Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 13

March 26, 2012

Volume 51, Issue 13

Pages 3029–3274

  1. Cover Picture

    1. Top of page
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    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. Flashback
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
    16. Preview
    1. Cover Picture: Na11Hg52: Complexity in a Polar Metal (Angew. Chem. Int. Ed. 13/2012) (page 3029)

      Dr. Constantin Hoch and Prof. Dr. Arndt Simon

      Article first published online: 1 FEB 2012 | DOI: 10.1002/anie.201200551

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      The most mercury-rich sodium amalgam, Na11Hg52, is prepared as single crystals by the combination of electrolytic and thermochemical methods. As C. Hoch and A. Simon show in their Communication on page 3262 ff. this amalgam has a close relationship to the chloralkali process and a surprisingly complex structure for a binary compound. Such mercury-rich amalgams serve as models of polar metals in which a transition from the classical metal–metal bonding towards ionic bonding occurs.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. Flashback
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
    16. Preview
    1. Inside Cover: Ribose Found in the Gas Phase (Angew. Chem. Int. Ed. 13/2012) (page 3030)

      Dr. Emilio J. Cocinero, Prof. Alberto Lesarri, Dr. Patricia Écija, Dr. Francisco J. Basterretxea, Prof. Jens-Uwe Grabow, Dr. José A. Fernández and Prof. Fernando Castaño

      Article first published online: 17 JAN 2012 | DOI: 10.1002/anie.201109101

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      Sugars in space: The rotational signature of ribose, the first C5 sugar to be detected in the gas phase, is reported by E. J. Cocinero, A. Lesarri, and co-workers in their Communication on page 3119 ff. Six conformers were detected by a combination of laser vaporization and microwave spectroscopy. All adopt a pyranoside (pyr) structure, stabilized by cooperative hydrogen-bond networks, rather than the furanose form usually found in biological compounds. This rotational spectrum opens the door to the radio-astronomical detection of the first sugar in space.

  3. Inside Back Cover

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. Flashback
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
    16. Preview
    1. Inside Back Cover: In Vitro and In Vivo Uncaging and Bioluminescence Imaging by Using Photocaged Upconversion Nanoparticles (Angew. Chem. Int. Ed. 13/2012) (page 3275)

      Yanmei Yang, Qing Shao, Renren Deng, Chao Wang, Xue Teng, Kai Cheng, Prof. Zhen Cheng, Prof. Ling Huang, Prof. Zhuang Liu, Prof. Xiaogang Liu and Prof. Bengang Xing

      Article first published online: 16 JAN 2012 | DOI: 10.1002/anie.201109102

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      Bioconjugation of photocaged D-luciferin with upconversion nanoparticles (UCNPs) for uncaging and bioluminescence imaging is reported by X. Liu, B. Xing, and co-workers in their Communication on page 3125 ff. Photon upconversion of near-infrared light by the biocompatible UCNPs causes D-luciferin to be released from the surface of the UCNPs, thus resulting in enhanced bioluminescence signals in vitro and in vivo with deep light penetration and minimum cell damage.

  4. Back Cover

    1. Top of page
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    6. Graphical Abstract
    7. Flashback
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
    16. Preview
    1. Back Cover: Bioinspired Five-Coordinate Iron(III) Complexes for Stabilization of Phenoxyl Radicals (Angew. Chem. Int. Ed. 13/2012) (page 3276)

      Marco M. Allard, Jason A. Sonk, Dr. Mary Jane Heeg, Bruce R. McGarvey, Prof. H. Bernhard Schlegel and Prof. Cláudio N. Verani

      Article first published online: 20 JAN 2012 | DOI: 10.1002/anie.201200098

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      Electrons at the crossroads within oxidation pathways stabilize five-coordinate, phenolate-rich iron(III) radical complexes. In their Communication on page 3178 ff., Verani and co-workers report bioinspired coordination compounds that possess low local symmetry, and show experimentally as well as by computational methods that subtle changes in the ligand and electrolyte lead to distinct sequences in which the ligand-appended phenolates are oxidized into phenoxyl species.

