European Journal of Inorganic Chemistry

Cover image for Vol. 2008 Issue 22

August 2008

Volume 2008, Issue 22

Pages 3391–3560

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Hybrid Organic–Inorganic Porphyrin–Polyoxometalate Complexes (Eur. J. Inorg. Chem. 22/2008) (page 3391)

      Clémence Allain, Sophie Favette, Lise-Marie Chamoreau, Jacqueline Vaissermann, Laurent Ruhlmann and Bernold Hasenknopf

      Version of Record online: 17 JUL 2008 | DOI: 10.1002/ejic.200890059

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
  4. Microreview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Ferrocene-Based Small Molecules for Multichannel Molecular Recognition of Cations and Anions (pages 3401–3417)

      Pedro Molina, Alberto Tárraga and Antonio Caballero

      Version of Record online: 9 JUL 2008 | DOI: 10.1002/ejic.200800474

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      The sensing properties of new acyclic and cyclic ferrocene-based structural motifs, in which the redox unit is linked by unsaturated aza bridges (azadiene, azine, urea, guanidine, azaheterocycles) to a chromogenic or fluorescent signalling unit, are described.

  5. Short Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Tetrahedral Assembly with Lanthanides: Toward Discrete Polynuclear Complexes (pages 3419–3422)

      Josef Hamacek, Gérald Bernardinelli and Yaroslav Filinchuk

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800455

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      3D arrangement of trivalent lanthanides (Eu–Lu) is controlled through self-assembly with a new tripodal ligand L. X-ray crystallography shows that four nine-coordinate cations adopt a regular tetrahedral arrangement in the solid state. These remarkable, highly charged structures are maintained in solution, as demonstrated by NMR spectroscopy, ESI-MS and spectrophotometry.

    2. Self-Assembled Two-Dimensional Water-Soluble Dipicolinate Cu/Na Coordination Polymer: Structural Features and Catalytic Activity for the Mild Peroxidative Oxidation of Cycloalkanes in Acid-Free Medium (pages 3423–3427)

      Marina V. Kirillova, Alexander M. Kirillov, M. Fátima C. Guedes da Silva and Armando J. L. Pombeiro

      Version of Record online: 7 JUL 2008 | DOI: 10.1002/ejic.200800355

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      The water-soluble Cu/Na coordination polymer [Cu(μ-dipic)2{Na2(μ-H2O)4}]n·2nH2O features a layered 2D metal–organic framework extendable to a 3D supramolecular assembly via multiple hydrogen bonds (blue dotted lines) between adjacent layers (different colours) and involving crystallization water molecules (red). It acts as a catalyst precursor for the mild peroxidative oxidation of cycloalkanes in acid-free medium.

    3. A Facially Capped Body-Centered Ni9W6 Cubane Modified with Sulfur-Containing Bidentate Ligands: Structure and Magnetic Properties (pages 3428–3431)

      Jeong Hak Lim, Houng Sik Yoo, Jae Il Kim, Jung Hee Yoon, Namgeun Yang, Eui Kwan Koh, Je-Geun Park and Chang Seop Hong

      Version of Record online: 7 JUL 2008 | DOI: 10.1002/ejic.200800416

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      A fully capped body-centered cubane cluster Ni9W6, whose periphery was modified with sulfur-containing bidentate ligands acting as potential anchoring sites to electrodes and substrates, was prepared. Magnetic studies of this cluster revealed that ferromagnetic couplings are operative through CN bridges, generating an S = 12 ground state.

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Hybrid Organic–Inorganic Porphyrin–Polyoxometalate Complexes (pages 3433–3441)

      Clémence Allain, Sophie Favette, Lise-Marie Chamoreau, Jacqueline Vaissermann, Laurent Ruhlmann and Bernold Hasenknopf

      Version of Record online: 17 APR 2008 | DOI: 10.1002/ejic.200701331

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      Polyoxometalates and metalloporphyrins were assembled by functionalization of Anderson-type molybdates or Lindqvist-type vanadates. Electrochemical and spectroscopical analyses reveal the influence of the organic and inorganic subunits on each other.

