European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 8

March 2014

Volume 2014, Issue 8

Pages 1262–1420

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. News
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. You have free access to this content
      Bulky Titanium Amides: C–H Bond Activation under Mild Conditions (Eur. J. Inorg. Chem. 8/2014)

      Christian Adler, Alexander Bekurdts, Detlev Haase, Wolfgang Saak, Marc Schmidtmann and Rüdiger Beckhaus

      Article first published online: 11 MAR 2014 | DOI: 10.1002/ejic.201490036

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      The cover picture shows the broad chemistry of the abundant dicyclohexylamidotitanium trichloride. The remarkable crystallization properties of the light red starting material are significant for all products obtained. All variations in the coordination sphere are always accompanied by color changes. In subsequent reactions, octahedrally coordinated complexes are formed by addition of Lewis bases as well as chelating N,N′- or P,P′-ligands. An excellent proton acceptor ligand can be introduced by complexation of a sterically demanding pentafulvene. In this way, selective C–H bond activation processes are initiated, and they lead to three- or four-membered titanacycles by spontaneous b- and g-C–H elimination reactions. Details are discussed in the article by R. Beckhaus et al. on p. 1289 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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      Bulky Titanium Amides: C–H Bond Activation under Mild Conditions (page 1262)

      Christian Adler, Alexander Bekurdts, Detlev Haase, Wolfgang Saak, Marc Schmidtmann and Rüdiger Beckhaus

      Article first published online: 11 MAR 2014 | DOI: 10.1002/ejic.201400107

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      Being inspired by catalytic applications of titanium amides in organic synthesis, we are particularly interested in the relationship between structure and bonding properties...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 1289 ff.

  3. Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 8/2014 (pages 1264–11264)

      Article first published online: 11 MAR 2014 | DOI: 10.1002/ejic.201490037

  4. Graphical Abstract

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    1. Graphical Abstract: Eur. J. Inorg. Chem. 8/2014 (pages 1265–1269)

      Article first published online: 11 MAR 2014 | DOI: 10.1002/ejic.201490038

  5. News

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    1. Masthead: Eur. J. Inorg. Chem. 8/2014 (page 1274)

      Article first published online: 11 MAR 2014 | DOI: 10.1002/ejic.201490040

  7. Short Communications

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    1. Cluster Compounds

      Self-Assembly of a Mixed-Valent Co32 Ring (pages 1275–1278)

      Yue-Ling Bai, Xiaoli Bao, Shourong Zhu, Jianhui Fang, Min Shao and Haiyan Shi

      Article first published online: 12 FEB 2014 | DOI: 10.1002/ejic.201301530

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      A mixed-valent 32 nuclear cyclic Co32 cluster, [CoII16CoIII164-O)16(tci)16(H2O)12]·40H2O [1, H3tci = tris(2-carboxyethyl)isocyanurate], built with four octanuclear [CoII4CoIII44-O)4]12+ units is synthesized and characterized. Magnetic studies confirm the paramagnetic nature, and cyclic voltammetry shows an irreversible oxidation at 1.0 V versus saturated calomel electrode.

    2. Multipodal Nanocrystals

      Facile Synthesis of Multipodal MnO Nanocrystals and Their Catalytic Performance (pages 1279–1283)

      Aram Kim, Dongwoo Shin, Mijong Kim, Chohye Yoon, Hyunjoon Song and Kang Hyun Park

      Article first published online: 13 FEB 2014 | DOI: 10.1002/ejic.201400070

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      Multipodal MnO nanocrystals are synthesized through thermal decomposition of a Mn-oleate complex. The MnO nanocrystals are single crystalline and uniform multipodal with an average estimated distance of (47 ± 2) nm between the tips of the two pods. These nanocrystals can efficiently catalyze the synthesis of a quinoxaline derivative from an α-hydroxy ketone with a 1,2-diamine.

