European Journal of Inorganic Chemistry

Cover image for Vol. 2008 Issue 28

October 2008

Volume 2008, Issue 28

Pages 4315–4473

  1. Cover Picture

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

      Rational Assembly of High-Spin Polynuclear Magnetic Complexes into Coordination Networks: the Case of a [Mn4] Single-Molecule Magnet Building Block (pages 4325–4342)

      Olivier Roubeau and Rodolphe Clérac

      Version of Record online: 29 AUG 2008 | DOI: 10.1002/ejic.200800603

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      The different forms of a rhombic [Mn4]single-molecule magnet and their assembly into infinite coordination networks are reviewed as a case study of how the rational design of extended arrays of high-spin complexes may afford unprecedented, interesting magnetic properties. Potential synthetic strategies and outcomes are discussed.

  5. Short Communications

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

      The Binary Ph2PCl/GaCl3 System: A Room-Temperature Molten Medium for P–P Bond Formation (pages 4343–4347)

      Jan J. Weigand, Neil Burford and Andreas Decken

      Version of Record online: 2 SEP 2008 | DOI: 10.1002/ejic.200800733

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      An equimolar reaction mixture of Ph2PCl and GaCl3 at room temperature results in the formation of a melt. The melt provides a facile and reactive source of the Ph2P+ cation, as demonstrated by P–P bond insertion into (PhP)5 to give the [Ph4P6]2+ dication and reductive coupling with gallium metal to give the diadduct Cl3GaPPh2PPh2GaCl3.

    2. Olefin Isomerisation Mechanism

      The Detection of PHIP Effects Allows New Insights into the Mechanism of Olefin Isomerisation during Catalytic Hydrogenation (pages 4348–4351)

      Alessandra Viale, Daniela Santelia, Roberta Napolitano, Roberto Gobetto, Walter Dastrù and Silvio Aime

      Version of Record online: 22 AUG 2008 | DOI: 10.1002/ejic.200800356

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      The use of parahydrogen to observe PHIP (parahydrogen-induced polarisation) effects in the 1H NMR spectra of the products provides more insight into the mechanism of isomerisation of olefins formed by hydrogenation of alkynes in the presence of RhI catalysts.

  6. Full Papers

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

      Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands (pages 4353–4359)

      Ka-Wang Chan, Yiu-Keung Sau, Qian-Feng Zhang, Wai-Yeung Wong, Ian D. Williams and Wa-Hung Leung

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200800460

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      Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(C6H4tBu-2)] with R2Q2 in refluxing toluene afforded [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}]2(μ-QR)2 (RQ = pTolS, PhSe). Reaction of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(μ-Cl)2 with Na2(bdt) gave [Ir(dtbpy)(CH2CMe2Ph)(bdt)]2. Oxidation of [Ir(dtbpy)(CH2CMe2Ph)(bdt)]2 with silver triflate led to dimerization of the bdt2– ligand by formation of an S–S bond.

    2. C–H Bond Activation

      Mild Oxidative Addition of C–H Bonds to a Hydrido-Bridged Dinuclear Complex of Iridium(II) Induced by the Coordination of Heteroatomic Ligands (pages 4360–4368)

      Yoshinori Takahashi, Ken-ichi Fujita and Ryohei Yamaguchi

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200800469

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      Mild oxidative addition of C–H bonds took place by the reaction of a hydrido-bridged dinuclear iridium(II) complex, [Cp*Ir(μ-H)]2, with donor ligands such as phosphorus compounds and sulfoxides.The proximity of the two iridium centers combined with the characteristic electron configuration (IrII–IrII) of [Cp*Ir(μ-H)]2 provides unique reactivities for these systems based on cooperative effects.

    3. Gd–DTPA Derivatives

      An Assessment of the Potential Relationship between the Charge of Gd–DTPA Complexes and the Exchange Rate of the Water Coordinated to the Metal (pages 4369–4379)

      Sophie Laurent, Luce Vander Elst, François Botteman and Robert N. Muller

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800541

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      The residence time of coordinated water (τM), a parameter of paramount importance for relaxivity, is compared in a series of Gd–DTPA derivatives carrying different global charges. The importance of the charge in the first coordination sphere of the metal and in its vicinity is reported.

    4. Nanocomposites

      From Single-Molecule Precursors to Coupled Ag2S/TiO2 Nanocomposites (pages 4380–4386)

      Márcia C. Neves, Olinda C. Monteiro, Rolf Hempelmann, Artur M. S. Silva and Tito Trindade

      Version of Record online: 28 AUG 2008 | DOI: 10.1002/ejic.200800110

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      A single-source approach using mild temperatures leads to morphological well-defined and coupled TiO2/metal–sulfidenanocomposites. Ag2S nanostructures are observed as nano-islands at the surface of TiO2 (anatase) particles, which were used as substrates. The growth of the metal sulfide at the surface can be controlled.

