European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 14

Early View (Online Version of Record published before inclusion in an issue)

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

ISI Journal Citation Reports © Ranking: 2013: 10/45 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie


  1. 1 - 53
  1. Full Papers

    1. Cationic Surfactants

      (9,10-Dihydroxyoctadecyl)ammonium: A Structurally Unique Class of Clay Intercalable Surfactants

      Luboš Jankovič, Juraj Kronek, Jana Madejová and Viktor Hronský

      Article first published online: 22 MAY 2015 | DOI: 10.1002/ejic.201500169

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      The structurally unique (9,10-dihydroxyoctadecyl)trimethylammonium (OH-ODTMA) surfactant is synthesized from oleylamine. The OH-ODTMA, ODTMA, and OLEYL-TMA amphiphiles are successfully intercalated within clay galleries. The amount of gauche conformers is significantly higher in the novel OH-ODTMA organoclay than in the ODTMA intercalate.

  2. Microreviews

    1. Bio-Inspired Si Coatings

      Bio-Inspired Formation of Silica Thin Films: From Solid Substrates to Cellular Interfaces

      Woo Kyung Cho and Sung Ho Yang

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500308

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      The bio-inspired formation of silica thin films on the surfaces of flat solids, microparticles, nanoparticles, and living cells is reviewed.

  3. Full Papers

    1. Sulfide Niobium Clusters

      Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

      Alexander V. Rogachev, Artem L. Gushchin, Pavel A. Abramov, Ekaterina A. Kozlova, Cristian Vicent, Dmitry Piryazev, Adam Barlow, Marek Samoc, Mark G. Humphrey, Rosa Llusar, Vladimir P. Fedin and Maxim N. Sokolov

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500319

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      A series of complexes, [Nb2S4(NCS)6L]2– and [Nb2S4(NCS)4L2], where L is a bipyridine, phenanthroline or 2-(2-pyridyl)benzimidazole has been prepared. TiO2 nanoparticles modified with (Et4N)2[Nb2S4(NCS)6(bipy)] exhibit photocatalytic activity for H2 generation from water in the presence of a sacrificial electron-donor system. The complexes function as optical limiters.

    2. Asymmetric Hydrogenation

      Catalytic Diamino-Sugar-Assisted Enantioselective Hydrogenation

      Matthias Böge and Jürgen Heck

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500306

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      The Noyori-type hydrogenation catalyst precursor is modified with methyl 2,3-diamino-4,6-O-benzylidene-2,3-dideoxy-α-D-hexopyranoside ligands (glucose, mannose, gulose, and talose). The trans-dichloridoruthenium(II) complexes are diastereoselectively formed. Enantiomeric excesses of up to 78 % are obtained in enantioselective hydrogenation reactions under normal hydrogen pressure.

    3. Energetic Heterocycles

      Synthesis and Characterization of Asymmetric 1,2-Dihydroxy-5,5′-bitetrazole and Selected Nitrogen-Rich Derivatives

      Katherina Hafner, Thomas M. Klapötke, Philipp C. Schmid and Jörg Stierstorfer

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500338

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      To study the performance increment of 5,5′-bitetrazole N-oxides a selective synthetic protocol toward asymmetric 1,2′-dihydroxy-5,5′-bitetrazole was established. The title compound completes the series of bitetrazole N-oxides, which represent an outstanding class of energetic materials.

    4. Diiron Benzenedithiolate Complexes

      Diiron Benzenedithiolate Complexes Relevant to the [FeFe] Hydrogenase Active Site

      Indresh Kumar Pandey, Shaikh M. Mobin, Naina Deibel, Biprajit Sarkar and Sandeep Kaur-Ghumaan

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500345

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      Bioinspired hydrogenase model complexes (A–E) with σ-donating ligands are known. Complexes of the type B and C with monodentate phosphine ligands (PPh3, PPh2Me, PPh2H) have been synthesized. The monosubstituted complexes with phosphine ligands participate in electrocatalytic proton reduction in the presence of acids.

    5. Heterobimetallic Complexes

      Paramagnetic ([5]Trovacenyl)phenylphosphane: Intramolecular Electronic Communication and Construction of Heterobimetallic Palladium and Chromium Complexes

      Feng Lu, Christoph Elschenbroich, Klaus Harms, Olaf Burghaus and Clemens Pietzonka

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500095

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      Group 15 P-bridged paramagnetic unsymmetric sandwich binuclear complex di([5]trovacenyl)phenylphosphane (2··) was synthesized and characterized by means of electrochemistry, electron paramagnetic resonance (EPR) spectroscopy, magnetic susceptometry, and X-ray diffraction analysis. It was applied as ligand to construct unprecedented heterobimetallic PdII/CrIV complexes.

