Chemistry - A European Journal

Cover image for Vol. 19 Issue 23

June 3, 2013

Volume 19, Issue 23

Pages 7253–7636

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: How Is a Metabolic Intermediate Formed in the Mechanism-Based Inactivation of Cytochrome P450 by Using 1,1-Dimethylhydrazine: Hydrogen Abstraction or Nitrogen Oxidation? (Chem. Eur. J. 23/2013) (page 7253)

      Dr. Hajime Hirao, Pratanphorn Chuanprasit, Ying Yi Cheong and Dr. Xiaoqing Wang

      Version of Record online: 24 MAY 2013 | DOI: 10.1002/chem.201390081

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      Mechanism-based inactivation (MBI) of cytochrome P450 (P450) enzymes in the human liver can impede the process of drug metabolism, that is, an essential step for administered drugs. As MBI involves bond-forming or bond-breaking chemical reactions, its understanding requires the use of quantum mechanical methods, and the knowledge thus obtained could usefully be exploited for the accurate prediction of P450 inhibitions. The mechanism of P450 MBI by a hydrazine compound is described in the Full Paper by H. Hirao and co-workers on page 7361 ff.

    2. You have free access to this content
      Back Cover: A Pyridyl-Monoannulated Naphthalene Diimide Motif Self-Assembles into Tuneable Nanostructures by Means of Solvophobic Control (Chem. Eur. J. 23/2013) (page 7640)

      Dr. Sheshanath V. Bhosale, Dr. Mukund Adsul, Ganesh V. Shitre, Sharad R. Bobe, Sidhanath V. Bhosale and Dr. Steven H. Privér

      Version of Record online: 24 MAY 2013 | DOI: 10.1002/chem.201390084

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      Solvophobic-controlled self-assembly of the core-substituted naphthalene diimide bearing pyridyl motifs leads to the formation of a variety of nanostructures (flakes, ropes, tubular, and spherical morphology, see pictures) with pH manipulation. The detection of HCl can be monitored by UV/Vis and fluorescence spectroscopy, as well as the naked eye, with a change in color (blue to red). The cycle is fully reversed by the addition of triethylamine. For more details, see the Communication by S. V. Bhosale et al. on page 7310 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
  4. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
    1. Asymmetric Catalysis

      Enantioselective Synthesis of Alcohols and Amines by Iridium-Catalyzed Hydrogenation, Transfer Hydrogenation, and Related Processes (pages 7274–7302)

      Dr. Agnieszka Bartoszewicz, Dr. Nanna Ahlsten and Prof. Dr. Belén Martín-Matute

      Version of Record online: 19 APR 2013 | DOI: 10.1002/chem.201202836

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      Chemical building blocks: Enantiopure alcohols and amines are very important building blocks used in the pharmaceutical, flavors, and fragrances industries. In this review, the preparation of these compounds by using iridium catalysis is discussed. The methods presented include the reduction of ketones or amines by using hydrogen (hydrogenations), isopropanol, formic acid, or formate (transfer hydrogenations; see scheme).

  5. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
    1. Asymmetric Synthesis

      Catalytic Enantioselective Allylation of Ketimines by Using Palladium Pincer Complexes with Chiral Bis(imidazoline)s (pages 7304–7309)

      Prof. Shuichi Nakamura, Kengo Hyodo, Masayuki Nakamura, Dr. Daisuke Nakane and Prof. Hideki Masuda

      Version of Record online: 30 APR 2013 | DOI: 10.1002/chem.201300685

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      Get selective! Enantioselective allylation of ketimines derived from isatins by using chiral 1,3-bis(imidazolin-2-yl)benzene (Phebim)–PdII complexes afforded products with good enantioselectivity (see scheme). The reaction was applied to a wide variety of ketimines. The obtained product can be converted to homoallylic amines and a spirocyclic amine without the loss of enantiopurity.

