ChemCatChem

Cover image for Vol. 5 Issue 6

June 2013

Volume 5, Issue 6

Pages 1213–1613

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Masthead
    5. News
    6. Concept
    7. Review
    8. Minireview
    9. Highlights
    10. Conference Report
    11. Communications
    12. Full Papers
    1. You have free access to this content
      Cover Picture: Minimizing the Formation of Coke and Methane on Co Nanoparticles in Steam Reforming of Biomass-Derived Oxygenates (ChemCatChem 6/2013) (page 1213)

      Dr. Junming Sun, Dr. Donghai Mei, Dr. Ayman M. Karim, Prof. Dr. Abhaya K. Datye and Prof. Dr. Yong Wang

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/cctc.201390024

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      Coke? No thank you! The cover picture shows the use of cobalt nanoparticles supported on graphitized activated carbon in acetone steam reforming (ASR). In their Communication on p. 1299 ff., D. Mei, Y. Wang et al. describe their catalyst's high selectivity to H2 (>80 %), low selectivity to methane (<5 %), and its strong resistance to coke formation. Conversion to acetone is approximately 98 % and remains almost constant (<2 % decrease) over 70 h time-on-stream. This observation is supported further by a theoretical analysis of the ASR reaction mechanism.

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      Inside Cover: Organometallic Catalysts for Use in a Fuel Cell (ChemCatChem 6/2013) (page 1214)

      Dr. Takahiro Matsumoto, Kyoungmok Kim, Dr. Hidetaka Nakai, Prof. Takashi Hibino and Prof. Seiji Ogo

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/cctc.201390025

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      An ingenious spin on fuel cells The cover picture shows a genie watching an organometallic fuel cell to observe its reaction mechanism. In their Full Paper on p. 1368 ff., T. Hibino, S. Ogo et al. describe an organometallic [NiIIRuIV] peroxo catalyst that functions as the cathode in a fuel cell with a 240 % increase in power output over their previous systems. The organometallic catalyst is active in both solid and solution phases and allows for observation of the mechanism, providing opportunity for further improvement to the hydrogen economy.

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      Inside Back Cover: Hydroxynitrile Lyases Do Not Catalyse the Promiscuous Addition of Cyanide to Imines (ChemCatChem 6/2013) (page 1615)

      Dr. Guzman Torrelo, Dr. Jianfeng Jin and Prof. Ulf Hanefeld

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/cctc.201390029

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      Blank reaction! The cover picture shows how hydroxynitrile lyases do not catalyze the addition of cyanide to an imine, which is mediated rather by the water present in the reaction media. In their Communication on p. 1304 ff., G. Torrelo et al. report that this addition, which is part of the classical Strecker synthesis, occurs in a non-enzymatic way and two structurally different hydroxynitrile lyases do not catalyze this reaction. These results discard the promiscuous catalytic activity attributed to these enzymes more than 10 years ago.

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      Back Cover: In Situ Fabrication of Ag/Ag3PO4/Graphene Triple Heterostructure Visible-Light Photocatalyst through Graphene-Assisted Reduction Strategy (ChemCatChem 6/2013) (page 1616)

      Dr. Baojiang Jiang, Yanhui Wang, Dr. Jian-Qiang Wang, Dr. Chungui Tian, Wenjun Li, Qingmao Feng, Dr. Qingjiang Pan and Prof. Honggang Fu

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/cctc.201390030

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      Never to fade away The cover picture shows visible-light photocatalysis by Ag/Ag3PO4/graphene triple heterostructure composites in the degradation of organic contaminants. In their Full Paper on p. 1359 ff., B. Jiang, H. Fu et al. describe the in situ fabrication of the Ag/Ag3PO4/graphene triple heterostructure through the redox reaction between Ag+ and graphene. This structure could improve the charge-separation rate under visible light and the inhibition of the photocorrosion phenomenon of Ag3PO4 gives high structural stability. This facile method has promise for the fabrication of diverse graphene-based heterostructure photocatalysts.

  2. Graphical Abstract

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    2. Cover Pictures
    3. Graphical Abstract
    4. Masthead
    5. News
    6. Concept
    7. Review
    8. Minireview
    9. Highlights
    10. Conference Report
    11. Communications
    12. Full Papers
  3. Masthead

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    1. MASTHEAD: ChemCatChem 6/2013 (page 1233)

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/cctc.201390027

  4. News

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  5. Concept

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    1. Diastereodivergent Processes in Palladium-Catalyzed Allylic Alkylation (pages 1239–1247)

      Maria Teresa Oliveira, Dr. Davide Audisio, Supaporn Niyomchon and Dr. Nuno Maulide

      Version of Record online: 21 FEB 2013 | DOI: 10.1002/cctc.201200644

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      Lost identity: Pd-catalyzed asymmetric allylic alkylation allows the quantitative deracemization of chiral substrates. The reaction can be diastereodivergent if multiple diastereomers of the product are possible and if a specific process offers the ability to generate each of them. Herein, the advances made in this field are summarized and novel diastereodivergent deracemization and diastereodivergent de-epimerization concepts are introduced and discussed.

