European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 16

June 2013

Volume 2013, Issue 16

Pages 2828–2970

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. News
    7. Further Masthead
    8. Full Papers
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      N-Heterocyclic Carbenes Functioning as Monoligating Clamps (Eur. J. Inorg. Chem. 16/2013)

      Matthieu Teci, Eric Brenner, Dominique Matt and Loïc Toupet

      Article first published online: 21 MAY 2013 | DOI: 10.1002/ejic.201390068

      Thumbnail image of graphical abstract

      The cover picture shows a palladium complex stabilized by an N-heterocyclic carbene bearing two non-rotating alkylfluorenyl substituents. N-heterocyclic carbene ligands of this type are sterically not very crowded, but they can nevertheless be used to prepare remarkably fast Suzuki–Miyaura cross-coupling catalysts. Their efficiency relies on their ability to behave like a “clamp” that can permanently protect two trans-located coordination sites. Details are discussed in the Short Communication by E. Brenner, D. Matt et al. on p. 2841 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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      N-Heterocyclic Carbenes Functioning as Monoligating Clamps (page 2828)

      Matthieu Teci, Eric Brenner, Dominique Matt and Loïc Toupet

      Article first published online: 21 MAY 2013 | DOI: 10.1002/ejic.201300475

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      Unexpectedly, these complexes showed activities equal or superior to those of the best Suzuki–Miyaura catalysts reported to date...

      This and more about the story behind the cover in the Cover Profile and about the research itself on p. 2841 ff.

  3. Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 16/2013 (page 2829)

      Article first published online: 21 MAY 2013 | DOI: 10.1002/ejic.201390069

  4. Graphical Abstract

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    1. Graphical Abstract: Eur. J. Inorg. Chem. 16/2013 (pages 2831–2835)

      Article first published online: 21 MAY 2013 | DOI: 10.1002/ejic.201390070

  5. News

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    1. Masthead: Eur. J. Inorg. Chem. 16/2013 (page 2840)

      Article first published online: 21 MAY 2013 | DOI: 10.1002/ejic.201390072

  7. Full Papers

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    1. Carbene Ligands

      N-Heterocyclic Carbenes Functioning as Monoligating Clamps (pages 2841–2848)

      Matthieu Teci, Eric Brenner, Dominique Matt and Loïc Toupet

      Article first published online: 8 MAR 2013 | DOI: 10.1002/ejic.201300087

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      N-Heterocyclic carbene ligands act as clamps with Pd centres to form highly active Suzuki–Miyaura cross-coupling catalysts. The remarkable performance displayed by these ligands relies on the presence of expanded 9-alkylfluorenyl substituents with a restricted rotational freedom, which results in a permanent, meridional confinement of the metal centre.

    2. Heterobimetallic Aluminoxanes

      Molecular Heterobimetallic Aluminoxanes and Aluminoxane Sulfides Containing Group 4 Metals (pages 2849–2857)

      Sandra Hidalgo-Bonilla, Ricardo Peyrot, Vojtech Jancik, Joaquín Barroso-Flores, Marisol Reyes-Lezama and Mónica Moya-Cabrera

      Article first published online: 11 APR 2013 | DOI: 10.1002/ejic.201300108

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      A series of Group 4 heterobimetallic aluminoxanes and aluminoxane sulfides have been prepared. The aluminoxane sulfides exhibit unprecedented Al–S–M (M = Zr, Hf) moieties. The structural and electronic features of these compounds were investigated by DFT calculations.

    3. Dual Imaging Agents

      D-Glucuronic Acid Coated Gd(IO3)3·2H2O Nanomaterial as a Potential T1 MRI-CT Dual Contrast Agent (pages 2858–2866)

      Eun Jung Lee, Woo Choul Heo, Jang Woo Park, Yongmin Chang, Ji-Eun Bae, Kwon Seok Chae, Tae Jeong Kim, Ji Ae Park and Gang Ho Lee

      Article first published online: 12 APR 2013 | DOI: 10.1002/ejic.201201481

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      D-Glucuronic acid coated Gd(IO3)3·2H2O nanomaterial is synthesized in one-pot and its T1 MRI-CT dual imaging properties are investigated. It has a very large r1 and strong X-ray absorption, which are prerequisites for high-performance T1 MRI-CT dual contrast agents.

    4. Heavy Chalcogenides

      Experimental and Computational Investigations of Tautomerism and Fluxionality in PCP- and PNP-Bridged Heavy Chalcogenides (pages 2867–2876)

      Philip J. W. Elder, Tristram Chivers and Ramalingam Thirumoorthi

      Article first published online: 15 APR 2013 | DOI: 10.1002/ejic.201201378

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      The monochalcogenides EPiPr2CH2PiPr2 (E = Se, Te) exist as CH2 tautomers in the solid state; the contrast in this finding with that of the preferential formation of PH tautomers by PNP-bridged analogues is addressed through DFT calculations. In solution, the PCP-bridged tellurium derivative undergoes rapid intermolecular tellurium exchange with an activation energy of 21.9 ± 3.2 kJ mol–1.

