European Journal of Inorganic Chemistry

Cover image for Vol. 2012 Issue 34

December 2012

Volume 2012, Issue 34

Pages 5583–5751

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. You have free access to this content
      Solvolysis of a Series of Cisplatin-Like Complexes – Comparison between DNA-Biosensor and Conductivity Data (Eur. J. Inorg. Chem. 34/2012)

      James A. Platts, Mauro Ravera, Elisabetta Gabano, Manuele Sardi, Sabrina Bianco and Domenico Osella

      Article first published online: 26 NOV 2012 | DOI: 10.1002/ejic.201290109

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      The cover picture shows the solvolysis and the interaction with DNA of a series of cis-[PtCl2(en*)] (en* = variously N-methylated ethylenediamines) complexes. The solvolysis of this kind of compounds was studied by means of a DNA-biosensor, conductivity measurements and DFT calculations. This chemistry is presented with Monte Cervino (Matterhorn, 4478 m) as background. The photo was taken from Mount Zerbion (2722 m), Aosta Valley, Italy, by Mauro Ravera. Details are discussed in the article by D. Osella et al. on p. 5625 ff.

  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. 1,3,2-Diazaborole Chemistry

      Modern 1,3,2-Diazaborole Chemistry – A Metamorphosis from Electrophilic to Nucleophilic Boron (pages 5595–5609)

      Lothar Weber

      Article first published online: 9 NOV 2012 | DOI: 10.1002/ejic.201200812

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      Lithium diazaborolyl compounds such as LiB(NDipCH)2 serve as convenient transfer reagents for the diazaborolyl anion to main group elements such as Mg, B, Al, and Si, transition metals such as Sc, Y, Ti, Hf, Rh, Ir, Pt, Cu, Ag, Au, and Zn, as well as the rare earth metals Lu and Gd. As potent boron-based nucleophiles, such metal diazaborolyl compounds display a rich chemistry towards organic electrophiles.

  5. Short Communications

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

      Reversing the Triazole Topology in a Cyclam-Triazole-Dye Ligand Gives a 10-Fold Brighter Signal Response to Zn2+ in Aqueous Solution (pages 5611–5615)

      Sandra Ast, Peter J. Rutledge and Matthew H. Todd

      Article first published online: 25 OCT 2012 | DOI: 10.1002/ejic.201201072

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      Switch it on... Simply flipping the triazole geometry between a dye and an azamacrocycle leads to a bright sensor for zinc ions that operates in aqueous buffer and with very high quantum yield.

    2. Cross-Conjugated Cr(III) Complexes

      Photoactive Chromium(III)–Cyclam Complexes with Axially Bound geminal-Diethynylethenes (pages 5616–5620)

      William P. Forrest, Zhi Cao, H. Rhodes Hambrick, Boone M. Prentice, Phillip E. Fanwick, Paul S. Wagenknecht and Tong Ren

      Article first published online: 6 NOV 2012 | DOI: 10.1002/ejic.201201235

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      Symmetric chromium(III) compounds bearing substituted cross-conjugated diethynylethene ligands as axial ligands were prepared and have noteworthy metal-centered emissions.

    3. Precursor Synthesis of Nanorods

      A Molecular Precursor Approach to 3D Aligned CuInS2 Chalcopyrite Nanorod Arrays (pages 5621–5624)

      Mikhail Pashchanka, Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 2 NOV 2012 | DOI: 10.1002/ejic.201200886

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      Herein, we report on the utility of single-source metal–ketoacidoximate precursors in the synthesis of stoichiometric CuInS2 (CIS) nanorods by endo-nanocasting of polymeric templates with indium and copper oximato complexes and thiourea as additional sulfur source. The utilized solution approach is very promising for future solar cell applications.

  6. Full Papers

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

      Solvolysis of a Series of Cisplatin-Like Complexes – Comparison between DNA-Biosensor and Conductivity Data (pages 5625–5631)

      James A. Platts, Mauro Ravera, Elisabetta Gabano, Manuele Sardi, Sabrina Bianco and Domenico Osella

      Article first published online: 24 AUG 2012 | DOI: 10.1002/ejic.201200677

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      The kinetics of solvolysis and interaction with DNA of a series of cis-[PtCl2(en*)] complexes were studied in water/co-solvent systems and compared with DFT calculations of activation barriers. The more rapid solvolysis shown in DMSO indicates that the affinity of the Pt core for the S-donor atoms of DMSO overcomes the effect of its steric hindrance.