  5. Graphical Abstract

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    7. Flashback
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    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 13/2012 (pages 3033–3044)

      Article first published online: 21 MAR 2012 | DOI: 10.1002/anie.201290022

  6. Flashback

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    11. Book Review
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    13. Essay
    14. Review
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    1. 50 Years Ago... (page 3042)

      Article first published online: 21 MAR 2012 | DOI: 10.1002/anie.201201199

  7. News

    1. Top of page
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    7. Flashback
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    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
    16. Preview
  8. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. Flashback
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
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    1. Ning Jiao (page 3056)

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108680

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      “My favorite piece of research is the next result. The most important thing I learned from my parents is to find other people's merits. …” This and more about Ning Jiao can be found on page 3056.

  9. News

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    11. Book Review
    12. Highlights
    13. Essay
    14. Review
    15. Communications
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  10. Book Review

    1. Top of page
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    13. Essay
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    1. Scent and Chemistry. The Molecular World of Odors. By Günther Ohloff, Wilhelm Pickenhagen and Philip Kraft. (page 3058)

      Ralf Günter Berger

      Article first published online: 7 MAR 2012 | DOI: 10.1002/anie.201201256

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      Verlag Helvetica Chimica Acta, Zurich, 2011. 350 pp., hardcover, € 79.00.—ISBN 978-3906390666

  11. Highlights

    1. Top of page
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    13. Essay
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    15. Communications
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    1. Protein Polymers

      Towards Bioactive Nanovehicles Based on Protein Polymers (pages 3060–3062)

      Dr. Elisabeth Garanger and Prof. Dr. Sébastien Lecommandoux

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201107734

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      Interdisciplinary: The application of protein-engineering techniques to polymer materials can lead to the design and preparation of biocompatible, biodegradable, stimuli-sensitive copolymers bearing biologically responsive peptide motifs (see picture).

    2. Enhanced Solvolysis

      A New Twist on Amide Solvolysis (pages 3063–3065)

      Prof. Jeffrey Aubé

      Article first published online: 22 FEB 2012 | DOI: 10.1002/anie.201108173

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      Planar but destabilized: Amides prepared from hindered amines and carbonyl compounds containing an electron-withdrawing substituent (EWG) have recently been shown to undergo solvolysis at greatly enhanced rates under neutral conditions. The key is increased access to a twisted amide conformation that undergoes a proton switch, ultimately leading to the observed products.

  12. Essay

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    15. Communications
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    1. C[BOND]H Functionalization

      On the Interpretation of Deuterium Kinetic Isotope Effects in C[BOND]H Bond Functionalizations by Transition-Metal Complexes (pages 3066–3072)

      Dr. Eric M. Simmons and Prof. John F. Hartwig

      Article first published online: 5 MAR 2012 | DOI: 10.1002/anie.201107334

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      Rate versus selectivity determining: The measurement of a kinetic isotope effect (KIE) can provide valuable information about the mechanism of a reaction, but care must be taken in the design and interpretation of KIE experiments. Depending on the experiment that is conducted, the observation of a primary KIE resulting from H/D substitution does not necessarily imply that C[BOND]H bond cleavage occurs during the rate-determining step of a reaction. FG=functional group.

  13. Review

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    13. Essay
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    15. Communications
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    1. Synthetic Methods

      Allenes in Catalytic Asymmetric Synthesis and Natural Product Syntheses (pages 3074–3112)

      Dr. Shichao Yu and Prof. Shengming Ma

      Article first published online: 23 JAN 2012 | DOI: 10.1002/anie.201101460

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      Creative and easy syntheses of chiral compounds and natural products are possible by using allenes. These compounds display exceptional physical and chemical properties, and thus offer new possibilities in catalytic asymmetric synthesis and the total synthesis of natural products. The remarkable progress made in these two topics is summarized selectively in this Review.

  14. Communications

    1. Top of page
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    1. Artificial Cells

      Triggered Gene Expression in Fed-Vesicle Microreactors with a Multifunctional Membrane (pages 3114–3118)

      Zohreh Nourian, Wouter Roelofsen and Dr. Christophe Danelon

      Article first published online: 13 JAN 2012 | DOI: 10.1002/anie.201107123

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      A minimal gene expression machinery has been encapsulated within large lipid vesicles that are immobilized on a microscope coverslip for fluorescence imaging (see picture). The engineered vesicle membrane acts as an exchange platform that enables the uptake of all necessary nutrients and tRNAs supplied in the outside environment, which initiates the internal synthesis of green fluorescent proteins (GFP) from a DNA template. Red: membrane dye, green: synthesized GFP.