    2. Binuclear Magnesium, Calcium and Zinc Complexes Based on Bis(salicylaldimine) Ligands with Rigid Bridges (pages 3442–3451)

      Sven Range, Dirk F.-J. Piesik and Sjoerd Harder

      Version of Record online: 7 JUL 2008 | DOI: 10.1002/ejic.200800308

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      Bis(salicylaldimine) ligands with rigid bridging units have been converted into bimetallic Mg, Ca and Zn complexes. In some cases homoleptic complexes with two salicylaldimine units have been isolated. For Mg and Ca also bimetallic heteroleptic amide complexes could be isolated. The heteroleptic Mg amide complexes are moderately active in the polymerization of rac-lactide giving an atactic polymer.

    3. On the Role of Tyrosine as Catalytic Base in Nitrile Hydratase (pages 3452–3459)

      Kathrin H. Hopmann and Fahmi Himo

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800250

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      Nitrile Hydratase (NHase) catalyzes the conversion of nitriles to amides. Two forms of NHase exist, employing either a low-spin CoIII or a FeIII ion in the active site. The precise reaction mechanism of NHase has not been established yet. Here we use density functional theory to investigate a recent proposal that a conserved second-shell tyrosine residue is the catalytic base of NHase.

    4. Chiral Diphosphite-Modified Rhodium(0) Nanoparticles: Catalyst Reservoir for Styrene Hydroformylation (pages 3460–3466)

      M. Rosa Axet, Sergio Castillón, Carmen Claver, Karine Philippot, Pierre Lecante and Bruno Chaudret

      Version of Record online: 7 JUL 2008 | DOI: 10.1002/ejic.200800421

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      High-pressure NMR spectroscopic studies performed during the course of a reaction shed some light on the behaviour ofdiphosphite-stabilized rhodium nanoparticles used as catalysts in styrene hydroformylation reaction.

    5. Selective Cleavage by Acids of One Metal–Carbon σ-Bond of a Bis(ortho-platinated) Triarylphosphane: A 31P NMR trans-Influence Series Based on the Unit Pt(κ2-C6H3-5-Me-2-PPh2)(PPh2-4-tol) (pages 3467–3481)

      Martin A. Bennett, Suresh K. Bhargava, Steven H. Privér and Anthony C. Willis

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/ejic.200800333

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      Selective cleavage of one metal–carbon σ-bond in cis-[Pt(κ2-C6H3-5-Me-2-PPh2)2] with strong acids gives complexes of the type cis-[PtX(κ2-C6H3-5-Me-2-PPh2)(PPh2-4-tol)] (X = Cl, Br, I, ONO2 and OCOCF3), from which a series of neutral and cationic derivatives can be derived. An extensive trans-influence series has been established based mainly on 31P NMR spectroscopic data.

    6. N-Heterocyclic Carbenes in Lewis Acid/Base Stabilised Phosphanylboranes (pages 3482–3492)

      Ariane Adolf, Ulf Vogel, Manfred Zabel, Alexey Y. Timoshkin and Manfred Scheer

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800305

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      Depending on the Lewis acid, the reaction between (C6F5)3E·PH2R and BH3·NHCMe (E = Ga or B, R = H, Cp*, Ph) leads to different products. The use of (C6F5)3Ga affords phosphanylboranes, whereas theuse of (C6F5)3B leads to ionic products. NHCMe was also found to replace NMe3 in (C6F5)3B·P(Ph)HBH2·NMe3 to give the corresponding phosphanylboranes.

    7. Ruthenium Dihydrogen Complex for C–H Activation: Catalytic H/D Exchange under Mild Conditions (pages 3493–3500)

      Martin H. G. Prechtl, Markus Hölscher, Yehoshoa Ben-David, Nils Theyssen, David Milstein and Walter Leitner

      Version of Record online: 25 JUN 2008 | DOI: 10.1002/ejic.200800359

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      Catalytic H/D exchange in hydrocarbons by means of a ruthenium dihydrogen complex under mild conditions is investigated by NMR and DFT calculations.

