Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

April 19, 2010

Volume 49, Issue 18

Pages 3091–3235

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
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    1. Cover Picture: The Ouroborand: A Cavitand with a Coordination-Driven Switching Device (Angew. Chem. Int. Ed. 18/2010) (page 3091)

      Fabien Durola and Julius Rebek Jr.

      Version of Record online: 9 APR 2010 | DOI: 10.1002/anie.201001499

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      The Armadillo Lizard is a South African reptile that holds its tail in its mouth as a defensive tactic. This is reminiscent of the Ouroboros, an ancient Greek symbol depicting a serpent swallowing its own tail, famous as the inspiration for Kekule's formulation of benzene 150 years ago. In their Communication on page 3189 ff., F. Durola and J. Rebek, Jr. report how a self-hosting cavitand, which is named an “Ouroborand”, can switch between closed and open states by addition of zinc ions. (Picture courtesy of P. le F. N. Mouton)

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
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    1. Inside Cover: A Simple Route to Univalent Gallium Salts of Weakly Coordinating Anions (Angew. Chem. Int. Ed. 18/2010) (page 3092)

      John M. Slattery, Alexander Higelin, Thomas Bayer and Ingo Krossing

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.201001595

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      Gallium(I) salts of weakly coordinating anions (WCAs), which are excellent sources of gallium in the oxidation state +1, are generated by a simple, high-yielding route. These salts open new areas of low-valent gallium chemistry that were previously inaccessible. In their Communication on page 3228 ff., I. Krossing, J. M. Slattery, and co-workers describe a salt of the [Ga(PPh3)3]+ ion as an example of a homoleptic gallium–phosphine complex.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
  5. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Pier Giorgio Cozzi (page 3110)

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.201000714

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      “I chose chemistry as a career because it is a nice combination of theory and practice. I would have liked to have discovered football! …” This and more about Pier Giorgio Cozzi can be found on page 3110.

  6. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
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    1. Computational Inorganic and Bioinorganic Chemistry. Edited by Edward I. Solomon, Robert A. Scott and R. Bruce King. (pages 3111–3113)

      Sason Shaik

      Version of Record online: 9 APR 2010 | DOI: 10.1002/anie.201000436

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      John Wiley & Sons, Hoboken 2009. 614 pp., hardcover € 155.00.—ISBN 978-0470699973

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Silver(II)

      Strong One-Dimensional Antiferromagnetic Interactions of Silver(II) Ions in Silver Sulfate (pages 3114–3115)

      Jürgen Köhler

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.201000448

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      The new complex silver(II) oxide AgSO4 was synthesized by a methathetic reaction of Ag(SbF6)2 and K2SO4 in anhydrous HF at −80 °C or by the reaction of AgF2 with H2SO4 at −35 °C. The magnetic moments of the rectangular planar coordinated Ag2+ ions in AgSO4 are antiferromagnetically coupled to the chains through the O–O edges of the sulfate ions (see picture). The Ag2+–Ag2+ super-superexchange interaction is unusually strong.

    2. Organolanthanides

      Heteroleptic Samarium(II) Complexes by Base-Induced Reduction (pages 3116–3118)

      Gerd Meyer

      Version of Record online: 5 MAR 2010 | DOI: 10.1002/anie.201000566

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      From SIR to BIR: Following the concept of the sterically induced reduction (SIR), the base-induced reaction (BIR) has now been discovered. [Sm(AlMe4)3] reacts with the bulky base 1,3,5-tricyclohexyl-1,3,5-triazacyclohexane (TCyTAC) in benzene to give [(TCyTAC)2SmII(AlMe4)2] (see picture; Sm red, Al dark gray, N green, C light gray) and ethane, and is in competition with C[BOND]H activation yielding [TCyTAC)2Sm{CH(AlMe3)3}] and methane.

