European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 12

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 3.12

ISI Journal Citation Reports © Ranking: 2012: 11/44 (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 - 57
  1. Short Communications

    1. Boryl Complexes

      Selective Synthesis of Unsymmetrical Diboryl PtII and Diaminoboryl CuI Complexes by B–B Activation of Unsymmetrical Diboranes(4) {pinB–B[(NR)2C6H4]}

      Corinna Borner and Christian Kleeberg

      Article first published online: 23 APR 2014 | DOI: 10.1002/ejic.201402234

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      Unsymmetrical diboranes(4) of the type {pinB–B[(NR)2C6H4]} are used as precursors for the selective synthesis of unprecedented unsymmetrical PtII diboryl and diaminoboryl CuI complexes by oxidative addition and σ-bond metathesis reactions, respectively. A versatile and modular route to the unsymmetrical diborane(4) compounds used is described; pin = pinacolato, Dipp = 2,6-diisopropylphenyl, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene.

  2. Full Papers

    1. Magnetic Properties

      Probing the Influence of the Ligands on the Magnetism of Dinuclear Manganese, Iron, and Chromium Complexes Supported by Aroylhydrazone

      Alex Domingo, David Specklin, Vitor Rosa, Samir Mameri, Vincent Robert and Richard Welter

      Article first published online: 23 APR 2014 | DOI: 10.1002/ejic.201402084

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      The influence of the different molecular regions of five dinuclear complexes constructed with aroylhydrazone ligands is explored through ab initio wave function calculations with localized orbitals. The role of the ligands is key to control the structure of the dimetallic core and, thus, determines the overall magnetism.

  3. Short Communications

    1. Polynuclear Cobalt Complexes

      A Planar Decanuclear Cobalt(II) Phosphonate

      Dipankar Sahoo, Ramesh K. Metre, Wolfgang Kroener, Klaus Gieb, Paul Müller and Vadapalli Chandrasekhar

      Article first published online: 22 APR 2014 | DOI: 10.1002/ejic.201400129

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      A decanuclear cobalt(II) phosphonate, [Co10{2,3,5,6-(Me)4C6HCH2PO3}8{2,3,5,6-(Me)4C6HCH2PO3H}4Cl6]·6Et3NH·10n-hexane·16H2O with a planar arrangement of the CoII ions is described. This compound shows slow relaxation of its dynamic magnetization.

  4. Full Papers

    1. Gold Antitumor Agents

      Synthesis, Characterization, and Cytotoxic Activity of AuI N,S-Heterocyclic Carbenes Derived from Peptides Containing L-Thiazolylalanine

      Alejandro Gutiérrez, M. Concepción Gimeno, Isabel Marzo and Nils Metzler-Nolte

      Article first published online: 22 APR 2014 | DOI: 10.1002/ejic.201402103

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      The first organometallic gold(I) bioconjugates of a thiazole-based peptide are reported. The N,S-heterocyclic carbene gold(I) derivatives were prepared from the corresponding thiazolium peptide salts either by following the Ag2O route or by reaction with a strong base. The new compounds display excellent in vitro cytotoxicity with IC50 values as low as 0.4 μM.

    2. Metathesis Reactions

      Theoretical Investigation of the Controlled Metathesis Reactions of Methylruthenium(II) Complexes with Terminal Acetylenes

      Yuxia Liu, Guang Chen, Hongliang Wang, Siwei Bi and Dongju Zhang

      Article first published online: 22 APR 2014 | DOI: 10.1002/ejic.201400123

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      DFT calculations have been performed to study the controlled metathesis mechanisms of trans-[Ru(CH3)2(dmpe)2] [dmpe = 1,2-bis(dimethylphosphanyl)ethane] with terminal acetylenes. Two important issues have been addressed, one of which is the role methanol plays in promoting the ligand metathesis between the methyl group and one alkynyl moiety.

    3. Paramagnetic Molecular Metals

      Metallic Charge-Transfer Salts of Bis(ethylenedithio)tetrathiafulvalene with Paramagnetic Tetrachloro(oxalato)rhenate(IV) and Tris(chloranilato)ferrate(III) Anions

      Samia Benmansour, Eugenio Coronado, Carlos Giménez-Saiz, Carlos J. Gómez-García and Carola Rößer

      Article first published online: 17 APR 2014 | DOI: 10.1002/ejic.201402023

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      Three new paramagnetic molecular conductors have been prepared with the magnetic anions [ReCl4(C2O4)]2– and [Fe(C6O4Cl2)3]3–. ET[ReCl4(C2O4)] [ET = bis(ethylenedithio)tetrathiafulvalene] is a semiconductor that contains ET2+ dications. ET4[ReCl4(C2O4)] is metallic down to 110 K. ET6[Fe(C6O4Cl2)3] has high conductivity and is the first radical salt with a tris(anilato)metalate anion.