    6. Metal Oxo Clusters

      On the Question of Site-Selective Ligand Exchange in Carboxylate-Substituted Metal Oxo Clusters

      Johannes Kreutzer, Matthias Czakler, Michael Puchberger, Ernst Pittenauer and Ulrich Schubert

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500193

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      The question of cluster degradation upon ligand exchange was probed for reactions of [Ti4Zr4O6(OBu)4(OMc)16] (OMc = methacrylate) and [Zr6O4(OH)4(OOCR)12]2·6RCOOH with acetylacetone (acacH). A [Ti(OBu)2(acac)2] unit was dissected from the bimetallic Ti/Zr cluster, while site-selective substitution of two carboxylate ligands occurred in the latter cluster.

    7. Photochromic Tungsten Oxide

      Aqueous Synthesis and Visible-Light Photochromism of Metastable h-WO3 Hierarchical Nanostructures

      Na Li, Yan Zhao, Yi Wang, Yan Lu, Yuehong Song, Zhifang Huang, Yawen Li and Jingzhe Zhao

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500132

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      Metastable hexagonal tungsten oxide (h-WO3) hierarchical nanostructures are prepared at low temperature. Growth of WO3 crystallites along the [001] direction results in the nanorod-assembled h-WO3 architectures. The h-WO3-rich samples all exhibit good recycled visible-light photochromic performance.

    8. Electrochemistry of Mn Complexes

      Structures, Electrochemical and Spectral Properties of a Series of [MnN(CN)3­(diimine)] Complexes

      Michael J. Murphy, Carol Hua, Jason R. Price, Deanna M. D'Alessandro and Cameron J. Kepert

      Article first published online: 15 MAY 2015 | DOI: 10.1002/ejic.201500012

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      The crystal structures, redox activities and spectral properties of five discrete [PPh4][MnN(CN)3(diimine)] complexes are reported. Through the modulation of the metal-to-ligand charge-transfer (MLCT) band by variation of the π-accepting capacity of the diimine ligand, the MnV/MnVI redox potential and solvatochromism can be tuned systematically.

    9. Zerofield Splitting Parameters

      Zero-Field Splitting in {MnIII33-O)} Core Single-Molecule Magnets Investigated by Inelastic Neutron Scattering and High-Field Electron Paramagnetic Resonance Spectroscopy

      Marc Sigrist, Philip L. W. Tregenna-Piggott, Kasper S. Pedersen, Mikkel A. Sørensen, Anne-Laure Barra, Jürg Hauser, Shi-Xia Liu, Silvio Decurtins, Hannu Mutka and Jesper Bendix

      Article first published online: 15 MAY 2015 | DOI: 10.1002/ejic.201500084

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      Highly resolved inelastic neutron scattering spectroscopy and high-field electron paramagnetic resonance spectroscopy yield a uniquely accurate picture of the ground-state energetics of trinuclear MnIII–oximate complexes. Variations in the magnitude of the anisotropy barriers leading to single-molecule magnet behavior of these systems can be explained in terms of molecular structures.

    10. Zintl Compounds

      Lithium-Filled Double-Deck-Layered Structure of the RELixCu2–yP2 (RE = La, Pr, Nd, Gd, Er; 0.82 ≤ x ≤ 1; 1.19 ≤ y ≤ 1.54) Series: Experimental and Theoretical Studies

      Eunyoung Jang, Gnu Nam, Hyein Woo, Junseong Lee, Mi-Kyung Han, Sung-Jin Kim and Tae-Soo You

      Article first published online: 15 MAY 2015 | DOI: 10.1002/ejic.201500387

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      Five rare-earth metal containing quaternary phosphide compounds show the “Li-filled” double-deck-layered structure, in which the Cu and P atoms consist of 2D puckered hexagonal double-deck layers.