    2. pH Sensors

      A Pyridyl-Monoannulated Naphthalene Diimide Motif Self-Assembles into Tuneable Nanostructures by Means of Solvophobic Control (pages 7310–7313)

      Dr. Sheshanath V. Bhosale, Dr. Mukund Adsul, Ganesh V. Shitre, Sharad R. Bobe, Sidhanath V. Bhosale and Dr. Steven H. Privér

      Version of Record online: 29 APR 2013 | DOI: 10.1002/chem.201300120

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      The supramolecular self-assembly of the core-substituted naphthalene diimide bearing pyridyl motifs leads to the formation of a variety of nanostructures with pH and solvent control. The detection of HCl can be monitored by UV/Vis and fluorescence spectroscopy, as well as the naked eye, with a change in colour (blue to red, see figure). The cycle is fully reversed by the addition of triethylamine (TEA).

    3. Porphyrinoids

      Synthesis of a [26]Hexaphyrin Bis-PdII Complex with a Characteristic Aromatic Circuit (pages 7314–7318)

      Tomoki Yoneda and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 26 APR 2013 | DOI: 10.1002/chem.201301030

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      Not one, but two: Metalation of a mono-PdII hexaphyrin (1) with [Pd(OCOCF3)2] gave a bis-PdII complex (2), which possesses a characteristic 26 π-aromatic circuit with two outer amino-pyrroles within a rectangular molecular framework. Complex 2 was readily deprotonated to afford a dianion, which was regioselectively methylated to give a methyl derivative. A similar methylation reaction of 1 produced a skeletally rearranged product that contained an N-confused pyrrole.

    4. Organocatalysis

      Organocatalytic Michael Addition of Malonates to Isatylidene-3-acetaldehydes: Application to the Total Synthesis of (−)-Debromoflustramine E (pages 7319–7323)

      Renrong Liu and Prof. Dr. Junliang Zhang

      Version of Record online: 23 APR 2013 | DOI: 10.1002/chem.201300977

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      Flustering oxindoles: An enantioselective synthesis of 3,3′-disubstituted oxindoles by conjugate addition of malonates to isatylidene-3-acetaldehydes in high yield and enantioselectivity is developed (see scheme). The synthetic utility of this reaction is demonstrated by the synthesis of three oxindole core structures and the asymmetric total synthesis of debromoflustramine E.

    5. Aromaticity

      Tetrathiafulvalene-Annulated Subphthalocyanines (pages 7324–7327)

      Dr. Soji Shimizu, Yoko Yamazaki and Prof. Nagao Kobayashi

      Version of Record online: 23 APR 2013 | DOI: 10.1002/chem.201300709

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      Peripheral expansion: A series of peripherally tetrathiafulvalene (TTF)-annulated subphthalocyanines was synthesized (see scheme). These compounds exhibited unique perturbed optical properties, such as a comparatively broad Q band absorption and gradual quenching of fluorescence upon increasing the number of TTF units, while electrochemical measurements revealed TTF-centered oxidation processes.

    6. Synthetic Methods

      Ruthenium-Catalyzed Direct C[BOND]H Amidation of Arenes Including Weakly Coordinating Aromatic Ketones (pages 7328–7333)

      Jiyu Kim, Jinwoo Kim and Prof. Dr. Sukbok Chang

      Version of Record online: 24 APR 2013 | DOI: 10.1002/chem.201301025

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      C[BOND]H activation: The ruthenium-catalyzed direct sp2 C[BOND]H amidation of arenes by using sulfonyl azides as the amino source is presented (see scheme). A wide range of substrates were readily amidated including arenes bearing weakly coordinating groups. Synthetic utility of the thus obtained products was demonstrated in the preparation of biologically active heterocycles.

    7. Coupling Reactions

      Synthesis of Arylacetates from Benzylic Alcohols and Oxalate Esters through Decarboxylative Coupling (pages 7334–7337)

      Matthias F. Grünberg and Prof. Dr. Lukas J. Gooßen

      Version of Record online: 26 APR 2013 | DOI: 10.1002/chem.201301033

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      Follow that dream: By combining a reversible transesterification between benzylic alcohols and dialkyl oxalates with catalytic decarboxylation of the resulting esters, a regiospecific C[BOND]C-bond-forming reaction to give α-arylacetates was achieved. In the overall process, CO2 and a volatile alcohol are the only byproducts. Various α-arylacetates were thus synthesized in high yields from easily accessible starting materials in the presence of catalytic amounts of Pd(OAc)2, dppp, and DABCO (see scheme).