    4. Ru(II) Complex Formation

      Kinetics and Mechanism of the Reduction of mer-Tris-picolinatoruthenium(III) by L-Ascorbic Acid

      Anna Katafias, Olga Impert, Przemysław Kita, Joanna Fenska, Stanisław Koter, Anna Kaczmarek-Kędziera, Henryk Różycki, Anna Bajek, Małgorzata Uzarska and Rudi van Eldik

      Article first published online: 17 APR 2014 | DOI: 10.1002/ejic.201301556

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      The reduction of mer-tris-picolinatoruthenium(III) by L-ascorbic acid as a function of pH can only be studied under well-selected reaction conditions to prevent the back-oxidation of tris-picolinatoruthenium(II) caused by traces of dioxygen. Under such conditions, the redox activity of L-ascorbic acid (AscH2) follows the sequence AscH2 << AscH << Asc2–.

    5. Molecular Conductors

      Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM-BEDT-TTF) with the Hexachlororhenate(IV) Anion

      Flavia Pop, Magali Allain, Pascale Auban-Senzier, José Martínez-Lillo, Francesc Lloret, Miguel Julve, Enric Canadell and Narcis Avarvari

      Article first published online: 14 APR 2014 | DOI: 10.1002/ejic.201400125

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      Two enantiomerically pure radical cation salts based on the (S,S)- and (R,R)-dimethylbis(ethylenedithio)tetrathiafulvalene (DM-BEDT-TTF) donor and the paramagnetic [ReCl6]2– dianion show semiconducting behaviour.

    6. Self-Assembly

      Self-Assembly between Dicarboxylate Ions and Dinuclear Lanthanide Complexes: A Surprisingly Complicated Problem

      Thomas Just Sørensen, Leila R. Hill, James A. Tilney, Octavia A. Blackburn, Michael W. Jones, Manuel Tropiano and Stephen Faulkner

      Article first published online: 11 APR 2014 | DOI: 10.1002/ejic.201402169

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      The forces that control the self-assembly between dicarboxylate guests and dinuclear lanthanide complexes are explored and are more complicated than anticipated.

    7. Co Cluster Compounds

      Magnetic Study of a Pentanuclear {Co2IIICo3II} Cluster with a Bent {CoII3} Motif

      Irene C. Lazzarini, Alejandro V. Funes, Luca Carrella, Lorenzo Sorace, Eva Rentschler and Pablo Alborés

      Article first published online: 11 APR 2014 | DOI: 10.1002/ejic.201402089

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      We report a new pentanuclear mixed-valent cobalt cluster exhibiting a {CoII3CoII2} core that can be conveniently described as two fused Co3–μ3–OH triangles with a strict unique sharing vertex point. We have analysed its magnetic behaviour by combining susceptibility, magnetisation and EPR data as well as broken-symmetry DFT calculations.

    8. Boronic Acid Reactivity

      Relative Kinetic Reactivities of Boronic Acids and Boronate Ions toward 1,2-Diols

      Takuya Okamoto, Asumi Tanaka, Eisuke Watanabe, Takehiro Miyazaki, Tomoaki Sugaya, Satoshi Iwatsuki, Masahiko Inamo, Hideo D. Takagi, Akira Odani and Koji Ishihara

      Article first published online: 11 APR 2014 | DOI: 10.1002/ejic.201400040

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      Kinetic results clearly show that boronic acids are more reactive than their respective conjugate boronate ions. This corrects the erroneous conclusion that the boronate ion reacts faster than its conjugate boronic acid by at least several orders of magnitude. The relative kinetic reactivities of boric acid and boronate ions are discussed in terms of mechanistic differences.

    9. Polyoxoniobates

      Nerve Agent Degradation with Polyoxoniobates

      Mark K. Kinnan, William R. Creasy, Lauren B. Fullmer, Heidi L. Schreuder-Gibson and May Nyman

      Article first published online: 11 APR 2014 | DOI: 10.1002/ejic.201400016

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      Polyoxometalates, like small pieces of metal oxide, can be dissolved or fixed on a surface to perform homogeneous or heterogeneous catalysis, respectively. Here we exploit the alkaline nature of polyoxoniobates to neutralize nerve agents in both solution and the solid state. Solution studies correlate reaction efficacy to the association of the dissolved polyoxoniobate with its counterions.

    10. Electron Correlation

      Molecular Conductors with Effectively Half-Filled Electronic States Based on Tetrathiafulvalene Derivatives Condensed with a 2-Isopropylidene-1,3-dithiole Ring

      Keisuke Furuta, Shuhei Kohno, Takashi Shirahata and Yohji Misaki

      Article first published online: 10 APR 2014 | DOI: 10.1002/ejic.201402006

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      Molecular conductors (3)2[M(CN)2] (M = Ag and Au) have been successfully prepared and their physical properties and structures have been investigated. The electronic nature of these salts is the effectively half-filled electronic state. (3)2[Au(CN)2] shows nonmetallic behavior below 50 K. These results suggest that the present salts lie on the border between the metallic and insulating phases.