    3. Dinuclear Europium(III) Complexes

      Crystal Structure and Spectroscopic Studies of a Dimeric Europium(III) β-Diketonate Complex Containing [3-(2-Pyridyl)-1-pyrazolyl]acetate (pages 1284–1288)

      Ana C. Coelho, Ana C. Gomes, José A. Fernandes, Filipe A. Almeida Paz, Susana S. Braga, Luís Rino, Luiz Pereira, Martyn Pillinger and Isabel S. Gonçalves

      Article first published online: 19 FEB 2014 | DOI: 10.1002/ejic.201301520

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      In the title dinuclear complex, each Eu3+ ion is coordinated to two O,O′-chelated 1-benzoyl-3,3,3-trifluoroacetonate groups and one N,N′-chelated [3-(2-pyridyl)-1-pyrazolyl]acetate ligand, and the two metal centers are linked by tridentate chelating–bridging carboxylate groups. Steady-state photoluminescence (PL), PL excitation, and time-resolved PL data are reported.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. News
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. Titanium Complexes

      Bulky Titanium Amides: C–H Bond Activation under Mild Conditions (pages 1289–1302)

      Christian Adler, Alexander Bekurdts, Detlev Haase, Wolfgang Saak, Marc Schmidtmann and Rüdiger Beckhaus

      Article first published online: 3 FEB 2014 | DOI: 10.1002/ejic.201400022

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      The solid-state structures of tetrahedral and octahedral titanium amide complexes with bulky dicyclohexylamido ligands reveal a characteristic close contact between the titanium atom and a carbon atom in the β-position. The exchange of a chlorine atom by a bulky pentafulvene ligand increases this effect. The introduction of other sterically demanding amines to complexes initiates a spontaneous C–H activation.

    2. Dye-Sensitized Solar Cells

      Near-IR Sensitization of Dye-Sensitized Solar Cells Using Thiocyanate-Free Cyclometalated Ruthenium(II) Complexes Having a Pyridylquinoline Ligand (pages 1303–1311)

      Takashi Funaki, Hitoshi Kusama, Nobuko Onozawa-Komatsuzaki, Kazuyuki Kasuga, Kazuhiro Sayama and Hideki Sugihara

      Article first published online: 31 JAN 2014 | DOI: 10.1002/ejic.201301459

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      Three thiocyanate-free cyclometalated ruthenium(II) complexes were designed and synthesized as near-IR sensitizers for dye-sensitized solar cells. The modification of the ligand structure can improve the photovoltaic performance of this class of cyclometalated ruthenium(II) complexes.

    3. Coordination Modes of s-Block Metals

      N,N′-Bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidinates of the s-Block Metals Lithium, Potassium, and Calcium (pages 1312–1321)

      Claas Loh, Susanne Seupel, Helmar Görls, Sven Krieck and Matthias Westerhausen

      Article first published online: 31 JAN 2014 | DOI: 10.1002/ejic.201301557

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      Depending on the hardness of the s-block metals, the coordination behavior of substituted N,N′-bis(diisopropylphenyl)amidinates vary. Hard cations favor the nitrogen bases whereas soft cations bind to the π-systems of the aryl groups (C gray, Li green, N blue, O red).

    4. Uranyl–Organic Frameworks

      Crystal Chemistry of Uranyl Carboxylate Coordination Networks Obtained in the Presence of Organic Amine Molecules (pages 1322–1332)

      Ionut Mihalcea, Natacha Henry and Thierry Loiseau

      Article first published online: 6 FEB 2014 | DOI: 10.1002/ejic.201301575

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      A new series of uranyl–organic carboxylates has been hydrothermally synthesized by using isophthalic or pyromelitic acid in the presence of 1,3-diaminopropane or a DMF/water solvent mixture. Their crystal structures revealed 1D and 2D coordination networks, which may intercalate protonated propanediammonium or dimethylammonium (from in situ thermal decomposition of DMF) species.