  8. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Zeolite Structures

      Extra-Large-Pore Zeolites: Bridging the Gap between Micro and Mesoporous Structures (pages 3120–3145)

      Jiuxing Jiang, Jihong Yu and Avelino Corma

      Version of Record online: 7 APR 2010 | DOI: 10.1002/anie.200904016

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      Zeolite XXL: Extra-large-pore zeolites (see structure) have been sought for a long time for their potential ability to support the reactions of bulkier molecules. This Review presents the role of synthesis parameters (effects of structure-directing agent, heteroatom, gel concentration, mineralization agents, etc) in producing extra-large-pore zeolites and includes the first mesoporous zeolites and their catalytic applications.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Solid-State Structures

      Al12K8[OC(CH3)3]18: A Wade, Zintl, or Metalloid Cluster, or a Hybrid of All Three? (pages 3146–3150)

      Patrick Henke, Nils Trapp, Christopher E. Anson and Hansgeorg Schnöckel

      Version of Record online: 25 MAR 2010 | DOI: 10.1002/anie.200907096

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      A molecular Zintl phase? Structural investigations and DFT calculations on the spectroscopic and thermodynamic properties of an Al12K8(OtBu)18 compound (see picture: Al blue, K yellow, O green) support the unusual bonding of this Al12 cluster and its role in a unified cluster model.

    2. Template-Directed Synthesis

      Polycatenation under Thermodynamic Control (pages 3151–3156)

      Mark A. Olson, Ali Coskun, Lei Fang, Ashish N. Basuray and J. Fraser Stoddart

      Version of Record online: 29 MAR 2010 | DOI: 10.1002/anie.201000421

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      Thermodynamic cat attacks! Iodide-catalyzed reversible nucleophilic attacks have been exploited to access side-chain polycatenanes under thermodynamic control. Multiple catenations occurring all along the polymer chain are entirely driven to completion by the intra- and intermolecular side-chain π⋅⋅⋅π stacking interactions of contiguous catenanes.

    3. Electron Transfer

      Tuning the Electronic Communication between Redox Centers Bound to Insulating Surfaces (pages 3157–3160)

      Dodzi Zigah, Cyril Herrier, Luc Scheres, Marcel Giesbers, Bruno Fabre, Philippe Hapiot and Han Zuilhof

      Version of Record online: 23 MAR 2010 | DOI: 10.1002/anie.200906924

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      Controlling communication: The electronic communication between ferrocenyl centers bound to insulating silicon surfaces can be efficiently controlled; scanning electrochemical microscopy (SECM) shows that both the surface coverage of the electroactive units and the nature of the redox mediator allow for this control. The lateral charge propagation can be precisely tuned from an extremely slow to a very fast process.

    4. Radiofluorination

      Fast Production of Highly Reactive No-Carrier-Added [18F]Fluoride for the Labeling of Radiopharmaceuticals (pages 3161–3164)

      Christian F. Lemaire, Joël J. Aerts, Samuel Voccia, Lionel C. Libert, Frédéric Mercier, David Goblet, Alain R. Plenevaux and André J. Luxen

      Version of Record online: 25 MAR 2010 | DOI: 10.1002/anie.200906341

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      Doing without water: The 18F labeling of radiopharmaceuticals requires nearly anhydrous solutions of [18F]fluoride. Aqueous K2CO3 is generally used to elute [18F]fluoride from an anion-exchange resin. Replacing aqueous K2CO3 with strong organic bases, such as the phosphazene base P2Et (conjugate acid shown), enabled the recovery of highly reactive [18F]fluoride and avoided the azeotropic evaporation of water, which is very difficult on a microchip device.

    5. Nanostructures

      Understanding Ionic Vacancy Diffusion Growth of Cuprous Sulfide Nanowires (pages 3165–3168)

      Xiaohua Liu, Matthew T. Mayer and Dunwei Wang

      Version of Record online: 23 MAR 2010 | DOI: 10.1002/anie.200906562

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      Designer stubble: The growth of Cu2S nanowires was found to be governed by the diffusion of copper ion vacancies. The resulting nanostructure morphologies depend on the defect density in the copper substrate. Balanced sulfur feeding produced uniform and aligned Cu2S nanowires (see picture) that hold great promise in converting solar energy at high efficiencies.