    11. Double Perovskites

      Charge Disproportionation and Magnetoresistivity in a Double Perovskite with Alternate Fe4+(d4) and Mn4+(d3) Layers

      Subodh Ganesanpotti, Cédric Tassel, Naoaki Hayashi, Yoshihiro Goto, Guillaume Bouilly, Takeshi Yajima, Yoji Kobayashi and Hiroshi Kageyama

      Article first published online: 10 APR 2014 | DOI: 10.1002/ejic.201402009

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      High-pressure oxygen intercalation of a brownmillerite phase Ca2Fe1.1Mn0.9O5 provides a fully oxidized layered double perovskite Ca2Fe1.1Mn0.9O6 with alternate Fe4+(d4) and Mn4+(d3) layers. Ca2Fe1.1Mn0.9O6 exhibits charge disproportionation and magneto-resistivity. Electron hopping through double-exchange ferromagnetic interactions between Fe4+ and Mn4+ is proposed.

    12. Ligand Design

      Tetrathiafulvalene-Based Phenanthroline Ligands: Synthesis, Crystal Structures, and Electronic Properties

      Esmah Belhadj, Abdelkrim El-Ghayoury, Thomas Cauchy, Magali Allain, Miloud Mazari and Marc Sallé

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201402073

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      Three redox-active phenanthroline–tetrathiafulvalene ligands incorporating different linkers between the accepting and the donating subunits have been synthesized. The critical effect of the linker on the intramolecular charge transfer between both parts is experimentally and theoretically studied.

    13. Chiral Self-Sorting

      Chiral Self-Sorting of trans-Chelating ­Chiral Ligands upon Formation of PdII Complexes

      Georg Meyer-Eppler, Filip Topić, Gregor Schnakenburg, Kari Rissanen and Arne Lützen

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201402057

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      Two bis(3-pyridyl) ligands based on a planar chiral [2.2]paracyclophane scaffold act as trans-chelating ligands for square-planar-coordinated metal centres such as palladium(II) ions. (Pseudo)racemic ligands undergo complete chiral self-sorting in a narcissistic self-recognition manner upon forming mononuclear homochiral [PdL2] complexes.

    14. Radical Cation Salts

      Metallic Bi- and Monolayered Radical Cation Salts Based on Bis(ethylenedithio)­tetrathiafulvalene (BEDT-TTF) with the Tris(oxalato)gallate Anion

      Tatiana G. Prokhorova, Lev I. Buravov, Eduard B. Yagubskii, Leokadiya V. Zorina, Sergey V. Simonov, Rimma P. Shibaeva and Vladimir N. Zverev

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201400132

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      Bilayered and monolayered metallic radical cation salts based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with the [GaIII(C2O4)3]3–· anion have been prepared and investigated. Metallic α and nonmetallic “pseudo-κ” layers of BEDT-TTF alternate in the structure of the bilayered salt, whereas the conducting layers in the monolayered salt have only metallic β″-type packing.

    15. CuS Photocatalysts

      Preparation by Solvothermal Synthesis, Growth Mechanism, and Photocatalytic Performance of CuS Nanopowders

      Yu-Qiao Zhang, Bo-Ping Zhang, Zhen-Hua Ge, Li-Feng Zhu and Yan Li

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201400098

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      CuS photocatalysts with various morphologies were synthesized from different copper and sulfur sources by a facile solvothermal method. The formation mechanisms and photocatalytic properties were studied in detail. In the photocatalysis process, CuS powders composed of nanoflowers and mixture of nanoneedles, nanoparticles, and nanoplates showed excellent catalytic activities.

    16. Crystal Engineering

      Mixed-Valence Biferrocenium Salts of Xn–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures

      Tomoyuki Mochida, Yusuke Funasako, Shizue Yamazaki and Hatsumi Mori

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201400093

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      Biferrocenium salts with Xn–TCNQ (X = F, Cl; n = 1, 2) exhibit a 1:2 D/A ratio, consisting of mixed-valence cations and anions containing acceptor dimers. These salts exhibit segregated-stack structures, mixed-stack structures, and intermediate structures depending on the donor substituents.

  5. Short Communications

    1. Coordination Polymer Gels

      Thermochromic and Piezochromic Effects of CoII–Imidazole-Based Supramolecular Gels as Logic Gates

      Sung Ho Jung, Jong Hun Moon, Jin Yong Lee and Jong Hwa Jung

      Article first published online: 8 APR 2014 | DOI: 10.1002/ejic.201402153

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      The ionochromic and piezochromic effects of an imidazole-based supramolecular gel with Co2+ were investigated. The effects of the supramolecular gel were controlled by various anions of cobalt and are the result of changes in the coordination geometry of the gels. Interestingly, the ionochromic and piezochromic effects act as AND and OR logic gates in the solid and gel states.

