Chemistry - A European Journal

Cover image for Vol. 19 Issue 11

March 11, 2013

Volume 19, Issue 11

Pages 3517–3774

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: A Total Synthesis of Spirastrellolide A Methyl Ester (Chem. Eur. J. 11/2013) (page 3517)

      Dipl.-Chem. Alexander Arlt, Dr. Stefan Benson, Saskia Schulthoff, Barbara Gabor and Prof. Alois Fürstner

      Article first published online: 1 MAR 2013 | DOI: 10.1002/chem.201390033

      Thumbnail image of graphical abstract

      Two worlds, one molecule… In their Full Paper on page 3596 ff. A. Fürstner et al. report a total synthesis of spirastrellolide A methyl ester, a complex macrolide isolated from a Caribbean sponge collected off Dominica. Several methodological spin-offs as well as preliminary structure–activity relationship data are also disclosed. Artwork: R. Homann for MPI für Kohlenforschung; photographs: Copyright: John Anderson/Fotolia.com, Copyright: Michael Teske/MPI für Kohlenforschung.

    2. You have free access to this content
      Back Cover: Development of a General Non-Noble Metal Catalyst for the Benign Amination of Alcohols with Amines and Ammonia (Chem. Eur. J. 11/2013) (page 3776)

      Xinjiang Cui, Xingchao Dai, Prof. Dr. Youquan Deng and Dr. Feng Shi

      Article first published online: 1 MAR 2013 | DOI: 10.1002/chem.201390036

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      An air and moisture stable heterogeneous non-noble metal catalyst, that is NiCuFeOx, was designed and prepared for the synthesis of N-substituted primary, secondary, tertiary, and cyclic amines by using ammonia, primary amines, or secondary amines as nitrogen sources and alcohols as alkylation reagents under base- and organic-ligand-free conditions. For more details see the Full Paper by Shi et al. on page 3665 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Graphical Abstract: Chem. Eur. J. 11/2013 (pages 3520–3528)

      Article first published online: 1 MAR 2013 | DOI: 10.1002/chem.201390034

  3. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Click Chemistry

      The “Click” Reaction Involving Metal Azides, Metal Alkynes, or Both: An Exploration into Multimetal Structures (pages 3534–3541)

      Prof. Dr. Luis Casarrubios, Dr. María C. de la Torre and Prof. Dr. Miguel A. Sierra

      Article first published online: 18 FEB 2013 | DOI: 10.1002/chem.201204596

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      Metals take over the click brigade: The use of CuI-catalyzed 1,3-cycloaddition of azides and alkynes (CuAAC) to prepare well-defined multimetallic structures is underdeveloped. Only isolated examples of the CuAAC with metal–η1-alkyne and metal–azide complexes to prepare multimetal entities have been reported. This concept sketches the potential of these reactions not only to prepare “a la carte” multimetal 1,2,3-triazole derivatives, but also to discover new and unprecedented reactions.

  6. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Cationic Amines

      Synthesis and Structure of Carbene-Stabilized N-Centered Cations [L2N]+, [L2NR]2+, [LNR3]2+, and [L3N]3+ (pages 3542–3546)

      Ágnes Kozma, Dr. Gopinadhanpillai Gopakumar, Dr. Christophe Farès, Prof. Dr. Walter Thiel and Dr. Manuel Alcarazo

      Article first published online: 21 FEB 2013 | DOI: 10.1002/chem.201204186

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      Crystallized! Mono-, di-, and tricationic amines that display unprecedented chemical environments around the central nitrogen atom have been structurally characterized. Cyclic voltammetry experiments and density functional calculations have been performed to gain insight into the electronic structure of these new compounds.

    2. Cycloaddition

      Intermolecular Gold-Catalyzed Cycloaddition of Alkynes with Oxoalkenes (pages 3547–3551)

      Carla Obradors and Prof. Antonio M. Echavarren

      Article first published online: 19 FEB 2013 | DOI: 10.1002/chem.201300131

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      As good as gold: Gold(I) catalyzes a new intermolecular reaction of terminal alkynes with functionalized alkenes that gives 8-oxabicyclo[3.2.1]oct-3-enes by a [2+2+2] cycloaddition process in which two C[BOND]C bonds and one C[BOND]O bond are formed (see scheme).