    2. Rotational Spectroscopy

      Ribose Found in the Gas Phase (pages 3119–3124)

      Dr. Emilio J. Cocinero, Prof. Alberto Lesarri, Dr. Patricia Écija, Dr. Francisco J. Basterretxea, Prof. Jens-Uwe Grabow, Dr. José A. Fernández and Prof. Fernando Castaño

      Article first published online: 28 DEC 2011 | DOI: 10.1002/anie.201107973

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      Sweet truth: The search for sugars in interstellar space is hampered by a lack of spectroscopic information. D-Ribose is now the first C5 sugar observed in the gas phase using microwave spectroscopy. The rotational spectrum revealed six conformations of free ribose, adopting preferentially β-pyranose rings and higher-energy α-pyranose forms. No evidence of α-/β-furanoses or linear forms was found, unlike biological systems, where β-furanoses are found in RNA.

    3. Bioimaging

      In Vitro and In Vivo Uncaging and Bioluminescence Imaging by Using Photocaged Upconversion Nanoparticles (pages 3125–3129)

      Yanmei Yang, Qing Shao, Renren Deng, Chao Wang, Xue Teng, Kai Cheng, Prof. Zhen Cheng, Prof. Ling Huang, Prof. Zhuang Liu, Prof. Xiaogang Liu and Prof. Bengang Xing

      Article first published online: 12 JAN 2012 | DOI: 10.1002/anie.201107919

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      Trading up: A bioimaging system that is based on caged D-luciferin/upconversion nanoparticle conjugate has been developed. The nanoparticles upconvert near-infrared light into UV light, which triggers the photorelease of D-luciferin (see scheme) and leads to enhanced fluorescence and bioluminescence signals in vitro and in vivo. The use of near-infrared light enables deep penetration into tissue in vivo with minimum cellular damage.

    4. Peptide Self-Assembly

      Cooperative Hierarchical Self-Assembly of Peptide Dendrimers and Linear Polypeptides into Nanoarchitectures Mimicking Viral Capsids (pages 3130–3133)

      Xianghui Xu, Hui Yuan, Jing Chang, Prof. Bin He and Prof. Zhongwei Gu

      Article first published online: 8 FEB 2012 | DOI: 10.1002/anie.201106080

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      Peptidesomes are nanoparticles that are built by a two-step self-assembly of globular peptide dendrimers with lysine endgroups (red spheres in picture) and poly(L-leucine) carrying one glutamic acid residue (blue lines with red dot). These viral-capsid-mimicking nanoarchitectures exhibit high gene transfection efficacy and thus are promising nonviral vectors for biomedical applications.

    5. Membrane Proteins

      Quantification of Membrane Protein Inhibition by Optical Ion Flux in a Droplet Interface Bilayer Array (pages 3134–3138)

      Dr. Oliver K. Castell, James Berridge and Dr. Mark I. Wallace

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201107343

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      Optical platforms for assaying membrane protein function offer a promising route to scalable high-throughput screening (see picture). For the first time quantitative measurements of membrane protein inhibition are reported in an optically addressable lipid bilayer array. Wide-field total internal reflection fluorescence (TIRF) imaging of Ca2+ flux enables the quantification of α-hemolysin inhibition by γ-cyclodextrin.

    6. Surface Chemistry

      Unique Electrochemical Adsorption Properties of Pt-Skin Surfaces (pages 3139–3142)

      Dr. Dennis F. van der Vliet, Dr. Chao Wang, Dongguo Li, Arvydas P. Paulikas, Dr. Jeffrey Greeley, Dr. Rees B. Rankin, Dr. Dusan Strmcnik, Dr. Dusan Tripkovic, Dr. Nenad M. Markovic and Dr. Vojislav R. Stamenkovic

      Article first published online: 20 FEB 2012 | DOI: 10.1002/anie.201107668

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      Thin skin: Pt-alloy catalysts, such as annealed Pt3Ni(111) (see STM image; color changes mark a single atomic step), with a surface layer of pure platinum, termed a Pt-skin surface, have very different electrochemical adsorption properties to monometallic Pt. The adsorption of hydrogen is largely suppressed (see CV, (—) Pt3Ni(111)-skin versus (••••) Pt(111)), making it hard to determine the electrochemically active surface area of catalysts with Pt-skin surfaces.

