Chemistry – An Asian Journal

Cover image for Vol. 7 Issue 6

June 2012

Volume 7, Issue 6

Pages 1117–1463

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
    11. Previews
    1. You have free access to this content
      Cover Picture: Naphthalene and Anthracene Complexes Sandwiched by Two {(Cp*)FeI} Fragments: Strong Electronic Coupling between the FeI Centers (Chem. Asian J. 6/2012) (page 1117)

      Dr. Tsubasa Hatanaka, Prof. Dr. Yasuhiro Ohki, Dr. Takashi Kamachi, Dr. Tomonori Nakayama, Prof. Dr. Kazunari Yoshizawa, Prof. Dr. Motomi Katada and Prof. Dr. Kazuyuki Tatsumi

      Article first published online: 25 MAY 2012 | DOI: 10.1002/asia.201290020

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      150 years of German–Japanese friendship was celebrated last year. This issue of Chemistry – An Asian Journal is a special issue dedicated to the occasion. It features top contributions from around the world, including an Essay on the development of biocatalytic processes in both countries, Focus Reviews on molecular spintronics and nonlinear optical properties of confined dyes, as well as over 30 original research papers. The cover picture by Kazuyuki Tatsumi et al. highlights the connection between Germany and Japan, just as the two iron centers in an anthracene double sandwich complex are electronically coupled, as reported by this group as a Full paper on page 1231 ff.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
    11. Previews
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      Inside Cover: Simple Ligand Effects Switch a Hydrogenase Mimic between H2 and O2 Activation (Chem. Asian J. 6/2012) (page 1118)

      Kyoungmok Kim, Dr. Takahiro Matsumoto, Dr. Andrew Robertson, Dr. Hidetaka Nakai and Prof. Seiji Ogo

      Article first published online: 25 MAY 2012 | DOI: 10.1002/asia.201290021

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      The twin catalytic capabilities of an aqueous phase hydrogenase mimic are illustrated. As described in their Full paper on page 1394 ff., Seiji Ogo et al. report that a very small change in the ligand system switches the catalyst between dihydrogen activation, to produce protons and electrons, and dioxygen activation, to produce reduced oxygen species. The harmonious blending of these two cycles opens up a new field in fuel cell catalysis by providing a starting point for future molecular catalysts. In addition, the crystal structure of the oxygen-bound catalyst gives an insight into the acquisition of oxygen tolerance by some NiFe hydrogenases.

  3. Editorials

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
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      Cooperation through the Decades (pages 1120–1121)

      Prof. Gerhard Erker, Prof. Yasuhiro Iwasawa, Prof. Jun Okuda and Prof. Kazuyuki Tatsumi

      Article first published online: 3 MAY 2012 | DOI: 10.1002/asia.201200294

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
    11. Previews
    1. Graphical Abstract: Chem. Asian J. 6/2012 (pages 1123–1133)

      Article first published online: 25 MAY 2012 | DOI: 10.1002/asia.201290022

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
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  6. Essays

    1. Top of page
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    4. Editorials
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    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
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    1. Biocatalytic Processes

      Development of Biocatalytic Processes in Japan and Germany: From Research Synergies to Industrial Applications (pages 1138–1153)

      Prof. Dr. Harald Gröger, Prof. Dr. Yasuhisa Asano, Prof. Dr. Uwe T. Bornscheuer and Prof. Dr. Jun Ogawa

      Article first published online: 30 APR 2012 | DOI: 10.1002/asia.201200105

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      Long tradition: Germany and Japan have long collaborated in the field of biocatalysis, driving industrial innovation in both countries. Biocatalysis first found its way into the chemicals industry by way of microbial processes. Further developments used isolated enzymes and tailor-made enzymes and cells for a range of processes that gave high conversion, optical purity, and space–time yield. Up to now, a broad range of industrialized biocatalytic processes have been developed in both countries (see scheme for selected products), which are summarized in this essay.