    8. The Use of Liquid–Liquid Interface (Biphasic) for the Preparation of Benzenetricarboxylate Complexes of Cobalt and Nickel (pages 3501–3514)

      Abhishek Banerjee, Partha Mahata and Srinivasan Natarajan

      Version of Record online: 25 JUN 2008 | DOI: 10.1002/ejic.200800152

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      Low-dimensional Co and Ni trimesate compounds were prepared at the interphase of two immiscible liquids by employing a biphasic route. The structures are stabilized by weak intermolecular forces such as hydrogen bonds, π···π interactions etc., and the studies of the physical properties show interesting magnetic and photoluminescence behaviour.

    9. Reactivity of Cationic Lanthanide(III) Monoporphyrinates towards Anionic Cyanometallates – Preparation, Crystal Structure, and Luminescence Properties of Cyanido-Bridged Di- and Trinuclear d–f Complexes (pages 3515–3523)

      Xunjin Zhu, Wai-Kwok Wong, Jianping Guo, Wai-Yeung Wong and Jie-Peng Zhang

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/ejic.200800192

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      A series of heterodimetallic, cyanometallate-linked monoporphyrinatolanthanide complexes of ytterbium or erbium and transition metals (Ni, Pt, Fe, Ag) have been synthesized and structurally characterized. Their photophysical studies reveal that these complexes have metalloporphyrin-based and near-infrared lanthanide emissions, the latter bands being quenched by the cyanometallate groups.

    10. Hydrocarboxylation of Terminal Alkenes in Supercritical Carbon Dioxide (pages 3524–3531)

      Clara Tortosa Estorach, Arantxa Orejón, Núria Ruiz, Anna M. Masdeu-Bultó and Gábor Laurenczy

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800282

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      The catalytic hydrocarboxylation of linear alkenes to carboxylic acids using supercritical carbon dioxide as a solvent was studied. High selectivities in acids have been obtained when adding a perfluorinated surfactant to the reaction mixture. Multinuclear high-pressure NMR spectroscopic studies in [D8]THF and in supercritical CO2 show the formation of Pd0 species.

    11. Silver(I) and Copper(I) Coordination Polymers Based on Thiaoxa-Macrocycles (pages 3532–3539)

      Hyun Jee Kim, Mi Ryoung Song, So Young Lee, Jai Young Lee and Shim Sung Lee

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800284

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      Two analogous dithiamacrocycles (17- and 18-membered) are synthesised. Five coordination polymers and one metallo-cyclic dimer were obtained from the reactions of the macrocycles with the silver(I) and copper(I) salts. The versatility of results is discussed in relation to macrocyclic ring flexibility, anions and π-π stacking.

    12. Substituent Effects in the Solid-State Assembly of Silver(I) Complexes of 4-Substituted 3,6-Di(2-pyridyl)pyridazines (pages 3540–3548)

      Edwin C. Constable, Catherine E. Housecroft, Markus Neuburger, Sébastien Reymann and Silvia Schaffner

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/ejic.200800290

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      Crystalline products isolated from the 1:1 reactions of AgBF4 and 4-R-3,6-di(2-pyridyl)pyridazine ligands have been structurally characterized, and reveal structure types: [AgL2][BF4], [Ag2L2][BF4]2, {[Ag3L2][BF4]3}n and {[Ag2(NCMe)2L2][BF4]2}n. Solution 1H and 13C NMR spectroscopic data are consistent with one ligand environment at room temperature for each complex.

    13. Synthesis, X-ray Crystallography, Spectroelectrochemistry and Computational Studies on Potential Copper-Based Radiopharmaceuticals (pages 3549–3560)

      Jason P. Holland, Peter J. Barnard, David Collison, Jonathan R. Dilworth, Ruth Edge, Jennifer C. Green, Julia M. Heslop, Eric J. L. McInnes, Christoph G. Salzmann and Amber L. Thompson

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/ejic.200800413

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      A new class of metal(II) bis(thiosemicarbazonato) complexes have been characterised as potential hypoxia-selective imagingagents for use in positron emission tomography. Spectroelectrochemical experiments have been used to study the reaction of the copper(I) anion with dioxygen and provide information on the mechanism of hypoxia selectivity.

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