    7. Bioimaging

      Click-Mediated Labeling of Bacterial Membranes through Metabolic Modification of the Lipopolysaccharide Inner Core (pages 3143–3146)

      Dr. Audrey Dumont, Dr. Annie Malleron, Monzer Awwad, Dr. Sam Dukan and Dr. Boris Vauzeilles

      Article first published online: 9 FEB 2012 | DOI: 10.1002/anie.201108127

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      Clicking bugs: Metabolically active Gram-negative bacteria can specifically incorporate an azide-modified analogue of 3-deoxy-D-manno-octulosonic acid (1; see scheme) into the lipopolysaccharides on their membranes. This process adds a bioorthogonal chemical reporter onto the cell surface and allows the rapid fluorescent labeling of viable cells by click chemistry.

    8. P-Doped Photocatalysts

      Phosphate Doping into Monoclinic BiVO4 for Enhanced Photoelectrochemical Water Oxidation Activity (pages 3147–3151)

      Won Jun Jo, Dr. Ji-Wook Jang, Dr. Ki-jeong Kong, Hyun Joon Kang, Jae Young Kim, Dr. Hwichan Jun, Dr. K. P. S. Parmar and Prof. Jae Sung Lee

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108276

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      A monoclinic BiVO4 lattice was doped with phosphate to enhance photoelectrochemical and photocatalytic water oxidation activity under visible light by a factor of about 30 compared with pristine BiVO4. Electrochemical impedance spectroscopy measurements and density functional calculations revealed that much improved charge transfer characteristics of BiVO4 are mainly responsible for the greatly enhanced photoelectrochemical activity.

    9. Hydrogen Catalysis

      Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic (pages 3152–3155)

      Dr. Stuart E. Smith, Dr. Jenny Y. Yang, Dr. Daniel L. DuBois and Dr. R. Morris Bullock

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201108461

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      An efficient ligand combination: A new bis(diphosphine) nickel(II) complex (see picture) is described. A ΔG° value of 0.84 kcal mol−1 for hydrogen addition for this complex was calculated from the experimentally determined equilibrium constant. This complex displayed reversible electrocatalytic activity for hydrogen production and oxidation at low overpotentials, which are characteristic for hydrogenase enzymes.

    10. High-Pressure Chemistry

      Hypervalent Octahedral SiH62− Species from High-Pressure Synthesis (pages 3156–3160)

      Kati Puhakainen, Daryn Benson, Dr. Johanna Nylén, Sumit Konar, Dr. Emil Stoyanov, Dr. Kurt Leinenweber and Prof. Ulrich Häussermann

      Article first published online: 9 FEB 2012 | DOI: 10.1002/anie.201108713

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      High-pressure conditions afford unique all-hydrido hypervalent complexes [SiH6]2− in the crystalline hydridosilicates A2SiH6 (A=K, Rb). Compared to normal-valent silanes the Si[BOND]H bond appears considerably enlarged, by about 0.15 Å. Accordingly, Si[BOND]H stretching frequencies are drastically reduced, by about 400–500 cm−1, thus reflecting the weakness of a hypervalent Si[BOND]H bond.

    11. Self-Assembly

      Self-Assembly of M24L48 Polyhedra Based on Empirical Prediction (pages 3161–3163)

      Dr. Jens Bunzen, Junji Iwasa, Pia Bonakdarzadeh, Eri Numata, Prof. Kari Rissanen, Dr. Sota Sato and Prof. Makoto Fujita

      Article first published online: 10 FEB 2012 | DOI: 10.1002/anie.201108731

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      Critical structural switch: A small initial difference in the angle within bidentate ligands (see scheme) is amplified into an incommensurable difference in the resultant structures (M12L24 or M24L48). This molecular-level emergent behavior was predicted from the empirical threshold of the ligand bend angle, determined by a ligand mixing experiment, for the critical M12L24/M24L48 switchover.

    12. Asymmetric Catalysis

      Asymmetric Copper-Catalyzed Addition of Grignard Reagents to Aryl Alkyl Ketones (pages 3164–3167)

      Ashoka V. R. Madduri, Dr. Syuzanna R. Harutyunyan and Prof. Adriaan J. Minnaard

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201109040

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      Chiral tertiary alcohols: A copper(I) catalyst with a chiral ferrocenyl diphosphine ligand facilitates the additive-free 1,2-addition of readily available Grignard reagents to aromatic ketones, thus providing access to chiral tertiary alcohols with excellent yields and enantioselectivities.