  7. Focus Reviews

    1. Top of page
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    4. Editorials
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    7. Essays
    8. Focus Reviews
    9. Communications
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    1. Molecular Spintronics

      Molecular Spintronics Based on Single-Molecule Magnets Composed of Multiple-Decker Phthalocyaninato Terbium(III) Complex (pages 1154–1169)

      Dr. Keiichi Katoh, Hironari Isshiki, Prof. Tadahiro Komeda and Prof. Masahiro Yamashita

      Article first published online: 19 APR 2012 | DOI: 10.1002/asia.201100992

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      I’m spinning around: This review summarizes the switching of the Kondo signal for [TbPc2] single-molecule magnets (SMMs) on Au(111), which is a spin one-half Kondo system owing to the ligand spin. The upper ligand can be rotated in a controlled manner, thereby switching the ligand spin on and off. Thus, information can be encoded at the single-molecular level by controlling the molecular spin through an electric current.

    2. Nonlinear Optics

      Efficient Nonlinear Optical Properties of Dyes Confined in Interlayer Nanospaces of Clay Minerals (pages 1170–1179)

      Dr. Yasutaka Suzuki, Yuta Tenma, Yukihiro Nishioka and Prof. Dr. Jun Kawamata

      Article first published online: 26 APR 2012 | DOI: 10.1002/asia.201200049

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      No feet of clay: Hybridization of organic chromophores with clay minerals maximizes nonlinear optical responses of the chromophores. Such hybrid materials were previously unsuitable as optical materials due to considerable light scattering. However, recent progress in the fabrication of hybrids has enabled the generation of low light-scattering self-standing films of clay/dye hybrids suitable for nonlinear optical devices.

  8. Communications

    1. Top of page
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    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
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    1. Charge-Transfer Complexes

      A Ternary Charge-Transfer Complex composed of Cyclotriveratrylene (CTV) and a Polyoxometalate (POM) with Quinone as an Electronic Modulator (pages 1180–1184)

      Shohei Tashiro, Shizuka Hashida and Mitsuhiko Shionoya

      Article first published online: 21 MAR 2012 | DOI: 10.1002/asia.201200057

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      Triple stack: A facile synthesis of charge-transfer-type crystals composed of CTV and POM was demonstrated. The crystals further accommodated 1,4-benzoquinone as a guest to form a ternary crystal with a donor–acceptor–acceptor arrangement. The electronic spectra of the crystals suggested that the incorporated quinone served as an electronic modulator to adjust the charge-transfer property.

    2. Push–Pull Chromophore

      Proacetylenic Reactivity of a Push–Pull Buta-1,2,3-triene: New Chromophores and Supramolecular Systems (pages 1185–1190)

      Yi-Lin Wu, Dr. Francesca Tancini, Dr. W. Bernd Schweizer, Daniela Paunescu, Prof. Dr. Corinne Boudon, Dr. Jean-Paul Gisselbrecht, Dr. Peter D. Jarowski, Prof. Dr. Enrico Dalcanale and Prof. Dr. François Diederich

      Article first published online: 28 FEB 2012 | DOI: 10.1002/asia.201100997

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      Proacetylenic: An aniline-based donor–acceptor-substituted butatriene exhibits not only cumulene-like dimerization to give a [4]radialene (λmax=756 nm), but also acetylene-like (proacetylenic) reactivity towards tetracyanoethene, affording via [2+2] cycloaddition–cycloreversion a NIR-absorbing zwitterionic chromophore (λmax=825 nm). The cationic charge on the imminium-type nitrogen in the zwitterion is evidenced by host–guest complexation with a tetraphosphonate cavitand.

    3. Aldol Reactions

      Direct-Type Aldol Reactions of Fluorenylidene-Protected/Activated Glycine Esters with Aldehydes for the Synthesis of β-Hydroxy-α-amino Acid Derivatives (pages 1191–1194)

      Dr. Raphaël Rahmani, Masatoshi Matsumoto, Dr. Yasuhiro Yamashita and Prof. Dr. Shū Kobayashi

      Article first published online: 29 MAR 2012 | DOI: 10.1002/asia.201200081

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      Two birds with one stone: Magnesium-base-catalyzed highly diastereoselective direct-type aldol reaction of glycine Schiff base bearing a fluorenylidene moiety as a protecting and activating group was developed. The desired reactions proceeded smoothly at low temperature, and the aldol products were obtained in high yield with high diastereoselectivity.