  6. Full Papers

    1. Ge(IV) Complex Degradation

      The Thermal Stability of Tris(methimazolyl)borates and Their Germanium Complexes

      Dawn Wallace, Kirsten Chalmers, Christopher A. Dodds, Iain A. Stepek, David R. Armstrong, Leonard E. A. Berlouis, John Reglinski and Mark D. Spicer

      Article first published online: 8 APR 2014 | DOI: 10.1002/ejic.201301588

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      A series of at-boron substituted soft scorpionate ligands ([RTmMe]) and their germanium(IV) complexes are reported and their thermal degradation explored. Two degradation pathways are observed; it is proposed that one involves alkyl migration (R = Me, nBu) whereas the other pathway proceeds by heterocycle formation (R = H, Ph).

    2. Core–Shell Structures

      Synthesis and Plasmonic Properties of Core–Shell Bimetallic Silver–Gold Nanoprisms Obtained through an Organometallic Route

      Julian Crespo, Alfonso Ibarra, José M. López-de-Luzuriaga, Miguel Monge and M. Elena Olmos

      Article first published online: 7 APR 2014 | DOI: 10.1002/ejic.201400023

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      Spherical silver nanoparticles serve as the template for the growth of an anisotropic gold prismatic shell through an organometallic approach. TEM, high-angle annular dark field/ scanning transmission electron microscopy (HAADF-STEM) techniques, EDS, UV/Vis, and 19F NMR spectroscopy have been used to explain the formation of these bimetallic core–shell heterostructures.

    3. Tinorganyl Moieties

      Attachment of Chelating Ligand Pockets to Tinorganyl Moieties

      Beatrix E. K. Barth, Klaus Harms and Stefanie Dehnen

      Article first published online: 4 APR 2014 | DOI: 10.1002/ejic.201400089

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      A new compound Ph3SnR, comprising a 2,2′,6′,2″-terpyridine-functionalized ligand R, has been synthesized in a five-step procedure. On attempting to halogenate this compound, a partially iodinated derivative was obtained that forms a head-to-tail connected dimer in the salt [(PhISn(CH2)3OPhttpy)2](I3)2 with the terpyridine units acting as chelating ligands.

  7. Short Communications

    1. Hydrosilylation

      Mild Hydrosilylation of Amides by Platinum N-Heterocyclic Carbene Catalysts

      Sabine Pisiewicz, Kathrin Junge and Matthias Beller

      Article first published online: 4 APR 2014 | DOI: 10.1002/ejic.201402083

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      The selective catalytic hydrosilylation of amides is reported. By using defined platinum/N-heterocyclic carbene (NHC) complexes, the reduction of secondary and tertiary amines proceeds in good yields under mild conditions.

  8. Full Papers

    1. Rare-Earth Complexes

      The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare-Earth 3,5-Dimethylpyrazolate Complexes [Ln(Me2pz)3(thf)]2

      Glen B. Deacon, Rita Harika, Peter C. Junk, Brian W. Skelton, Daniel Werner and Allan H. White

      Article first published online: 4 APR 2014 | DOI: 10.1002/ejic.201400099

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      Contrasting structures and bridging Me2pz groups for Ln = La–Pr and Ln = Nd–Lu are described.

    2. Hexacoordinate Silicon

      Neutral Hexacoordinate Silicon(IV) Complexes with a Tridentate Dianionic O,N,X Ligand (X = O, N, S), Bidentate Monoanionic X,N Ligand (X = O, S), and Phenyl Ligand: Compounds with a SiO3N2C, SiSO2N2C, SiO2N3C, SiSON3C, or SiS2ON2C Skeleton

      Jörg Weiß, Johannes A. Baus, Christian Burschka and Reinhold Tacke

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400083

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      A series of neutral hexacoordinate silicon(IV) complexes have been synthesized and structurally characterized by NMR spectroscopy and single-crystal X-ray diffraction. These studies were performed with a special emphasis on comparing the respective O/NMe/S analogues 4a/5a/6a and 4b/5b/6b and the O/S pairs 4a/4b, 5a/5b, and 6a/6b with respect to their structures and NMR spectroscopic parameters.

    3. Metal–Organic Frameworks

      Construction of Metal–Organic Frameworks Consisting of Dinuclear Metal Units Based on 5-Hydroxyisophthalate and Flexible Dipyridyl Ligands

      Xiaoju Li, Tena Guan, Xiaofang Guo, Xinxiong Li and Zhenjiang Yu

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400092

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      Four CoII and CuII metal–organic frameworks consisting of dinuclear metal units have been constructed from rigid 5-hydroxyisophthalate (ip-OH) and flexible dipyridyl ligands. The ip-OH bridging modes and the metal coordination geometries are very different in the four complexes. Magnetic studies indicate the existence of antiferromagnetic exchange between the metal centers.

  9. Short Communications

    1. A Luminescent Metallacycle

      A Luminescent Rhenium(I) Metallacycle with Oxygen and Nitrogen Donor Atoms: Photophysical and Theoretical Studies

      Dibyendu Bhattacharya

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400067

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      A new N,O-bischelator-bridged D-type self-assembled ReI metallacycle exhibits unusual multiple emission with moderate luminescence (Φem = 0.26, average radiative decay lifetime, τr = 0.052 μs). An improvement of the luminescence efficiency on traversing from ReC3N3 to ReC3N2O to ReC4N2 has been established based on photophysical and DFT results.