    8. Borate Materials

      Na11B21O36X2 (X=Cl, Br): Halogen Sodium Borates with a New Graphene-Like Borate Double Layer (pages 7338–7341)

      Dr. Xiaoyu Dong, Hongping Wu, Yunjing Shi, Hongwei Yu, Prof. Dr. Zhihua Yang, Bingbing Zhang, Dr. Zhaohui Chen, Dr. Yun Yang, Zhenjun Huang, Prof. Dr. Shilie Pan and Prof. Dr. Zhongxiang Zhou

      Version of Record online: 29 APR 2013 | DOI: 10.1002/chem.201300902

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      Borate not graphene: The [B6O12]6− single borate layer is a graphene-like layer (see figure). The weak Na+[BOND]Br(Cl) ionic connection between the layers leads to the layer cleavage, and difficulty of the block crystal growth.

    9. pH Sensors

      Boron–Phenylpyrrin Dyes: Facile Synthesis, Structure, and pH-Sensitive Properties (pages 7342–7347)

      Prof. Yuting Chen, Dongdong Qi, Luyang Zhao, Wei Cao, Chunhua Huang and Prof. Jianzhuang Jiang

      Version of Record online: 30 APR 2013 | DOI: 10.1002/chem.201203345

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      Boron–phenylpyrrin dyes: In the presence of BF3⋅OEt2, 4-(diethylamino)salicylaldehyde reacts with substituted pyrroles to give boron–phenylpyrrin dyes, which contain a central boron-containing seven-membered ring. Upon protonation in acidic solution, the complexes, with a large Stokes shift, exhibit a color change and a unique red shift in both the electronic absorption and fluorescence emission spectra (see picture), thus rendering them new analogues of boron–dipyrrin dyes that can be used as pH sensors.

  6. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
    1. Nanomaterials

      Hydrolysis of Tetravalent Cerium for a Simple Route to Nanocrystalline Cerium Dioxide: An In Situ Spectroscopic Study of Nanocrystal Evolution (pages 7348–7360)

      Dr. Atsushi Ikeda-Ohno, Dr. Christoph Hennig, Stephan Weiss, Dr. Tsuyoshi Yaita and Prof. Dr. Gert Bernhard

      Version of Record online: 29 APR 2013 | DOI: 10.1002/chem.201204101

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      Nanocrystal evolution: A multi-spectroscopic approach has revealed that the hydrolysis of tetravalent cerium (CeIV) produces a colloidal solution of fine cerium dioxide (CeO2) nanocrystals (see figure). A simple synthetic concept of nanocrystalline metal oxides is proposed based on the obtained results.

    2. Reaction Mechanisms

      How Is a Metabolic Intermediate Formed in the Mechanism-Based Inactivation of Cytochrome P450 by Using 1,1-Dimethylhydrazine: Hydrogen Abstraction or Nitrogen Oxidation? (pages 7361–7369)

      Dr. Hajime Hirao, Pratanphorn Chuanprasit, Ying Yi Cheong and Dr. Xiaoqing Wang

      Version of Record online: 16 APR 2013 | DOI: 10.1002/chem.201300689

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      Interaction to inactivation: Hydrazines act as mechanism-based inactivators of cytochrome P450 enzymes, which are responsible for drug metabolism in the human body. A density functional theory study provides a clear view on how an aminonitrene-type metabolic intermediate is generated from 1,1-dimethylhydrazine through reaction with the reactive compound I intermediate of cytochrome P450 (see figure).

    3. Total Synthesis

      Total Syntheses and Biological Reassessment of Lactimidomycin, Isomigrastatin and Congener Glutarimide Antibiotics (pages 7370–7383)

      Dr. Kévin Micoine, Dipl.-Chem. Peter Persich, Dr. Josep Llaveria, My-Hanh Lam, Dr. Andreas Maderna, Dr. Frank Loganzo and Prof. Alois Fürstner

      Version of Record online: 17 APR 2013 | DOI: 10.1002/chem.201300393

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      On the contrary! Alkyne metathesis powered a synthesis-driven (re)evaluation of bipartite glutarimide antibiotics, including lactimidomycin and isomigrastatin, which feature highly strained polyunsaturated macrolide head groups. Rather than being potent cell migration inhibitors as previously claimed, lactimidomycin and progeny were found to be acutely cytotoxic, causing cell death before any specific interference with cell motility could set in.