    4. Asymmetric Catalysis

      Asymmetric Calcium Catalysis: Highly Enantioselective Carbonyl-Ene and Friedel–Crafts Reactions for the Synthesis of Quaternary α-Hydroxy Esters Bearing a Trifluoromethyl Group (pages 1195–1198)

      Prof. Dr. Magnus Rueping, Teerawut Bootwicha, Supakeat Kambutong and Dr. Erli Sugiono

      Article first published online: 21 MAR 2012 | DOI: 10.1002/asia.201200063

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      Enantioselective calcium-catalyzed addition reactions of styrene and indole derivatives with trifluoropyruvates have been developed. The alkaline-earth metal-catalyzed reactions proceed smoothly to afford the corresponding products in high yields and with good to excellent enantioselectivities under mild reaction conditions.

    5. Carbonylative Dimerization

      Palladium-Catalyzed Carbonylative Dimerization of Styrenes to 1,5-Diarylpent-1-en-3-ones (pages 1199–1202)

      Dr. Xiao-Feng Wu, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 19 JAN 2012 | DOI: 10.1002/asia.201100836

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      A general palladium-catalyzed carbonylative dimerization of styrenes has been developed. Starting from commercial available styrenes, symmetrical 1,5-diarylpent-1-en-3-ones were produced in good to excellent yields (see scheme; dppp=1,3-bis(diphenylphosphino)propane).

    6. Artificial Metalloenzymes

      Artificial Dicopper Oxidase: Rational Reprogramming of Bacterial Metallo-β-lactamase into a Catechol Oxidase (pages 1203–1207)

      Dr. Nobutaka Fujieda, Atsuhiko Hasegawa, Ken-ichi Ishihama and Prof. Shinobu Itoh

      Article first published online: 16 MAR 2012 | DOI: 10.1002/asia.201101014

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      Teaching metalloenzymes new tricks: An artificial type III dicopper oxidase has been developed using a hydrolytic enzyme, metallo-β-lactamase, as a metal-binding platform. The triple mutant D88G/S185H/P224G redesigned by computer-assisted structural analysis showed spectroscopic features similar to those of type III copper proteins and exhibited a high catalytic activity in the oxidation of catechols under aerobic conditions.

    7. C[BOND]H Activation

      Undirected Arene and Chelate-Assisted Olefin C-H Bond Activation: [RhIIICp*]-Catalyzed Dehydrogenative Alkene–Arene Coupling as a New Pathway for the Selective Synthesis of Highly Substituted Z Olefins (pages 1208–1212)

      Dr. Joanna Wencel-Delord, Corinna Nimphius, Prof. Dr. Frederic W. Patureau and Prof. Dr. Frank Glorius

      Article first published online: 2 MAR 2012 | DOI: 10.1002/asia.201101018

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      Undirected/Directed Cross-Coupling: A new dehydrogenative RhIII-catalyzed cross-coupling reaction between bromoarenes bearing no directing group and vinylic substrates substituted by a chelating group is reported. An original reaction mechanism enables the use of internal alkenes in a Z-selective coupling. The application of 1,3-disubstituted or 1,2-homodisubstituted arenes leads to the formation of highly functionalized, complex, and valuable olefins as one single isomer.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Essays
    8. Focus Reviews
    9. Communications
    10. Full Papers
    11. Previews
    1. Metal Hydrides

      Thermal Ammonia Activation by Cationic Transition-Metal Hydrides of the First Row – Small but Mighty (pages 1214–1220)

      Robert Kretschmer, Dr. Maria Schlangen and Prof. Dr. Helmut Schwarz

      Article first published online: 7 MAR 2012 | DOI: 10.1002/asia.201101045

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      Wanted—Dead or Alive: The reactions of cationic transition-metal hydrides MH+ of the first row with ammonia have been studied both experimentally and computationally. All ions investigated are wanted; they don′t spare ammonia and react predominantly under N[BOND]H bond activation (Sc, Ti, Cr), ligand exchange (Co, Ni), or proton transfer (Mn, Fe, Zn).