    11. Polyoxometalates

      Preparation and Structural Characteri­zation of Mono-Ru-Substituted α2-Dawson-Type Phosphotungstate with a Carb­onyl Ligand and Other Ru(CO)-Substituted Heteropolytungstates

      Kensuke Nishiki, Hiromi Ota, Shuhei Ogo, Tsuneji Sano and Masahiro Sadakane

      Article first published online: 13 MAY 2015 | DOI: 10.1002/ejic.201500226

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      New mono-RuII(CO) substituted heteropolytungstates, including Keggin derivatives [GeW11O39RuII(CO)]6– and [PW11O39RuII(CO)]5– and Dawson-type phosphotungstates [α1-P2W17O61RuII(CO)]8– and [α2-P2W17O61RuII(CO)]8–, were prepared.

  4. Microreviews

    1. DNA Interactions with Cu Complexes

      Possible DNA-Interacting Pathways for Metal-Based Compounds Exemplified with Copper Coordination Compounds

      Rosa F. Brissos, Amparo Caubet and Patrick Gamez

      Article first published online: 11 MAY 2015 | DOI: 10.1002/ejic.201500175

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      In this microreview, the main routes towards DNA damage mediated by metal complexes are described concisely. Emphasis is placed on the great potential of copper coordination compounds for which some illustrative examples are given.

  5. Full Papers

    1. C–F/C–H Bond Activation

      Synthesis of Iron Hydrides by Selective C–F/C–H Bond Activation in Fluoroaryl­imines and Their Applications in Catalytic Reduction Reactions

      Lin Wang, Hongjian Sun and Xiaoyan Li

      Article first published online: 11 MAY 2015 | DOI: 10.1002/ejic.201500313

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      The selective activation of C–H/C–F bonds was realized in the reactions of Fe(PMe3)4 with fluorophenylimines by controlling the substituents of the fluorophenylimines. Iron hydrides were obtained through C–F bond activation with the assistance of silanes. These iron hydrides show excellent catalytic activity in the hydrosilylations of aldehydes, ketones, and α,β-unsaturated aldehydes.

    2. Dinuclear Nickel(II) Complexes

      Syntheses, Spectroscopy, and Structural Analyses of Dinuclear Chiral-at-Metal μ-Aqua-tetrakis[(R or S)-N-1-(Ar)ethyl­sal­icylaldiminato]di-Λ- or -Δ-nickel(II) Complexes

      Mohammed Enamullah, Mohammad Abdul Quddus, Mohammad Rezabul Hasan, Gennaro Pescitelli, Roberto Berardozzi, Guido J. Reiß and Christoph Janiak

      Article first published online: 11 MAY 2015 | DOI: 10.1002/ejic.201500128

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      Dinuclear μ-aqua-tetrakis[(R or S)-N-1-(Ar)ethylsalicylaldiminato]di-Λ- or -Δ-nickel(II) complexes have been synthesized from enantiopure Schiff bases. Their X-ray structures show each Ni surrounded by two salicylaldiminates, one bridging salicyl-O, and an aqua ligand in a distorted octahedral with diastereoselective induction-at-Ni through R or S ligand chirality to give the Λ or Δ configuration.

    3. Pendant Ligands

      Assessment of Catalysis by Arene-Ruthenium Complexes Containing Phosphane or NHC Groups bearing Pendant Conjugated Diene Systems

      Johann Baraut, Alexandre Massard, Florian Chotard, Ewen Bodio, Michel Picquet, Philippe Richard, Yannick Borguet, François Nicks, Albert Demonceau and Pierre Le Gendre

      Article first published online: 8 MAY 2015 | DOI: 10.1002/ejic.201500054

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      The synthesis of two arene-ruthenium complexes incorporating new hybrid phosphane- or NHC-linked diene ligands is described. Preliminary assessment of their catalytic performances in atom-transfer radical addition (ATRA) and polymerization (ATRP), olefin cyclopropanation, ring-opening metathesis polymerization (ROMP), and enol ester synthesis is reported.

    4. Quaternary Semiconductors

      Raman Spectroscopy as a Superior Tool To Understand the Synthetic Pathway of ­Cu2FeSnS4 Nanoparticles

      Binbin Zhou, Xiunan Yan, Pan Li, Liangbao Yang and Daoyang Yu

      Article first published online: 8 MAY 2015 | DOI: 10.1002/ejic.201500189

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      Few studies have systematically reported the growth mechanism of Cu2FeSnS4 nanoparticles. The XRD patterns of these quaternary compounds are difficult to interpret, as their structural similarity to the binary chalcogenides of the same elements results in overlapping diffraction peaks. We use Raman spectroscopy as a sensitive characterization technique to understand the pathway to Cu2FeSnS4.