    4. Electronic Structure

      Four-Center Oxidation State Combinations and Near-Infrared Absorption in [Ru(pap)(Q)2]n (Q=3,5-Di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, pap=2-Phenylazopyridine) (pages 7384–7394)

      Dr. Dipanwita Das, Hemlata Agarwala, Dr. Abhishek Dutta Chowdhury, Tuhin Patra, Dr. Shaikh M. Mobin, Prof. Dr. Biprajit Sarkar, Prof. Dr. Wolfgang Kaim and Prof. Dr. Goutam Kumar Lahiri

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201204620

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      Proven not innocent! All four redox-active components of [Ru(pap)(Q)2]n behave non-innocently in not immediately predictable ways according to structural, spectroelectrochemical, and computational information for the accessible forms between n=2+ and n=2− (see figure). Cations, anions, and neutral forms are distinguished by significant near-infrared absorptions (λmax>1000 nm).

    5. Diborane–Metal Bonding

      Bonding in Diborane–Metal Complexes: A Quantum-Chemical and Experimental Study of Complexes Featuring Early and Late Transition Metals (pages 7395–7409)

      Arne Wagner, Dr. Elisabeth Kaifer and Prof. Dr. Hans-Jörg Himmel

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201300348

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      Bond deal for diboranes: The synthesis of new diborane complexes combined with experimental and DFT investigations show how B[BOND]H and B[BOND]B bonds can be specifically activated depending on the chosen transition-metal fragment (see figure).

    6. Scandium Nitrate

      An Efficient Method to Separate Sc3N@C80 Ih and D5h Isomers and Sc3N@C78 by Selective Oxidation with Acetylferrocenium [Fe(COCH3C5H4)Cp]+ (pages 7410–7415)

      Maira R. Cerón, Dr. Fang-Fang Li and Prof. Dr. Luis Echegoyen

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201204219

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      Endohedral metallofullerenes: Sc3N@C80 Ih and D5h isomers and Sc3N@C78 were selectively separated by using a chemical oxidation and reduction method based on their different oxidation potentials (see figure).

    7. C60 Cycloaddition

      Why Do Cycloaddition Reactions Involving C60 Prefer [6,6] over [5,6] Bonds? (pages 7416–7422)

      Dr. Israel Fernández, Prof. Dr. Miquel Solà and Prof. Dr. F. Matthias Bickelhaupt

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201300648

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      Why [6,6]? The preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 is experimentally well-established (see figure). However, the reasons (i.e., physical factors) behind this preference are so far completely unknown. By means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method, a definite answer to the question in the title is provided.

    8. Organic Synthesis

      Total Synthesis of the Postulated Structure of Fulicineroside (pages 7423–7436)

      Ruben Bartholomäus, Fabian Dommershausen, Dr. Markus Thiele, Narayan S. Karanjule, Dr. Klaus Harms and Prof. Dr. Ulrich Koert

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201204545

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      Natural product reassignment: Total synthesis of the proposed structures for fulicineroside and its aglycone fulicinerine has been achieved (see figure). Key issues were the tetrasubstituted dibenzofuran and the trisaccharide with its β-linkage between L-rhodinose and L-rhamnose. A comparison with the reported data for the natural product and the aglycone suggests a misassignment of the structure of the natural product.

    9. Micelles

      Temperature-Responsive Mixed-Shell Polymeric Micelles for the Refolding of Thermally Denatured Proteins (pages 7437–7442)

      Xue Liu, Yang Liu, Zhenkun Zhang, Fan Huang, Qian Tao, Rujiang Ma, Yingli An and Prof. Linqi Shi

      Version of Record online: 8 APR 2013 | DOI: 10.1002/chem.201300634

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      Heroes in a mixed shell: Core–shell–corona polymeric micelles with a temperature-induced hydrophobic shell can act as an artificial chaperone in a process that involves the capture of thermally denatured proteins, thus preventing their aggregation, followed by assisted refolding during cooling (see figure).