    3. Metal–Organic Frameworks

      Zipping and Unzipping of a Paddlewheel Metal–Organic Framework to Enable Two-Step Synthetic and Structural Transformation (pages 3552–3557)

      Dr. Paul Smart, Dr. Charles A. Mason, Jason R. Loader, Dr. Anthony J. H. M. Meijer, Prof. Alastair J. Florence, Dr. Kenneth Shankland, Dr. Ashleigh J. Fletcher, Dr. Stephen P. Thompson, Dr. Michela Brunelli, Dr. Adrian H. Hill and Prof. Lee Brammer

      Article first published online: 11 FEB 2013 | DOI: 10.1002/chem.201204492

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      MOF zipper: Thermal removal of axial pyridine ligands from the non-covalently pillared metal–organic framework [Zn2(camph)2(py)2]⋅2EtOH prompts migration of alternate camphorate ligands to zip Zn centers from adjacent layers into continuous chains within the nonporous material [Zn2(camph)2] (see scheme). Unzipping to generate new pillared, layered MOFs occurs on exposure to new axial ligands.

    4. Kinetics

      Reaction-Pathway Selection in the Structural Dynamics of a Heme Protein (pages 3558–3562)

      Dr. Karin Nienhaus, Dr. Stephan Lutz, Prof. Dr. Markus Meuwly and Prof. Dr. G. Ulrich Nienhaus

      Article first published online: 7 FEB 2013 | DOI: 10.1002/chem.201203558

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      Choose your way: A reaction-pathway selection mechanism in neuroglobin has been elucidated by studying the wild-type (wt) protein and residue 109 mutants. By combining molecular-dynamics simulations and kinetic experiments, the structural changes accompanying the ligand-binding reaction and their functional implications have been resolved (see scheme).

    5. Peptidomimetics

      Cyclic isoDGR Peptidomimetics as Low-Nanomolar αvβ3 Integrin Ligands (pages 3563–3567)

      Michele Mingozzi, Alberto Dal Corso, Dr. Mattia Marchini, Ileana Guzzetti, Dr. Monica Civera, Prof. Dr. Umberto Piarulli, Dr. Daniela Arosio, Dr. Laura Belvisi, Dr. Donatella Potenza, Dr. Luca Pignataro and Prof. Dr. Cesare Gennari

      Article first published online: 19 FEB 2013 | DOI: 10.1002/chem.201204639

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      A perfect fit: Shown here is the docking best pose of a low-nanomolar αvβ3 integrin ligand cyclo[DKP-isoDGR] (atom color tube representation; see figure) into the receptor binding pocket, overlaid on the bound conformation of Cilengitide (green tube representation). The extended isoDGR conformation permits all the important interactions with the extracellular domain of the αvβ3 integrin. The metal ion in the MIDAS region is represented by a magenta sphere.

    6. C[BOND]H Activation

      Theoretical Studies for Large Tunneling and the Hydrogen-Transfer Mechanism in the C[BOND]H Activation of CH3CN by a Di(μ-oxo)diiron(IV) Complex: A Model for Intermediate Q in Soluble Methane Monooxygenase (pages 3568–3572)

      Binh Khanh Mai and Prof. Yongho Kim

      Article first published online: 10 FEB 2013 | DOI: 10.1002/chem.201204488

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      Tracking the transfer: The potential-energy surface along the intrinsic reaction coordinate was constructed to study the detailed mechanism of hydrogen transfer in the C[BOND]H activation of CH3CN by a di(μ-oxo)diiron(IV) complex (see figure). The diiron core structure is distorted significantly before the actual hydrogen transfer, and the reduction of FeIV to FeIII occurs gradually with the hydrogen transfer.