    5. Bonding in Cu(II) Complexes

      Ligand-Field Strength and Symmetry-Restricted Covalency in CuII Complexes – a Near-Edge X-ray Absorption Fine Structure Spectroscopy and Time-Dependent DFT Study

      Giulia Mangione, Luciano Pandolfo, Mauro Sambi, Giovanni Ligorio, Marco Vittorio Nardi, Albano Cossaro, Luca Floreano and Maurizio Casarin

      Article first published online: 8 MAY 2015 | DOI: 10.1002/ejic.201500222

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      The legitimacy of using the position of the CuII L3 edge to get information about the ligand-field strength and the possibility of a Cu–ligand symmetry-restricted covalency underestimation when using the CuII L3-edge intensity as a gauge are discussed.

    6. Zintl Compounds

      Ba5Tr2(Ge,Sn)2P8 and Ba5Tr5(Ga,Tt)2P12 (Tr = Al, Ga; Tt = Ge, Sn): Phosphides with Triel and Tetrel Mixing

      Ming-Yan Pan, Sheng-Qing Xia, Xiao-Cun Liu and Xu-Tang Tao

      Article first published online: 8 MAY 2015 | DOI: 10.1002/ejic.201500251

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      A series of multinary phosphide Zintl compounds, Ba5Ga2GeSnP8, Ba5Al2GeSnP8, Ba5Ga6GeP12, and Ba5Ga6SnP12, have been synthesized. The compounds feature two new structure types, which are closely related by the triel-P chains. Extensive mixing between the triel and tetrel elements determines the structure of these phases, which is understood by incorporation of the Zintl concept.

  6. Short Communications

    1. Single Molecule Magnets

      A Disk-Like CoII3DyIII4 Coordination Cluster Exhibiting Single Molecule Magnet Behavior

      Edward Loukopoulos, Benjamin Berkoff, Alaa Abdul-Sada, Graham J. Tizzard, Simon J. Coles, Albert Escuer and George E. Kostakis

      Article first published online: 8 MAY 2015 | DOI: 10.1002/ejic.201500241

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      The use of (E)-4-(2-hydroxy-3-methoxybenzylideneamino)-2,3-dimethyl-1-phenyl-1,2-dihydropyrazol-5-one (HL) in Co/Ln chemistry for the first time affords a disk-like heptanuclear CoII3DyIII4 coordination cluster displaying single molecule magnet (SMM) behavior. This topology is hitherto unobserved in CoII/DyIII chemistry.

  7. Full Papers

    1. Homodinuclear Complexes

      Dinuclear Zinc and Cobalt Complexes with Imidazolyl and N-Methylmidazolyl Units and Their Solution Speciation and Redox Properties

      Merle Kügler, Joanna Gałęzowska, Florian Schendzielorz, Sebastian Dechert, Serhiy Demeshko and Inke Siewert

      Article first published online: 6 MAY 2015 | DOI: 10.1002/ejic.201500221

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      Dinuclear cobalt and zinc complexes based on a new ligand system with 1H-imidazolyl units are synthesised. The dependence of the species distribution and the redox properties on the protonation state of the ligand are examined. The potential of the Co2+/Co3+ redox couple shifts by ca. 1.1 V upon deprotonation of all of the imidazolyl units.

    2. Metal Amine Sulfonamide Complexes

      A Useful Route to Metal Complexes of Poorly Coordinating Sulfonamides

      Matilde Fondo, Cristina Portela-García, Arthur H. Baleeiro-Tadiotto, Ana M. García-Deibe and Jesús Sanmartín-Matalobos

      Article first published online: 5 MAY 2015 | DOI: 10.1002/ejic.201500205

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      The direct coordination of 2-tosylaminomethylaniline to Zn2+, Cd2+ and Pd2+ ions is not possible. However, with a coordinating Schiff base derivative as a starting material, the Zn2+, Cd2+ and Pd2+ complexes can be obtained efficiently at room temperature.

    3. Hydrogen Peroxide Detection

      Facile Synthesis of (110)-Plane-Exposed Au Microflowers as High Sensitive Hydrogen Peroxide Sensors

      Fengjiao Yu, Zhong Liu and Wuzong Zhou

      Article first published online: 5 MAY 2015 | DOI: 10.1002/ejic.201500164

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      A 3D flower-like Au microstructure with a dominantly exposed active (110) plane was synthesized by a simple, facile method. This special structure exhibits excellent sensing capability towards H2O2 with a wide linear response range.