    5. Encapsulated Polyoxometalates

      Europium Polyoxometalates Encapsulated in Silica Nanoparticles – Characterization and Photoluminescence Studies (pages 2877–2886)

      Cristina S. Neves, Carlos M. Granadeiro, Luís Cunha-Silva, Duarte Ananias, Sandra Gago, Gabriel Feio, Patricia A. Carvalho, Peter Eaton, Salete S. Balula and Eulália Pereira

      Article first published online: 12 APR 2013 | DOI: 10.1002/ejic.201201482

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      Europium polyoxometalates with distinct europium coordination are encapsulated in silica nanoparticles by a microemulsion methodology. Their surface is further functionalized with appropriate organic groups to originate biocompatible nanomaterials with suitable photoluminescent properties.

    6. Li-Ion Batteries

      Synthesis of Monoclinic Li[Li0.2Mn0.54Ni0.13Co0.13]O2 Nanoparticles by a Layered-Template Route for High-Performance Li-Ion Batteries (pages 2887–2892)

      Shen Qiu, Zhongxue Chen, Feng Pei, Fayuan Wu, Yue Wu, Xinping Ai, Hanxi Yang and Yuliang Cao

      Article first published online: 12 APR 2013 | DOI: 10.1002/ejic.201300005

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      A layered-template method was used to synthesis the Li[Li0.2Mn0.54Ni0.13Co0.13]O2 nanoparticles with a monoclinic structure. Due to the presence of the monoclinic structure, the cycling stability and rate capability of the Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode are excellent.

    7. Alkylruthenium Complexes

      Alkylruthenium Complexes Containing Polypyridyl Ligands: Synthesis, Characterization, and Immobilization on Silica (pages 2893–2899)

      Enrique Kwan Huang, Wai-Man Cheung, Ka-Wang Chan, Frank Leung-Yuk Lam, Xijun Hu, Qian-Feng Zhang, Ian D. Williams and Wa-Hung Leung

      Article first published online: 12 APR 2013 | DOI: 10.1002/ejic.201300043

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      The alkylation of [Ru(tbtpy)(CO)Cl2] (tbtpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,6″-terpyridyl) with Me3SiCH2MgCl afforded a mixture of trans-[Ru(tbtpy)(CH2SiMe3)2(CO)] and trans-[Ru(tbtpy)(CH2SiMe3)Cl(CO)]. trans-[Ru(tbtpy)(CH2SiMe3)2(CO)] and mer-[Ru(dtbpy)(CH2SiMe3)3(NO)] were immobilized on SBA-15 by elimination of SiMe4 and the grafted species showed catalytic behavior.

    8. Phosphonous Acid Ligands

      Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of Electronic and Steric Effects of Phosphonous Acid Ligands and Their Chlorophosphite Ligand Precursors in Tungsten Pentacarb­onyl Complexes (pages 2900–2911)

      Samantha D. Hastings, Houston Byrd, Leanne N. Gray, Michael J. Jablonsky, Jason L. Freeman and Gary M. Gray

      Article first published online: 17 APR 2013 | DOI: 10.1002/ejic.201300121

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      Steric and electronic properties of chlorophosphite ligands derived from 2,2′-biphenol or (±)-1,1′-bi-2-naphthol and their corresponding phosphonous acid ligands in tungsten(0) pentacarbonyl have been studied by using multinuclear NMR spectroscopy and X-ray crystallography. The identity of the biaryl group does not affect either the steric or the electronic properties of the ligands.

    9. Organotin Compounds

      Dinuclear Monomeric and Macrocyclic Organotin Dithiocarbamates Derived from 1,10-Diaza-18-crown-6 and 4,4′-Trimethylenedipiperidine (pages 2912–2922)

      Norma A. Celis, Raul Villamil-Ramos, Herbert Höpfl, Irán F. Hernández-Ahuactzi, Mario Sánchez, Luis S. Zamudio-Rivera and Victor Barba

      Article first published online: 15 APR 2013 | DOI: 10.1002/ejic.201300134

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      Dinuclear monomeric and macrocyclic complexes derived from diorganotin dithiocarbamates are prepared by using ligands with azacrown and dipiperidine spacers. The macrocyclic structures have different conformations depending on the R2Sn group, which also changes the size of the cavity suitable for guest inclusion. The structures show supramolecular arrays through C–H···S and C–H···Cl interactions.