    7. Asymmetric Catalysis

      Asymmetric Michael Reaction Catalyzed by Proline Lithium Salt: Efficient Synthesis of L-Proline and Isoindoloisoquinolinone Derivatives (pages 3573–3578)

      Kun Xu, Sheng Zhang, Yanbin Hu, Zhenggen Zha and Prof. Zhiyong Wang

      Article first published online: 10 FEB 2013 | DOI: 10.1002/chem.201202409

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      Lithium makes it possible: The enantioselective Michael addition of aldehydes to nitroalkenes was catalyzed by the readily available proline lithium salt. Remarkably, the asymmetric Michael reaction was scaled up to 50 mmol with 23:1 d.r. and 90 % ee.

    8. Synthetic Methods

      Direct Synthesis of Diverse β-Fluoroethylamines by a Multicomponent Protocol (pages 3579–3583)

      Prof. Dr. G. K. Surya Prakash, Laxman Gurung, Dr. Parag V. Jog, Dr. Shinji Tanaka, Tisa Elizabeth Thomas, Nimisha Ganesh, Prof. Dr. Ralf Haiges, Dr. Thomas Mathew and Prof. Dr. George A. Olah

      Article first published online: 10 FEB 2013 | DOI: 10.1002/chem.201204621

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      No imines! A direct multicomponent protocol for the synthesis of highly diverse derivatives of β-fluoro(phenylsulfonyl)ethylamine has been developed (see scheme) by use of a Mannich-type reaction from their molecular subunits, α-fluoro-α-nitro(phenylsulfonyl)methane (1 a) or α-fluorobis(phenylsulfonyl)methane (1 b), formalin, and various primary and secondary amines. The products are obtained in high yields and selectivity even, in many cases, without the use of base.

    9. Transmetalation

      From Cyclopropenes to Tetrasubstituted Furans: Tandem Isomerization/Alkenylation Sequence with Cu/Pd Relay Catalysis (pages 3584–3589)

      Chuanling Song, Lin Ju, Mingchao Wang, Pengcheng Liu, Yuanzhe Zhang, Prof. Jianwu Wang and Prof. Zhenghu Xu

      Article first published online: 21 FEB 2013 | DOI: 10.1002/chem.201203997

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      Pon de relay: A convenient and efficient synthesis of alkene-functionalized furans from cyclopropenes, which proceeds through an isomerization/olefination cascade sequence under copper–palladium relay catalysis, has been developed (see scheme).

  7. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Metal–Organic Frameworks

      Assembly of Framework-Isomeric 4 d–4 f Heterometallic Metal–Organic Frameworks with Neutral/Anionic Micropores and Guest-Tuned Luminescence Properties (pages 3590–3595)

      Dr. Jing-xin Ma, Dr. Xiao-feng Huang, Dr. Xue-qin Song and Prof. Dr. Wei-sheng Liu

      Article first published online: 18 FEB 2013 | DOI: 10.1002/chem.201204022

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      In the frame: Framework-isomeric three-dimensional Cd–Ln (Ln=Gd, Tb) heterometallic metal–organic frameworks (HMOFs; see figure) with neutral or anionic pores were designed based on a lanthanide metalloligand strategy. HMOFs with Ln=Tb can act as luminescent metal–organic frameworks with light-emitting properties that can be modulated by guest solvent molecules or manganese counterions.

    2. Total Synthesis

      A Total Synthesis of Spirastrellolide A Methyl Ester (pages 3596–3608)

      Dipl.-Chem. Alexander Arlt, Dr. Stefan Benson, Saskia Schulthoff, Barbara Gabor and Prof. Alois Fürstner

      Article first published online: 18 FEB 2013 | DOI: 10.1002/chem.201203965

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      Molecular splendor: A concise total synthesis of spirastrellolide A methyl ester is presented, which contains no less than 21 chiral centers plus three olefinic sites within its complex polyketide frame. The assembly process centered on a late-stage unveiling of the signature C15–C16 alkene, only after the methyl branch at C24 had been properly set by a substrate-controlled hydrogenation. The required elaborate exo-methylene precursor, in turn, was formed by dithiane chemistry, an alkyl-Suzuki coupling, and a Yamaguchi lactonization.