    4. Tetraphenylporphyrin Complexes

      Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of ZnII Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato-N, Thiocyanato-N, and Cyanido Ligands

      Zouhour Denden, Khaireddine Ezzayani, Eric Saint-Aman, Frédérique Loiseau, Shabir Najmudin, Cecilia Bonifácio, Jean-Claude Daran and Habib Nasri

      Article first published online: 1 MAY 2015 | DOI: 10.1002/ejic.201403214

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      The [Zn(TPP)X] (TPP = meso-tetraphenylporphyrinato and X = N3, NOC, NCS or CN) complex ions were characterized by X-ray diffraction. The effect of the nature of the pseudohalide axial ligand X on the redox and photophysical properties of these species in dichloromethane has also been studied by cyclic voltammetry, absorption, steady-state and time-resolved fluorescence techniques.

    5. Cyclometalated Compounds

      Reactivity Diversification – Synthesis and Exchange Reactions of Cobalt and Iron 2-Alkenylpyridine/-pyrazine Complexes Obtained by Vinylic C(sp2)–H Activation

      Robert Beck, Sebnem Camadanli, Ulrich Flörke and Hans-Friedrich Klein

      Article first published online: 30 APR 2015 | DOI: 10.1002/ejic.201500225

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      The regioselective cyclometalation reactions of 2-alkenylpyridine/-pyrazine derivatives with Co(CH3)(PMe3)4 provide cobalt complexes by vinylic C(sp2)–H activation. These cobalt complexes smoothly add iodomethane but readily demetalate with carbon monoxide. Conversely, reductive elimination through the release of ethane is the dominant reaction with the same ligands and Fe(CH3)2(PMe3)4.

    6. Hydroboration

      Synthesis and Hydroboration of a Mixed-Donor Iminoboryl Complex of Platinum

      Johannes Brand, Holger Braunschweig, Rian D. Dewhurst, Florian Hupp and Katharina Lang

      Article first published online: 30 APR 2015 | DOI: 10.1002/ejic.201500215

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      The first iminoboryl complex with a non-phosphine donor ligand has been isolated and fully characterized. This iminoboryl complex was found to undergo facile hydroboration with catecholborane, leading to an N-borylated hydroboryl complex.

    7. Mn–Carboxylate Catalysts

      Too Many Cooks Spoil the Broth – Variable Potencies of Oxidizing Mn Complexes of a Hexadentate Carboxylato Ligand

      Claire Deville, Maik Finsel, David P. de Sousa, Barbara Szafranowska, Julian Behnken, Simon Svane, Andrew D. Bond, Rune Kirk Seidler-Egdal and Christine J. McKenzie

      Article first published online: 29 APR 2015 | DOI: 10.1002/ejic.201500210

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      A manganese(II) complex of a hexadentate ligand catalyzes epoxidation. However, reaction conditions are critical since several metal-based oxidants with varying potencies can be generated. This observation is probably general for related catalysts, and consequences include decreased selectivity and competing water oxidation.

    8. Photocatalytic Nanosheets

      Bi2WO6 Nanosheets Synthesized by a Hydrothermal Method: Photocatalytic Activity Driven by Visible Light and the Superhydrophobic Property with Water Adhesion

      Chengyu Yang, Yan Huang, Taohai Li and Feng Li

      Article first published online: 29 APR 2015 | DOI: 10.1002/ejic.201500183

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      Bi2WO6 nanosheets with excellent photocatalytic activity and the superhydrophobic property were prepared at pH = 9 by a hydrothermal method.

    9. Thermoelectrics

      Semiconducting BiOCuSe Thermoelectrics and Its Metallic Derivative Bi2YO4Cu2Se2

      Ta-Lei Chou, Girish C. Tewari, Ting-Shan Chan, Ying-Ya Hsu, Jin-Ming Chen, Hisao Yamauchi and Maarit Karppinen

      Article first published online: 29 APR 2015 | DOI: 10.1002/ejic.201500159

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      X-ray absorption spectroscopy at multiple absorption edges is successfully employed to elaborate the differences in chemical bonding and charge balance between the two layered oxyselenide compounds, semiconducting BiOCuSe and metallic Bi2YO4Cu2Se2, both being potential hosts for high-performance thermoelectrics.