    2. Protein Inhibitors

      Synthesis of Optically Pure Norcantharidin Analogue NCA-01, a Highly Selective Protein Phosphatase 2B Inhibitor, and its Derivatives (pages 1221–1230)

      Dr. Tadashi Shimizu , Masato Iizuka, Hiroko Matsukura, Dr. Daisuke Hashizume and Prof. Dr. Mikiko Sodeoka

      Article first published online: 5 APR 2012 | DOI: 10.1002/asia.201200077

      Protein phosphatase 2B inhibitor: Optically pure norcantharidin analogue NCA-01, a highly selective inhibitor of protein phosphatase 2B (PP2B), has been synthesized. The PP2B-inhibitory activity of NCA-01 and its derivatives were independent of the enantiomeric form.

    3. Sandwich Complexes

      Naphthalene and Anthracene Complexes Sandwiched by Two {(Cp*)FeI} Fragments: Strong Electronic Coupling between the FeI Centers (pages 1231–1242)

      Dr. Tsubasa Hatanaka, Prof. Dr. Yasuhiro Ohki, Dr. Takashi Kamachi, Dr. Tomonori Nakayama, Prof. Dr. Kazunari Yoshizawa, Prof. Dr. Motomi Katada and Prof. Dr. Kazuyuki Tatsumi

      Article first published online: 12 APR 2012 | DOI: 10.1002/asia.201101037

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      Caught in the middle: Dinuclear {(Cp*)FeI} complexes (Cp*=η5-C5Me5) bridged by naphthalene (left) and anthracene (right) were prepared. These complexes exhibited large electrochemical potential separations between successive one-electron redox events and the mixed valence complexes were synthesized by chemical oxidation.

    4. Organometallic Cages

      Self-Assembled Hexanuclear Organometallic Cages: Synthesis, Characterization, and Host–Guest Properties (pages 1243–1250)

      Dr. Ying-Feng Han, Hao Li, Zhi-Fang Zheng and Prof. Dr. Guo-Xin Jin

      Article first published online: 5 MAR 2012 | DOI: 10.1002/asia.201100999

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      The perfect host: The synthesized iridium- and rhodium-based hexanuclear organometallic cages (figure, left) can form inclusion systems with a wide variety of π-donor substrates. The 1:1 complexation of the resulting supramolecular assemblies were confirmed by 1H NMR spectroscopy, and the formation of discrete 1:1 donor–acceptor complexes, such as [Pt(acac)2]⊂6 a (figure, right), were confirmed by their single-crystal X-ray analyses.

    5. Heterogeneous Catalysis

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      Kelvin Probe Force Microscopy Study of a Pt/TiO2 Catalyst Model Placed in an Atmospheric Pressure of N2 Environment (pages 1251–1255)

      Ryohei Kokawa, Dr. Masahiro Ohta, Prof. Akira Sasahara and Prof. Hiroshi Onishi

      Article first published online: 18 APR 2012 | DOI: 10.1002/asia.201101001

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      A clear view: A catalyst model comprising platinum nanoparticles deposited on a TiO2(110) wafer was characterized with Kelvin probe force microscopy. The topography and local work function of individual nanoparticles were observed with single-nanometer resolution in a N2 environment of one atmospheric pressure. The ability of the microscope was demonstrated in observing charge transfer across metal–oxide interfaces even in the presence of vapor.

    6. C[BOND]H Arylation

      Mechanistic Studies on the Pd-catalyzed Direct C[BOND]H Arylation of 2-Substituted Thiophene Derivatives with Arylpalladium Bipyridyl Complexes (pages 1256–1260)

      Marc Steinmetz, Kirika Ueda, Prof. Dr. Stefan Grimme, Dr. Junichiro Yamaguchi, Dr. Sylvia Kirchberg, Prof. Dr. Kenichiro Itami and Prof. Dr. Armido Studer

      Article first published online: 14 FEB 2012 | DOI: 10.1002/asia.201101011

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      The counteranion does the job! Reactions of 2-substituted thiophenes with cationic PhPdbipy complexes afforded either the corresponding C(4) or C(5)-phenylated thiophene derivatives depending on the counteranion present. DFT calculations revealed that reactions occur via carbopalladation and not via electrophilic palladation.

