European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 11

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

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  1. 1 - 62
  1. Full Papers

    1. Supercarpacitors

      Ultra-Fast Microwave Synthesis of 3D Flower-Like Co9S8 Hierarchical Architectures for High-Performance Supercapacitor Applications

      Li Yin, Longqiang Wang, Xiaohong Liu, Yansong Gai, Linghao Su, Baohan Qu and Liangyu Gong

      Article first published online: 20 APR 2015 | DOI: 10.1002/ejic.201500120

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      Ultra-fast microwave irradiation is used to synthesize 3D flower-like Co9S8 hierarchical architectures. The materials display both high discharge capacity and long cycle life under charge–discharge cycling for supercapacitors.

  2. Short Communications

    1. Mechanism for Au(III) Catalysis

      Homogeneous Catalysis with AuIII: Insights into the Mechanism of the Alkoxylation of Alkynes

      Zhi Xiang Wong and Matthias Lein

      Article first published online: 17 APR 2015 | DOI: 10.1002/ejic.201500152

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      A thorough mechanistic study of gold(III)-catalyzed addition of methanol to propyne was carried out by using density functional theory. Each individual process is assisted by explicitly included solvent methanol, which also acts as the nucleophile. Results showed that the double nucleophilic attacks proceed fast over low activation barriers with the last hydrogen migration as the rate-determining step.

  3. Full Papers

    1. Oxide Copper Complexes

      Investigations Concerning [Cu4OX6L4] Cluster Formation of Copper(II) Chloride with Amine Ligands Related to Benzylamine

      Sabine Becker, Ulrich Behrens and Siegfried Schindler

      Article first published online: 17 APR 2015 | DOI: 10.1002/ejic.201500115

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      The μ4-oxido motif is well known in copper clusters and often forms spontaneously and unexpectedly. However, little is known about the reaction conditions that generate μ4-oxido clusters. Here, a systematic investigation of μ4-oxido cluster formation is reported. The effects of the ligand environment, central chalcogenide atom, and bridging halide ligands on cluster formation are investigated.

    2. Mixed-Framework Silicates

      Two Structure Types Based on Si6O15 Rings: Synthesis and Structural and Spectroscopic Characterisation of Cs1.86K1.14DySi6O15 and Cs1.6K1.4SmSi6O15

      Maria Wierzbicka-Wieczorek, Martin Göckeritz, Uwe Kolitsch, Christoph Lenz and Gerald Giester

      Article first published online: 16 APR 2015 | DOI: 10.1002/ejic.201500091

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      Two (Cs,K)-REE3+ silicates (REE3+ = Dy or Sm) containing Si6O15 rings represent mixed tetrahedral-octahedral framework structure types. Their crystal structures were characterised by single-crystal X-ray diffraction and photoluminescence spectroscopy. The presence of REE3+ cations in the structures causes emission bands in the visible yellow-to-orange spectral range.

    3. Zr Metal-Organic Frameworks

      Improved Synthesis of a Zirconium(IV) Muconate Metal–Organic Framework: Characterization, Stability and Gas Sorption Properties

      Amlan Buragohain and Shyam Biswas

      Article first published online: 14 APR 2015 | DOI: 10.1002/ejic.201500133

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      The improved synthetic procedure, characterization, thermal and chemical stability and gas adsorption properties of the previously reported ZrIV muconate compound are presented.

    4. Fe-Based Photosensitizer

      An Iron-Based Photosensitizer with Extended Excited-State Lifetime: Photophysical and Photovoltaic Properties

      Thibaut Duchanois, Thibaud Etienne, Cristina Cebrián, Li Liu, Antonio Monari, Marc Beley, Xavier Assfeld, Stefan Haacke and Philippe C. Gros

      Article first published online: 14 APR 2015 | DOI: 10.1002/ejic.201500142

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      A new iron(II) complex with a record 16 ps triplet metal-to-ligand charge-transfer (3MLCT) state lifetime has been designed and evaluated as a photosensitizer in a laboratory dye-sensitized solar cell (DSSC), which led to measurable photocurrent and power-conversion efficiency. Such an improvement of the photophysical properties of iron-based complexes opens the way to applications that go far beyond energy production.