  10. Full Papers

    1. Iridium Complexes

      Intramolecular π Stacking in Cationic Iridium(III) Complexes with Phenyl-Functionalized Cyclometalated Ligands: Synthesis, Structure, Photophysical Properties, and Theoretical Studies

      Peng Li, Guo-Gang Shan, Hong-Tao Cao, Dong-Xia Zhu, Zhong-Min Su, Rukkiat Jitchati and Martin R. Bryce

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400007

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      A combined experimental and theoretical study of the cationic iridium complexes [Ir(dppy)2phen]PF6 (1) and [Ir(tppy)2phen]PF6 (2) is described. The complexes are green photoemitters. Strong intramolecular π–π stacking leads to enhanced distortions in the geometry of the complexes, which is detrimental to their use in light-emitting electrochemical cells (LECs).

    2. DNA Cleavage

      Synthesis, Crystal Structures, and DNA Cleavage Activities of Manganese(II) Complexes: A Good Example of the Synergy between Metal Ions Prompting DNA Cleavage

      Li-Na Zhu, Huan-Rui Gao, Hai-Xian Wang, Ming-Yuan Xu and Xiao-Zeng Li

      Article first published online: 3 APR 2014 | DOI: 10.1002/ejic.201400044

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      The higher DNA cleavage abilities of multinuclear MnII complexes than their mononuclear analogue and the highest DNA cleavage efficiency of the complex with the shortest Mn···Mn distance and the strongest magnetic coupling between the MnII ions confirm the great effect of the synergy between metal centers on DNA cleavage efficiencies.

    3. Self-Assembly

      Self-Assembled Cages from the Electroactive Bis(pyrrolo)tetrathiafulvalene (BPTTF) Building Block

      Sébastien Bivaud, Sébastien Goeb, Jean-Yves Balandier, Marcos Chas, Magali Allain and Marc Sallé

      Article first published online: 31 MAR 2014 | DOI: 10.1002/ejic.201400060

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      An expeditive synthesis of electroactive di- and tetratopic ligands based on bis(pyrrolo)tetrathiafulvalene (BPTTF) is described. The coordination-driven self-assembly of these ligands with cis-protected PtII complexes affords the first examples of 3D cages incorporating the electron-rich TTF unit. These ligands are also able to undergo an original conversion to heteroleptic dithiolene complexes.

  11. Microreviews

    1. Copper Peptides

      De Novo Designed Copper α-Helical Peptides: From Design to Function

      Matteo Tegoni

      Article first published online: 31 MAR 2014 | DOI: 10.1002/ejic.201400057

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      De novo designed α-helical peptides have been used to design structural and functional copper sites in minimum protein scaffolds. The design of structural copper Type 1, Type 2, Type A, and Cu–SCys centers in α-helical constructs is described. Catalytic copper Type 2 centers are also presented, along with their functional features.

  12. Short Communications

    1. Red Emitters

      Hexamolybdenum Cluster Complexes with Pyrene and Anthracene Carboxylates: Ultrabright Red Emitters with the Antenna Effect

      Kaplan Kirakci, Karla Fejfarová, Monika Kučeráková and Kamil Lang

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201402076

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      An antenna system based on a hexamolybdenum cluster complex with strongly absorbing ligands displays unprecedented brightness of red emission upon excitation in the near-UV region.

  13. Full Papers

    1. Graphene–Porphyrin Structures

      Structures Self-Assembled from Anionic Graphene and Cationic Manganese Porphyrin: Characterization and Application in Artificial Photosynthesis

      Amir Kaplan, Eli Korin and Armand Bettelheim

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201400054

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      Carboxylic-rich graphene oxide and MnIII tetrakis(N-methyl-4-pyridinio)porphyrin form self-assembled structures through π–π stacking interactions. When adsorbed on iron/hematite photoanodes, these structures show substantial activity towards the photoelectrochemical oxidation of water.

    2. Waste Prevention

      Sodium “Activation” of Silano-Phosphonate Modified Mesoporous TiO2 Leading to Improved Rare-Earth Element Extraction

      Mícheál P. Moloney, Jérémy Causse, Cedric Loubat and Agnès Grandjean

      Article first published online: 27 MAR 2014 | DOI: 10.1002/ejic.201400027

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      Mesoporous silano-phosphate functionalised TiO2 particles are used to separate Ce3+ from Sr2+ and Cs+, as well as other rare earths. Unlike SiO2, the resistance of TiO2 to strong base allowed for the phosphonate to be activated by a base, increasing its sorption ability threefold.