  8. Short Communications

    1. Silylium Compounds

      The Ion-Like Supersilylium Compound tBu3Si–F–Al[OC(CF3)3]3

      Alexandra Budanow, Michael Bolte, Matthias Wagner and Hans-Wolfram Lerner

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500323

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      Access to the supersilylated and trimethylsilylated halonium salts [R3Si–X–SiR3]{Al[OC(CF3)3]4} (R = tBu, X = Br, I; R = Me, X = Br, I) was achieved. Degradation of these halonium salts results in the formation of the ion-like silylium compounds tBu3Si–F–Al[OC(CF3)3]3 and Me3Si–F–Al[OC(CF3)3]3.

  9. Full Papers

    1. P-Bridged Diplatinum Complexes

      Carbonylation of Hydrido–Phosphanido-Bridged Dinuclear Platinum Complexes

      Mario Latronico, Piero Mastrorilli, Vito Gallo, Stefano Todisco, Maria Michela Dell'Anna and Antonino Rizzuti

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500160

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      The singly bridged dicarbonyl PtI compound 2+ can be obtained, both in solution and in the solid state, either by carbonylation of the solvento species [1-L]2+ or by carbonylation of 5 followed by the addition of HBF4.

    2. Carbon Nitrides

      Template-Free Synthesis of Three-Dimensional Nanoporous Bulk Graphitic Carbon Nitride with Remarkably Enhanced Photocatalytic Activity and Good Separation Properties

      Jianchao Shen, Hui Yang, Qianhong Shen, Yu Feng, Qifeng Cai and Huiying Yang

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500105

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      A facile template-free method is presented for the fabrication of nanoporous graphitic carbon nitride (g-C3N4) with a three-dimensional (3D) interconnected framework through a two-step protonation. The material exhibits excellent photocatalytic activity owing to its 3D nanoporous structure and highly efficient charge separation and transfer.

  10. Short Communications

    1. Cleavage of Polyenes

      Regioselective Cleavage of Electron-Rich Double Bonds in Dienes to Carbonyl Compounds with [Fe(OTf)2(mix-BPBP)] and a Combination of H2O2 and NaIO4

      Peter Spannring, Vital A. Yazerski, Jianming Chen, Matthias Otte, Bert M. Weckhuysen, Pieter C. A. Bruijnincx and Robertus J. M. Klein Gebbink

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500213

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      The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0–50 °C) and short reaction times (70 min).

  11. Full Papers

    1. Dioxo-Mo and -W Catalysts

      Dioxomolybdenum(VI) and -Tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation

      Antoine Dupé, Md. Kamal Hossain, Jörg A. Schachner, Ferdinand Belaj, Ari Lehtonen, Ebbe Nordlander and Nadia C. Mösch-Zanetti

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500055

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      Four new molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene or hydroxyglycolene substituents were synthesized and found to catalyze olefin epoxidation reactions under eco-friendly conditions.

    2. Group 13 Complexes

      Bis(phosphinimino)amide Supported Borondihydride and Heteroleptic Dihalo Compounds of Group 13

      Kuldeep Jaiswal, Billa Prashanth, Deependra Bawari and Sanjay Singh

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500144

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      Synthesis of a rare borondihydride complex has been made possible through the use of a relatively strong donor monoanionic bis(phosphinimino)amide ligand. Crucially, the ligand backbone is void of any reactive acidic hydrogen. The same ligand has also made feasible the synthesis of some heteroleptic dihalo derivatives of group 13 elements.

    3. Spin Crossover Complexes

      Spin Crossover in cis Manganese(III) Quinolylsalicylaldiminates

      Jitnapa Sirirak, David J. Harding, Phimphaka Harding, Keith S. Murray, Boujemaa Moubaraki, Lujia Liu and Shane G. Telfer

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500196

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      We report the redox pairs [Mn(qsal-X)2]0/+ in which the MnIII cations exhibit spin crossover despite the cis O donors.

    4. Ruthenium Catalysts

      Ruthenium Carboxylate Complexes as Efficient Catalysts for the Addition of Carboxylic Acids to Propargylic Alcohols

      Janine Jeschke, Christian Gäbler, Marcus Korb, Tobias Rüffer and Heinrich Lang

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500203

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      Ruthenium carboxylate complexes were applied in the synthesis of diverse β-oxo esters by the addition of carboxylic acids to propargylic alcohols. The catalytic system tolerates a broad range of functional groups and even facilitates the successful conversion of challenging substrates such as sterically demanding steroids.