    5. Layered Quaternary Compounds

      Hg5AsS2I3 – A Narrow-Band-Gap 2D Layered Compound with Different Trapped I Anions

      Yong Liu, Hui-Yi Zeng, Bin-Wen Liu, Geng-E Wang and Guo-Cong Guo

      Article first published online: 14 APR 2015 | DOI: 10.1002/ejic.201500150

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      The structure consists of 1[Hg(1)2Hg(2)2As2/2S2] eight-membered-ring chains bridged by Hg atoms to form [Hg(1)2Hg(2)2Hg(3)As2/2S2] layers with inner- and interlayer electrostatic interactions between I and Hg.

    6. Amine–Boranes

      Rehydrogenation of Aminoboranes to Amine–Boranes Using H2O: Reaction Scope and Mechanism

      Erin M. Leitao and Ian Manners

      Article first published online: 13 APR 2015 | DOI: 10.1002/ejic.201500117

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      The conversion of aminoboranes to amine–boranes using water has been demonstrated and the mechanism investigated using deuterium labeling studies and model reactions.

    7. N-Heterocyclic Carbenes

      Determining the Ligand Properties of N-Heterocyclic Carbenes from 77Se NMR Parameters

      Kathrin Verlinden, Hannes Buhl, Walter Frank and Christian Ganter

      Article first published online: 10 APR 2015 | DOI: 10.1002/ejic.201500174

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      The electronic properties of a range of N-heterocyclic carbenes have been evaluated by using the 77Se NMR chemical shifts of NHC–Se adducts, to map the π-acceptor character, and 1JCSe coupling constants, which provide insights into the σ-donor ability of the respective carbene. DFT calculations were conducted to rationalize the data. The NMR-derived parameters have been compared with TEP values.

    8. Ru Anticancer Compounds

      Hydrogen Bonding and Anticancer Properties of Water-Soluble Chiral p-Cymene RuII Compounds with Amino-Oxime Ligands

      Yosra Benabdelouahab, Laura Muñoz-Moreno, Malgorzata Frik, Isabel de la Cueva-Alique, Mohammed Amin El Amrani, María Contel, Ana M. Bajo, Tomás Cuenca and Eva Royo

      Article first published online: 9 APR 2015 | DOI: 10.1002/ejic.201500097

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      The ability of water-soluble, chiral arene RuII compounds with amino-oxime ligands to aggregate in solution by means of hydrogen bonding is described. The compounds do not interact with plasmid (pBR322) DNA but display strong cytotoxic and antimetastatic effects in vitro against androgen-unresponsive human prostate cancer PC3 cell line.

    9. Manganese Antioxidants

      Structurally Diverse Manganese(II)–Diclofenac Complexes Showing Enhanced Antioxidant Activity and Affinity to Serum Albumins in Comparison to Sodium Diclofenac­

      Marianthi Zampakou, Vassilis Tangoulis, Catherine P. Raptopoulou, Vassilis Psycharis, Athanasios N. Papadopoulos and George Psomas

      Article first published online: 9 APR 2015 | DOI: 10.1002/ejic.201500078

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      The interaction of MnII ions with the nonsteroidal anti-inflammatory drug (NSAID) sodium diclofenac in the presence of 1,10-phenanthroline or 2,2′-dipyridylamine leads to the formation of a trinuclear or a mononuclear complex, respectively. The complexes show noteworthy antioxidant activity and significant binding affinity for serum albumins.

    10. Aluminum Cycloaddition Catalysts

      Monomeric or Dimeric Aluminum Complexes as Catalysts for Cycloaddition between CO2 and Epoxides

      So Han Kim, Sang Yeop Han, Jeong Hee Kim, Yi Young Kang, Junseong Lee and Youngjo Kim

      Article first published online: 9 APR 2015 | DOI: 10.1002/ejic.201500184

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      The aluminum complexes 13 demonstrate catalytic activity for cycloaddition between CO2 and epoxides in the presence of cocatalysts.

    11. BODIPY Conjugates

      Panchromatic Borane–aza-BODIPY Conjugate: Synthesis, Intriguing Optical Properties, and Selective Fluorescent Sensing of Fluoride Anions

      Chinna Ayya Swamy P, Ragam N. Priyanka, Sanjoy Mukherjee and Pakkirisamy Thilagar

      Article first published online: 9 APR 2015 | DOI: 10.1002/ejic.201500089

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      A broadband visible near-IR emissive triarylborane–aza-BODIPY conjugate was synthesized and characterized. The compound shows selective response towards fluoride anions with responses in the both visible and near-IR regions.