    3. Biotransformations

      Biotransformations of Anticancer Ruthenium(III) Complexes: An X-Ray Absorption Spectroscopic Study (pages 3609–3619)

      Dr. Aviva Levina, Dr. Jade B. Aitken, Yee Yen Gwee, Zhi Jun Lim, Mimi Liu, Dr. Anannya Mitra Singharay, Pok Fai Wong and Prof. Peter A. Lay

      Article first published online: 30 JAN 2013 | DOI: 10.1002/chem.201203127

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      Combating cancer: Widely studied anticancer RuIII complexes, NAMI-A ((ImH)[RuIIICl4(Im)(dmso)]; Im=imidazole) and KP1019 ((IndH)[RuIIICl4(Ind)2]; Ind=indazole), undergo extensive ligand-exchange reactions with isolated proteins, blood serum, cell-culture media and human cancer cells (see scheme). Detailed studies have been performed to find the reasons for the different biological activities of these drugs.

    4. Non-Covalent Interactions

      You have full text access to this OnlineOpen article
      Theoretical Insights into the Nature of Halogen Bonding in Prereactive Complexes (pages 3620–3628)

      Dr. J. Grant Hill and Xiaojun Hu

      Article first published online: 18 FEB 2013 | DOI: 10.1002/chem.201204312

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      Theoretical best-estimates are presented for the geometries and interaction energies of halogen-bonded complexes of dihalogens and ammonia. Dispersion, electrostatics and charge transfer all contribute significantly to the interaction energy, and manipulation of the relative orientations of the subunits indicates lower directionality than previously supposed. The electrostatic potential map indicates electrostatics and charge transfer upon complex formation (see figure).

    5. DFT Calculations

      Revealing Unexpected Mechanisms for Nucleophilic Attack on S[BOND]S and Se[BOND]Se Bridges (pages 3629–3638)

      Dr. Gavin S. Heverly-Coulson, Prof. Russell J. Boyd, Prof. Otilia Mó and Prof. Manuel Yáñez

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201203328

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      Don't burn your bridges, break them! In contrast to the generally accepted view, nucleophilic attack on disulfide and diselenide linkages does not always lead to S[BOND]S or Se[BOND]Se bond cleavage. The observed reactivity depends also on the nature of the nucleophile and on the bonding environment of the S or Se atom that undergoes the nucleophilic attack (see scheme).

    6. Metal–Organic Frameworks

      Solvatochromic Behavior of Chiral Mesoporous Metal–Organic Frameworks and Their Applications for Sensing Small Molecules and Separating Cationic Dyes (pages 3639–3645)

      Dr. Chun-Yi Sun, Prof. Xin-Long Wang, Chao Qin, Jun-Ling Jin, Zhong-Min Su, Peng Huang and Kui-Zhan Shao

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201203080

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      Selective adsorption and separation of cationic dyes over anionic and neutral dyes based on ionic selectivity was achieved by means of two rationally constructed anionic chiral mesoporous metal–organic frameworks. Moreover, rare solvatochromic phenomena and interesting guest-dependent luminescence properties were observed (see figure).

    7. Conducting Materials

      Electronic Properties of p-Xylylene and p-Phenylene Chains Subjected to Finite Bias Voltages: A New Highly Conducting Oligophenyl Structure (pages 3646–3654)

      Nicolas Ramos-Berdullas and Prof. Dr. Marcos Mandado

      Article first published online: 23 JAN 2013 | DOI: 10.1002/chem.201203324

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      Highly conducting carbon molecular wires: The electronic properties of two different p-xylylene-like chains and the p-phenylene chain attached to gold contacts, having molecular formulas AuCH2(C6H4)nCH2Au (pX1), Au2C(C6H4)nCAu2 (pX2), and Au(C6H4)nAu with n=1–5, were investigated theoretically, including their responses to finite bias voltages. The new oligophenyl structure pX2 displays appropriate electronic characteristics, which stem from effective coupling of the local electronic structures of the benzene units (see figure), to be a highly conducting molecular device.