  6. Review

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    1. You have full text access to this OnlineOpen article
      Biocatalytic Methods for C[BOND]C Bond Formation (pages 1248–1272)

      Dr. Kateryna Fesko and Dr. Mandana Gruber-Khadjawi

      Version of Record online: 21 FEB 2013 | DOI: 10.1002/cctc.201200709

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      One plus One makes One: This review describes the latest results regarding optimizations and applications of the novel as well as known enzymes for carbon-carbon bond formation.

  7. Minireview

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    1. From Oxide-Supported Palladium to Intermetallic Palladium Phases: Consequences for Methanol Steam Reforming (pages 1273–1285)

      Dr. Harald Lorenz, Dr. Christoph Rameshan, Thomas Bielz, Prof. Norbert Memmel, Werner Stadlmayr, Lukas Mayr, Dr. Qian Zhao, Dr. Soipatta Soisuwan, Prof. Dr. Bernhard Klötzer and Dr. Simon Penner

      Version of Record online: 20 FEB 2013 | DOI: 10.1002/cctc.201200712

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      Steam powered: Recent work towards unraveling the CO2 selectivity of a number of unsupported and supported Pd[BOND]X intermetallic compounds (X=Zn, Ga, In, Sn, and Ge) is reviewed and the importance of bifunctional synergy between the catalyst constituents for establishing a state of pronounced CO2 selectivity is highlighted.

  8. Highlights

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    1. Ship in a Bottle: In situ Confined Growth of Complex Yolk-shell Catalysts (pages 1287–1288)

      James Goebl and Prof. Yadong Yin

      Version of Record online: 15 APR 2013 | DOI: 10.1002/cctc.201300129

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      Ship in a Bottle: The confined synthesis of binary anisotropic nanoparticle catalysts within a hollow support allows for the creation of highly complex new catalyst architectures.

    2. Asymmetric Allylic Alkylation of Alkene through Direct C (sp3)-H Functionalization (pages 1289–1290)

      Dr. Guihua Chen, Kang Chen and Prof. Zhang-Jie Shi

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/cctc.201300015

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      Put your Trost in this reaction: The first catalytic asymmetric Tsuji–Trost reaction via allylic C[BOND]H activation was realized using a new class of chiral phosphoramidite ligands. This work represents a considerable breakthrough in palladium catalyzed asymmetric allylic C[BOND]H alkylations.

    3. Enantioselective Intramolecular 1,5-Hydride Transfer/Cyclization through the Direct Functionalization of C(sp3)-H Bonds Adjacent to a Heteroatom: From Nitrogen to Oxygen (pages 1291–1293)

      Prof. Dr. Min Wang

      Version of Record online: 5 APR 2013 | DOI: 10.1002/cctc.201200692

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      Direct and effective: the asymmetric catalytic 1,5-hydride transfer/cyclization, internal redox process, has recently been reported. This transformation is an effective method to functionalization of sp3-C[BOND]H bond adjacent to heteroatom.

    4. Nickel Catalyst Boosts Solar Hydrogen Generation of CdSe Nanocrystals (pages 1294–1295)

      Gongming Wang and Prof. Yat Li

      Version of Record online: 3 APR 2013 | DOI: 10.1002/cctc.201300034

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      The sun has got his hat on! A simple, robust and highly active nickel complex catalyst was reported for photo-generation of hydrogen. The Ni catalyst modified CdSe nanocrystal system achieved a benchmark turnover frequency of >600 000 and extraordinary longevity of 360 h.

  9. Conference Report

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    1. German Catalysis, Celebrated in Weimar (pages 1297–1298)

      Dr. Marc Armbrüster, Dr. Malte Behrens, Dr. Barthel Engendahl, Dr. Mehtap Oezaslan, Dr. Marcus Rose and Dr. Christoph Sprung

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cctc.201300310

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      Catalysis, reloaded: At the 46th annual meeting of the German Catalysis Society, hosted by DECHEMA, 300 researchers presented innovative catalytic systems and concepts, with overlaps between homogeneous, heterogeneous, and biocatalysis described in many cases. The conference, attended by over 500 participants, was also an excellent forum for nano-, electro-, and photocatalysis, with a strong industrial focus.

  10. Communications

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    11. Communications
    12. Full Papers
    1. Minimizing the Formation of Coke and Methane on Co Nanoparticles in Steam Reforming of Biomass-Derived Oxygenates (pages 1299–1303)

      Dr. Junming Sun, Dr. Donghai Mei, Dr. Ayman M. Karim, Prof. Dr. Abhaya K. Datye and Prof. Dr. Yong Wang

      Version of Record online: 1 MAR 2013 | DOI: 10.1002/cctc.201300041

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      Small and active: Co nanoparticles supported on graphitized activated carbon are highly stable and selective for acetone steam reforming. DFT calculations were performed to analyze the reaction mechanism. The present work provides insight into the rational design of catalysts that can selectively oxidize species arising from C[BOND]C bond cleavage of biomass-derived oxygenates to maximize H2 selectivity and minimize the formation of coke and methane.