    6. Hydroperoxides

      Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes (pages 3169–3172)

      Frédérique Battin-Leclerc, Olivier Herbinet, Pierre-Alexandre Glaude, René Fournet, Zhongyue Zhou, Liulin Deng, Huijun Guo, Mingfeng Xie and Fei Qi

      Version of Record online: 1 APR 2010 | DOI: 10.1002/anie.200906850

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      Intermediate detected: The design of internal combustion engines relies on a good understanding of the mechanism of the auto-ignition of hydrocarbons. A key assumption of this mechanism, which was commonly accepted but never proven, has now been experimentally demonstrated: the formation of ketohydroperoxides has been observed under conditions close to those actually observed before the auto-ignition.

    7. Core–Shell Nanoparticles

      PtSn Intermetallic, Core–Shell, and Alloy Nanoparticles as CO-Tolerant Electrocatalysts for H2 Oxidation (pages 3173–3176)

      Zhufang Liu, Greg S. Jackson and Bryan W. Eichhorn

      Version of Record online: 25 MAR 2010 | DOI: 10.1002/anie.200907019

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      More order, more tolerance: PtSn intermetallic and alloy nanoparticles (NPs) were prepared by the co-reduction of [Pt(acac)2] (acac=acetylacetonate) and SnCl4. The intermetallic NPs can convert to PtSn@Pt core–shell NPs after potential cycling in CO-saturated H2SO4 solution. Electrochemical studies demonstrated the core–shell and intermetallic electrocatalysts had substantially higher CO tolerance than PtSn alloy, PtRu alloy, and monometallic Pt.

    8. Nitrated Heterocycles

      Selective Preparation of 3,4,5-Trinitro-1H-Pyrazole: A Stable All-Carbon-Nitrated Arene (pages 3177–3181)

      Grégoire Hervé, Christian Roussel and Hervé Graindorge

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.201000764

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      Lowering the boom: 3,4,5-trinitro-1H-pyrazole (TNP, see picture) has been prepared by the unexpected nitration of 3,5-dinitropyrazole with a super-electrophile generated from 20–30 % sulfuric oleum mixed with nitric acid. The remarkable stability of TNP results from the preservation of the ring geometry and the specific conformation of the nitro group at C4 which confers low acidity on the material.

    9. Organometallic Reagents

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      Structurally Stimulated Deprotonation/Alumination of the TMP Anion (pages 3182–3184)

      Ben Conway, Alan R. Kennedy, Robert E. Mulvey, Stuart D. Robertson and Joaquin García Álvarez

      Version of Record online: 23 MAR 2010 | DOI: 10.1002/anie.201000181

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      Coerced conversion: Long utilized as a strong Brønsted base, the tetramethylpiperidine (TMP) anion is forced to convert to a Brønsted acid in the presence of a potassium–aluminate species. The new compound [(TMEDA)K(μ-TMP*)(μ-iBu)Al(iBu)] was obtained where TMP* represents a CH3- and NH-deprotonated dianionic variant of TMP (see scheme).

    10. Turbo-Grignard Reagents

      Diisopropylamide and TMP Turbo-Grignard Reagents: A Structural Rationale for their Contrasting Reactivities (pages 3185–3188)

      David R. Armstrong, Pablo García-Álvarez, Alan R. Kennedy, Robert E. Mulvey and John A. Parkinson

      Version of Record online: 29 MAR 2010 | DOI: 10.1002/anie.201000539

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      Turbocharged! A neutral dimeric molecule in crystal form, the diisopropylamido turbo-Grignard reagent “(iPr2N)MgCl⋅LiCl” (see structure; blue N, red O, green Mg, yellow Cl, black C) separates into several charged ate species in dynamic exchange with each other in THF solution as determined by a combination of EXSY and DOSY NMR studies.