    5. Ruthenium(II) Complex

      Base-Catalyzed Hydrolysis of a RuII–Chloro–dmso Complex and Its Reactivity towards L-Methionine (pages 1333–1344)

      Małgorzata Brindell, Karol Dyduch, Agnieszka Adamowicz, Elżbieta Urbanowicz, Maria Oszajca, Artur Michalak, Grażyna Stochel and Rudi van Eldik

      Article first published online: 3 FEB 2014 | DOI: 10.1002/ejic.201301154

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      Detailed NMR characterization of the reaction product with L-methionine, supported by theoretical calculations, indicated that the NH2 group is the primary target for coordination to the metal center and not the thioether moiety.

    6. Phosphine Ligands

      Homoleptic Copper(I), Silver(I), and Gold(I) Bisphosphine Complexes (pages 1345–1355)

      Adrien Kaeser, Omar Moudam, Gianluca Accorsi, Isabelle Séguy, Jose Navarro, Abdelhalim Belbakra, Carine Duhayon, Nicola Armaroli, Béatrice Delavaux-Nicot and Jean-François Nierengarten

      Article first published online: 6 FEB 2014 | DOI: 10.1002/ejic.201301349

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      Copper(I), silver(I), and gold(I) [M(PP)2]BF4 complexes have been prepared from two bisphosphine ligands, namely, 1,2-bis(diphenylphosphino)benzene (dppb) and bis[2-(diphenylphosphino)phenyl]ether (POP). Their electronic properties have been systematically investigated and rationalized as a combination of steric and electronic effects as well as by differences in their coordination geometries.

    7. Semi-Conductive Materials

      Quasi-Planar Organic Synthon and S···X (X = S or H–C) Contacts in Flat Copper Coordination Chains: Syntheses, Structures and Conductive Behaviour (pages 1356–1363)

      Hai-Bin Zhu, Ru-Yu Shan, Yan-Fang Wu and Yong-Bing Lou

      Article first published online: 3 FEB 2014 | DOI: 10.1002/ejic.201301401

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      The assembly of quasi-planar organic synthon TEPB with CuI and CuCl2 produced two flat coordination chain structures (1 and 2) that incorporate S···S and C–H···S contacts in their packing structures. Complex 1 is an insulator, whereas 2 shows conductive properties with an a.c. conductivity of 5.90 × 10–9 S cm–1 at room temperature.

    8. Metallo-Cavitands

      Resorcinarenyl-Phosphines in Suzuki–Miyaura Cross-Coupling Reactions of Aryl Chlorides (pages 1364–1372)

      Laure Monnereau, Hani El Moll, David Sémeril, Dominique Matt and Loïc Toupet

      Article first published online: 6 FEB 2014 | DOI: 10.1002/ejic.201301473

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      Palladium complexes containing cavitand-phosphines based on a resorcinarene skeleton display high reactivity in Suzuki–Miyaura cross-coupling reactions. The unusual performance of these ligands essentially relies on their bulkiness and ability to bind the metal centre in a hemilabile fashion.

    9. Crystal Engineering

      Broadly Tunable Emission from CaMoO4:Bi Phosphor Based on Locally Modifying the Microenvironment Around Bi3+ Ions (pages 1373–1380)

      Fengwen Kang, Mingying Peng, Shanhui Xu, Zhijun Ma, Guoping Dong and Jianrong Qiu

      Article first published online: 4 FEB 2014 | DOI: 10.1002/ejic.201301481

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      Broadly tunable bismuth emission is observed in the host CaMoO4 when the local microenvironment around Bi3+ is modified by alkali ions. Energy transfer can take place from the MoO42– group to Bi3+ at lower temperature but not at higher temperature. The dependence of the excited states 3P0 and 3P1 on temperature is responsible for the evolution of the Bi3+ emission lifetime with temperature.