    7. Femtochemistry

      Strong Nuclear Ring Currents and Magnetic Fields in Pseudorotating OsH4 Molecules Induced by Circularly Polarized Laser Pulses (pages 1261–1295)

      Dr. Ingo Barth, Dr. Christian Bressler, Prof. Shiro Koseki and Prof. Jörn Manz

      Article first published online: 2 MAR 2012 | DOI: 10.1002/asia.201100776

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      Larger than ever before: A huge nuclear ring current—1.53 e per fs—and as a consequence, a gigantic magnetic field—623 Tesla—may be induced by means of a circularly polarized laser pulse that is designed to drive the pseudorotation of the central nucleus of the tetrahedral OsH4 molecule.

    8. Quantum Chemistry

      Are They Linear, Bent, or Cyclic? Quantum Chemical Investigation of the Heavier Group 14 and Group 15 Homologues of HCN and HNC (pages 1296–1311)

      Dr. Deepa Devarajan and Prof. Dr. Gernot Frenking

      Article first published online: 13 APR 2012 | DOI: 10.1002/asia.201200022

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      To bend or not to bend: The potential-energy surface of the system involving atoms H, X, and E (X=N–Bi; E=C–Pb) has been studied to answer a number of questions about the geometry of HCN and HNC and the bonding between the group 14 and 15 elements in the heavier analogues of the HCN–HNC system. The results of charge- and energy-decomposition analyses of the systems are presentedfor the charge f.

    9. Dyes

      Tuning the Spectroscopic, Electrochemical, and Photovoltaic Properties of Triaryl Amine Based Sensitizers through Ring-Fused Thiophene Bridges (pages 1312–1319)

      Quan Liu, Quan-You Feng, Prof. Hiroko Yamada, Prof. Zhong-Sheng Wang, Prof. Noboru Ono, Prof. Xiao-Zeng You and Prof. Zhen Shen

      Article first published online: 27 JAN 2012 | DOI: 10.1002/asia.201100748

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      Sensitive souls: A series of sensitizers for dye-sensitized solar cells features ring-fused thiophene bridges between donor and acceptor moieties. The absorption spectra of the push–pull sensitizers all exhibit intense intramolecular charge transfer bands in the visible region (see picture), and solar cells based on the dyes show good incident photon to current conversion efficiencies.

    10. Ring-Opening Polymerization

      Group 3 Metal Initiators with an [OSSO]-Type Bis(phenolate) Ligand for the Stereoselective Polymerization of Lactide Monomers (pages 1320–1330)

      Dipl.-Chem. Andreas Kapelski, Dr. Jean-Charles Buffet, Dr. Thomas P. Spaniol and Prof. Jun Okuda

      Article first published online: 24 FEB 2012 | DOI: 10.1002/asia.201100826

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      Backbone requirements: A series of rare-earth metal bis(dimethylsilylamido) complexes with [OSSO]-type bis(phenolate) ligands [Ln{N(SiHMe2)2}3(thf)x] (Ln=Sc, x=1; Y, x=2; thf=tetrahydrofuran; see picture) were synthesized and used in the ring-opening polymerization of rac- and meso-lactides.

    11. Polyoxometalates

      Stabilization of High-Valence Ruthenium with Silicotungstate Ligands: Preparation, Structural Characterization, and Redox Studies of Ruthenium(III)-Substituted α-Keggin-Type Silicotungstates with Pyridine Ligands, [SiW11O39RuIII(Py)]5− (pages 1331–1339)

      Prof. Dr. Masahiro Sadakane, Sachie Moroi, Yoshifumi Iimuro, Dr. Natalya Izarova, Prof. Dr. Ulrich Kortz, Prof. Dr. Shinjiro Hayakawa, Kazuo Kato, Dr. Shuhei Ogo, Dr. Yusuke Ide, Prof. Dr. Wataru Ueda and Prof. Dr. Tsuneji Sano

      Article first published online: 6 FEB 2012 | DOI: 10.1002/asia.201100853

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      Py in the sky: Preparation, structural characterization, and redox studies of RuIII–pyridine-substituted α-Keggin-type silicotungstate hybrid molecules, [SiW11O39RuIII(Py)]5−, are reported. RuIV was stabilized in silicotungstate.