    8. Bioinorganic Chemistry

      Unsymmetrical Binding Modes of the HOPNO Inhibitor of Tyrosinase: From Model Complexes to the Enzyme (pages 3655–3664)

      Dr. Constance Bochot, Dr. Elisabeth Favre, Dr. Carole Dubois, Dr. Benoit Baptiste, Prof. Luigi Bubacco, Prof. Pierre-Alain Carrupt, Gisèle Gellon, Dr. Renaud Hardré, Prof. Dominique Luneau, Dr. Yohann Moreau, Dr. Alessandra Nurisso, Dr. Marius Réglier, Prof. Guy Serratrice, Dr. Catherine Belle and Dr. Hélène Jamet

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201202643

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      An uneven bridge: The binding mode of HOPNO, a tyrosinase inhibitor, was explored by combining model complexes and theoretical computations. An unsymmetrical dicopper model complex induces an unsymmetrical bridging binding mode of HOPNO. An unsymmetrical binding mode is also obtained on the enzyme (see figure) and is linked to hydrogen-bond formation with the second coordination sphere controlling the orientation of HOPNO in the binding site.

    9. Heterogeneous Catalysis

      Development of a General Non-Noble Metal Catalyst for the Benign Amination of Alcohols with Amines and Ammonia (pages 3665–3675)

      Xinjiang Cui, Xingchao Dai, Prof. Dr. Youquan Deng and Dr. Feng Shi

      Article first published online: 18 FEB 2013 | DOI: 10.1002/chem.201203417

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      Non-noble? No problem! A simple NiCuFeOx catalyst exhibits excellent activity and generality in selective alcohol amination with ammonia to produce many examples of primary or secondary amines, secondary aliphatic alcohol amination, diol amination, and alcohol amination with dimethylamine (see scheme).

    10. Coordination Chemistry

      2-(2′-Pyridyl)-4,6-diphenylphosphinine versus 2-(2′-Pyridyl)-4,6-diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic RhIII and IrIII Complexes Based on Aromatic Phosphorus Heterocycles (pages 3676–3684)

      Iris de Krom, Leen E. E. Broeckx, Dr. Martin Lutz and Prof. Dr. Christian Müller

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201203621

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      A bidentate P,N hybrid ligand allows for access to cationic phosphinine-based RhIII and IrIII complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications (see figure). The coordination chemistry of this ligand towards RhIII and IrIII was investigated and compared with 2-(2′-pyridyl)-4,6-diphenylpyridine, which showed remarkable differences between the structurally related heterocycles.

    11. Host–Guest Systems

      Encapsulation-Induced Remarkable Stability of a Hydrogen-Bonded Heterocapsule (pages 3685–3692)

      Keisuke Ichihara, Prof. Hidetoshi Kawai, Yuka Togari, Emi Kikuta, Hitomi Kitagawa, Prof. Seiji Tsuzuki, Dr. Kenji Yoza, Prof. Masamichi Yamanaka and Prof. Kenji Kobayashi

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201203937

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      Be my guest: The perfect match of dimensions, as well as dispersion and electrostatic interactions, of the acetylenic parts (triple bonds) of guest (3 a) with the aromatic inner space of the self-assembled hydrogen-bonded capsule (1 ⋅ 2) extraordinarily enhance the thermodynamic stability of the guest–capsule complex (see scheme).

    12. Magnetic Properties

      Three-Axis Anisotropic Exchange Coupling in the Single-Molecule Magnets NEt4[MnIII2(5-Brsalen)2(MeOH)2MIII(CN)6] (M=Ru, Os) (pages 3693–3701)

      Dr. Jan Dreiser, Kasper S. Pedersen, Dr. Alexander Schnegg, Dr. Karsten Holldack, Joscha Nehrkorn, Marc Sigrist, Dr. Philip Tregenna-Piggott, Dr. Hannu Mutka, Dr. Høgni Weihe, Dr. Vladimir S. Mironov, Prof. Jesper Bendix and Prof. Oliver Waldmann

      Article first published online: 5 FEB 2013 | DOI: 10.1002/chem.201203781

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      Intriguing coupling: A three-axis anisotropic exchange coupling is revealed in the isostructural single-molecule magnets Mn-Os-Mn and Mn-Ru-Mn by terahertz frequency-domain electron paramagnetic resonance, inelastic neutron scattering, and magnetic measurements (see picture). This peculiar behavior is explained by the presence of orbitally dependent exchange.