    13. Highly Enantioselective Synthesis of 3-Substituted Furanones by Palladium-Catalyzed Kinetic Resolution of Unsymmetrical Allyl Acetates (pages 3168–3173)

      Bin Mao, Dr. Yining Ji, Dr. Martín Fañanás-Mastral, Dr. Giuseppe Caroli, Auke Meetsma and Prof. Dr. Ben L. Feringa

      Article first published online: 16 FEB 2012 | DOI: 10.1002/anie.201109075

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      Resolving the issue: A near-perfect Pd-catalyzed kinetic resolution of 1,3-disubstituted unsymmetrical allylic acetates uses silyl enol ethers as nucleophiles to access the important 3-substituted-furanone scaffold (see scheme; DACH=diaminocyclohexyl, dba=dibenzylideneacetone). The reaction proceeds under mild conditions and provides the desired products with excellent chemo-, regio-, and enantioselectivity.

    14. Porphyrinoids

      A meso-Spiro[Cyclopentadiene-Isoporphyrin] from a Phenylethynyl Porphyrin Platinum(II) Pincer Complex (pages 3174–3177)

      Shoma Anabuki, Prof. Dr. Hiroshi Shinokubo, Dr. Naoki Aratani and Prof. Dr. Atsuhiro Osuka

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201109091

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      A good catch: The oxidation of a phenylethynyl PtII pincer complex with iodine led to formal reductive elimination but without the liberation of PtII, which was caught by the 2-pyridyl substituents on the NiII porphyrin. The unique reactivity of the PtII pincer complex led to the formation of a meso-spiro[cyclopentadiene-isoporphyrin].

    15. Coordination Chemistry

      Bioinspired Five-Coordinate Iron(III) Complexes for Stabilization of Phenoxyl Radicals (pages 3178–3182)

      Marco M. Allard, Jason A. Sonk, Dr. Mary Jane Heeg, Bruce R. McGarvey, Prof. H. Bernhard Schlegel and Prof. Cláudio N. Verani

      Article first published online: 12 DEC 2011 | DOI: 10.1002/anie.201103233

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      Give me five! Two five-coordinate complexes of iron with geometries that are based on those found in redox-versatile enzymes have been synthesized. The phenolate-rich, pentadentate N2O3 phenylene–diamine/triphenolate ligands confer a low local symmetry on the complex so that only subtle modifications in the structure of the ligands are sufficient to completely change the sequence in which the metal and the ligands are oxidized (see scheme).

    16. Photocatalysis

      Co-Monomer Control of Carbon Nitride Semiconductors to Optimize Hydrogen Evolution with Visible Light (pages 3183–3187)

      Jinshui Zhang, Guigang Zhang, Xiufang Chen, Dr. Sen Lin, Lennart Möhlmann, Dr. Grzegorz Dołęga, Dr. Grzegorz Lipner, Prof. Markus Antonietti, Prof. Siegfried Blechert and Prof. Xinchen Wang

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201106656

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      Bottom–up synthesis of graphitic carbon nitride semiconductor catalysts for the photocatalytic evolution of hydrogen by visible light is achieved through the polymerization of dicyandiamide with organic monomers bearing cyano groups, amino groups, or both. This strategy allows ample opportunity to adjust the physical and chemical properties of the resulting heterogeneous carbon-nitride-based organocatalysts.

    17. The Surface-Structure Sensitivity of Dioxygen Activation in the Anatase-Photocatalyzed Oxidation Reaction (pages 3188–3192)

      Dr. Yubao Zhao, Prof. Wanhong Ma, Dr. Yue Li, Hongwei Ji, Prof. Chuncheng Chen, Prof. Huaiyong Zhu and Prof. Jincai Zhao

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201107149

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      The reaction pathways by which oxygen is incorporated into the substrate in the photocatalytic oxidation of terephthalic acid (TPTA) are vastly different on {001} and {101} facets of an anatase single crystal. This was established by controlling the percentage of {101} and {001} facets, isotopically tracing the origins of the hydroxy group, and studying dioxygen consumption and variance in the concentration of hydroxylation intermediate.

