European Journal of Inorganic Chemistry

Cover image for Vol. 2011 Issue 11

April 2011

Volume 2011, Issue 11

Pages 1677–1839

  1. Cover Picture

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

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

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

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

      Role of Siloxides in Transition Metal Chemistry and Homogeneous Catalysis (pages 1689–1698)

      Clemens Krempner

      Version of Record online: 14 MAR 2011 | DOI: 10.1002/ejic.201100044

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      In this critical review, applications of well-defined transition metal siloxides as “single site” catalysts in homogeneous catalysis are highlighted. For example, O=V(OSiPh3)3 efficiently catalyzes atom-economic reactions of propargyl and allenic alcohols withimines or aldehydes. Alkylidyne complex (Ph3SiO)3Mo≡CPh(ether) mediates the ring-closing alkyne metathesis of bis(alkynes) to biologically important products in high yields.

  5. Short Communication

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

      Synthesis and Reactivity of New Pyrazolyl-Functionalized Potassium Silanides (pages 1699–1702)

      Brian McNerney, Bruce Whittlesey and Clemens Krempner

      Version of Record online: 2 MAR 2011 | DOI: 10.1002/ejic.201001291

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      Easy synthetic access to pyrazolyl-functionalized neopentasilanes allowed for the preparation of the first stable pyrazolyl-substituted potassium silanides in highyields. These species are useful synthons for the synthesis of functionalized silyl tungsten carbonyl complexes and donor functionalized cyclotetrasilanes.

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communication
    7. Full Papers
    1. Hydrogen Storage in Porous Solids

      Enthalpy–Entropy Correlation for Hydrogen Adsorption on MOFs: Variable-Temperature FTIR Study of Hydrogen Adsorption on MIL-100(Cr) and MIL-101(Cr) (pages 1703–1708)

      Gemma Turnes Palomino, Carlos Palomino Cabello and Carlos Otero Areán

      Version of Record online: 19 JAN 2011 | DOI: 10.1002/ejic.201001116

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      Variable-temperature infrared (VTIR) spectroscopy reveals an enthalpy–entropy correlation for hydrogen adsorption, which should facilitate intelligent design of MOFs and other porous hydrogen storage materials.

    2. New Scorpionate Ligands

      Synthesis, Molecular Structure, and Physical Properties of the Complexes [{PhB(pz)2(CH2SMe)}2M] (M = MnII, FeII; pz = pyrazol-1-yl) Containing a Novel [N,N,S]-Heteroscorpionate Ligand (pages 1709–1718)

      Christian Reus, Kai Ruth, Sandor Tüllmann, Michael Bolte, Hans-Wolfram Lerner, Birgit Weber, Max C. Holthausen and Matthias Wagner

      Version of Record online: 4 MAR 2011 | DOI: 10.1002/ejic.201000552

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      With the synthesis of the [N,N,S] scorpionate [PhB(pz)2(CH2SMe)], the homologous series of smoothly varying ligands [PhB(pz)x(CH2SMe)3–x] (x = 0–3) has been completed, and a gradual fine-tuning of key physical parameters (e.g. redox potentials, spin state, UV/Vis absorptions) is now possible by choice of the ligand with the best-suited donor set.

    3. Hybrid Molecular Metal Oxides

      Synthesis and Theoretical Hirshfeld Analysis of a Supramolecular Heteropolyoxovanadate Architecture (pages 1719–1724)

      Mathias Grabau, Johannes Forster, Kirsten Heussner and Carsten Streb

      Version of Record online: 1 MAR 2011 | DOI: 10.1002/ejic.201001155

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      A supramolecular organic–inorganic polyoxovanadate framework has been assembled using amphiphilic organic counterions as structure-directing agents. The heteropolyoxovanadate clusters aggregate into hydrogen-bonded chains, allowing the formation of hydrophobic cavities between the organic counterions. The use of theoretical Hirshfeld analysis of intermolecular interactions has been critically assessed. Combination with other crystallographic techniques allowed the evaluation of the dominating intermolecular interactions.

    4. Molybdenum Alkoxides

      Facile Access to Homo- and Heteroleptic, Triply Bonded Dimolybdenum Hexaalkoxides with Unsaturated Alkoxide Ligands (pages 1725–1732)

      Sebastian Krackl, Jian-Gong Ma, Yilmaz Aksu and Matthias Driess

      Version of Record online: 25 FEB 2011 | DOI: 10.1002/ejic.201001236

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      Additional functionalities (Fc) in the alkoxide ligands have been introduced in homo- and heteroleptic, triply bonded dimolybdenum alkoxides. The obtained alkoxides show interesting spectroscopic and structural features in comparison to their homoleptic analogues. They represent potential starting materials for immobilization on supports and synthesis of organic-inorganic hybrid materials.