    13. Hydrogen Bonding

      [Pd(Fmes)2(tmeda)]: A Case of Intermittent C[BOND]H⋅⋅⋅F[BOND]C Hydrogen-Bond Interaction in Solution (pages 3702–3709)

      Dr. Camino Bartolomé, Dr. Fernando Villafañe, Dr. Jose M. Martín-Alvarez, Dr. Jesús M. Martínez-Ilarduya and Prof. Dr. Pablo Espinet

      Article first published online: 1 FEB 2013 | DOI: 10.1002/chem.201203512

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      Misleading clue: The restricted rotation of two o-CF3 groups observed in the low-temperature 19F NMR spectra of [Pd(Fmes)2(tmeda)] in CD2Cl2, which led to the search for a C[BOND]H⋅⋅⋅F[BOND]C hydrogen-bond interaction, turns out to be a deceptive clue, but the study proves that this bond does exist as an intermittent interaction (see scheme).

    14. Template Synthesis

      Templating Irreversible Covalent Macrocyclization by Using Anions (pages 3710–3714)

      Prof. Evgeny A. Kataev, Dr. Grigory V. Kolesnikov, Rene Arnold, Herman V. Lavrov and Prof. Victor N. Khrustalev

      Article first published online: 31 JAN 2013 | DOI: 10.1002/chem.201204306

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      Just as good as cations: Inorganic anions were used as templates to control irreversible covalent macrocyclization between a diamine and an activated diacid (see scheme). Investigation of the mechanism of the templated reaction revealed that the reaction is kinetically controlled and structures of intermediates play a decisive role in determining the mode of macrocyclization.

    15. Cycloaddition

      Reaction of N-Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si-C-S)- and Five (Si-C-C-C-S)-Membered Ring Systems (pages 3715–3720)

      Dr. Ramachandran Azhakar, Dr. Rajendra S. Ghadwal, Prof. Dr. Herbert W. Roesky, Prof. Dr. Ricardo A. Mata, Hilke Wolf, Regine Herbst-Irmer and Prof. Dr. Dietmar Stalke

      Article first published online: 30 JAN 2013 | DOI: 10.1002/chem.201203242

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      Rings ‘n‘ things: Three- and five-membered rings (see figure) bearing the (Si-C-S) and (Si-C-C-C-S) units have been synthesized by the reactions of LSiCl (L=PhC(NtBu)2) and L′Si (L′=CH{(C[DOUBLE BOND]CH2)(CMe)(2,6-iPr2C6H3N)2}) with the thioketone 4,4′-bis(dimethylamino)thiobenzophenone.

    16. Semiconductors

      Enhanced Performance of Benzothieno[3,2-b]thiophene (BTT)-Based Bottom-Contact Thin-Film Transistors (pages 3721–3728)

      Dr. Peng-Yi Huang, Dr. Liang-Hsiang Chen, Yu-Yuan Chen, Wen-Jung Chang, Juin-Jie Wang, Dr. Kwang-Hwa Lii, Dr. Jing-Yi Yan, Dr. Jia-Chong Ho, Dr. Cheng-Chung Lee, Prof. Choongik Kim and Prof. Ming-Chou Chen

      Article first published online: 29 JAN 2013 | DOI: 10.1002/chem.201204110

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      Rock bottom: A new and improved synthetic method was developed for the efficient realization of three new benzothieno[3,2-b]thiophene (BTT) derivatives. These compounds were employed in organic thin-film transistors and exhibited the p-channel characteristic with good electrical performance (see graph). Their device characteristics were correlated with their film morphologies and the microstructures of their corresponding compounds.