    10. Asymmetric Hydrogenation

      Formation of Trinuclear Rhodium-Hydride Complexes [{Rh(PP*)H}3- (μ2-H)33-H)][anion]2—During Asymmetric Hydrogenation? (pages 7443–7451)

      C. Kohrt, Dr. W. Baumann, Dr. A. Spannenberg, Dr. H.-J. Drexler, Prof. Dr. I. D. Gridnev and Prof. Dr. D. Heller

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201204336

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      Catalyst–substrate complexes containing the ligands tBu-BisP*, Tangphos, Me-BPE, DCPE, DCPB, and mono- ([Rh(PP*)(MeOH)2H2]BF4) or dinuclear ([{Rh(PP*)H}22-H)3]BF4) Rh-hydride species, are described (see figure). A sequence for the formation of the trinuclear Rh-hydride complexes is suggested. The presence of these complexes should be taken into account when discussing the mechanism of asymmetric hydrogenation.

    11. Biosensors

      Ultrasensitive SERS Detection of Lysozyme by a Target-Triggering Multiple Cycle Amplification Strategy Based on a Gold Substrate (pages 7452–7460)

      Dr. Peng He, Yan Zhang, Lijun Liu, Wenping Qiao and Prof. Shusheng Zhang

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201203224

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      Target triggering: An ultrasensitive surface enhanced Raman scattering (SERS) method for the detection of lysozyme is reported. Based on aptamer-based target-triggering multiple cycle amplification and gold nanoparticle (AuNP) bio-barcode Raman probe enhancement on the gold substrate (see figure), the SERS signals are significantly enhanced and concentrations of lysozyme as low as 1 fM could be detected.

    12. Photochemistry

      Intramolecular [2+2] Photocycloaddition of 3- and 4-(But-3-enyl)oxyquinolones: Influence of the Alkene Substitution Pattern, Photophysical Studies, and Enantioselective Catalysis by a Chiral Sensitizer (pages 7461–7472)

      Mark M. Maturi, Matthias Wenninger, Dr. Rafael Alonso, Dr. Andreas Bauer, Dr. Alexander Pöthig, Prof. Dr. Eberhard Riedle and Prof. Dr. Thorsten Bach

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201300203

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      Upon UV irradiation quinolones A undergo a rapid cyclization at the T1 level (τ≈1 ns) through the respective 1,4-diradicals (e.g., 1), leading to the [2+2]-photocycloaddition products in high yields. Lifetimes and transient absorption spectra have been carefully measured. The high cyclization rate is one key element in the enantioselective formation of products, such as 3, when sensitized by catalyst (+)-2 (10 mol %).

    13. Quantum Dots

      Protein-Directed Synthesis of Mn-Doped ZnS Quantum Dots: A Dual-Channel Biosensor for Two Proteins (pages 7473–7479)

      Dr. Peng Wu, Ting Zhao, Yunfei Tian, Dr. Lan Wu and Prof. Dr. Xiandeng Hou

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201204035

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      2 proteins, 1 sensor: Protein-directed synthesis of phosphorescent Mn-doped ZnS quantum dots (QDs) is reported. By exploring the phosphorescence and resonance light scattering (RLS) of the QDs, and the specific protein–protein interactions with bovine serum albumin (BSA) as the substrate, a dual-channel sensor was developed that employs only one type of QD for the detection of two different proteins (see figure).

    14. Photochemistry

      A Redox-Mediator-Free Solar-Driven Z-Scheme Water-Splitting System Consisting of Modified Ta3N5 as an Oxygen-Evolution Photocatalyst (pages 7480–7486)

      Su Su Khine Ma, Prof. Kazuhiko Maeda, Dr. Takashi Hisatomi, Masashi Tabata, Prof. Akihiko Kudo and Prof. Kazunari Domen

      Version of Record online: 12 APR 2013 | DOI: 10.1002/chem.201300579

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      Split me! A redox-mediator-free Z-scheme water-splitting system capable of working under simulated sunlight was achieved by using Ir/CoOx/Ta3N5 in combination with Ru/SrTiO3:Rh as a H2-evolution photocatalyst.