    12. Stability of Chelate Complexes

      Hindrance, Donor Ability of MenNN Chelates and Overall Stability of Pentacoordinate [PtCl22-CH2=CH2)(MenNN)] Complexes as Observed by η2-Olefin 1JPt,C Modulation: An NMR Study

      Michele Benedetti, Daniela Antonucci, Chiara R. Girelli and Francesco P. Fanizzi

      Article first published online: 9 APR 2015 | DOI: 10.1002/ejic.201500103

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      The effect of steric hindrance around bis-nitrogen donors on the metal–olefin bond, according to the Dewar–Chatt–Ducanson model, is described. Low hindrance around bis-nitrogen donors corresponds to a weaker metal–olefin interaction, whereas high steric hindrance around bis-nitrogen donors corresponds to a stronger metal–olefin interaction.

    13. 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. Polymetalates

      Comparative Study of the Reactivity of Zirconium(IV)-Substituted Polyoxometalates towards the Hydrolysis of Oligopeptides

      Hong Giang T. Ly, Gregory Absillis and Tatjana N. Parac-Vogt

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500161

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      The hydrolytic activity of ZrIV-substituted Lindqvist-, Keggin-, and Wells–Dawson-type polyoxometalates towards the peptide bonds in tri- and tetrapeptides is investigated by kinetic methods and multinuclear NMR spectroscopy. The peptides are hydrolyzed completely in nearly neutral and neutral pH media. The Keggin complex is the most active towards peptide bond hydrolysis in the studied peptides.

    15. Redox-Active Urea Azine Ligands

      Urea Azines (Bisguanidines): Electronic Structure, Redox Properties, and Coordination Chemistry

      Hendrik Herrmann, Matthias Reinmuth, Sven Wiesner, Olaf Hübner, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500228

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      Electron donors: This article analyses the electronic structure of urea azines and shows that they are strong organic electron donors and redox-active ligands.

  4. Short Communications

    1. NHC–Borates

      Facile Rearrangement of a Bis(N-heterocyclic carbene)borate Chelate Ligand and Access to [:GeX]+ Complexes (X = H, Cl)

      Yun Xiong, Shenglai Yao, Tibor Szilvási and Matthias Driess

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500154

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      Flip the chelate: The unexpected solvent-dependent potassium-induced isomerization of a potassium bis(N-heterocyclic carbene)borate in toluene afforded a unique potassium imidazolyl–NHC–borate isomer, which was successfully utilized for the synthesis and isolation of unprecedented chloro- and hydridogermyliumylideneborate complexes.

  5. 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.

  6. Full Papers

    1. Cu Porphyrin Sensor

      A Copper Porphyrin for Sensing H2S in Aqueous Solution via a “Coordinative-Based” Approach

      Silvia Mirra, Stefano Milione, Maria Strianese and Claudio Pellecchia

      Article first published online: 7 APR 2015 | DOI: 10.1002/ejic.201500070

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      We devised a new, fast, simple, and cost-effective probe for monitoring hydrogen sulfide. Proof-of-principle results that a copper porphyrin complex can be successfully implemented as a turn-on sensing system for H2S via a coordinative-based approach are reported.

  7. Short Communications

    1. Unsymmetrical Selenides

      Potassium and Magnesium Complexes of the (Iminophosphoranyl)(selenophosphoranyl)methanide Ligand [CH(PPh2Se)(PPh2NSiMe3)]

      Ramalingam Thirumoorthi and Tristram Chivers

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500216

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      (Iminophosphoranyl)(selenophosphoranyl)methanide complexes of K and Mg were synthesized by reactions of the neutral ligand CH2(PPh2Se)(PPh2NSiMe3) with KH or Mg{N(SiMe3)2}2. The N,Se-chelated K complex forms a centrosymmetric dimer through weak K···Se interactions, while the two ligands are Se,C,N-coordinated to the metal in the homoleptic Mg complex.

  8. Microreviews

    1. 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.

  9. 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. Fluorescence Probes

      Fluorescence Quenching of a Europium Coordination Compound for the Detection of Trace Amounts of Water: Uncovering the Response Mechanism by Structural Confirmation

      Li Song, Ye-Wen Wu, Wen-Xiang Chai, Yin-Song Tao, Chang Jiang and Qiu-Hua Wang

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500062

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      The luminescence-quenching effect of Eu(DAF)2(NO3)3 (1, DAF = 4,5-diazafluorene) is applied to the detection of water in CH3CN. The response mechanism is first uncovered through the confirmation of e structure of the resultant nonluminous compound [Eu(NO3)2(H2O)5](NO3)(DAF)2·H2O (2). Theoretical calculations of the absorption spectra are also reported.