    11. Self-Hosting Cavitand

      The Ouroborand: A Cavitand with a Coordination-Driven Switching Device (pages 3189–3191)

      Fabien Durola and Julius Rebek Jr.

      Version of Record online: 18 MAR 2010 | DOI: 10.1002/anie.200906753

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      Molecular switch: The ouroborand coordinates an internal side chain in its cavity, just as it were swallowing its own tail. The presence or absence of zinc(II) in solution switches the cavity between open and closed states to external guests (see scheme: deep blue sphere: Zn).

    12. Host–Guest Chemistry

      Photochemical Control of Reversible Encapsulation (pages 3192–3195)

      Henry Dube, Dariush Ajami and Julius Rebek Jr.

      Version of Record online: 22 MAR 2010 | DOI: 10.1002/anie.201000876

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      Remote control: Molecules can be transferred in a chemical system between capsules and bulk solution by using light and heat. The principle is based on the isomerization of azobenzene, the trans isomer of which is encapsulated, but the cis isomer is not (see picture; C gray and brown, Br mauve; O red, N blue, H white). The photochemical control can also be used to switch between different capsular assemblies.

    13. Synthetic Methods

      Three-Component Reaction Using the Bestmann–Ohira Reagent: A Regioselective Synthesis of Phosphonyl Pyrazole Rings (pages 3196–3199)

      Kishor Mohanan, Anthony R. Martin, Loic Toupet, Michael Smietana and Jean-Jacques Vasseur

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.200906781

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      BOR-n to run: A new one-pot multicomponent reaction involving the use of an aldehyde, a cyanoacid derivative, and the Bestmann–Ohira reagent (BOR) has been developed for the synthesis of substituted phosphonyl pyrazoles. This process was also combined with a copper-catalyzed azide–alkyne 1,3-dipolar cycloaddition to generate five new bonds and two heterocyclic rings in a one-pot fashion.

    14. Graphene Defects

      Carbon Spiral Helix: A Nanoarchitecture Derived from Monovacancy Defects in Graphene (pages 3200–3202)

      Xingfa Gao, Lili Liu, Stephan Irle and Shigeru Nagase

      Version of Record online: 23 MAR 2010 | DOI: 10.1002/anie.200907347

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      The planar, magnetic isomer is the most stable form of interior graphene monovacancies, whereas the nonplanar, nonmagnetic spiro isomer is more stable for those closer to the edge of graphene sheets. On thermal annealing, interior monovacancies migrate towards the outermost periphery of graphene flakes. The spiro isomer is a suitable structural building block for the synthesis of carbon spiral helices (see picture).

    15. Solid-State Electroreduction

      Metal-to-Oxide Molar Volume Ratio: The Overlooked Barrier to Solid-State Electroreduction and a “Green” Bypass through Recyclable NH4HCO3 (pages 3203–3206)

      Wei Li, Xianbo Jin, Fulong Huang and George Z. Chen

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.200906833

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      Beating the barrier: The metal-to-oxide molar volume ratio Vm/Vo determines whether electroreduction of a metal oxide forms a porous metal shell that allows reduction to proceed (Vm/Vo≪1), or nonporous one that causes it to cease (Vm/Vo≥1; see picture). In the case of TiO2 (Vm/Vo≈1), this barrier to reduction to Ti can be circumvented by recyclable use of NH4HCO3 as a fugitive porogenic agent.

    16. Targeting DNA⋅RNA Hybrids

      Probing the Molecular Recognition of a DNA⋅RNA Hybrid Duplex (pages 3207–3210)

      Richard T. Wheelhouse, Nichola C. Garbett, Niklaas J. Buurma and Jonathan B. Chaires

      Version of Record online: 29 MAR 2010 | DOI: 10.1002/anie.200907235

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      Curiouser and curiouser! A biarylpyrimidine ligand (see picture: N blue, H cyan, S yellow) shows a marked structure and sequence selectivity for the poly(dA)⋅poly(rU) hybrid duplex. An intercalative binding site was discovered where the ligand occupies a surprising ten base pairs. A strong correlation between hybrid duplex and DNA triplex binding indicates new directions for ligand design.