    2. Hydroxynitrile Lyases Do Not Catalyse the Promiscuous Addition of Cyanide to Imines (pages 1304–1307)

      Dr. Guzman Torrelo, Dr. Jianfeng Jin and Prof. Ulf Hanefeld

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/cctc.201200804

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      Blank reaction: Ten years ago, it was reported that hydroxynitrile lyase (HNL) from defatted almond meal shows catalytic promiscuity in the addition of cyanide to imines. Here we provide experimental evidence that this addition occurs in a non-enzymatic reaction, and two structurally different HNLs do not catalyse this reaction.

    3. Manipulation of the Reducibility of Ceria-Supported Au Catalysts by Interface Engineering (pages 1308–1312)

      Lei Wang, Dr. Gang Lu, Dan Yang, Jin Wang, Zhibin Zhu, Prof. Zhixiang Wang and Prof. Kebin Zhou

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/cctc.201300043

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      Baby face: Interface engineering of ceria-supported Au catalysts was achieved by a combination of DFT calculations and synthetic techniques. The reducibility of the Au/ceria catalysts was determined by the interfacial [BOND]Au[BOND]O[BOND]Cen[BOND] structures.

    4. Direct C[BOND]H bond Arylation in Water Promoted by (O,O)- and (O,N)-Chelate Ruthenium(II) Catalysts (pages 1313–1316)

      Dr. Keisham S. Singh and Prof. Dr. Pierre H. Dixneuf

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201300031

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      Two strong arms to hold the catalyst: (O,O) and (O,N)-chelate ruthenium(II) complexes obtained from kojic acid or glycine are efficient catalysts for the (hetero)arylation of Cmath image[BOND]H bonds if associated to potassium pivalate. Moreover, the catalysts operate in water.

    5. Cationic-Rhodium-Catalyzed Kinetic Resolution of Allylic Alcohols through a Redox Isomerization Reaction in a Noncoordinating Solvent (pages 1317–1320)

      Kai Ren, Lei Zhang, Bei Hu, Mengmeng Zhao, Yahui Tu, Dr. Xiaomin Xie, Dr. Tony Y. Zhang and Prof. Zhaoguo Zhang

      Version of Record online: 1 MAR 2013 | DOI: 10.1002/cctc.201300014

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      On the [Rh]oad again: A series of optically pure allylic alcohols is obtained through the Rh/BINAP-catalyzed redox isomerization of racemic allylic alcohols. An improved system involves the use of cationic rhodium and a noncoordinating solvent, in which aromatic and aliphatic allylic alcohols are effectively resolved with kf/ks (kf=rate of fast reaction, ks=rate of slow reaction) values up to 24.

    6. Synthesis of Cyclic Carbonates from Epoxides and CO2 under Mild Conditions Using a Simple, Highly Efficient Niobium-Based Catalyst (pages 1321–1324)

      Antoine Monassier, Dr. Valerio D'Elia, Dr. Mirza Cokoja, Dr. Hailin Dong, Dr. Jérémie D. A. Pelletier, Prof. Dr. Jean-Marie Basset and Prof. Dr. Fritz E. Kühn

      Version of Record online: 20 FEB 2013 | DOI: 10.1002/cctc.201200916

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      Like a sore thumb: Niobium stands out among neighboring transition metals for its catalytic performance in the synthesis of cyclic carbonates. Readily available NbCl5 is a very efficient catalyst for the preparation of industrially relevant carbonates at ambient temperature, low CO2 pressure, and low concentrations. DMAP=N,N-dimethylaminopyridine.

    7. Enantioselective Synthesis of N-Substituted Aspartic Acids Using an Engineered Variant of Methylaspartate Ammonia Lyase (pages 1325–1327)

      Dr. Vinod Puthan Veetil, Hans Raj, Dr. Marianne de Villiers, Pieter G. Tepper, Prof. Dr. Frank J. Dekker, Prof. Dr. Wim J. Quax and Prof. Dr. Gerrit J. Poelarends

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200906

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      Unnatural reactions: We report the synthesis of a large variety of N-substituted aspartic acids by addition of structurally diverse amines to fumaric acid; the reactions are catalyzed by a previously engineered variant of methylaspartate ammonia lyase. The additions are highly enantioselective and yield only the L enantiomers of the corresponding amino acid products (>99 % ee).

    8. Lignin-Based Green Catalyst for the Chemical Fixation of Carbon Dioxide with Epoxides To Form Cyclic Carbonates under Solvent-Free Conditions (pages 1328–1333)

      Zhilian Wu, Prof. Haibo Xie, Xue Yu and Prof. Enhui Liu

      Version of Record online: 12 FEB 2013 | DOI: 10.1002/cctc.201200894

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      Fixated on CO2: Lignin, the second most-abundant biorenewable polymer on our planet, was successfully used as a catalyst in the presence of KI in the cycloaddition of CO2 with a series of epoxides. This method represents an integrated and ideal green process for the utilization of “carbon-neutral” resources.