    3. 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.

    4. 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.

  10. Short Communications

    1. Diphospholides

      One-Pot Synthesis of a 1,2-Diphospholide by Double C–H Deprotonation

      Lily S. H. Dixon, Peter D. Matthews, Sophia A. Solomon and Dominic S. Wright

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500177

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      Almost “In-denyl”: 5,7-Dimethyl-1,2-benzodiphosphol-1-ide (1), a species valence-isoelectronic with the indenyl anion, is simply prepared in a one-pot synthesis by treatment of MesPH2 with nBuLi and Sb(NMe2)3. This transformation involves an unprecedented double C–H deprotonation of a CH3 group by a redox-active main group base.

  11. Full Papers

    1. Phosphorus Heterocycles

      Phosphaindazole: A Phosphorus–Carbon Aromatic Heterocycle

      Ivana Jevtovikj, Menyhárt B. Sárosi, Anup K. Adhikari, Peter Lönnecke and Evamarie Hey-Hawkins

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500172

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      A straightforward synthetic route to a novel phosphorus–carbon heterocycle, phosphaindazole, which is the phosphorus analogue of indazole or indene, was developed from sodium tetraphosphanediide [Na2(P4Mes4)](Mes = 2,4,6-Me3C6H2) and nBuLi.

  12. Short Communications

    1. Ru–Indane Complexes

      Synthesis, Structure, and Reactivity of Ruthenium(0) Indane Complexes fac-[Ru(NCMe)3(CO)2(InX3)] (X = Cl, Br)

      Masumi Itazaki, Masaki Ito and Hiroshi Nakazawa

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500112

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      The first ruthenium indane complexes, fac-[Ru(NCMe)3(CO)2(InX3)] (X = Cl, Br), were synthesized by the reaction of Ru3(CO)12 with 3 equiv. of InX3. Reaction of fac-[Ru(NCMe)3(CO)2(InX3)] (X = Cl: 1, Br: 2) with PPh3 at a 1:1 molar ratio afforded cis,cis,trans-[Ru(NCMe)2(CO)2(InX3)(PPh3)] (X = Cl: 3, Br: 4) as a result of the trans-effect of InX3.

  13. Full Papers

    1. Gold–NHC Catalysts

      Anionic N-Heterocyclic Carbene Complexes of Gold(I) as Precatalysts for Silver-Free Cycloisomerization of Enynes

      Stéphanie Bastin, Cécile Barthes, Noël Lugan, Guy Lavigne and Vincent César

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500168

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      The anionic maloNHC–gold(I) complexes, synthesized as their Li+, K+, and Et4N+ salts, were fully characterized and used as precatalysts in the silver-free Au-catalyzed cycloisomerization reaction of 1,6-enynes. It was revealed that the nature of the countercation has a strong influence on the catalyst efficiency. The potassium salt appeared to be the best catalyst affording yields of up to 99 %.

    2. Nanocomposite Photocatalysts

      Fabrication and Photocatalytic Properties of TiO2/Reduced Graphene Oxide/Ag Nanocomposites with UV/Vis Response

      Xueli Gou, Yongliang Cheng, Bin Liu, Bingjun Yang and Xingbin Yan

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201403238

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      TiO2·rGO/Ag composite nanofibers are prepared by wrapping reduced graphene oxide (rGO) sheets around TiO2 nanofibers and then loading Ag nanoparticles onto the surfaces of TiO2/rGO. The introduction of rGO and Ag creates a marked improvement in the photocatalytic activity of the TiO2 nanofibers.

    3. 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.

  14. Short Communications

    1. Perrhenate Ion Encapsulation

      Second-Sphere Complexation of Thorium(IV) by Cucurbit[6]uril with Included Perrhenate Counterions – Crystal Structure and Hirshfeld Surface Analysis

      Pierre Thuéry

      Article first published online: 30 MAR 2015 | DOI: 10.1002/ejic.201500171

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      Aquated thorium cations are held at both portals of cucurbit[6]uril (CB6) by ion–dipole and hydrogen-bonding interactions, one perrhenate anion being included in the macrocycle cavity. Hirshfeld surfaces are used to visualize short contacts between the species present.