    2. Carbon Dioxide Utilization

      Catalytic Hydrocarboxylation of Olefins with CO2 and H2 – a DFT Computational Analysis (pages 5632–5641)

      Thomas G. Ostapowicz, Markus Hölscher and Walter Leitner

      Article first published online: 5 OCT 2012 | DOI: 10.1002/ejic.201200965

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      Carbon dioxide utilization in chemical synthesis is highly desired, because CO2 is an abundant, cheap, and nontoxic reagent. Herein, we present a detailed computational study, in which the possibility of a catalytic hydrocarboxylation reaction is explored. Conceivable catalytic cycles were devised for this reaction, as well as for the most relevant side reaction pathways.

    3. Molecular Magnetism

      Two Cobalt(II) Cubane Compounds: The Key Role of Small Ligand Changes on the Crystal Packing and Magnetic Properties (pages 5642–5648)

      Guilherme P. Guedes, Stéphane Soriano, Nadia M. Comerlato, Nivaldo L. Speziali, Paul M. Lahti, Miguel A. Novak and Maria G. F. Vaz

      Article first published online: 2 OCT 2012 | DOI: 10.1002/ejic.201200615

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      The synthesis, crystal structures and magnetic properties of two new cobalt(II) cubane compounds are described. Both structures consist of a tetranuclear system in a cubane framework with a Co4O4 core. These compounds are interesting examples that show how small structural changes in molecule-based magnetic compounds can strongly affect the overall magnetic properties.

    4. Carbon Nitride Precursors

      Exploring the Route to 1,3,5-Triazine-2,4,6-triisocyanate (C6N6O3), a Hydrogen-Free Molecular Precursor for Polymeric C–N–(O) Materials (pages 5649–5657)

      Carsten Ludwig Schmidt and Martin Jansen

      Article first published online: 26 SEP 2012 | DOI: 10.1002/ejic.201200783

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      In this work, the five-step synthesis of 1,3,5-triazine-2,4,6-triisocyanate [C3N3(NCO)3] is reported. This product was studied by thermal and spectroscopic methods as well as chemical transformation reactions. Due to high chemical reactivity of the isocyanate groups, oligomerisation/polymerisation of the molecular compound occurred easily at room temperature to form amorphous uretdione-type polymers.

    5. Coordination Chemistry

      Structure and Bonding of Tetracyanopyrrolides (pages 5658–5667)

      Martin Becker, Jörg Harloff, Thomas Jantz, Axel Schulz and Alexander Villinger

      Article first published online: 20 SEP 2012 | DOI: 10.1002/ejic.201200790

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      Salts containing the binary tetracyanopyrrolide anion (TCP) were synthesized from tetracyano-1,4-dithiin and sodium azide. The planar TCP anion, which might be regarded as a pseudohalide, is C2v symmetric and represents a multifunctional binary CN ligand as demonstrated in a series of solid-state structures.

    6. Ionic Liquids

      POSS–Tetraalkylammonium Salts: A New Class of Ionic Liquids (pages 5668–5676)

      Paola Cardiano, Giuseppe Lazzara, Sundar Manickam, Placido Mineo, Stefana Milioto and Sandra Lo Schiavo

      Article first published online: 8 OCT 2012 | DOI: 10.1002/ejic.201200874

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      A new family of organic/inorganic hybrid polyhedral oligomeric silsesquioxane (POSS) ionic liquids is reported. Their bulk and solution properties are dependent on the nature of the cation.

    7. Multimodal Imaging

      Synthesis and Characterization of Bifunctional SiO2@(Y0.95–xGdxEu0.05)2O3 Nanocomposites for Magnetic Resonance and Optical Imaging (pages 5677–5684)

      Huan Liu, Li Li, Xiu-Mei Tian, Wen-Yong Hu, Xiao-Yan Kuang and Yuan-Zhi Shao

      Article first published online: 9 OCT 2012 | DOI: 10.1002/ejic.201200875

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      We report a facile method for the preparation of bifunctional SiO2@(Y0.95–xGdxEu0.05)2O3 nanocomposites for magnetic resonance (MR) and optical imaging. Increasing the content of Gd led to a significant enhancement of the emission intensity and presented a maximum MR intensity at x = 0.45. After internalization in RAW 264.7 cells, the nanoparticles showed bright intracellular luminescence.

    8. Chain Compounds

      Magneto-Structural Study of an Oxamato-Bridged PdIICoII Chain: X-ray Crystallographic Evidence of a Single-Crystal-to-Single-Crystal Phase Transition (pages 5685–5693)

      Willian X. C. Oliveira, Marcos A. Ribeiro, Carlos B. Pinheiro, Wallace C. Nunes, Miguel Julve, Yves Journaux, Humberto O. Stumpf and Cynthia L. M. Pereira

      Article first published online: 11 OCT 2012 | DOI: 10.1002/ejic.201200831

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      The synthesis, magnetic properties and thermotropic structural phase transition are described for a new one-dimensional oxamato-bridged PdIICoII chain compound. An important spin–orbit coupling of the quasi-magnetically isolated octahedral high-spin CoII ion occurs in the chain compound.