    18. π-Conjugation Control

      Trinitroxide-Trioxytriphenylamine: Spin-State Conversion from Triradical Doublet to Diradical Cation Triplet by Oxidative Modulation of a π-Conjugated System (pages 3193–3197)

      Dr. Shuichi Suzuki, Atsuki Nagata, Dr. Masato Kuratsu, Prof. Dr. Masatoshi Kozaki, Dr. Rika Tanaka, Prof. Dr. Daisuke Shiomi, Dr. Kenji Sugisaki, Dr. Kazuo Toyota, Prof. Dr. Kazunobu Sato, Prof. Dr. Takeji Takui and Prof. Dr. Keiji Okada

      Article first published online: 16 FEB 2012 | DOI: 10.1002/anie.201107265

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      Spin-state conversion: Oxidation of trinitroxide-trioxytriphenylamine introduces extended π conjugation, resulting in a ground-state spin conversion from the antiferromagnetic coupling in the neutral spin-doublet state to the ferromagnetic coupling in the cation spin-triplet state. The reversible conversion between the two states was confirmed by a change in the UV/Vis absorption under electrochemical oxidative/reductive conditions.

    19. Diazo Compounds

      Indium-Catalyzed Cycloisomerizations of Cyclopropene-3,3-Dicarbonyl Compounds: Efficient Access to Benzo-Fused Heteroaromatics and Heterobiaryls (pages 3198–3202)

      Lien H. Phun, Joel Aponte-Guzman and Prof. Stefan France

      Article first published online: 16 FEB 2012 | DOI: 10.1002/anie.201107717

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      Rapid access: The title reaction generates highly functionalized benzo-annulated heterocycles and heterobiaryls. This method is amenable to a diverse array of heteroaromatics, thus allowing rapid access to benzothiophenes, benzofurans, indoles, indolizines, and pyrido[1,2-a]indoles (see scheme; Tf=trifluoromethanesulfonyl).

    20. Single-Molecule Switches

      Observation of Electrochemically Controlled Quantum Interference in a Single Anthraquinone-Based Norbornylogous Bridge Molecule (pages 3203–3206)

      Dr. Nadim Darwish, Dr. Ismael Díez-Pérez, Dr. Paulo Da Silva, Prof. Dr. Nongjian Tao, Prof. Dr. J. Justin Gooding and Prof. Dr. Michael N. Paddon-Row

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201107765

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      A single-molecular switch based on the anthraquinone/hydroanthraquinone redox reaction is reported (see picture). A single norbornyl anthraquinone unit can be switched between a low-conducting and a high-conducting form using electrochemical gating. The potential range, upon which the conductance enhancement is observed, can be varied using different pH values of the electrolyte.

    21. Inclusion Complexes

      Selective Guest Exchange in Encapsulation Complexes Using Light of Different Wavelenghts (pages 3207–3210)

      Dr. Henry Dube and Prof. Julius Rebek Jr.

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201108074

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      A matter of light: Selective control over the assembly of two distinct encapsulation complexes in solution is achieved by using light of two wavelengths and heat. Guest exchange can be triggered in a sequential or parallel fashion, depending on the wavelength applied, and three combinations of encapsulation complexes (see scheme) are accessible. Photoisomerization of azobenzene (red capsule) and hemithioindigo guests (yellow capsule) are used as triggers.

    22. Nanostructures

      Synthesis of Hollow CdxZn1−xSe Nanoframes through the Selective Cation Exchange of Inorganic–Organic Hybrid ZnSe–Amine Nanoflakes with Cadmium Ions (pages 3211–3215)

      Xuan Wu, Yifu Yu, Yang Liu, You Xu, Cuibo Liu and Prof. Dr. Bin Zhang

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201108098

      Thumbnail image of graphical abstract

      Tiny frames: The selective cation-exchange of unpurified ZnSe–diethylenetriamine (DETA) hybrid nanosheets with cadmium ions, followed by the dissolution of DETA and subsequent Ostwald ripening, leads to hollow CdxZn1−xSe nanoframes with tunable compositions (see scheme). These nanoframes are highly active in the photocatalytic hydrogen evolution from water-splitting.

    23. Phosphoproteomics

      Overcoming the Instability of Gaseous Peptide Phosphate Ester Groups by Dimetal Protection (pages 3216–3219)

      Simon Svane, Fedor Kryuchkov, Dr. Anders Lennartson, Prof. Christine J. McKenzie and Prof. Frank Kjeldsen

      Article first published online: 20 FEB 2012 | DOI: 10.1002/anie.201108481

      Thumbnail image of graphical abstract

      Complex protection: Fragmentation of phosphorylated peptide ions by collision-activated dissociation (CAD) is possible without facile detachment of the phosphate ester group when it is protected by a digallium complex (see scheme). The application of this dimetal phosphate ester stabilization (DIMPES) approach is believed to hold enormous potential for application in phosphoproteomics.