    3. Catalytic Hydrolysis

      A Heterobimetallic FeIIIMnII Complex of an Unsymmetrical Dinucleating Ligand: A Structural and Functional Model Complex for the Active Site of Purple Acid Phos­phatase of Sweet Potato

      Biswanath Das, Henrik Daver, Amrendra Singh, Reena Singh, Matti Haukka, Serhiy Demeshko, Franc Meyer, George Lisensky, Martin Jarenmark, Fahmi Himo and Ebbe Nordlander

      Article first published online: 26 MAR 2014 | DOI: 10.1002/ejic.201301375

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      Catalytic hydrolysis of a phosphodiester bond was investigated by using a mixed-valence heterodinuclear FeIIIMnII complex of the dinucleating ligand as catalyst. Computational modeling and kinetic results indicate that a μ-hydroxo FeIIIMnII complex is the active catalyst that binds the substrate in a monodentate fashion at the Mn ion.

  14. Short Communications

    1. Tungstophosphoric Acid Catalysts

      Synthesis and Characterization of Tungstophosphoric Acid/Pentaethylenehexamine/ZrSBA-15 and Its Use in the Selective Oxidation of Benzyl Alcohol under Solvent-Free Conditions

      Ling-Yan Meng, Shang-Ru Zhai, Shi Li, Bin Zhai, Qing-Da An and Xiao-Wei Song

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201402028

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      A layer-by-layer deposition strategy was used for the preparation of a tungstophosphoric acid/pentaethylenehexamine/ZrSBA-15 composite. This recyclable material was stable at high temperatures and in polar solvents, and it exhibited excellent catalytic properties (84.7 % conversion, >99 % selectivity) in the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (BzH).

  15. Full Papers

    1. Oxidovanadium Complexes

      Mitochondria-Targeted Photoinduced Anticancer Activity of Oxidovanadium(IV) Complexes of Curcumin in Visible Light

      Puja Prasad, Ila Pant, Imran Khan, Paturu Kondaiah and Akhil R. Chakravarty

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201402001

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      A Schiff-base oxidovanadium(IV) complex of curcumin bearing a pendant naphthalimide specifically targets cellular mitochondria and exhibits remarkable photocytotoxicity in visible light with low dark toxicity in keratinocyte HaCaT and breast cancer MCF-7 cells. The apoptotic cell death involves 1O2 and ·OH species.

    2. Luminescent Coordination Polymers

      Nitrile-Supported Coordination Polymers of Cerium(III) Bromide

      Kalyan V. Vasudevan, William L. Boncher, Nickolaus A. Smith, Michael W. Blair, Brian L. Scott, Bryan L. Bennett, Markus P. Hehlen, Ross E. Muenchausen and John C. Gordon

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201400030

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      Cerium bromide coordination polymers have been prepared and structurally authenticated on the basis of X-ray diffraction data. The photoluminescence spectra of the polymers feature considerably redshifted emission bands compared to the characteristic emission observed for CeBr3 single crystals.

    3. Luminescence

      Photophysical Properties of a Series of Rhenium Selenide Cluster Complexes Containing Nitrogen-Donor Ligands

      Wade B. Wilson, Kevin Stark, Dean B. Johnson, YiXin Ren, Hitoshi Ishida, David L. Cedeño and Lisa F. Szczepura

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301626

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      The photophysical properties of thirteen [Re6Se8]2+ clusters containing N-donor ligands are reported. The impact of para substituents on luminescence was investigated by using a series of benzonitrile and phenyl-substituted tetrazolate complexes. CV and DFT studies support metal-to-ligand charge transfer (MLCT) character in the excited-state wave function for the p-nitrobenzonitrile complex.

    4. Oxide Semiconductors

      Dimethylmalonato Zinc Complexes as Molecular Precursors for Electronic Grade Zinc Oxide: Towards a Systematic Ligand Design by Understanding Molecular Decomposition Mechanisms

      Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301525

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      Zn complexes with malonato ligands functionalized in the 2-position are suitable precursors for solution processed ZnO. A detailed investigation of the decomposition mechanism shows the influence of nitro and hydroxylimino groups on the ceramisation process. The precursors allow the formation of nanocrystalline ZnO which can be used as semiconductor material in field-effect transistors.

    5. Ring-Opening Polymerization

      Synthesis, Structure, and Catalytic Activity of Tridentate, Base-Functionalized β-Ketiminate Zinc Complexes in Ring-Opening Polymerization of Lactide

      Christoph Scheiper, Dennis Dittrich, Christoph Wölper, Dieter Bläser, Joachim Roll and Stephan Schulz

      Article first published online: 25 MAR 2014 | DOI: 10.1002/ejic.201301462

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      Several NNO zinc complexes were synthesized and structurally characterized by single-crystal X-ray diffraction. In addition, their catalytic activity in the ring-opening polymerization (ROP) of lactide is presented. The polymerization occurs through a modified activated-monomer mechanism.