    9. One-Pot, Two-Step Protocol for the Catalytic Asymmetric Synthesis of Optically Active N,O- and O,O-Acetals (pages 1334–1339)

      M. Fatih Polat, Lara Hettmanczyk, Dr. Wei Zhang, Dr. Zoltan Szabo and Dr. Johan Franzén

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/cctc.201200860

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      N,O problem: An asymmetric catalytic one-pot N,O- and O,O-acetalization cascade is presented. This strategy is based on catalytic asymmetric conjugate addition and subsequent acid-catalyzed acetal formation that allows efficient and fast construction of functionalized dioxabicyclo- and oxaazabicyclo[3.3.1]nonane structures that are important motifs in several natural products and pharmaceutically interesting compounds.

    10. Ruthenium(II)[BOND]Phosphite Complexes as Catalysts for the Hydrogenation of Carbon Dioxide (pages 1340–1343)

      Dr. Keven Muller, Dr. Yu Sun and Prof. Dr. Werner R. Thiel

      Version of Record online: 21 FEB 2013 | DOI: 10.1002/cctc.201200818

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      Ru(II) for the home team: Ruthenium complexes of simple and cheap phosphite ligands give high activities in the hydrogenation of carbon dioxide under supercritical conditions. The activities correlate well with the steric demand of the substituents.

    11. Efficient Synthesis of Cyclic Carbonates by MgII/Phosphine-Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides (pages 1344–1349)

      Yiping Ren and Prof. Jae-Jin Shim

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/cctc.201200770

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      Green synthesis of cyclic carbonates: Magnesium(II)/phosphine complexes are developed for the synthesis of cyclic carbonates through the coupling of epoxides and carbon dioxide. Various cyclic carbonates are prepared in excellent yields under extremely mild, solvent-free conditions at relatively low temperatures and pressures. The catalyst system shows excellent recyclability, and the cyclic carbonates can be separated easily.

    12. Unusually High Activity of Pt Islands on Rh(1 1 1) Electrodes for Ethanol Oxidation (pages 1350–1353)

      Dr. Vinicius Del Colle, Dr. Vitali Grozovski, Prof. Enrique Herrero and Prof. Juan M. Feliu

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/cctc.201200687

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      Dream island: Monoatomic, high-platinum islands deposited on a Rh(1 1 1) electrode have an electrocatalytic activity for ethanol oxidation that is 20 times higher than that measured on platinum electrodes. On these islands, CO2 and acetic acid are the final products.

    13. Confinement Effect on Ag Clusters in the Channels of Well-Ordered Mesoporous TiO2 and their Enhanced Photocatalytic Performance (pages 1354–1358)

      Ting Li, Wei Zhou, Prof. Jianqiang Wang, Yang Qu, Chungui Tian, Kai Pan, Guohui Tian and Prof. Honggang Fu

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/cctc.201200896

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      Pug-walls: The confinement effect of ordered mesoporous TiO2 results in the formation of highly dispersed Ag clusters with strong interactions between the clusters and the pore walls. The mesoporous Ag/TiO2 composite exhibits excellent photocatalytic activity under UV/Vis light, owing to the Schottky barrier favoring the separation of photogenerated electron/hole pairs and to surface plasmon resonance, thus improving photocatalytic performance.

  11. Full Papers

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    1. In Situ Fabrication of Ag/Ag3PO4/Graphene Triple Heterostructure Visible-Light Photocatalyst through Graphene-Assisted Reduction Strategy (pages 1359–1367)

      Dr. Baojiang Jiang, Yanhui Wang, Dr. Jian-Qiang Wang, Dr. Chungui Tian, Wenjun Li, Qingmao Feng, Dr. Qingjiang Pan and Prof. Honggang Fu

      Version of Record online: 11 FEB 2013 | DOI: 10.1002/cctc.201200684

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      Triple chase! The Ag/Ag3PO4/graphene triple heterostructure composites are fabricated through the redox reaction between Ag+ and graphene. The triple heterostructure can improve the charge separation rate under visible-light irradiation. Simultaneously, photocorrosion can be inhibited effectively, which leads to the high structural stability. Thus, the novel Ag/Ag3PO4/graphene triple heterostructure demonstrates improved photocatalytic activity and structural stability under visible-light irradiation.

    2. Organometallic Catalysts for Use in a Fuel Cell (pages 1368–1373)

      Dr. Takahiro Matsumoto, Kyoungmok Kim, Dr. Hidetaka Nakai, Prof. Takashi Hibino and Prof. Seiji Ogo

      Version of Record online: 9 JAN 2013 | DOI: 10.1002/cctc.201200595

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      Running rings around fuel cells: The performance of a fuel cell is increased by using organometallic catalysis. An organometallic [NiIIRuIV] peroxo catalyst functions as the cathode catalyst in a fuel cell with a much greater efficiency than our previous systems. The organometallic catalyst acts in both solid and solution phases and allows for observation of the mechanism, providing opportunity for further improvement.