  15. Full Papers

    1. Magnetic Nanoclusters

      Synthesis, Crystal Structure, and Magnetic Properties of a Family of Undecanuclear [CuII9LnIII2] Nanoclusters

      Wei-Wei Kuang, Li-Li Zhu, Li-Cun Li and Pei-Pei Yang

      Article first published online: 30 MAR 2015 | DOI: 10.1002/ejic.201500064

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      Four isostructural undecanuclear heterometallic compounds with an unprecedented [Cu9Ln2] core, which can be viewed as a [3 × 3] [Cu9] grid and two [LnCu4] tetragonal pyramids that share a common [Cu4] vertex, have been synthesized. [Cu9Gd2] (2) exhibits a significant magnetocaloric effect, whereas [Cu9Tb2] (3) and [Cu9Dy2] (4) display slow relaxation of the magnetization.

    2. Drug Delivery

      pH-Sensitive Gold Nanorods with a Mesoporous Silica Shell for Drug Release and Photothermal Therapy

      Ting Zhang, Zeyang Ding, Huiming Lin, Liru Cui, Chunyu Yang, Xin Li, Hao Niu, Na An, Ruihan Tong and Fengyu Qu

      Article first published online: 30 MAR 2015 | DOI: 10.1002/ejic.201403247

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      A pH-sensitive nanocarrier with a gold nanorod (GNRs) core and mesoporous silica shell (GNR@mSiO2) was synthesized. Doxorubicin hydrochloride (DOX) was loaded onto the mesoporous silica with Schiff base bonding, and enhanced drug release was observed under acidic conditions owing to the sensitive Schiff base linker. The synergistic effect of chemotherapy and hyperthermia shown by this nanocarrier can be expected to lead to improved cancer treatment.

    3. Perovskite Catalysts

      Fe,Pd Co-Incorporated LaCoO3 Perovskites: Modification of Thermal Stability and Catalytic Activity for Gasoline Vehicle Exhaust Purification

      Lingjun Hu, Chen Zhou, Chunzheng Wu, Shenghu Zhou, Wei Guo Wang and Hongfeng Yin

      Article first published online: 30 MAR 2015 | DOI: 10.1002/ejic.201403196

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      A series of Fe,Pd co-doped LaCoO3 perovskites have been studied as three-way catalysts. A mechanism is proposed for the enhancement of the stability of the perovskite structure by Fe doping as well as the catalytic performance for the simultaneous elimination of CO, NO, and C3H8.

    4. Luminescent Metal Sulfonates

      Influence of Metal Cations and Coordination Modes on Luminescent Group 1 and 2 Metal Sulfonate Complexes Constructed from 4,4′-Dihydroxybiphenyl-3,3′-disulfonic Acid

      Yi-Zhe Yu, Ya-Nan Li, Zhao-Peng Deng, Zhi-Biao Zhu, Li-Hua Huo and Shan Gao

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500170

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      The self-assembly of 4,4′-dihydroxybiphenyl-3,3′-disulfonic acid with group 1 and 2 metal salts results in diverse second-coordination-sphere networks, hybrid layers, interdigitating 2D + 2D [RIGHTWARDS ARROW] 3D architectures, and 3D pillared-layered networks tuned by the metal cations and the coordination mode of the ligand.

    5. Ferrocene–Viologen Compounds

      Ferrocenyl–Bipyridinium Cations and Their Platinum Complexes Related to Viologens – Preparation, Redox Properties, and Crystal Structures

      Tomoyuki Mochida, Yusuke Funasako, Yukiko Nezu, Koji Hagiwara and Ryo Horikoshi

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500077

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      4,4′-Bipyridinium cations bearing ferrocenyl or ferrocenylphenyl substituents at the N-positions were prepared as donor–acceptor compounds. Platinum(II)-bridged diferrocene compounds were also prepared by using bipyridinium cations. These cations display multistage redox properties, and the compounds exhibit broad charge-transfer absorption bands in the range 450–800 nm.

    6. Spin-Crossover Complexes

      Effects of Big Planar Anions on the Spin Transition of a Mononuclear Manganese(III) Complex with a Hexadentate Schiff-Base Ligand

      Shi Wang, Yong-Hua Li and Wei Huang

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500024

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      Spin-crossover in d4 ions is a most rare event. Changing the size of the anion from NO3 to [Pt(mnt)2] and [Ni(dmit)2] leads to significant changes in the overall crystal packing of Mn ion-pair complexes and furthermore in the spin state of the MnIII center.