    10. Boride Chemistry

      Experimental and Theoretical Investigations of the Ternary Boride NbRuB with a Layerlike Structure Type (pages 1381–1388)

      Mohammed Mbarki, Rachid St. Touzani and Boniface P. T. Fokwa

      Article first published online: 4 FEB 2014 | DOI: 10.1002/ejic.201301488

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      NbRuB has a new intergrowth crystal structure, which contains Re3B- and AlB2-type structures. DFT calculations indicate a deep pseudogap in its density of states (DOS) curve and predict isoelectronic and electron-poorer phases. Bonding analysis indicates that the B2 dumbbell is the strongest bond, but the interlayer Nb–B, Ru–B, and Ru–Nb bonds are responsible for the structural stability.

    11. Transmetalation Chemistry

      Copper(I) Complexes of Phenanthro-Annulated N-Heterocyclic Carbenes: Synthesis and Transmetalation Reactions (pages 1389–1393)

      Jaroslaw Mormul, Manfred Steimann and Ulrich Nagel

      Article first published online: 30 JAN 2014 | DOI: 10.1002/ejic.201301499

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      Copper complexes with phenanthro-annulated N-heterocyclic carbene ligands were prepared from imidazolium salts and Cu2O. Initial transmetalation experiments with [RhCl(cod)] showed an equilibrium in most solvents. Two rhodium complexes could be prepared using acetonitrile as the solvent. One was prepared in a two phase mixture of chloroform and aqueous CaCl2.

    12. Frustrated Lewis Pairs

      A Phosphino Calix[4]arene Bis-Frustrated Lewis Pair (pages 1394–1398)

      Gareth E. Arnott, Philip Moquist, Constantin G. Daniliuc, Gerald Kehr and Gerhard Erker

      Article first published online: 31 JAN 2014 | DOI: 10.1002/ejic.201301529

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      The synthesis and X-ray structure of a calix[4]arene bis-frustrated Lewis pair is described for the first time. This compound is the first example of a frustrated Lewis pair system capable of doubly activating H2 as well as the first use of a calixarene in frustrated Lewis pair chemistry.

    13. Iodosulfanes

      Iodo(trisyl)sulfane: Reactivity of a Stable Alkanesulfenyl Iodide towards Antithyroid Drugs (pages 1399–1406)

      Cathleen Wismach, Peter G. Jones, Wolf-Walther du Mont, Govindasamy Mugesh, Ulrich Papke, H. Bernhard Linden, Massimiliano Arca and Vito Lippolis

      Article first published online: 6 FEB 2014 | DOI: 10.1002/ejic.201301576

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      Iodination of tris(trimethylsilyl)methanethiol (TsiSH) in tetrahydrofuran provides stable violet iodo(trisyl)sulfane (TsiSI) 3, which exhibits iodine–iodine contacts between pairs of TsiSI molecules in the solid state. TsiSI reacts with the antithyroid drugs 6-n-propyl- and 6-methylthiouracil (PTU, MTU) and with methylmethimazole (MMI) to deliver unsymmetric disulfides like Tsi-S-S-PTU.

    14. Copper(II) Speciation

      Speciation Behavior of Copper(II) Acetate in Simple Organic Solvents – Revealing the Effect of Trace Water (pages 1407–1412)

      Alexandra Tsybizova, Bradford L. Ryland, Nikos Tsierkezos, Shannon S. Stahl, Jana Roithová and Detlef Schröder

      Article first published online: 6 FEB 2014 | DOI: 10.1002/ejic.201400036

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      Understanding catalyst behavior: Copper(II) acetate tents to aggregate extensively in organic solvents. However, even trace amounts of water can efficiently suppress the aggregation. This finding is supported by ESI-MS and electron paramagnetic resonance (EPR) measurements.

    15. Aggregation and Structure Elucidation

      Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions (pages 1413–1420)

      Jens Langer, Robert Geitner and Helmar Görls

      Article first published online: 4 FEB 2014 | DOI: 10.1002/ejic.201301584

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      The disaggregation of polymeric potassium bis(diphenylphosphanyl)methanide into discrete mono- or dinuclear entities as well as the resulting changes in coordination mode of the anionic ligand were studied. The process depends on the nature of the mono-, bi- and oligodentate neutral oxygen or nitrogen donor ligand added.

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