    3. Catalysis of Enantioselective Strecker Reaction in the Synthesis of D-Homophenylalanine Using Recyclable, Chiral, Macrocyclic MnIII–Salen Complexes (pages 1374–1385)

      S. Saravanan, Dr. Noor-ul H. Khan, Prasanta K. Bera, Dr. Rukhsana I. Kureshy, Dr. Sayed H. R. Abdi, Prathibha Kumari and Dr. Hari C. Bajaj

      Version of Record online: 12 APR 2013 | DOI: 10.1002/cctc.201200700

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      Salen away to sea: A convenient approach to the asymmetric Strecker reaction was established by synthesizing chiral, mono- and dinuclear, macrocyclic MnIII–salen complexes possessing achiral and chiral linkers. These complexes showed very good catalytic ability for the enantioselevtive Strecker reaction of aldimines.

    4. X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction (pages 1386–1394)

      Dr. Luis R. Aramburo, Dr. Javier Ruiz-Martínez, Dr. Linn Sommer, Dr. Bjørnar Arstad, Robison Buitrago-Sierra, Prof. Dr. Antonio Sepúlveda-Escribano, Prof. Dr. Henny W. Zandbergen, Prof. Dr. Unni Olsbye, Prof. Dr. Frank M. F. de Groot and Prof. Dr. Bert M. Weckhuysen

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200670

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      Full steam ahead: In situ scanning transmission X-ray microscopy has been used in combination with catalytic testing and bulk characterization methods to study the effect of a hydrothermal treatment on the reactivity and stability of H-SAPO-34 during the methanol-to-hydrocarbons reaction.

    5. Knowledge Extraction from Catalysis of the Past: A Case of Selective CO Oxidation over Noble Metal Catalysts between 2000 and 2012 (pages 1395–1406)

      Dr. M. Erdem Günay and Prof. Ramazan Yildirim

      Version of Record online: 11 MAR 2013 | DOI: 10.1002/cctc.201200665

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      Extracting knowledge from past data: A simple method is designed by using various data mining tools, such as decision trees, clustering techniques, and artificial neural networks, to extract valuable knowledge from the experimental data for selective CO oxidation in the literature; this way, some useful trends, rules, and correlations, which are not easily comprehensible to the naked eye, are deduced systematically.

    6. Dye Degradation by Layer-by-Layer Immobilised Peroxidase/Redox Mediator Systems (pages 1407–1415)

      Prof. Dr. Raffaele Saladino, Dr. Melissa Guazzaroni, Dr. Claudia Crestini and Dr. Marcello Crucianelli

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/cctc.201200660

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      Environmentally benign bio-catalysts: The role of a poly-electrolyte coating in the immobilisation of peroxidases was studied. Efficient yields for the degradation of several dyes were obtained with H2O2 in the presence of different redox mediators. Generally, azo dyes were degraded with higher yields.

    7. Enhancing the Electrocatalytic Activity of Pt–Pd Catalysts by Introducing Porous Architectures (pages 1416–1425)

      Dr. Xiangheng Niu, Dr. Hongli Zhao, Dr. Chen Chen and Prof. Dr. Minbo Lan

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/cctc.201200658

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      When the bubble bursts: Remarkable enhancement of the electrocatalytic activity of Pt–Pd catalysts was achieved by introducing porous architectures with three-dimensional dendritic microstructures, which were fabricated in situ by means of a novel periodic hydrogen-evolution-assisted electrodeposition strategy (see scheme). The resulting catalyst exhibited significantly improved catalytic properties for glucose electrooxidation.

    8. AgBr Nanocrystals from Plates to Cubes and Their Photocatalytic Properties (pages 1426–1430)

      Dr. Hua Wang, Dr. Yang Liu, Pengfei Hu, Liang He, Prof. Jinghong Li and Prof. Lin Guo

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/cctc.201200629

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      Crystal evolution: AgBr nanocrystals, evolving from plates through truncated cubes and finally to regular cubes, corresponding to a progressive shrinkage of exposed {1 1 1} facets and enlargement of exposed {1 0 0} facets, are prepared and their growth mechanism investigated. These nanocrystals exhibit facet-dependent photocatalytic properties.

    9. Control of the Interphases Formation Degree in Co3O4/ZnO Catalysts (pages 1431–1440)

      Dr. Fernando Rubio-Marcos, Dr. Vanesa Calvino-Casilda, Prof. Dr. Miguel A. Bañares and Prof. Dr. José F. Fernandez

      Version of Record online: 7 FEB 2013 | DOI: 10.1002/cctc.201200620

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      Keep dry and carry on: ZnO supported Co3O4 nanoparticles are highly active in the transformation of renewable materials through carbonylation of glycerol by urea. The activity of the catalyst is modulated by interaction of the nanoparticles with the ZnO support, which depends on the preparation stage. The Co3O4/ZnO catalyst system prepared by a dry mixing method at room temperature is very promising for this reaction.