  16. Short Communications

    1. Titanium Aminophenolate Systems

      Potent Reactivity in Solubilised Oxo-Titanium Polymers

      Alastair J. Nielson and Joyce M. Waters

      Article first published online: 25 MAR 2015 | DOI: 10.1002/ejic.201403135

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      [TiO(salen)]n polymers solubilised in aldehyde solution show potent activity when ortho substituents are present on the salicylidene ligand aromatic rings. Unprecedented carbon-based chemistry is demonstrated by the formation of new ligands about the titanium centre.

  17. Full Papers

    1. Copper Selenides

      Monoclinic Copper(I) Selenide Nanocrystals and Copper(I) Selenide/Palladium Heterostructures: Synthesis, Characterization, and Surface-Enhanced Raman Scattering Performance

      Long Zhang, Shulin Zhao, Yafei Li, Yaqian Lan, Min Han, Zhihui Dai and Jianchun Bao

      Article first published online: 25 MAR 2015 | DOI: 10.1002/ejic.201500008

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      Monoclinic Cu2Se nanocrystals and Cu2Se/Pd heterostructures have been synthesized by simple and facile methods. Owing to strong synergistic effects and phase-dependent characteristics, the surface-enhanced Raman scattering performance of the Cu2Se/Pd heterostructure is superior to those of Cu2Se, Pd, CuSe/Pd, and Cu2–xSe/Pd.

    2. Hypervalent P Heterocycles

      Phenylpyrazole-Based Hypervalent Phosphorus Compounds: From Positional Isomerism to Stacking Interactions

      Alexander N. Kornev, Vyacheslav V. Sushev, Yulia S. Panova, Natalia V. Zolotareva, Evgenii V. Baranov, Georgy K. Fukin and Gleb A. Abakumov

      Article first published online: 24 MAR 2015 | DOI: 10.1002/ejic.201500102

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      The dichlorophosphino derivative of 3,5-dimethyl-1-phenyl-1H-pyrazole exists in solution as an equilibrium mixture of positional isomers. Its reduction leads to cationic diphosphines with a chloride bridge between the phosphorus atoms. The hypervalent N···P (1.774–1.885 Å) and Hal···P interactions influence the behavior in solution and the arrangement of molecules in the crystal form.

    3. Bimetallic Coordination Polymers

      External-Template-Assisted Formation of Octacyanometalate-Based MV–MnII (M = W, Mo) Bimetallic Coordination Polymers with Magnetic Properties

      Jun Qian, Jingchun Hu, Hirofumi Yoshikawa, Jinfang Zhang, Kunio Awaga and Chi Zhang

      Article first published online: 24 MAR 2015 | DOI: 10.1002/ejic.201403223

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      2D coordination polymers {{[μ4-M(CN)8]2[Mn(dmf)3]2[Mn(dmf)4]}·2DMF}n (M = W, Mo) and a 1D chain compound {{[μ4-Mo(CN)8][Mn(dmf)4]2}·(ClO4)}n are constructed by external-template-assisted formation in the presence and absence of bis(benzimidazol-2′-yl)pyridine. All three compounds can be assembled into 3D supramolecular structures, and two of the compounds exhibit typical ferrimagnetic properties.

    4. Mesoporous Materials

      Facile Preparation of Ammonium Molybdophosphate/Al-MCM-41 Composite Material from Natural Clay and Its Use in Cesium Ion Adsorption

      Chunyan Sun, Feng Zhang, Xiao Wang and Fangqin Cheng

      Article first published online: 23 MAR 2015 | DOI: 10.1002/ejic.201500114

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      A composite ammonium molybdophosphate/Al-MCM-41 material is synthesized by a one-pot method with natural clay as the silica and aluminum source. A modified “liquid-phase transport” step allows the use of impure natural clay as the starting material to produce pure product without sedimentation pretreatment. The composite material is effective for the adsorption of cesium ions from brine.

    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. Ternary Polygermanides

      Flux Crystal Growth of the Ternary Polygermanide LaPtGe2, a p-Type Metal

      Daniel E. Bugaris, Mihai Sturza, Fei Han, Jino Im, Duck Young Chung, Arthur J. Freeman and Mercouri G. Kanatzidis

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500019

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      Plate crystals of LaPtGe2 have been grown from a molten indium flux. This compound crystallizes in the CeNiSi2-type structure. Electrical resistivity, Hall effect, and thermopower measurements have shown that LaPtGe2 exhibits p-type metallic behavior, which is consistent with electronic band structure calculations.