    5. Cluster Synthesis

      Syntheses of Ir4(CO)65-C5Me4H)2 and Ir73-CO)3(CO)125-C5Me5) from Pentametallic Molybdenum-Iridium Cluster Precursors

      Junhong Fu, Michael D. Randles, Alan L. Criddle, Graeme J. Moxey, Torsten Schwich, Robert Stranger, Marie P. Cifuentes and Mark G. Humphrey

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500188

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      Reactions of molybdenum-iridium clusters with iridium-containing reagents afforded new homometallic clusters. Ir73-CO)3(CO)125-C5Me5) possesses three semi-face-capping CO ligands, while Ir4(CO)65-C5Me4H) is formally very electron-deficient; theoretical studies suggest stabilization by significant intracluster multiple Ir–Ir bonding.

    6. Redox-Active Molybdopterins

      Synthesis, Structure and Redox Properties of Asymmetric (Cyclopentadienyl)(ene-1,2-dithiolate)cobalt(III) Complexes Containing Phenyl, Pyridyl and Pyrazinyl Units

      James P. Dicks, Muhammad Zubair, E. Stephen Davies, C. David Garner, Carola Schulzke, Claire Wilson and Jonathan McMaster

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500138

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      Structural, electrochemical, spectroscopic and theoretical studies of [(η5-C5H5)Co(dithiolene)] complexes suggest that the pyran ring-opened form of the molybdenum cofactor of Mo- and W-containing oxygen-atom-transfer enzymes may participate in the redox reactions involved in the catalytic cycle.

    7. Emission in Zn–Salophens

      Unexpected Emission Properties of a 1,8-Naphthalimide Unit Covalently Appended to a Zn–Salophen

      Martina Piccinno, Gemma Aragay, Francesco Yafteh Mihan, Pablo Ballester and Antonella Dalla Cort

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500258

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      Fluorescence switching of 1,8-naphthalimide: A zinc–salophen complex quenches the emission of 1,8-naphthalimide both in the covalently linked and in the supramolecular assembly. The nonfluorescent 1:1 complex was exploited as an on-off-on receptor for anions according to the fluorescent indicator displacement assay approach.

  12. Short Communications

    1. Polyoxometalate Catalysts

      Viral Nanotemplates Armed with Oxygenic Polyoxometalates for Hydrogen Peroxide Detoxification

      Debora Vilona, Antonio Sorarù, Chiara Maccato, Rossella Bortolaso, Livio Trainotti, Federica Valentini, Aldrei Boaretto, Cinzia Cepek, Marcella Bonchio and Mauro Carraro

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500155

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      A polyoxometalate with oxygenic activity was anchored on the TMV (tobacco mosaic virus). The rod-like biogenic template enables the formation of catalytic nanoarrays for H2O2 dismutation.

  13. Full Papers

    1. Mn Oxidation Catalysts

      Mechanistic Links in the in-situ Formation of Dinuclear Manganese Catalysts, H2O2 Disproportionation, and Alkene Oxidation

      Davide Angelone, Shaghayegh Abdolahzadeh, Johannes W. de Boer and Wesley R. Browne

      Article first published online: 21 APR 2015 | DOI: 10.1002/ejic.201500195

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      The in situ formation of catalytically active species through the reduction of a precatalyst, H2O2 disproportionation and alkene oxidation are linked to a common active species.

    2. Water Oxidation

      A Bioinspired System for Light-Driven Water Oxidation with a Porphyrin Sensitizer and a Tetrametallic Molecular Catalyst

      Mirco Natali, Elisa Deponti, Debora Vilona, Andrea Sartorel, Marcella Bonchio and Franco Scandola

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500063

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      The photoinduced events and the light-driven water-oxidation ability of a bioinspired, three-component catalyst/photosensitizer/acceptor molecular system are investigated.

  14. Microreviews

    1. Homonuclear Metal String Complexes

      From Homonuclear Metal String Complexes to Heteronuclear Metal String Complexes

      Shao-An Hua, Ming-Chuan Cheng, Chun-hsien Chen and Shie-Ming Peng

      Article first published online: 7 APR 2015 | DOI: 10.1002/ejic.201403237

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      This microreview describes the development of metal string complexes, from homonuclear to heteronuclear ones, including their synthesis and physical properties.

    2. Diiron Monooxygenases

      Controlling the Activities of the Diiron Centre in Bacterial Monooxygenases: Lessons from Mutagenesis and Biodiversity

      Tim Nichol, J. Colin Murrell and Thomas J. Smith

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500043

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      The soluble diiron monooxygenases (SDIMOs) are a diverse group of enzymes that use a diiron active centre to add oxygen to a wide range of organic molecules. Here we review how natural biodiversity and laboratory mutagenesis studies have revealed how the protein scaffold of SDIMOs controls the activity of the enzymes and the presentation of substrates to the diiron site.