    10. Asymmetric Cyanoethoxy Carbonylation Reaction of Aldehydes Catalyzed by a TiIV Macrocyclic Complex: An Efficient Synthetic Protocol for β-Blocker and α1-Adrenergic Receptor Agonists (pages 1441–1448)

      Arghya Sadhukhan, Dr. Manoj K. Choudhary, Dr. Noor-ul H. Khan, Dr. Rukhsana I. Kureshy, Dr. Sayed H. R. Abdi and Hari C. Bajaj

      Version of Record online: 9 JAN 2013 | DOI: 10.1002/cctc.201200617

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      A crown of titanium: A new class of chiral macrocyclic TiIV–salen complexes are efficient, recyclable, and scalable catalysts for the asymmetric addition of ethyl cyanoformate to aldehydes, which is useful for the synthesis of bioactive compounds. The figure shows the best-performing ligand with two salen units linked flexibly in a crown ether-like motif.

    11. Compositional and Morphological Changes of Ordered PtxFey/C Oxygen Electroreduction Catalysts (pages 1449–1460)

      Dr. Liang Chen, Mickey C. Y. Chan, Feihong Nan, Dr. Christina Bock, Dr. Gianluigi A. Botton, Dr. Patrick H. J. Mercier and Dr. Barry R. MacDougall

      Version of Record online: 1 MAR 2013 | DOI: 10.1002/cctc.201200614

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      Pulling the platinum card: Changes in the O2 reduction (ORR) activity and the structure of carbon-supported PtxFey catalysts upon electrochemical stress testing are investigated. The dissolution of Pt induced by potential cycling clearly contributes to the observed decrease in the Pt surface area and mass ORR activity for the PtxFey/C catalysts.

    12. Fischer–Tropsch Synthesis Over Cobalt Supported On Silica-Incorporated Mesoporous Carbon (pages 1461–1471)

      Dr. Prashant R. Karandikar, Dr. Jo-Yong Park, Dr. Yun-Jo Lee, Dr. Ki-Won Jun, Dr. Kyoung-Su Ha, Dr. Geun Jae Kwak, Hae-Gu Park and Joo Yeong Cheon

      Version of Record online: 11 MAR 2013 | DOI: 10.1002/cctc.201200433

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      CSI: Carbon–Silica Investigations: The incorporation of silica in the porous carbon framework modifies the surface chemistry of the hydrophobic support through oxygenated functional groups, resulting in preferential Co adsorption in the vicinity of silica. This encouraged greater dispersion and reducibility of cobalt than seen for carbon-supported cobalt catalysts. The deactivation of cobalt over carbon supported catalyst is reduced by the hybridization of carbon using silica particles.

    13. Microwave-Assisted Ethanol Reduction as a New Method for the Preparation of Highly Active and Stable CNT-Supported PtRu Electrocatalysts for Methanol Oxidation (pages 1472–1480)

      Abu Bakr Ahmed Amine Nassr and Prof. Dr. Michael Bron

      Version of Record online: 8 APR 2013 | DOI: 10.1002/cctc.201200742

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      Microwaves assist everything! A facile microwave-assisted synthesis route for the preparation of PtRu/carbon nanotube electrocatalysts is presented, in which an ethanol/water mixture is used as a solvent/reducing agent. The prepared catalysts are highly active in methanol electrooxidation. After reduction at higher temperatures, the degree of alloying and catalyst stability are enhanced.

    14. Cyclopalladated Arylimine Self-Assembly Films for Suzuki Reaction (pages 1481–1489)

      Dr. Na Zhao, Prof. Dr. Tiesheng Li, Zhen Zhai, Jingjing Qiu, Prof. Dr. Wenjian Xu, Dr. Hui Liu and Prof. Dr. Yangjie Wu

      Version of Record online: 11 FEB 2013 | DOI: 10.1002/cctc.201200730

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      Cyclos and cycles: Cyclopalladated arylimine complexes are immobilized on solid slides and characterized. The heterogeneous catalyst obtained exhibits 10 times the catalytic performance of its homogeneous counterpart. None of the reactions require the use of ligands, air isolation, or assistant solvents. The catalysts are run for 8 cycles without deactivation. A Suzuki reaction mechanism is proposed.

    15. Mechanistic Insights into the Reduction of Carbon Dioxide with Silanes over N-Heterocyclic Carbene Catalysts (pages 1490–1496)

      Siti Nurhanna Riduan, Prof. Jackie Y. Ying and Dr. Yugen Zhang

      Version of Record online: 6 MAR 2013 | DOI: 10.1002/cctc.201200721

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      Which silane reacts first? Experimental results and DFT calculations of the N-heterocyclic carbene catalyzed reduction of carbon dioxide to methanol with silanes indicated that the overall process involved a three-step cascade reaction with the first hydrosilylation as the rate-determining step (see picture). This mechanism explains the pathway to the methoxide end product and the high hydrogen transfer yield.

    16. Methylated β-Cyclodextrin-Capped Ruthenium Nanoparticles: Synthesis Strategies, Characterization, and Application in Hydrogenation Reactions (pages 1497–1503)

      Dr. Nguyet Trang Thanh Chau, Dr. Soraya Handjani, Jean-Paul Guegan, Dr. Miguel Guerrero, Prof. Eric Monflier, Dr. Karine Philippot, Dr. Audrey Denicourt-Nowicki and Prof. Alain Roucoux

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/cctc.201200718

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      Supramolecular nanocatalysts! Ruthenium nanoparticles stabilized by methylated β-cyclodextrins in water can be prepared using either a one-pot or a cascade reduction process (see picture). This preparation of nanoparticles can be used for the hydrogenation of arenes in biphasic media.