    5. Aluminum Hydrazide Cages

      From tert-Butylhydrazine Adducts of AlR3 (R = Me, CMe3) to Oligonuclear AlN Cage Compounds – Evidence for a Hydrazine Twist Across an Al3 Triangle (pages 1733–1743)

      Werner Uhl, Elke Hagemeier, Marcus Layh, Babak Rezaeirad, Jutta Kösters, Ernst-Ulrich Würthwein, Nugzar Ghavtadze and Werner Massa

      Version of Record online: 1 MAR 2011 | DOI: 10.1002/ejic.201001308

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      The two adjacent donor atoms of the hydrazine ligand give rise to unique coordination behavior that favours the formation of heterocyclic or cage-like metal hydrazides. Novel cage compounds were obtained by the thermolysis of trialkylaluminumhydrazine adducts. Their structures may be derived from Al4N4 heterocubanes or from a type of norbornane skeleton.

    6. Fullerene Redox States

      Synthesis and IR Spectroelectrochemical Studies of a [60]Fulleropyrrolidine-(tricarbonyl)chromium Complex: Probing C60 Redox States by IR Spectroscopy (pages 1744–1749)

      Claes-Henrik Andersson, Gustav Berggren, Sascha Ott and Helena Grennberg

      Version of Record online: 4 MAR 2011 | DOI: 10.1002/ejic.201100011

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      Methods to attach a tricarbonylchromium-based IR probe to C60 have been evaluated. A new C60-tricarbonylchromium complex was successfully prepared via 1,3-dipolar cycloaddition. This compound was characterized by cyclic voltammetry and IR-based electrochemistry; the latter suggests communication between the two electroactive moieties. Furthermore, the redox state of the fullerene can be determined by IR spectroscopy.

    7. Oxidative Addition

      Facile Oxidative Addition of Organic Halides to Heteroleptic and Homoleptic Pd0–N-Heterocyclic Carbene Complexes (pages 1750–1761)

      Jung-Hyun Lee, Hyeong-Tak Jeon, Yong-Joo Kim, Kyung-Eun Lee, Young Ok Jang and Soon W. Lee

      Version of Record online: 4 MAR 2011 | DOI: 10.1002/ejic.201001257

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      Facile oxidative additions of various organic halides as well as small alkyl halides such as dichloromethane and chloroform toward heteroleptic PMe3–NHC–Pd0 (NHC = N-heterocyclic carbene) complexes or homoleptic bis(NHC)–Pd0 complexes were examined.

    8. Thiaphosphirane

      Synthesis and Some Chemical Properties of a 1,2λ3σ3-Thiaphosphirane (pages 1762–1767)

      Kostiantyn V. Turcheniuk, Alexander B. Rozhenko and Igor V. Shevchenko

      Version of Record online: 2 MAR 2011 | DOI: 10.1002/ejic.201001192

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      A rare example of the addition of sulfur to a phosphaalkene double bond leading to a 1,2λ33-thiaphosphirane ring has been found. Hexafluoroacetone does not oxidize the three-valent phosphorus atom but adds to the P–S bond to form the previously unknown 1,4,2λ33-oxathiaphospholaneheterocyclic system.

    9. Amino AlcoholsAmino Alcohols

      From a Simple Pyrazole-Derived 1,2-Amino Alcohol to Mono- and Multinuclear Complexes by Tailoring Hydrogen Bond Patterns (pages 1768–1775)

      Christoph K. Seubert, Yu Sun, Yanhua Lan, Annie K. Powell and Werner R. Thiel

      Version of Record online: 23 FEB 2011 | DOI: 10.1002/ejic.201001231

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      The hydroxy group of 2-[(1,5-dimethyl)pyrazol-3-yl]propan-2-ol, coordinated to transition metal sites, allows the formation of hydrogen bonds in the periphery of the complexes.The hydroxy group of 2-[(1,5-dimethyl)pyrazol-3-yl]propan-2-ol, coordinated to transition metal sites, allows the formation of hydrogen bonds in the periphery of the complexes.

    10. Dye-Sensitized Solar Cells

      Performance of Dye-Sensitized Solar Cells Based on MWCNT/TiO2–xNx Nanocomposite Electrodes (pages 1776–1783)

      Wei Guo, Yihua Shen, Liqiong Wu, Yurong Gao and Tingli Ma

      Version of Record online: 4 MAR 2011 | DOI: 10.1002/ejic.201001241

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      To enhance electron transport and charge collection efficiency, fibrous-type MWCNT fibrils were introduced into TiO2–xNx and TiO2 photoelectrodes to fabricate dye-sensitized solar cells. The role played byMWCNTs was systemically investigated. This paper also discusses electron lifetime, electron transport, and charge collection efficiency in DSCs based on MWCNT/TiO2 and MWCNT/TiO2–xNx electrodes.

    11. Terpyridine–Thiol Complexes

      Efficient Synthetic Approaches To Access Ruthenium(II) Complexes with 2-(Trimethylsilyl)ethyl- or Acetyl-Protected Terpyridine–Thiols (pages 1784–1791)

      Hui-Min Wen, Dao-Bin Zhang, Li-Yi Zhang, Lin-Xi Shi and Zhong-Ning Chen

      Version of Record online: 10 MAR 2011 | DOI: 10.1002/ejic.201001249

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      A series of thiol-functionalized terpyridines with protective groups, such as acetyl (Ac), 2-(trimethylsilyl)ethyl (TMSE), and tert-butyl (tBu), together with the corresponding ruthenium(II) complexes were synthesized, and feasible synthetic approaches were thus established.