    6. Lanthanides

      Magnetic Studies of Redox-Active Tetrathiafulvalene-Based Complexes: Dysprosium vs. Ytterbium Analogues

      Julie Jung, Tamyris T. da Cunha, Boris Le Guennic, Fabrice Pointillart, Cynthia L. M. Pereira, Javier Luzon, Stéphane Golhen, Olivier Cador, Olivier Maury and Lahcène Ouahab

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201400121

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      The crystal-field energy splitting of the ground-state multiplets of the complexes Dy and Yb was evaluated, and they demonstrate Ising and non-Ising character. Both anisotropy axis directions for the MJ ground states were determined in agreement with the oblate and prolate electronic distribution for DyIII and YbIII ions. This results in SMM and non-SMM behaviour for Dy and Yb, respectively.

    7. Cucurbituril Supramolecular Arrays

      Cucurbituril-Based Supramolecular Self-Assemblies Formed in the Presence of Alkali Metal and Cadmium Ions

      Hang Cong, Yi Zhao, Li-Li Liang, Kai Chen, Xiao-Jie Chen, Xin Xiao, Yun-Qian Zhang, Qian-Jiang Zhu, Sai-Feng Xue and Zhu Tao

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201400004

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      We describe herein three new cucurbituril-based coordination supramolecular arrays self-assembled in the presence of alkali metal and cadmium ions.

    8. Lanthanide Complexes

      Lanthanide Complexes with Tetradentate N,N′,O,O′-Dipyridyl-Based Ligands: Structure, Stability, and Photophysical Properties

      Nataliya E. Borisova, Andrey A. Kostin, Elizaveta A. Eroshkina, Marina D. Reshetova, Konstantin A. Lyssenko, Evgenia N. Spodine and Lada N. Puntus

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201301271

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      Complexes of LnIII with N,N′,O,O′-tetradentate dipyridyl-based ligands were synthesized. Their structures were studied by X-ray diffraction, and their binding constants were determined by UV/Vis titration. Structure–property relationships were partly revealed by DFT calculations of the potential energy surface (PES) for three ligands, which show different efficiencies in extracting AmIII.

    9. Isotropic 3D π-Conductors

      Isotropic Three-Dimensional Molec­ular Conductor Based on the Coronene Radical Cation

      Yukihiro Yoshida, Mitsuhiko Maesato, Yoshihide Kumagai, Motohiro Mizuno, Kazuhide Isomura, Hideo Kishida, Masanari Izumi, Yoshihiro Kubozono, Akihiro Otsuka, Hideki Yamochi, Gunzi Saito, Kaplan Kirakci, Stéphane Cordier and Christiane Perrin

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400119

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      The first coronene cation radical salt was electrochemically obtained by combining coronene with a highly-symmetric Mo6Cl142– cluster unit. The salt has a cubic structure with Pmequation imagem symmetry, and merohedrally disordered coronenes undergo an in-plane flipping rotation. The randomly charge-disproportionated coronenes form an isotropic three-dimensional π-conducting network.

    10. Bioorganometallic Complexes

      Self-Assembly Properties of NCN Pincer Palladium(II) Complexes Bearing a Uracil Moiety

      Toshiyuki Moriuchi, Ryohei Ohata, Yuki Sakamoto and Toshikazu Hirao

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400131

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      Bioorganometallic compounds were designed by the combination of NCN pincer complexes with a uracil moiety to form intermolecular hydrogen-bonded assemblies, wherein the hydrogen-bonding patterns were found to depend on the ancillary ligands.

    11. Coordination Chemistry

      Insights into Different Donor Abilities in Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

      Alexander Hoffmann, Ulrich Flörke and Sonja Herres-Pawlis

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400056

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      Eleven bis(pyrazolyl)methane complexes of the 3d metal ions iron(II), cobalt(II), copper(II) and zinc(II) are reported. Structural studies of these complexes and theoretical analysis by density functional theory show an interesting donor competition between the pyridinyl and pyrazolyl functions of the ligand.

    12. Metallacycles

      Cyclometalated Complexes of Platinum(II) with 2-Vinylpyridine

      Antonio Zucca, Luca Maidich, Veronica Carta, Giacomo L. Petretto, Sergio Stoccoro, Maria Agostina Cinellu, Maria I. Pilo and Guy J. Clarkson

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400052

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      The synthesis, and analytical and spectroscopic characterization of a series of cyclometalated complexes of platinum(II) with 2-vinylpyridine (L) is reported in detail. The five-membered cyclometalated ring is particularly stable, likely due to partial electronic delocalisation.

    13. Zintl Compounds

      Crystal and Electronic Structures and Magnetic Properties of Eu3Tt2As4 (Tt = Si, Ge)

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

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201301622

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      Two new Zintl compounds, Eu3Si2As4 and Eu3Ge2As4, were synthesized by using the metal flux method and their crystal structures were determined by single-crystal X-ray diffraction. The magnetic properties of Eu3Ge2As4 were measured and the coexistence of ferromagnetic and antiferromagnetic order was observed in the compound, which was confirmed by theoretical calculations.