    17. Molecular Machines

      An Automatic Molecular Dispenser of Chloride (pages 3729–3734)

      Prof. Giuseppe Alibrandi, Dr. Valeria Amendola, Dr. Greta Bergamaschi, Dr. Riccardo Dollenz, Prof. Luigi Fabbrizzi, Prof. Maurizio Licchelli and Dr. Carmelo Lo Vecchio

      Article first published online: 31 JAN 2013 | DOI: 10.1002/chem.201203933

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      Titrations at the molecular level: The combined activity of cryptand 1 (the motor; see scheme) and of the dicopper(II) cryptate 2 (the dispenser) delivered chloride to the solution at a programmed rate from the inside of the reaction vessel.

    18. Nanostructures

      Systematic Synthesis of ZnO Nanostructures (pages 3735–3740)

      Dr. Peng Li, Dr. Dingsheng Wang, Zhe Wei, Dr. Qing Peng and Prof. Dr. Yadong Li

      Article first published online: 23 JAN 2013 | DOI: 10.1002/chem.201203730

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      Pyramid scheme: A facile and mild method has been developed to synthesize various ZnO nanostructures (see figure) and a possible formation mechanism is proposed. The heterogeneous growth of hexagonal ZnO nanopyramids is also observed by using the presynthesized gold nanocrystals as seeds. The unique optical properties of the ZnO nanostructures have been investigated.

    19. NO Chemistry

      Reactions of Hydrated Singly Charged First-Row Transition-Metal Ions M+(H2O)n (M=V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) toward Nitric Oxide in the Gas Phase (pages 3741–3750)

      Dipl.-Chem. Christian van der Linde, Dr. Robert F. Höckendorf, Dr. O. Petru Balaj and Prof. Dr. Martin K. Beyer

      Article first published online: 25 JAN 2013 | DOI: 10.1002/chem.201203459

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      Every molecule counts: The reactivity of hydrated metal ions can be tuned by the size of the hydration shell. Following collisions with NO (see graphic), Fe+(H2O)n and Zn+(H2O)n form HNO preferentially for n≈15–20, whereas HMnOH+(H2O)n−1 do so for n≤4.

    20. Copper(II) Complexes

      Affinity, Speciation, and Molecular Features of Copper(II) Complexes with a Prion Tetraoctarepeat Domain in Aqueous Solution: Insights into Old and New Results (pages 3751–3761)

      Dr. Giuseppe Di Natale, Dr. Katalin Ősz, Dr. Csilla Kállay, Dr. Giuseppe Pappalardo, Dr. Daniele Sanna, Prof. Giuseppe Impellizzeri, Prof. Imre Sóvágó and Prof. Enrico Rizzarelli

      Article first published online: 25 JAN 2013 | DOI: 10.1002/chem.201202912

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      Conjugate to elucidate: Conjugation of copper(II) complexes with polyethyleneglycol improves the solubility of the tetraoctarepeat peptide, allowing the investigation of the copper(II) binding modes at different metal-to-ligand ratios (see figure). The observed speciation and binding clarify the conflicting results originating from the underestimation of all metal–ligand equilibria and the ensuing speciation.

    21. DNA Chemistry

      Multi-Pathway Excited State Relaxation of Adenine Oligomers in Aqueous Solution: A Joint Theoretical and Experimental Study (pages 3762–3774)

      Dr. Akos Banyasz, Dr. Thomas Gustavsson, Dr. Delphine Onidas, Dr. Pascale Changenet-Barret, Dr. Dimitra Markovitsi and Dr. Roberto Improta

      Article first published online: 18 JAN 2013 | DOI: 10.1002/chem.201202741

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      UVA versus UVC: Experiments and calculations show that, after absorption of ultraviolet light, the excited states of DNA adenine single strands can decay to the ground state by following different pathways. These involve mainly stacked adenine dimers and are related to either π–π* or charge-transfer electronic transitions. The preferred decay path is largely determined by the energy of the absorbed photon (see figure).

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