    10. Solid-State Chemistry

      Synthesis, Crystal Structures and Properties of the First Lanthanum Selenide Chlorides, LaSeCl and La3Se4Cl (pages 2923–2929)

      Christian M. Schurz, Susanne Frunder and Thomas Schleid

      Article first published online: 16 APR 2013 | DOI: 10.1002/ejic.201300138

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      The crystal structures of the first lanthanum selenide chlorides, LaSeCl and La3Se4Cl, are described in terms of condensed bi- and tricapped trigonal prisms [LaSenClm]11/12– (n = 5, 5+1, 7; m = 1, 2, 4). A phase-pure sample of La3Se4Cl displays an optical band gap of 1.75 eV. Both show high stability towards air, water and inorganic bases, but decompose upon contact with acids.

    11. Dibromobenzobarrelene Derivatives

      Synthesis of Dibromobenzobarrelene Derivatives and Catalytic Activity of Their Rhodium Complexes (pages 2930–2939)

      Maik Schlesinger, Max Hofmann, Tobias Rüffer, Dieter Schaarschmidt, Heinrich Lang, Sergio Theilacker, Markus Schürmann, Klaus Jurkschat and Michael Mehring

      Article first published online: 17 APR 2013 | DOI: 10.1002/ejic.201300161

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      The synthesis by means of a [4+2] cycloaddition approach of six novel dibromobenzobarrelenes with diverse substitution patterns at the barrelene framework, including chiral derivatives, is reported as well as the functionalization of 6,8-dibromo-1,3,10-trimethyl-1,4-dihydro-1,4-ethenonaphthalene to give carboxylic acid and phosphonic acid ester derivatives.

    12. Dinuclear Niobium Complexes

      Synthesis, Characterization and Reactivity of New Dinuclear Guanidinate Diimidoniobium Complexes (pages 2940–2946)

      David Elorriaga, Fernando Carrillo-Hermosilla, Antonio Antiñolo, Isabel López-Solera, Rafael Fernández-Galán, Amparo Serrano and Elena Villaseñor

      Article first published online: 11 APR 2013 | DOI: 10.1002/ejic.201300025

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      Dinuclear alkyl diimidoniobium complexes reacted with catalytically obtained guanidines to yield guanidinate complexes. Double bis(iminoacyl) derivatives were obtained by a migratory insertion reaction of 2,6-dimethylphenyl isocyanide.

    13. Tunable LED Phosphors

      Tunable and White-Light Emission from Single-Phase Ca2YF4PO4:Eu2+,Mn2+ Phosphors for Application in W-LEDs (pages 2947–2953)

      Dongling Geng, Mengmeng Shang, Yang Zhang, Ziyong Cheng and Jun Lin

      Article first published online: 15 APR 2013 | DOI: 10.1002/ejic.201300090

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      The tunable luminescence and energy-transfer properties of Ca2YF4PO4:Eu2+,Mn2+ phosphors with potential application in LEDs have been investigated.

    14. Multinuclear Compounds

      Chlorosilanes and 3,5-Dimethylpyrazole: Multinuclear Complexes, Acetonitrile Insertion and 29Si NMR Chemical-Shift Anisotropy Studies (pages 2954–2962)

      Florian Bitto, Konstantin Kraushaar, Uwe Böhme, Erica Brendler, Jörg Wagler and Edwin Kroke

      Article first published online: 11 APR 2013 | DOI: 10.1002/ejic.201300109

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      The reaction of trichlorosilane with 3,5-dimethylpyrazole (Hpz*) in acetonitrile afforded dinuclear silicon compounds. Their outstanding feature is the formal insertion of one or two molecules of MeCN into the former N–Si bond of a Sipz* moiety. These compounds were examined with single-crystal X-ray diffraction, 29Si cross-polarisation (CP)/magic-angle spinning (MAS) NMR spectroscopy and quantum chemical calculations.

    15. Hybrid Materials

      Lanthanide-Functionalized SBA-15 Mesoporous Hybrids – Ultraviolet-Visible Excitation and Visible–NIR Emission (pages 2963–2970)

      Yan-Jing Gu and Bing Yan

      Article first published online: 15 APR 2013 | DOI: 10.1002/ejic.201300142

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      Ln3+ (Eu3+, Nd3+, Yb3+) organic–inorganic mesoporous hybrid materials are prepared. The hybrids contain lanthanide complexes covalently grafted to 2-methyl-9-hydroxyphenalenone (MHPO) functionalized ordered mesoporous SBA-15 and with 1,10-phenanthroline as a second ligand. The materials exhibit the characteristic visible (Eu3+) and near-infrared (NIR) luminescence (Nd+ and Yb3+) of lanthanides.

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