    15. Computational Chemistry

      Tetragermacyclobutadiene: Energetically Disfavored with Respect to Its Structural Isomers (pages 7487–7495)

      J. Wayne Mullinax, David S. Hollman and Prof. Henry F. Schaefer III

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201203481

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      Germaphobe: The structure and energetics of tetragermacyclobutadiene and its structural isomers were investigated by using coupled-cluster methods and focal-point analysis to extrapolate to the complete basis-set limit. The Ge4H4 isomers exhibited non-planar structures and less double bonding than in C4H4.

    16. Dye-Sensitized Solar Cells

      Molecular Design Rule of Phthalocyanine Dyes for Highly Efficient Near-IR Performance in Dye-Sensitized Solar Cells (pages 7496–7502)

      Prof. Dr. Mutsumi Kimura, Hirotaka Nomoto, Hiroyuki Suzuki, Takuro Ikeuchi, Dr. Hiroyuki Matsuzaki, Dr. Takuro N. Murakami, Dr. Akihiko Furube, Dr. Naruhiko Masaki, Dr. Matthew J. Griffith and Prof. Dr. Shogo Mori

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201300716

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      All dyed out! Zinc phthalocyanine dyes were designed and optimized in order to increase the absorption of red light in dye-sensitized solar cells (see figure). By optimizing the structure of the adsorption site and reducing the size of bulky substituents, a high power conversion efficiency of 5.9 % was obtained.

    17. Density Functional Calculations

      Dense Iodine-Rich Compounds with Low Detonation Pressures as Biocidal Agents (pages 7503–7509)

      Dr. Chunlin He, Jiaheng Zhang and Prof. Dr. Jean'ne M Shreeve

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201300565

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      Agent defeat weapons: Fifteen iodo compounds and six iodyl compounds with an iodine content between 45.3 and 89.0 % were synthesized. The high concentration and easy accessibility of iodine and/or iodine-containing species is very important in developing materials suitable as agent defeat weapons (see figure).

    18. Tellurium Redox Chemistry

      Multi-faceted Reactivity of Alkyltellurophenols Towards Peroxyl Radicals: Catalytic Antioxidant Versus Thiol-Depletion Effect (pages 7510–7522)

      Dr. Riccardo Amorati, Dr. Luca Valgimigli, Dr. Peter Dinér, Dr. Khadijeh Bakhtiari, Dr. Mina Saeedi and Prof. Lars Engman

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201300451

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      Anti- and pro-oxidants: Hydroxyaryl alkyl tellurides are unconventional antioxidants able to quench chain-carrying peroxyl radicals with rate constants as high as 107M−1 s−1 by a mechanism involving oxygen atom transfer to tellurium followed by reaction of the RO. radical with the phenol (see figure). They can also catalytically decompose both the ROO. radical and H2O2 in the presence of excess thiols.

    19. Phosphorus Chemistry

      Reactions of Pyridyl-Functionalized, Chelating λ3-Phosphinines in the Coordination Environment of RhIII and IrIII (pages 7523–7531)

      Iris de Krom, Dr. Evgeny A. Pidko, Dr. Martin Lutz and Prof. Dr. Christian Müller

      Version of Record online: 4 APR 2013 | DOI: 10.1002/chem.201300321

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      RhIII and IrIII complexes based on the λ3-P,N hybrid ligand 2-(2′-pyridyl)-4,6-diphenylphosphinine (1) react selectively at the P[DOUBLE BOND]C double bond to give chiral coordination compounds of the type [(1HOH)Cp*MCl]Cl, which can be deprotonated to form [(1HO)Cp*IrCl] and [(1⋅OH)Cp*RhCl] (see figure). These new transformations in the coordination environment of RhIII and IrIII provide an easy and general access to new transition-metal complexes containing λ5σ4-phosphinine ligands.