    24. Cascade Cyclization

      Benzofurans from Benzophenones and Dimethylacetamide: Copper-Promoted Cascade Formation of Furan O1[BOND]C2 and C2[BOND]C3 Bonds Under Oxidative Conditions (pages 3220–3224)

      María J. Moure, Dr. Raul SanMartin and Prof. Esther Dominguez

      Article first published online: 9 FEB 2012 | DOI: 10.1002/anie.201108513

      Thumbnail image of graphical abstract

      DMA donates: Copper(II) acetate and 8-hydroxyquinoline promote the formation of a benzofuran core through a cascade of copper-catalyzed processes wherein the key carbon atom comes from the dimethylacetamide (DMA) solvent. Strong evidence for the participation of a Wacker cyclization catalyzed solely by copper is provided, not only in the title reaction from benzophenones but also from 2-hydroxy-α-arylstyrene derivatives.

    25. Homogeneous Catalysis

      Platinum-Catalyzed Hydrosilylations of Internal Alkynes: Harnessing Substituent Effects to Achieve High Regioselectivity (pages 3225–3230)

      Douglas A. Rooke and Prof. Eric M. Ferreira

      Article first published online: 8 FEB 2012 | DOI: 10.1002/anie.201108714

      Thumbnail image of graphical abstract

      Rule of thumb: The high yielding title reaction is described with a focus on understanding the factors that govern the regioselectivity of the process (see scheme). Electronic, steric, and functional group properties all influence the selectivity, an understanding of which allows the selective formation of trisubstituted vinylsilanes, which are synthetically useful compounds for accessing stereodefined alkenes.

    26. Synthetic Methods

      Cross Coupling of Acyl and Aminyl Radicals: Direct Synthesis of Amides Catalyzed by Bu4NI with TBHP as an Oxidant (pages 3231–3235)

      Zhaojun Liu, Jie Zhang, Shulin Chen, Erbo Shi, Yuan Xu and Prof. Dr. Xiaobing Wan

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201108763

      Thumbnail image of graphical abstract

      A radical solution: A Bu4NI/tert-butyl hydroperoxide (TBHP) catalyzed synthesis of amides through a cross-coupling reaction between acyl and aminyl radicals is described. This method involves the combination of aldehyde C[BOND]H bond functionalization and decarbonylation of N,N-disubstituted formamides (see scheme). The cross-coupling is metal-free, has a wide substrate scope, operational simplicity, and gives high yields on scale-up.

    27. Asymmetric Catalysis

      Lewis Base Catalyzed Enantioselective Additions of an N-Silyl Vinylketene Imine (pages 3236–3239)

      Prof. Scott E. Denmark and Dr. Tyler W. Wilson

      Article first published online: 20 FEB 2012 | DOI: 10.1002/anie.201108795

      Thumbnail image of graphical abstract

      Outside the limits: In the title reaction the nucleophile 1 represents a synthetic equivalent of nucleophilic allylic nitriles and addresses some of the current limitations associated with reactions of allylic nitrile anions. Unsaturated nitriles containing a trisubstituted double bond are obtained in high yield, with excellent site selectivity and good to excellent stereoselectivity (see scheme; LDA=lithium diisopropylamide).

    28. Carbene Chemistry

      Anionic N-Heterocyclic Carbenes That Contain a Weakly Coordinating Borate Moiety (pages 3240–3244)

      Dipl.-Chem. Sabrina Kronig, M. Sc. Eileen Theuergarten, Dr. Constantin G. Daniliuc, Prof. Dr. Peter G. Jones and Prof. Dr. Matthias Tamm

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201108813

      Thumbnail image of graphical abstract

      Piggyback ride: Anionic N-heterocyclic carbenes are presented that bear their negative charge in the form of a weakly coordinating anionic borate moiety in the backbone. This class of carbene can be used in silver-free routes for the preparation of neutral, single-source gold(I) catalysts, the performance of which is comparable with that of other cationic gold(I) catalysts in enyne rearrangements.