    17. Phosphite-Thiazoline versus Phosphite-Oxazoline for Pd-Catalyzed Allylic Substitution Reactions: A Case for Comparison (pages 1504–1516)

      Javier Mazuela, Oscar Pàmies and Montserrat Diéguez

      Version of Record online: 12 FEB 2013 | DOI: 10.1002/cctc.201200711

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      Come together, right now, over ee: Through the combination of substrates with phosphite-oxazoline or phosphite-thiazoline ligands, we identify one of the few catalytic systems that provide high regio- and enantioselectivities in both enantiomers of the alkylation product for a wide range of hindered and unhindered mono-, di-, and trisubstituted substrates with several carbon nucleophiles.

    18. Improved para-Xylene Selectivity in meta-Xylene Isomerization Over ZSM-5 Crystals with Relatively Long b-Axis Length (pages 1517–1523)

      Yan Liu, Xiaozhao Zhou, Dr. Xinmei Pang, Yinying Jin, Dr. Xiangju Meng, Prof. Xiaoming Zheng, Dr. Xionghou Gao and Prof. Feng-Shou Xiao

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/cctc.201200691

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      Join the chain gang: Chain-like ZSM-5 crystals that are synthesized in the presence of starch show higher p-xylene selectivity in m-xylene isomerization than normal, mesoporous, and sheet-like ZSM-5 crystals.

    19. Effect of Noble Metals on the Strength of Brønsted Acid Sites in Bifunctional Zeolites (pages 1524–1530)

      Dominic Santi, Dr. Sandra Rabl, Dr. Vincenzo Calemma, Michael Dyballa, Prof. Dr. Michael Hunger and Prof. Dr. Jens Weitkamp

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/cctc.201200675

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      Noble metals change everything: The introduction of noble metals (M) into zeolites causes a decrease in the strength of Brønsted acid sites (Si(OH)Al). This effect is attributed to the charge transfer between the noble metal and the support-framework oxygen atoms, which affects the OH bond strength in the Si(OH)Al groups.

    20. Isolation, Characterization, and Identification of Catalytically Active Species in the MoO3/SiO2 Catalyst during Solid Acid Catalyzed Reactions (pages 1531–1537)

      Trupti V. Kotbagi, Dr. Ankush V. Biradar, Dr. Shubhangi B. Umbarkar and Dr. Mohan K. Dongare

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/cctc.201200662

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      Water is beneficial, too! The MoO3/SiO2 catalyst with very high acidity is prepared by the sol–gel process, and its characterization reveals the in situ formation of reduced silicomolybdic acid on silica nanoparticles in the presence of water, which acts as catalytically active species that dissolves in the reaction medium and gives high activity responsible for the esterification of ethanol and acetic acid.

    21. Direct Nucleophilic Substitution of Free Allylic Alcohols in Water Catalyzed by FeCl3⋅6 H2O: Which is the Real Catalyst? (pages 1538–1542)

      Paz Trillo, Dr. Alejandro Baeza and Prof. Carmen Nájera

      Version of Record online: 12 FEB 2013 | DOI: 10.1002/cctc.201200650

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      Taking a leaf out of the green book: The use of FeCl36 H2O as an efficient water-compatible catalyst for the allylic substitution of free alcohols is disclosed. This inexpensive, low-toxic, and easily accessible FeIII salt used as the catalyst in a process conducted in pure water as the solvent represents an environmentally friendly alternative to previously reported methods and allows the introduction of a broad range of nitrogenated and carbon nucleophiles.

    22. From Regioselective Condensation to Regioselective N-Alkylation: A Novel and Environmentally Benign Strategy for the Synthesis of N,N′-Alkyl Aryl Ureas and N,N′-Dialkyl Ureas (pages 1543–1552)

      Dr. Feng Li, Chunlou Sun, Haixia Shan, Xiaoyuan Zou and Jianjiang Xie

      Version of Record online: 9 JAN 2013 | DOI: 10.1002/cctc.201200648

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      Watch out, the borrowers are about! N,N′-alkyl aryl ureas and N,N′-dialkyl ureas were synthesized by a transition metal-catalyzed regioselective N3-alkylation of the N-monosubstituted ureas with alcohols. This opens up the design of regioselective N-alkylation of amines with alcohols based on the regioselective condensation of amines with aldehydes, facilitating the progress of the “hydrogen autotransfer” (or “hydrogen-borrowing”)

    23. Deactivation Pathways of the Catalytic Activity of Metal–Organic Frameworks in Condensation Reactions (pages 1553–1561)

      Dr. Maksym Opanasenko, Dr. Amarajothi Dhakshinamoorthy, Prof. Dr. Jiří Čejka and Prof. Dr. Hermenegildo Garcia

      Version of Record online: 5 FEB 2013 | DOI: 10.1002/cctc.201200643

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      What is the poison? Three different condensation reactions were chosen as model reaction to determine the nature of the poisons causing structural instability (see picture), and varied product selectivity for two related metal–organic framework catalysts, Fe(BTC) and synthetic MIL-100(Fe). Undesired intermediates or byproducts were found to block the pores, whereas phenolic substrates could substitute the metal ligands thus destabilizing the catalyst structure.