    14. Photoresponsive Conductors

      Photofunctional Conductors Based on TTF-BODIPY Dyads Bearing p-Phenylene and p-Phenylenevinylene Spacers

      Keijiro Tsujimoto, Reiko Ogasawara, Takahiro Nakagawa and Hideki Fujiwara

      Article first published online: 17 MAR 2014 | DOI: 10.1002/ejic.201400103

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      New D–A-type TTF-BODIPY dyads (TTF = tetrathiafulvalene and BODIPY = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) with a p-phenylene or p-phenylenevinylene spacer have been synthesized. These dyads exhibit photoresponsive conducting properties such as photoelectric conversion functionality in thin-film samples and photoinduced conductivity in their single-crystal samples.

    15. Polymers

      Phosphorus–Boron-Based Polymers Obtained by Dehydrocoupling of Ferrocenylphosphine–Borane Adducts

      Souvik Pandey, Peter Lönnecke and Evamarie Hey-Hawkins

      Article first published online: 13 MAR 2014 | DOI: 10.1002/ejic.201402021

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      A new class of phosphine–borane adducts with ferrocenyl substituents, including the depicted ionic monomer containing a planar-chiral ferrocene moiety, was prepared and employed in transition-metal-catalyzed dehydrocoupling {with [{Rh(μ-Cl)(1,5-cod)}2] (cod = 1,5-cyclooctadiene) as catalyst} to give the first ferrocenyl-substituted poly(phosphinoboranes).

  16. Short Communications

    1. Catalyst Immobilization

      Transfer Hydrogenation Catalysis by a N-Heterocyclic Carbene Iridium Complex on a Polyoxometalate Platform

      Gloria Modugno, Angele Monney, Marcella Bonchio, Martin Albrecht and Mauro Carraro

      Article first published online: 7 MAR 2014 | DOI: 10.1002/ejic.201402020

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      A divacant Keggin polyanion has been bisfunctionalized with a N-heterocyclic carbene (NHC) iridium(I) organometallic complex, as confirmed by multinuclear NMR and mass spectroscopy. The resulting supported homogeneous complex efficiently catalyzes the transfer hydrogenation from iPrOH to benzophenone [with a turnover number (TON) of 680 and a turnover frequency (TOF) of up to 540 h–1].

    2. Molecular Metals

      Pressure-Induced Metallic Conductivity in the Single-Component Molecular Crystal [Ni(dmit)2]

      Hengbo Cui, Takao Tsumuraya, Tsuyoshi Miyazaki, Yoshinori Okano and Reizo Kato

      Article first published online: 6 MAR 2014 | DOI: 10.1002/ejic.201400130

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      Four-probe electrical resistivity measurements on the single-component molecular crystal [Ni(dmit)2] (dmit = 1,3-dithiole-2-thione-4,5-dithiolate) up to 25.5 GPa by using a diamond anvil cell (DAC) technique with high-quality hydrostatic conditions reveal a metallic state above 15.9 GPa. Ab initio DFT calculations and tight-binding band calculations indicate a 3D Fermi surface under high pressure, which explains the metallic state.

  17. Full Papers

    1. SERS Substrates

      Exotic 3D Hierarchical ZnO–Ag Hybrids as Recyclable Surface-Enhanced Raman Scattering Substrates for Multifold Organic Pollutant Detection

      Xuan He, Hui Wang, Qi Zhang, Zhongbo Li and Xiaochuan Wang

      Article first published online: 6 MAR 2014 | DOI: 10.1002/ejic.201402014

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      Recyclable and sensitive surface-enhanced Raman scattering (SERS) sensors for the detection of organic pollutants were fabricated by an efficient and green approach from 3D hierarchical ZnO–Ag hybrids. The unique repeatable detection of rhodamine 6G (R6G) and 2,4-dichlorophenoxyacetic acid (2,4-D) demonstrates a new route to eliminate the single-use problem of traditional SERS substrates.

    2. Catalyst Design

      [(1,3-Bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazole-2-ylidene)PdCl2(NEt3)]: “Throwing Away” a Different Ancillary Ligand to Enhance the Catalytic Activity at Room Temperature

      Daniel Guest, Ming-Tsz Chen, Graham J. Tizzard, Simon J. Coles, Michael Lewis Turner and Oscar Navarro

      Article first published online: 13 FEB 2014 | DOI: 10.1002/ejic.201400072

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      Low loadings of [(IPr*)PdCl2(TEA)] {IPr* = 1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene, TEA = triethylamine} catalyze the Buchwald–Hartwig amination reactions of aryl chlorides at room temperature in excellent yields, without the need for an inert atmosphere to set up or perform the reactions.

    3. Main Group Clusters

      [Sb7Se8Br2]3+ and [Sb13Se16Br2]5+ – Double and Quadruple Spiro Cubanes from Ionic Liquids

      Ejaz Ahmed, Joachim Breternitz, Matthias F. Groh, Anna Isaeva and Michael Ruck

      Article first published online: 8 JAN 2014 | DOI: 10.1002/ejic.201301155

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      Reactions under smooth conditions in ionic liquids facilitate the formation of the large heteronuclear main group polycations [Sb7Se8Br2]3+ and [Sb13Se16Br2]5+.

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