMe2⋅LiCl) and an organic halide RX (R=aryl, alkenyl, alkynyl; X=I, Br, Cl) without any external catalyst results in a smooth and direct cross-coupling reaction taking place. This approach enables the efficient, chemo-/stereoselective formation of coupling products with broad functional group compatibility.

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Structural Characterization of a Hydroperoxo Nickel Complex and Its Autoxidation: Mechanism of Interconversion between Peroxo, Superoxo, and Hydroperoxo Species

Christoph A. Rettenmeier, Prof. Hubert Wadepohl and Lutz H. Gade

Structural Characterization of a Hydroperoxo Nickel Complex and Its Autoxidation: Mechanism of Interconversion between Peroxo, Superoxo, and Hydroperoxo SpeciesPincer-stabilized nickel(I) complexes readily react with molecular oxygen to form dinuclear 1,2-μ-peroxo-bridged nickel(II) complexes, which are the major components of a dynamic equilibrium with the corresponding mononuclear superoxo species. The peroxo complexes further react with hydrogen peroxide to give the corresponding nickel(II) hydroperoxides.

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Free-Standing Gold-Nanoparticle Monolayer Film Fabricated by Protein Self-Assembly of α-Synuclein

Junghee Lee, Dr. Ghibom Bhak, Dr. Ji-Hye Lee, Woohyun Park, Minwoo Lee, Dr. Daekyun Lee, Prof. Noo Li Jeon, Prof. Dae H. Jeong, Prof. Kookheon Char and Prof. Seung R. Paik

Free-Standing Gold-Nanoparticle Monolayer Film Fabricated by Protein Self-Assembly of α-SynucleinFilm producer: Protein-based free-standing gold-nanoparticle monolayer films are fabricated by self-assembly between α-synuclein proteins coating the nanoparticles. The film can be scaled-up to 4-inch-wafer size. The high flexibility of the film in solvent allows it to wrap round curved surfaces on the micrometer-scale. Additionally, the monolayer film is readily patterned into free-floating multi-hole sheets and an unprecedented film containing two different sized nanoparticles is also fabricated (see photo).

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A Covalent Approach for Site-Specific RNA Labeling in Mammalian Cells

Fahui Li, Jianshu Dong, Xiaosong Hu, Weimin Gong, Jiasong Li, Jing Shen, Huifang Tian and Jiangyun Wang

A Covalent Approach for Site-Specific RNA Labeling in Mammalian CellsTag and click: The ability to specifically label RNAs in vitro and in mammalian cells would be highly significant for RNA research, however, covalent RNA labeling methods with scope and versatility comparable to those for protein labeling have not been reported. A method was developed for the site- and sequence-specific covalent labeling of RNAs in mammalian cells, based on the action of tRNAIle2-agmatidine synthetase (Tias) and click chemistry.

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Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica Architectures

Dr. Silvia Bracco, Dr. Mario Beretta, Dr. Alice Cattaneo, Prof. Angiolina Comotti, Prof. Andrea Falqui, Dr. Ke Zhao, Prof. Charles Rogers and Prof. Piero Sozzani

Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica ArchitecturesOriented molecular rotors: Fluorinated molecular rotors (see picture) were engineered in mesoporous hybrid organosilica architectures with crystalline order in their walls. The rotor dynamics was established by magic angle spinning NMR and dielectric measurements, indicating a rotational correlation time as short as 10−9 s at 325 K. The dynamics was modulated by I2 vapors entering the pores.

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Flow-Enabled Self-Assembly of Large-Scale Aligned Nanowires

Bo Li, Chuchu Zhang, Beibei Jiang, Dr. Wei Han and Prof. Zhiqun Lin

Flow-Enabled Self-Assembly of Large-Scale Aligned NanowiresMetallic nanowires are obtained by using highly oriented DNA nanowires as templates. A swelling-induced transfer printing technique is employed to transfer the ultralong DNA nanowires onto a desirable substrate; metallic nanowires are then generated by exposing the DNA nanowires preloaded with metal salts to an oxygen plasma.

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Caterpillar Track Complexes in Template-Directed Synthesis and Correlated Molecular Motion

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

Caterpillar Track Complexes in Template-Directed Synthesis and Correlated Molecular MotionTurning 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.

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Impact of Hydrogenolysis on the Selectivity of the Fischer–Tropsch Synthesis: Diesel Fuel Production over Mesoporous Zeolite Y-Supported Cobalt Nanoparticles

Xiaobo Peng, Dr. Kang Cheng, Dr. Jincan Kang, Bang Gu, Xiang Yu, Prof. Dr. Qinghong Zhang and Prof. Dr. Ye Wang

Impact of Hydrogenolysis on the Selectivity of the Fischer–Tropsch Synthesis: Diesel Fuel Production over Mesoporous Zeolite Y-Supported Cobalt NanoparticlesGas up! A mesoporous zeolite Y-supported cobalt catalyst, which is highly selective for the direct conversion of syngas into diesel fuel, has been developed by effective control of hydrogenolysis. The sizes of the cobalt particles and support mesopores are key factors in determining the activity and selectivity of hydrogenolysis.

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