    29. Microreactors

      Lithiation of 1,2-Dichloroethene in Flow Microreactors: Versatile Synthesis of Alkenes and Alkynes by Precise Residence-Time Control (pages 3245–3248)

      Dr. Aiichiro Nagaki, Chika Matsuo, Songhee Kim, Dr. Kodai Saito, Atsuo Miyazaki and Prof. Jun-ichi Yoshida

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201108932

      Thumbnail image of graphical abstract

      It′s all about the timing: Precise control of the residence time (tRx; see picture) of reactive intermediates in flow microreactors enables the reaction pathway of lithiated 1,2-dichloroethene to be switched to produce either alkenes or alkynes. This method also allows versatile syntheses of asymmetric disubstituted dichloroalkenes and alkynes.

    30. Renewable Resources

      Tungsten Trioxide Promoted Selective Conversion of Cellulose into Propylene Glycol and Ethylene Glycol on a Ruthenium Catalyst (pages 3249–3253)

      Yue Liu, Chen Luo and Prof. Dr. Haichao Liu

      Article first published online: 24 FEB 2012 | DOI: 10.1002/anie.201200351

      Thumbnail image of graphical abstract

      Chopped up: The success of the title reaction strongly depends on the domain size of the WO3 crystallites, and the type of support. Structurally stable WO3 plays a bifunctional role in the promotion of the hydrolysis of cellulose into sugar intermediates, and more significantly in the selective cleavage of the C[BOND]C bonds in these sugars.

    31. Nanoparticle Colloids

      Utilizing the Krafft Phenomenon to Generate Ideal Micelle-Free Surfactant-Stabilized Nanoparticle Suspensions (pages 3254–3257)

      Sarah Dölle, Bob-Dan Lechner, Ji Hyun Park, Stefan Schymura, Prof. Jan P. F. Lagerwall and Prof. Giusy Scalia

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201106793

      Thumbnail image of graphical abstract

      Cool tubes: Micelle formation is inhibited at temperatures below the Krafft temperature TK, therefore the dispersion of carbon nanotubes (CNTs) below TK results in better exfoliation, higher particle loading, and a dramatically reduced final amount of surfactant (see AFM images). The concept is not restricted to CNTs but is also readily applicable to other nanoparticle types.

    32. Hybrid Materials

      A Modular Approach for the Synthesis of Nanostructured Hybrid Materials with Tailored Properties: The Simultaneous Twin Polymerization (pages 3258–3261)

      Tina Löschner, Alexander Mehner, Dr. Silke Grund, Dr. Andreas Seifert, Dr. Andreas Pohlers, Dr. Arno Lange, Dr. Gerhard Cox, Dr. Hans-Joachim Hähnle and Prof. Dr. Stefan Spange

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108011

      Thumbnail image of graphical abstract

      A third twin: Homopolymers are formed by the copolymerization of two twin monomers. Using the new method of simultaneous twin polymerization, complex hybrid materials can be synthesized in a targeted manner (see scheme), in which, depending upon the combination of twin monomers used, nanostructured hybrid materials with different compositions and properties can be obtained.

    33. Sodium Mercury Amalgams

      Na11Hg52: Complexity in a Polar Metal (pages 3262–3265)

      Dr. Constantin Hoch and Prof. Dr. Arndt Simon

      Article first published online: 10 JAN 2012 | DOI: 10.1002/anie.201108064

      Thumbnail image of graphical abstract

      The mercury puzzle: Using the new technique of electrocrystallization the sodium mercury alloy Na11Hg52 could be obtained in a phase pure form. This amalgam is a key component in the industrially important chloralkali process. The combination of different bonding situations in this phase results in it having the typical properties of a “bad” metal.

    34. Hydrogen-Atom Transfer

      H2O Activation for Hydrogen-Atom Transfer: Correct Structures and Revised Mechanisms (pages 3266–3270)

      Prof. Dr. Andreas Gansäuer, Maike Behlendorf, Asli Cangönül, Christian Kube, Dr. Juan M. Cuerva, Prof. Dr. Joachim Friedrich and Dr. Maurice van Gastel

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201107556

      Thumbnail image of graphical abstract

      In contradiction to what has been postulated before, the formation of cationic hydrated TiIII complexes is crucial for the activation of H2O towards hydrogen-atom transfer (HAT). The relevant intermediates have been characterized by modern EPR methods (see spectrum) and cyclic voltammetry. The structural assignments were verified by a comprehensive computational study. The calculated bond dissociation energies are in agreement with a previous kinetic investigation.

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      Article first published online: 21 MAR 2012 | DOI: 10.1002/anie.201290023

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