    12. Porphyrinoids

      Synthesis of A2B6-Type [36]Octaphyrins: Copper(II)-Metalation-Induced Fragmentation Reactions to Porphyrins and N-Fusion Reactions of meso-(3-Thienyl) Substituents (pages 1340–1346)

      Hirotaka Mori, Dr. Naoki Aratani and Prof. Dr. Atsuhiro Osuka

      Article first published online: 23 JAN 2012 | DOI: 10.1002/asia.201100919

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      Make ’em and break ’em: A2B6-type [36]octaphyrins were prepared in moderate yields by the cross condensation of tetrapyrromethane with aryl aldehydes. Compounds bearing 2,4,6-trifluorophenyl, 2,6-dichlorophenyl, and phenyl substituents underwent CuII-metalation-induced fragmentation to give AB3-type CuII porphyrins, while that bearing a 3-thienyl substituent underwent N-thienyl fusion to provide a modestly aromatic [38]octaphyrin (see scheme).

    13. Frustrated Lewis Pairs

      Reaction of Frustrated Lewis Pairs with Ketones and Esters (pages 1347–1356)

      Dr. Bao-Hua Xu, Raul Alfonso Adler Yanez, Hiroshi Nakatsuka, Prof. Dr. Masato Kitamura, Dr. Roland Fröhlich, Dr. Gerald Kehr and Prof. Dr. Gerhard Erker

      Article first published online: 7 MAR 2012 | DOI: 10.1002/asia.201100960

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      Off the beaten path: Some frustrated Lewis pairs (FLP) react with unsaturated ketones and esters by means of conjugate addition to the activated carbon–carbon double or triple bond to give the respective P/B addition products. This is different from the FLP reactivity towards, for example, cinnamaldehyde, where 1,2-addition to the carbonyl group is observed.

    14. Catalytic Arylation

      Catalytic Arylation of a C[BOND]H Bond in Pyridine and Related Six-Membered N-Heteroarenes Using Organozinc Reagents (pages 1357–1365)

      Isao Hyodo, Dr. Mamoru Tobisu and Prof. Dr. Naoto Chatani

      Article first published online: 22 MAR 2012 | DOI: 10.1002/asia.201100971

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      Less is more: Pyridine, pyrazine, quinoline and related electron-deficient N-heteroarenes can be arylated at the most electrophilic site using organozinc reagents through nickel catalysis. This protocol serves as a complementary method to catalytic direct arylation reactions.

    15. Photocatalysis

      Highly Dispersed Platinum Nanoparticles on TiO2 Prepared by Using the Microwave-Assisted Deposition Method: An Efficient Photocatalyst for the Formation of H2 and N2 from Aqueous NH3 (pages 1366–1371)

      Kojirou Fuku, Dr. Takashi Kamegawa, Dr. Kohsuke Mori and Prof. Hiromi Yamashita

      Article first published online: 7 FEB 2012 | DOI: 10.1002/asia.201100984

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      Nuked catalysts! Nanosized platinum particles loaded on TiO2 (Pt–TiO2) were synthesized by using a microwave-assisted deposition method with the aim of developing a highly efficient photocatalyst for the decomposition of aqueous NH3 into H2 and N2 in a stoichiometric molar ratio under inert conditions (see picture).