    17. Genetic Code Expansion

      A Facile System for Genetic Incorporation of Two Different Noncanonical Amino Acids into One Protein in Escherichia coli (pages 3211–3214)

      Wei Wan, Ying Huang, Zhiyong Wang, William K. Russell, Pei-Jing Pai, David H. Russell and Wenshe R. Liu

      Version of Record online: 25 MAR 2010 | DOI: 10.1002/anie.201000465

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      Two's company: Using a wild-type or evolved PylRS-pylTUUA pair to suppress ochre mutation and an evolved MjTyrRS-Mjequation image pair to suppress amber mutation, two different noncanonical amino acids (NAAs) have been concomitantly incorporated into one protein in E. coli with high efficiency (see picture, with NAAs 14; GFP=green-fluorescent protein).

    18. Cycloaddition

      Efficient Construction of Oxa- and Aza-[n.2.1] Skeletons: Lewis Acid Catalyzed Intramolecular [3+2] Cycloaddition of Cyclopropane 1,1-Diesters with Carbonyls and Imines (pages 3215–3218)

      Siyang Xing, Wenyan Pan, Chang Liu, Jun Ren and Zhongwen Wang

      Version of Record online: 25 MAR 2010 | DOI: 10.1002/anie.201000563

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      Building bridges: A Lewis acid promoted intramolecular [3+2] cycloaddition of cyclopropane 1,1-diesters with aldehydes, ketones, and imines (see scheme) has been developed to provide a general and efficient strategy for construction of bridged oxa- and aza-[n.2.1] (n=2,3,4) skeletons. To highlight this method, the core of platensimycin was also constructed.

    19. Si–Si Metathesis

      Gold(I)-Mediated Silicon–Silicon Bond Metathesis at Room Temperature (pages 3219–3223)

      Marion Wilfling and Karl W. Klinkhammer

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.200905950

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      Digging for gold: Treatment of K[Au{Si(SiMe3)3}2] with Me3SiCl at room temperature leads to redox processes and Si[BOND]Si bond metathesis reactions. Numerous very unusual gold complexes are formed, such as the aurate shown.

    20. Heterogeneous Catalysis

      Subsurface-Controlled CO2 Selectivity of PdZn Near-Surface Alloys in H2 Generation by Methanol Steam Reforming (pages 3224–3227)

      Christoph Rameshan, Werner Stadlmayr, Christian Weilach, Simon Penner, Harald Lorenz, Michael Hävecker, Raoul Blume, Tulio Rocha, Detre Teschner, Axel Knop-Gericke, Robert Schlögl, Norbert Memmel, Dmitry Zemlyanov, Günther Rupprechter and Bernhard Klötzer

      Version of Record online: 29 MAR 2010 | DOI: 10.1002/anie.200905815

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      More than skin deep: In spite of their identical 1:1 surface composition, the geometric and electronic structures of a multilayer and monolayer PdZn surface alloy are different, as are their catalytic selectivities. The CO2 selective multilayer alloy features surface ensembles of PdZn exhibiting a “Zn-up/Pd-down” corrugation (see picture). These act as “bifunctional” active sites both for water activation and for the conversion of methanol into CO2. On the monolayer alloy CO and not CO2 is produced.

    21. Low-Valent Gallium

      A Simple Route to Univalent Gallium Salts of Weakly Coordinating Anions (pages 3228–3231)

      John M. Slattery, Alexander Higelin, Thomas Bayer and Ingo Krossing

      Version of Record online: 31 MAR 2010 | DOI: 10.1002/anie.201000156

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      Pyramidal [Ga(PPh3)3]+ (see picture) is the first structurally characterized homoleptic gallium–phosphine complex. The synthesis of this ion was aided by the development of a facile route to gallium(I) salts with weakly coordinating anions (WCAs). These salts are an outstanding source of gallium in the oxidation state +1 for the generation of previously unknown low-valent gallium compounds.

  10. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    11. Preview

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