    7. Supported Bimetallic Catalysts

      Room-Temperature Hydrogenation of Citral Catalyzed by Palladium–Silver Nanocrystals Supported on SnO2

      Shuo Wang, Rongan Shen, Zheng Chen, Jiaxi Wang, Dingsheng Wang and Yadong Li

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500057

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      We have developed two strategies to optimize Pd catalysts for the selective hydrogenation of citral and exploited a catalyst (Pd0.6Ag0.4–SnO2/C) with the best catalytic performance (the conversion of citral reached 99 %, and the selectivity was up to 96 %).

    8. Molecular Docking

      Synthesis, Crystal Structures, Molecular Docking, and Urease Inhibitory Activities of Transition-Metal Complexes with a 1,2,4-Triazolecarboxylic Acid Derived Ligand

      Yong-Peng Xu, Yue-Hu Chen, Zhi-Jian Chen, Jie Qin, Shao-Song Qian and Hai-Liang Zhu

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500050

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      Four novel crystals of copper, zinc, and iron complexes based on 1,2,4-triazole carboxylic acid derivatives were determined by single-crystal X-ray diffraction. The inhibitory activity and kinetic studies were tested in vitro against jack bean urease. The computational predications, biological evaluation, and mechanism study will help in the discovery of new urease inhibitors.

    9. Metalloenzyme Models

      Synthesis and Characterization of 4-, 5-, and 6-Coordinate Tris(1-ethyl-4-isopropylimidazolyl-κN)phosphine Cobalt(II) Complexes

      Chanel R. Easley, Jia Li, Atanu Banerjee, Manashi Panda, William W. Brennessel, Reza Loloee, Enrique Colacio and Ferman A. Chavez

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201403203

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      [Co(T1Et4iPrIP)X2] {T1Et4iPrIP = tris(1-ethyl-4-isopropylimidazolyl)phosphine; X = OTf (1), Cl (2), Br (3)}, and [Co(T1Et4iPrIP)(CH3CN)3](OTf)2 (4) are reported. Dissolution of 1 in MeCN affords 4. Reaction of 1 with Cl or Br yields 2 or 3, respectively. DFT studies indicate that 1 has the largest HOMO–LUMO gap, which suggests that the formation of 2 or 3 from 1 is primarily sterically driven.

    10. Magnetic Manganese Helices

      Pentanuclear and Octanuclear Manganese Helices

      Hiroki Sato, Momoyo Yamaguchi, Tatsuya Onuki, Mao Noguchi, Graham N. Newton, Takuya Shiga and Hiroki Oshio

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201500096

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      Pentanuclear and octanuclear manganese helices are obtained by the reactions of a multidentate polypyridine ligand with manganese nitrate and chloride. The Mn ions in the pentanuclear complex are in a mixture of +2 and +3 valence states, whereas those of the octanuclear complex are homodivalent. Both compounds show antiferromagnetic interactions.

    11. Immobilized Chiral Catalysts

      Chiral Ruthenium Catalyst Immobilized within Magnetically Retrievable Mesoporous Silica Microcapsules for Aqueous Asymmetric Transfer Hydrogenations

      Amani Zoabi, Suheir Omar and Raed Abu-Reziq

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201403212

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      We report the design of a “quasi-homogeneous” catalytic system, based on a modified Noyori Ru-TsDPEN catalyst confined within mesoporous silica-based microreactors, for the efficient asymmetric transfer hydrogenation of ketones in water. The new system demonstrates excellent reactivity and enantioselectivity characteristic of homogeneous catalysts, but can be easily recovered.

    12. Triazole-Based Coordination Polymers

      The Effects of Alkaline-Earth Counterions on the Architectures, Band-Gap Energies, and Proton Transfer of Triazole-Based Coordination Polymers

      K. S. Asha, Arthur C. Reber, Anthony F. Pedicini, Shiv N. Khanna and Sukhendu Mandal

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201403162

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      The effects of alkaline-earth ions on the architectures, band-gap energies, and proton transfer of triazole-based coordination polymers are investigated.

  18. Microreviews

    1. Transition Metal NHC Catalysis

      Accessible Syntheses of Late Transition Metal (Pre)Catalysts Bearing N-Heterocyclic Carbene Ligands

      David J. Nelson

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201500061

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      Selected examples of the synthesis of useful (pre)catalysts bearing N-heterocyclic carbenes (NHCs) are discussed. All of these examples avoid the generation and isolation of free carbenes and the use of strong, sensitive bases; therefore, they are presented as useful preparative methods that can allow these catalysts to be utilised more widely.