    9. Energetic Materials

      The 1,4,5-Triaminotetrazolium Cation (CN7H6+): A Highly Nitrogen-Rich Moiety (pages 5694–5700)

      Thomas M. Klapötke, Davin G. Piercey and Jörg Stierstorfer

      Article first published online: 5 OCT 2012 | DOI: 10.1002/ejic.201200964

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      The amination of 1,5-diamino-1,2,3,4-tetrazole with tosylhydroxylamine yielded 1,4,5-triaminotetrazolium tosylate. Metathesis reactions yielded energetic bromide, nitrate, and nitrotetrazolate 2-oxide salts. Owing to the exceedingly high nitrogen content of the cation (>84 % !), the calculated heats of formation and the experimental explosive and thermal sensitivities are exceedingly high.

    10. Octahedral Complexes

      Rational Synthesis of a Family of Neutral Monomeric Heteroleptic Titanium Complexes Based on an Octahedral TiO4N2 Motif (pages 5701–5713)

      David Michael Weekes, Nathalie Baradel, Nathalie Kyritsakas, Pierre Mobian and Marc Henry

      Article first published online: 2 NOV 2012 | DOI: 10.1002/ejic.201200560

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      A rational approach leading to a family of complexes incorporating a TiO4N2 framework is proposed. The detailed characterisation of these titanium-based octahedral complexes is described. Also, a full thermodynamic analysis of the reactions allowing the formation of these species is presented.

    11. Silicon Etching

      Etching Silicon with HF–HNO3–H2SO4/H2O Mixtures – Unprecedented Formation of Trifluorosilane, Hexafluorodisiloxane, and Si–F Surface Groups (pages 5714–5721)

      Marcus Lippold, Uwe Böhme, Christoph Gondek, Martin Kronstein, Sebastian Patzig-Klein, Martin Weser and Edwin Kroke

      Article first published online: 8 OCT 2012 | DOI: 10.1002/ejic.201200674

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      Vibrational spectroscopic investigations of the acidic wet chemical silicon etching process with HF–HNO3–H2SO4 mixtures indicate that trifluorosilane (HSiF3) and hexafluorodisiloxane (F3SiOSiF3) are generated. At the same time fluorine-terminated silicon surfaces are formed as proved by X-ray photoelectron spectroscopy (XPS).

    12. Ammonia–Borane Decomposition

      Catalytic Thermal Decomposition of Ammonia–Borane by Well-Dispersed Metal Nanoparticles on Mesoporous Substrates Prepared by Magnetron Sputtering (pages 5722–5728)

      Gongbiao Xin, Junzhi Yang, Wei Li, Jie Zheng and Xingguo Li

      Article first published online: 27 SEP 2012 | DOI: 10.1002/ejic.201200752

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      Pd, Ni, and Pt nanoparticles were well dispersed on mesoporous substrates using a magnetron sputtering method. Catalysts prepared in this way showed promising catalytic effects on the kinetic properties of ammonia–borane thermal dehydrogenation.

    13. Structure and Magnetism

      μ3- vs. μ-Hydroxido Bridges – Peripheral Function Controls the Nuclearity of Hydroxido-Bridged Copper(II) Complexes (pages 5729–5740)

      Fatima Zohra Chiboub Fellah, Jean-Pierre Costes, Laure Vendier, Carine Duhayon, Sonia Ladeira and Jean-Pierre Tuchagues

      Article first published online: 5 OCT 2012 | DOI: 10.1002/ejic.201200819

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      [{Cu2(L3)2(μ-OH)(ClO4)}2] is the first example of a ferromagnetic monohydroxido-bridged dinuclear CuII complex. N2O Schiff base ligands from the condensation of salicylaldehydes with diamines control the nuclearity: without an OMe substituent α to the Ophenoxido atom, µ3-OH3-OMe) bridged trinuclear species are obtained; with an α-substituent, µ-HO single-bridged dinuclear species are obtained.

    14. Inorganic–Organic Hybrid Materials

      Organozinc- and Imidazole-Modified Periodic Mesoporous Organosilicas by Means of Molecular Grafting (pages 5741–5751)

      Yucang Liang, Egil Severin Erichsen, Chen Song and Reiner Anwander

      Article first published online: 2 OCT 2012 | DOI: 10.1002/ejic.201200820

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      Cagelike cubic and hexagonal periodic mesoporous organosilicas were used as supports for surface modification with functional organic groups and organozinc by molecular grafting. Surface species, surface ligand exchange, and the coordination behavior of the functional group with ZnEt2 were investigated and characterized.

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