    24. Rhodium-Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2-Vinyl-5-Methyl-1,3-Dioxane (pages 1562–1569)

      Dr. Jérémy Ternel, Dr. Jean-Luc Dubois, Dr. Jean-Luc Couturier, Prof.Dr. Eric Monflier and Prof.Dr. Jean-François Carpentier

      Version of Record online: 21 JAN 2013 | DOI: 10.1002/cctc.201200630

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      Ligands of mass formylation: The acetal VMD derived from acrolein and MPD is hydroformylated with rhodium catalysts under homogeneous conditions with perfect chemoselectivity for the aldehydes. Diphosphine ligands with a narrow bite angle (≈85°), such as dppe, favor the branched aldehyde with selectivities up to 78 %, whereas those with a large bite angle (≈110°), such as xantphos, produce the linear aldehyde with up to 91 % selectivity.

    25. Laccase-Catalyzed C[BOND]S and C[BOND]C Coupling for a One-Pot Synthesis of 1,4-Naphthoquinone Sulfides and 1,4-Naphthoquinone Sulfide Dimers (pages 1570–1577)

      Dr. Kevin W. Wellington, Dr. Gregory E. R. Gordon, Lindelani A. Ndlovu and Prof. Paul Steenkamp

      Version of Record online: 1 MAR 2013 | DOI: 10.1002/cctc.201200606

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      A beautiful couple: Oxidative C[BOND]S and C[BOND]C bond formation with aryl and alkyl thiols is catalyzed under mild conditions in a reaction vessel open to air at pH 4.5 in the presence of a commercial laccase (Novozym 51003 or Suberase) and a cosolvent (DMF) to afford 1,4-naphthoquinone sulfides. Although both monothiolation and dithiolation of the 1,4-naphthohydroquinone are accomplished, the latter is favored.

    26. Aerobic Liquid-Phase Oxidation of Ethylbenzene to Acetophenone Catalyzed by Carbon Nanotubes (pages 1578–1586)

      Jin Luo, Prof. Feng Peng, Dr. Hao Yu, Dr. Hongjuan Wang and Dr. Wenxu Zheng

      Version of Record online: 30 JAN 2013 | DOI: 10.1002/cctc.201200603

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      Carbon nanotubes (CNTs) as a metal-free catalyst exhibited high activity and excellent stability for the aerobic oxidation of ethylbenzene (EB) to acetophenone (AcPO) in the liquid phase. The results demonstrated that the CNTs played an important role in the decomposition of 1-phenylethyl hydroperoxide (PEHP) and contributed to the production of AcPO.

    27. Support effects in a Rh diamine complex heterogenized on carbon materials (pages 1587–1597)

      C. C. Gheorghiu, Prof. C. Salinas Martínez de Lecea and Prof. M. C. Román Martínez

      Version of Record online: 19 FEB 2013 | DOI: 10.1002/cctc.201200598

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      A nosy partner: Partial complex reduction during hydrogenation reactions was observed in carbon xerogels supports leading to a catalytic activity enhancement. Selectivity to an intermediate product can be modulated by the mesopore size of the support.

    28. Hydrodeoxygenation of Phenol and Derivatives over an Ionic Liquid-Like Copolymer Stabilized Nanocatalyst in Aqueous Media (pages 1598–1605)

      Prof. Dr. Jinzhu Chen, Jing Huang, Dr. Limin Chen, Prof. Dr. Longlong Ma, Prof. Dr. Tiejun Wang and Dr. Uzma I. Zakai

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/cctc.201200582

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      Bio-oil to fuels: Highly selective hydrodeoxygenation of phenolic bio-oil related phenols to alkanes is achieved in aqueous media over a dual-functional catalyst system consisting of water-soluble ionic liquid-like copolymer (A)-stabilized nanocatalysts and a mineral acid. HDO=hydrodeoxygenation.

    29. Copper-Incorporated Porous Polydivinylbenzene as Efficient and Recyclable Heterogeneous Catalyst in Ullmann Biaryl Ether Coupling (pages 1606–1613)

      Liang Wang, Jian Zhang, Jing Sun, Longfeng Zhu, Haiyan Zhang, Fujian Liu, Dafang Zheng, Dr. Xiangju Meng, Prof. Xiaodong Shi and Prof. Feng-Shou Xiao

      Version of Record online: 25 JAN 2013 | DOI: 10.1002/cctc.201200578

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      Recycling at its best: A copper-incorporated porous, Schiff base-modified polydivinylbenzene is an effective heterogeneous catalyst for the Ullmann coupling reaction. The porous, solid-supported catalysts have excellent reactivity and can be readily recycled with a slight decrease in catalyst reactivity, rendering them practical heterogeneous catalysts that best reproduce the homogeneous catalyst reactivity.

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