  15. Full Papers

    1. Luminescent MOFs

      Photoluminescence Tuning and Water Detection of Yttrium Diazinedicarboxylate Materials through Lanthanide Doping

      Javier Cepeda, Sonia Pérez-Yáñez, Garikoitz Beobide, Oscar Castillo, Jose Ángel García and Antonio Luque

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500090

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      Six diazinedicarboxylate-based yttrium(III) coordination compounds are prepared through different synthetic approaches. Activation by lanthanide doping enables the modulation of the emission colour. Coupling the luminescence with reversible water capture/release opens up the way to a functional material that shows promise as a water sensor.

    2. Oxygen Atom Transfer

      Electronic Fine-Tuning of Oxygen Atom Transfer Reactivity of cis-Dioxomolybdenum(VI) Complexes with Thiosemicarbazone Ligands

      Aurélien Ducrot, Bethany Scattergood, Ben Coulson, Robin N. Perutz and Anne-K. Duhme-Klair

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500059

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      Thiosemicarbazone ligands (H2LR) derived from para-substituted salicylaldehydes allow the electronic properties and catalytic activities of cis-dioxo MoVI complexes of composition [MoO2(LR)MeOH] to be fine-tuned by electron-donating or electron-withdrawing groups R.

    3. Tyrosinase Models

      Catalytic Models of Tyrosinase: Reactivity Differences between Systems Based on Mono- and Binucleating Ligands

      Julia Schottenheim, Claus Gernert, Benjamin Herzigkeit, Jan Krahmer and Felix Tuczek

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500029

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      A tyrosinase model based on the binucleating ligand Lpy2 was developed and characterized. The ligand Lpy2 contains a combination of an imine and a pyridine function in the sidearms that are bridged by a flexible alkyl spacer. The Cu2Lpy2 complex catalyzes the conversion of monophenol DTBP-H into the o-quinone DTBQ (TON = 18). An electron-poor substrate is converted into the semiquinone.

    4. Immobilized Biocatalysts

      The Electrically Wired Molybdenum Domain of Human Sulfite Oxidase is Bioelectrocatalytically Active

      Roberto Spricigo, Silke Leimkühler, Lo Gorton, Frieder W. Scheller and Ulla Wollenberger

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500034

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      Human sulfite oxidase and its catalytic molybdenum-cofactor-containing domain were wired to an electrode with poly(vinylpyridine)–[osmium(N,N′-methyl-2,2′-biimidazole)3]2+/3+, which mediated the electron transfer between either of the enzyme cofactors and the electrode, as demonstrated by electrocatalytic turnover currents.

    5. V-Catalyzed Oxidative Bromination

      Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

      Federica Sabuzi, Ekaterina Churakova, Pierluca Galloni, Ron Wever, Frank Hollmann, Barbara Floris and Valeria Conte

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500086

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      Catalysis of thymol bromination by vanadium derivatives is directly compared to catalysis by a V-dependent bromoperoxidase. All reactions were performed under mild and sustainable conditions with relatively inexpensive reagents. Appealing results were obtained in terms of selectivity and sustainability.

    6. Chiral Complexes for Oxidations

      Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand

      Maria Lucia Perrone, Eliana Lo Presti, Simone Dell'Acqua, Enrico Monzani, Laura Santagostini and Luigi Casella

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201500046

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      A dinuclear copper(II) complex derived from a chiral hexadentate nitrogen ligand is reported as a new catalyst for asymmetric oxidations. For biogenic catechols as model substrates, the best enantioselectivity is obtained in the oxidation of the methyl esters of L-/D-Dopa, for which 70 % ee is obtained in favor of the L enantiomer.

    7. Oxidase and Catalase Mimics

      Mononuclear Iron(III) Complexes as Functional Models of Catechol Oxidases and Catalases

      Elena Badetti, Blerina Gjoka, Eszter Márta Nagy, Gérald Bernardinelli, Peter E. Kündig, Cristiano Zonta and Giulia Licini

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403225

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      Amino triphenolate iron(III) complexes promote effectively, at room temperature, the aerobic auto-oxidation of 3,5-di-tert-buthylcatechol to the corresponding o-benzoquinone (oxidase mimicking) and hydrogen peroxide dismutation (catalase mimicking).


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