  19. Full Papers

    1. Metal Oxo Clusters

      You have full text access to this OnlineOpen article
      Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters

      Johannes Kreutzer, Michael Puchberger, Christine Artner and Ulrich Schubert

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201403209

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      Ligand exchange in Zr4O2(OOCR)12 clusters proceeds with retention of the cluster core. A new scrambling reaction is introduced for the preparation of mixed-ligand clusters.

    2. Zinc Sulfonate Rectangles

      Molecular Rectangles with Rod-Shaped Disulfonic Acids

      Christina Zitzer, Thomas W. T. Muesmann, Karina Hunfeld, Jens Christoffers and Mathias S. Wickleder

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201403171

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      Rod-shaped disulfonic acids are suitable for the construction of zinc-based molecular rectangles. These rectangles form flexible lattices that incorporate solvent molecules. The removal of the solvent molecules leads to disulfonates of astonishingly high thermal stability, in strong contrast to the behavior of comparable polycarboxylates.

    3. Ni-Based Sonogashira Catalysts

      Modulating Sonogashira Cross-Coupling Reactivity in Four-Coordinate Nickel Complexes by Using Geometric Control

      Anette Petuker, Christian Merten and Ulf-Peter Apfel

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500148

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      Two tripodal phosphines CH3E(CH2PPh2)3 (E = C, Si) are applied as ligands in Ni-catalyzed cross-coupling reactions; various coordination modes at the Ni center can be achieved. For the first time, experimental evidence is provided to prove that tetrahedral instead of planar (PR3)2NiCl2 moieties are required to perform effective Sonogashira coupling reactions.

    4. Polymerization Catalysts

      Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

      Cédric Boulho, Harmen S. Zijlstra and Sjoerd Harder

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500123

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      The targeted synthesis of a new bimetallic aluminum/zirconium species with remaining Lewis acidity on aluminum gives a dimeric Al–O–Zr complex. In the presence of methylalumoxane, this μ-oxo complex is able to activate ethylene to produce polyethylene with high activity.

    5. Main-Group Coordination Chemistry

      Germanium(II) and Tin(II) Halide Complexes Containing the Triimido Sulfur(VI) Phosphanyl Ligand

      Elena Carl and Dietmar Stalke

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500074

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      The P-functionalized triimido sulfur ligand [(NtBu)3SCH2PPh2] can be used without ligand scrambling to stabilize synthetically useful group 14 metal(II) halides. It chelates the metal through two S-bound imido nitrogen atoms only. The additional coordination site is provided by the phosphorus atom; although with germanium the P side-arm is pendant, it forms a long-range interaction with tin.

    6. Hydrodesufurization

      Niobium–Containing Lindqvist Isopolyanions [NbxW6–xO19](2+x)– Used as Precursors for Hydrodesulfurization Catalysts with Isomerization Properties

      Karolina Bouadjadja-Rohan, Christine Lancelot, Michel Fournier, Audrey Bonduelle-Skrzypczak, Antoine Hugon, Olivier Mentré and Carole Lamonier

      Article first published online: 13 MAR 2015 | DOI: 10.1002/ejic.201403160

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      [NbxW6–xO19](2+x)– Lindqvist type isopolyanions were synthesized and characterized to prepared NbWNi-based alumina-supported hydrodesulfurization catalysts. Nb-containing catalysts showed improved CC6 isomerization properties under HDS conditions (H2 pressure and H2S presence) compared to those of a reference NiW catalyst related to the acid properties induced by niobium.

    7. Organostannylenes

      On the Reactivity of RSnCl and RSiMe3 {R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2} towards BF3·OEt2: Competing Lewis Acidities

      Michael Wagner, Michael Lutter, Christina Dietz, Marc H. Prosenc and Klaus Jurkschat

      Article first published online: 11 MAR 2015 | DOI: 10.1002/ejic.201500014

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      The reactions of boron trifluoride with the organostannylene RSnCl {R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2} and the organosilane RSiMe3 provided the corresponding 1:1 and 1:2 complexes, respectively, through the formation of P=O[RIGHTWARDS ARROW]B interactions. The experimental results are supported by DFT calculations.

    8. 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.

    9. 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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