    16. Nucleophilic Substitution Reactions

      SN1-Type Substitution Reactions of N-Protected β-Hydroxytyrosine Esters: Stereoselective Synthesis of β-Aryl and β-Alkyltyrosines (pages 1372–1382)

      David Wilcke, Dr. Eberhardt Herdtweck and Prof. Dr. Thorsten Bach

      Article first published online: 7 MAR 2012 | DOI: 10.1002/asia.201101016

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      The choice of protecting groups decides about the stereochemical fate of the intermediate benzylic carbocation formed in the reactions of substrates 1. If the ester group is significantly bulkier than the amino group, syn-products (syn-2) prevail. If the size of the amino group is increased by dibenzylation and the ester group is small, the respective anti-products (anti-3) are formed with significant diastereoselectivity.

    17. Platinacycles

      Reaction of “Non-Symmetrical” 1,2,4-Trithiolanes with [(phosphane)Pt02-nbe)] Complexes (pages 1383–1393)

      Dr. Thomas Weisheit, Dr. Antje Kriltz, Dr. Helmar Görls, Prof. Dr. Grzegorz Mlostoń, Prof. Dr. Wolfgang Imhof and Prof. Dr. Wolfgang Weigand

      Article first published online: 13 MAR 2012 | DOI: 10.1002/asia.201101017

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      Tri(thio) Lanes Express: The reactions of two unsymmetrical 1,2,4-trithiolanes with phosphane Pt02-nbe) complexes were studied. Based on kinetic measurements of the thermally induced fragmentation of a six-membered platinacycle by using UV/Vis spectroscopy along with DFT-calculations, a refined mechanism for the reactions of [Pt0(PPh3)22-nbe)] with 1,2,4-trithiolanes was proposed.

    18. Ligand Effects

      Simple Ligand Effects Switch a Hydrogenase Mimic between H2 and O2 Activation (pages 1394–1400)

      Kyoungmok Kim, Dr. Takahiro Matsumoto, Dr. Andrew Robertson, Dr. Hidetaka Nakai and Prof. Seiji Ogo

      Article first published online: 1 MAR 2012 | DOI: 10.1002/asia.201101020

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      At the flick of a switch: A [NiRu] biomimetic system for O2-tolerant [NiFe]hydrogenases was constructed. Electron donation to the [NiRu] center switched the system between activation of H2 and O2. Furthermore, a [NiRu]–peroxo species, which was capable of oxidizing p-hydroquinone, was considered as a biomimetic analogue of O2-bound species (OBS) of O2-tolerant [NiFe]hydrogenases.

    19. Electrophilicity Parameters

      Electrophilicities of Bissulfonyl Ethylenes (pages 1401–1407)

      Dr. Haruyasu Asahara and Prof. Dr. Herbert Mayr

      Article first published online: 27 MAR 2012 | DOI: 10.1002/asia.201101046

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      Quantifying Electrophilicity: Kinetics of the reactions of 1,1-bissulfonyl-ethylenes with carbon nucleophiles have been determined to integrate these Michael acceptors in our comprehensive electrophilicity scales and to compare them with other electrophiles. The electrophilicities depend only slightly on conformational restrictions, and as a rule of thumb, one can assume that two geminal phenylsulfonyl groups exert a similar activation as one nitro group.

    20. Organometallic Chemistry

      Hydrido(hydrosilylene)tungsten Complexes: Dynamic Behavior and Reactivity Toward Acetone (pages 1408–1416)

      Dr. Takahito Watanabe, Dr. Hisako Hashimoto and Prof. Hiromi Tobita

      Article first published online: 22 MAR 2012 | DOI: 10.1002/asia.201101058

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      Silyl smooth transitions! Hydrogen migration between the tungsten center and the silylene ligand or acetone molecule coordinated to the silylene ligand occurred extensively in hydrido(hydrosilylene)tungsten complexes. W[BOND]H/Si[BOND]H exchange, α-H abstraction, hydrosilylation, and C[DOUBLE BOND]O bond cleavage in the reaction with acetone were all regarded to be driven by the strong Lewis acidity of the silylene ligand (see scheme).