    12. Fluorous Copper Complexes

      Copper(I) Complexes of Bipyridine and Terpyridine with Fluorous Tails and the Formation of Crystalline Materials with Fluorous Layers (pages 1792–1796)

      Vedichi Madhu, Yael Diskin-Posner and Ronny Neumann

      Version of Record online: 23 FEB 2011 | DOI: 10.1002/ejic.201001296

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      Copper(I) complexes of bipyridine (Y-shaped trigonal planar) and terpyridine (tetrahedrally distorted square-planar) with fluorous tails showed crystal packing with segregation of the aromatic units and the fluorous tails. Layered structures that are tilted in two different dimensions as well as “herring bone” structures with accordion-like fluorous layers were observed.

    13. Aerobic Diol Oxidation

      Chemoselective Aerobic Diol Oxidation by Palladium(II)–Pyridine Catalysis (pages 1797–1805)

      Lorenzo Bettucci, Claudio Bianchini, Jonathan Filippi, Alessandro Lavacchi and Werner Oberhauser

      Version of Record online: 2 MAR 2011 | DOI: 10.1002/ejic.201001300

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      Neutral and cationic palladium(II) complexes with pyridine ligands were synthesized and employed as catalyst precursors for the aerobic K2CO3-assisted oxidation of unprotected diols to chemoselectivelygive hydroxy ketones. Within the series of catalyst precursors studied, the bis-cationic compound [Pd(4-EtPy)4](OTs)2 (Py = pyridine, OTs = p-toluenesulfonate) emerged as the most promising.

    14. Solar Cell Sensitizers

      Strategies for Optimizing the Performance of Cyclometalated Ruthenium Sensitizers for Dye-Sensitized Solar Cells (pages 1806–1814)

      Paolo G. Bomben, Kim D. Thériault and Curtis P. Berlinguette

      Version of Record online: 11 MAR 2011 | DOI: 10.1002/ejic.201001345

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      A series of tris-heteroleptic cyclometalated ruthenium sensitizers have been developed for dye-sensitized solar cell applications. Each metal complex contains two 2,2′-bipyridine ligands, one bearing anchoringgroups, and an anionic cyclometalating ligand. Cell performance is shown to be dominated by the ground-state oxidation potentials of the complexes.

    15. Platinum Complex Polymorphs

      A Polymorphic Platinum(II) Complex: Yellow, Red, and Green Polymorphs and X-ray Crystallography of [Pt(fdpb)Cl] [Hfdpb = 1,3-Bis(5-trifluoromethyl-2-pyridyl)benzene] (pages 1815–1823)

      Yuta Nishiuchi, Asuka Takayama, Takayoshi Suzuki and Kazuteru Shinozaki

      Version of Record online: 23 FEB 2011 | DOI: 10.1002/ejic.201001359

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      Polymorphs of a platinum(II) complex were prepared, and their crystal structures were clarified by X-ray crystallography. Mechanical grinding changed the polymorphs from the crystalline to the amorphous phase. Heating caused the transition between the amorphous and the crystal phase and the crystal–crystal transformations of the green form to the red from and of the red form to the yellow form.

    16. Chiral Palladacycles

      Cyclometallated Palladium Diphosphane Compounds Derived from the Chiral Ligand (S)-PhCH(Me)NMe2. Michael Addition Reactions to the Vinylidene Double Bond (pages 1824–1832)

      Roberto Mosteiro, Alberto Fernández, Digna Vázquez-García, Margarita López-Torres, Antonio Rodríguez-Castro, Nina Gómez-Blanco, José M. Vila and Jesús J. Fernández

      Version of Record online: 7 MAR 2011 | DOI: 10.1002/ejic.201000873

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      Chiral palladacycles were prepared from ligand 1. Those that involve the functionalized diphosphane vdpp may give complexes that bear more than one stereogenic center, which originate after the Michael addition to the vinylidene double bond.

    17. Precursors for Ni Thin Films

      Synthesis and Characterization of Nickel(II) Aminoalkoxides: Application to Molecular Precursors for MOCVD of Ni Thin Films (pages 1833–1839)

      Seung Ho Yoo, Hana Choi, Hyo-Suk Kim, Bo Keun Park, Sun Sook Lee, Ki-Seok An, Young Kuk Lee, Taek-Mo Chung and Chang Gyoun Kim

      Version of Record online: 1 MAR 2011 | DOI: 10.1002/ejic.201001132

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      New NiII aminoalkoxide precursors, Ni(dmamp)2 (1), Ni(deamp)2 (2), and Ni(emamp)2 (3), for preparing Ni thin films were synthesized and characterized. Thermal properties of 13 show high volatility. By MOCVD, 1 gave both hexagonal-phase(250 °C) and cubic-phase thin films (400 °C). A reaction pathway was proposed for 1 in which Ni is formed by γ-elimination and then reductive elimination.

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