    20. Oligomers

      Comprehensive Analysis of Fragment Orbital Interactions to Build Highly π-Conjugated Thienylene-Substituted Phenylene Oligomers (pages 7532–7546)

      Dr. Jean-Charles Florès, Dr. Marie-Agnès Lacour, Dr. Xavier Sallenave, Prof. Françoise Serein-Spirau, Prof. Jean-Pierre Lère-Porte, Prof. Joël J. E. Moreau, Dr. Karinne Miqueu, Dr. Jean-Marc Sotiropoulos and Dr. David Flot

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201203869

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      π in the sky: Thienylene[BOND]phenylene oligomers with fluorinated and dialkoxylated phenylene fragments have been designed and prepared. UV photoelectron spectroscopy and DFT calculations highlight how the resulting strong conjugation depends on the energetics of the π orbitals of the molecular fragments, which are related to the nature of the substituents (F, OMe) on the phenylene groups (see figure).

    21. Graphene

      Doped Graphene as a Metal-Free Carbocatalyst for the Selective Aerobic Oxidation of Benzylic Hydrocarbons, Cyclooctane and Styrene (pages 7547–7554)

      Dr. Amarajothi Dhakshinamoorthy, Dr. Ana Primo, Dr. Patricia Concepcion, Prof. Dr. Mercedes Alvaro and Prof. Dr. Hermenegildo Garcia

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201300653

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      Oxidation at graphene: Boron- and nitrogen-doped graphenes are excellent catalysts for promoting the oxidation of benzylic hydrocarbons, cyclooctane, and styrene with molecular oxygen at 0.5 wt % under atmospheric pressure and solvent-free conditions (see figure).

    22. Organocatalysis

      Highly Regioselective Organocatalyzed Synthesis of Pyrazoles from Diazoacetates and Carbonyl Compounds (pages 7555–7560)

      Lei Wang, Jiayao Huang, Prof. Xiaojie Gong and Prof. Dr. Jian Wang

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201300047

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      Dipoles apart: In situ formed enamines react with diazoacetates under mild conditions to afford the corresponding polysubstituted pyrazoles in good-to-excellent yields through an inverse-electron-demand 1,3-dipolar cycloaddition process (see scheme).

    23. Asymmetric Catalysis

      Asymmetric Synthesis of trans-β-Lactams by a Kinugasa Reaction on Water (pages 7561–7567)

      Zhenling Chen, Dr. Lili Lin, Min Wang, Prof. Dr. Xiaohua Liu and Prof. Dr. Xiaoming Feng

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201204373

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      Walking on water: Asymmetric Kinugasa reactions on pure water without any organic co-solvents afforded synthetically useful trans-β-lactams in good yields, enantioselectivities, and diastereoselectivities (up to 90 % yield, 98 % ee, and >99:1 d.r.).

    24. Metallacycles

      Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)methanide Ligands (pages 7568–7574)

      Martin Haehnel, Dr. Sven Hansen, Jacqueline B. Priebe, Dr. Anke Spannenberg, Dr. Perdita Arndt, Prof. Dr. Angelika Brückner and Prof. Dr. Uwe Rosenthal

      Version of Record online: 8 APR 2013 | DOI: 10.1002/chem.201300218

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      Strained metallacycles: Heterometallacyclic complexes of the type [Cp2M(L)(κ2-P,P-Ph2PC(X)PPh2)] (M=Ti, X=H, SiMe3, no L; M=Zr, X=H, L=H; M=Hf, X=H, SiMe3, L=Cl) have been prepared through salt elimination pathways, from which the corresponding metallacycles have been obtained in very high yields. Analysis of the structure and bonding of these complexes has revealed that in-plane aromaticity plays an important role in their stabilization, especially in the case of paramagnetic TiIII complexes (see figure).

    25. Charge Transfer

      Precise Control of Intramolecular Charge-Transport: The Interplay of Distance and Conformational Effects (pages 7575–7586)

      Christina Schubert, Dr. Mateusz Wielopolski, Lars-Hendrik Mewes, Dr. Gustavo de Miguel Rojas, Dr. Cornelia van der Pol, Dr. Kathryn C. Moss, Prof. Martin R. Bryce, Prof. Jacques E. Moser, Prof. Timothy Clark and Prof. Dirk M. Guldi

      Version of Record online: 10 APR 2013 | DOI: 10.1002/chem.201204055

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      Finely tuned transfer: Chemical modification of the oligo-fluorene linkers between Fc and C60 units enables fine-tuning of photoinduced charge-transfer processes in new donor–bridge–acceptor conjugates (see illustration).