    21. Protic Pincer Complexes

      Synthesis, Structures, and Reactivities of Pincer-Type Ruthenium Complexes Bearing Two Proton-Responsive Pyrazole Arms (pages 1417–1425)

      Akihiro Yoshinari, Akira Tazawa, Prof. Dr. Shigeki Kuwata and Prof. Dr. Takao Ikariya

      Article first published online: 19 MAR 2012 | DOI: 10.1002/asia.201200014

      Thumbnail image of graphical abstract

      A pinch of proton: Pincer-type ruthenium complex featuring two proton-delivering pyrazole arms underwent sequential deprotonation to afford , which was further converted into side-on peroxo complex and end-on dinitrogen complex . Dinuclear complex with a less hindered pincer ligand was also synthesized.

    22. Photosensitizers

      Unsymmetric Platinum(II) Bis(aryleneethynylene) Complexes as Photosensitizers for Dye-Sensitized Solar Cells (pages 1426–1434)

      Dr. Feng-Rong Dai, Dr. Yung-Chung Chen, Lai-Fan Lai, Dr. Wen-Jun Wu, Chao-Hua Cui, Gui-Ping Tan, Xing-Zhu Wang, Prof. Jiann-T'suen Lin, Prof. He Tian and Prof. Wai-Yeung Wong

      Article first published online: 11 APR 2012 | DOI: 10.1002/asia.201200027

      Tuning organometallic dyes: The synthesis, characterization, and photovoltaic properties of a new series of unsymmetric platinum(II) bis(aryleneethynylene) photosensitizers (see Figure) for dye-sensitized solar cells are described. The incorporation of a strongly electron-donating group significantly enhances the absorption abilities of the complexes. A power conversion efficiency of up to 1.57 % was achieved under illumination of an AM 1.5G solar cell simulator.

    23. Oxazoles

      Gold Catalysis: One-Pot Alkylideneoxazoline Synthesis/Alder-Ene Reaction (pages 1435–1442)

      Prof. Dr. A. Stephen K. Hashmi and Dipl.-Chem. Anna Littmann

      Article first published online: 20 MAR 2012 | DOI: 10.1002/asia.201200046

      Thumbnail image of graphical abstract

      The famous five: The one-pot reaction of readily available N-propargylamides and azodicarboxylates provided functionalized oxazoles through a five-step cycloisomerization/Alder-ene reaction pathway.

    24. Organic Light-Emitting Diodes

      Carbazolyl Benzo[1,2-b:4,5-b′]difuran: An Ambipolar Host Material for Full-Color Organic Light-Emitting Diodes (pages 1443–1450)

      Dr. Chikahiko Mitsui, Dr. Hayato Tsuji, Dr. Yoshiharu Sato and Prof. Dr. Eiichi Nakamura

      Article first published online: 29 MAR 2012 | DOI: 10.1002/asia.201200062

      Thumbnail image of graphical abstract

      The (Ambi)Polar Express: A newly designed ambipolar material, CZBDF, was synthesized. CZBDF possesses a wide-gap character, well-balanced and high hole and electron mobilities of larger than 10−3 cm2 V−1 s−1, and a high thermal stability. This material functions as an emissive material and a host material for OLEDs and enabled us to produce heterojunction as well as p-i-n homojunction OLED devices that emit full-color visible light with high efficiency.

    25. Donor–Acceptor Systems

      Dendronized Fullerene–Porphyrin Conjugates in ortho, meta, and para Positions: A Charge-Transfer Assay (pages 1451–1459)

      Evangelos Krokos, Christina Schubert, Fabian Spänig, Michaela Ruppert, Prof. Dr. Andreas Hirsch and Prof. Dr. Dirk M. Guldi

      Article first published online: 19 MAR 2012 | DOI: 10.1002/asia.201200068

      Thumbnail image of graphical abstract

      Get into position: A series of porphyrin—fullerene conjugates have been synthesized and studied in both nonaqueous and aqueous solutions. The microenvironment around the redox-active components has been altered through varying the topology of the dendrimers attached to the porphyrin (see scheme). Photophysical and chemical investigations provide insights into the effect that this has on electron transfer.

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      Preview: Chem. Asian J. 7/2012 (page 1463)

      Article first published online: 25 MAY 2012 | DOI: 10.1002/asia.201290024

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