    26. Boronic Acids

      Arylboronic Acid Chemistry under Electrospray Conditions (pages 7587–7594)

      Dr. Lifang Wang, Dr. Chaofeng Dai, Sarah Kathryn Burroughs, Dr. Siming Liu Wang and Prof. Binghe Wang

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201204290

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      Mass-ive findings: A systematic analysis of the chemical behavior of arylboronic acids under ESI-MS conditions is reported (see scheme). Such information is critical to understanding the gas-phase chemistry of boronic acids in an ESI mass spectrometer chamber in general and the MS analysis of boronic acids and their macromolecular conjugates in particular.

    27. C[BOND]H activation

      Autocatalytic Intermolecular versus Intramolecular Deprotonation in C[BOND]H Bond Activation of Functionalized Arenes by Ruthenium(II) or Palladium(II) Complexes (pages 7595–7604)

      Indira Fabre, Niklas von Wolff, Dr. Gaëtan Le Duc, Dr. Emmanuel Ferrer Flegeau, Dr. Christian Bruneau, Prof. Pierre H. Dixneuf and Dr. Anny Jutand

      Version of Record online: 17 APR 2013 | DOI: 10.1002/chem.201203813

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      Acetate aid: The activation of the C[BOND]H bond of 1-phenylpyrazole and 2-phenyl-2-oxazoline by [Ru(OAc)2(p-cymene)] is an autocatalytic intermolecular process aided by free acetate (see figure). In contrast, activation by Pd(OAc)2 proceeds through a concerted metalation–deprotonation (CMD) mechanism through an intramolecular and irreversible process that is assisted by ligated acetate. A cyclometalated dimeric PdII PdII complex is formed, the bielectronic electrochemical oxidation of which leads to a dimeric [PdIII PdIII]2+ complex.

    28. Peroxide Synthesis

      Potent Antimalarial 1,2,4-Trioxanes through Perhydrolysis of Epoxides (pages 7605–7619)

      Dr. Hong-Dong Hao, Dr. Sergio Wittlin and Prof. Dr. Yikang Wu

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201300076

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      Molybdenum magic: Facile perhydrolysis of a highly hindered epoxide was achieved with the aid of a molybdenum catalyst. The resulting hydroperoxide was readily converted into a 1,2,4-trioxane, from which natural qinghaosu (QHS, or artemisinin; see scheme) and a range of analogues were constructed. Some of the newly accessed trioxanes showed in vitro antimalarial activity comparable to or even better than that of chloroquine and artesunate.

    29. Luminescence

      Dithiazolo[5,4-b:4′,5′-d]phosphole: A Highly Luminescent Electron-Accepting Building Block (pages 7620–7630)

      Dr. Xiaoming He, Alva Y. Y. Woo, Dr. Javier Borau-Garcia and Prof. Dr. Thomas Baumgartner

      Version of Record online: 8 APR 2013 | DOI: 10.1002/chem.201204375

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      Sliding down with a glow: Incorporation of nitrogen atoms into the dithienophosphole scaffold generates a new building block, dithiazolo[5,4-b:4′,5′-d]phosphole (see scheme), that combines intense luminescence with high electron affinity. A family of conjugated small molecules and a polymer based on this building block have been synthesized by a click reaction that also serves as a selective colorimetric and fluorescent sensor for CuII.

    30. Graphene

      Facile Fabrication of Nanoparticles Confined in Graphene Films and Their Electrochemical Properties (pages 7631–7636)

      Sheng Chen, Prof. Junwu Zhu, Ling Qiu, Prof. Dan Li and Prof. Xin Wang

      Version of Record online: 9 APR 2013 | DOI: 10.1002/chem.201300262

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      Sandwich-like structures: Confinement of Ni(OH)2 particles in a graphene film has resulted in a new sandwich-like structure with excellent electrode kinetics and electrochemical stability. This system is a promising candidate for supercapacitor materials (see figure).

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