    5. Luminescent Materials

      2-Thiopheneacetato-Based One-Dimensional Coordination Polymer of Tb3+: Enhancement of Terbium-Centered Luminescence in the Presence of Bidentate Nitrogen Donor Ligands (pages 4387–4394)

      Shyni Raphael, M. L. P. Reddy, Alan H. Cowley and Michael Findlater

      Version of Record online: 20 AUG 2008 | DOI: 10.1002/ejic.200800506

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      Three new complexes of Tb3+ with 2-thiopheneacetic acid have been synthesized and their photophysical properties investigated. The quantum yields of the ternary complexes were found to be significantly enhanced by the presence of the bidentate nitrogen donor ligands due to the effective energy transfer from the co-ligands (1,10-phenanthroline or bathophenanthroline).

    6. Pb Amino Acid Complexes

      The Added Value of Solid-State Pb NMR Spectroscopy to Understand the 3D Structures of Pb Amino Acid Complexes (pages 4395–4403)

      Laura Gasque, Michiel A. Verhoeven, Sylvain Bernès, Fabiola Barrios, Jaap G. Haasnoot and Jan Reedijk

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200800535

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      Single-crystal X-ray diffraction and solid-state 207Pb NMR spectroscopy experiments have been conducted on four lead amino acid complexes. The NMR spectroscopicexperiments show one, two, one, and four lead sites for the Hile, leu, Hasp, and Hval complexes, respectively, in agreement with the crystal structures.

    7. Cu II Catalysts for Oxidation

      Di-, Tetra-, and Polynuclear Copper(II) Complexes: Active Catalysts for Oxidation of Toluene and Benzene (pages 4404–4412)

      Partha Roy, Koushik Dhara, Mario Manassero and Pradyot Banerjee

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800556

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      A series of di-, tetra-, and polynuclear copper(II) complexes with N2O donor ligand has been synthesized, and it was found thatthey are active catalysts for the oxidation of toluene and benzene by using hydrogen peroxide as a catalyst.

    8. Chalcogenium Dinitramides

      Synthesis and Structures of Triorganochalcogenium (Te, Se, S) Dinitramides (pages 4413–4419)

      Thomas M. Klapötke, Burkhard Krumm and Matthias Scherr

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800565

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      The reactions of triorganochalcogenium halides with a dinitramide transfer reagent result in the first triorganochalcogenium dinitramides, which were characterized by NMR spectroscopy and vibrational data. The crystal structures for the phenyl salts [Ph3Te][N(NO2)2] and [Ph3Se][N(NO2)2] are reported.

    9. Carbene Complexes

      Template Synthesis of Platinum Complexes with Benzoxazolin-2-ylidene Ligands (pages 4420–4424)

      F. Ekkehardt Hahn, Daniel Klusmann and Tania Pape

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800592

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      Dicarbene complex 5 was obtained from the corresponding 2-(trimethylsiloxy)phenyl isocyanide complex by cleavage of the O–SiMe3 bonds and subsequent cyclization of the isocyanide ligands to N-heterocyclic carbene (NHC) ligands. The carbene ligands in 5 were found in an unusual coplanar arrangement enforced by the formation of an N2–HN2···N1 hydrogen bond.

    10. Organometallic Phosphonate Inhibitors

      Non-Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase (pages 4425–4432)

      Cornelis A. Kruithof, Harmen P. Dijkstra, Martin Lutz, Anthony L. Spek, Maarten R. Egmond, Robertus J. M. Klein Gebbink and Gerard van Koten

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800654

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      A straightforward protocol is described to place non-natural organometallic fragments into the active site of lipases, giving easy access to enzyme-organometallic hybrids. Thereby, the possibility for fine-tuning of the chemical environment (second coordination sphere) around a synthetic metal center inside a protein pocket for diagnostic and catalytic purposes is opened up.

    11. Hexacoordinate Si–S Complexes

      Synthesis and Structural Characterization of Novel Neutral Hexacoordinate Silicon(IV) Complexes with SiS2O2N2 Skeletons (pages 4433–4439)

      Stefan Metz, Christian Burschka and Reinhold Tacke

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200800657

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      Neutral hexacoordinate silicon(IV) complexes with Si–S bonds were synthesized, starting from Si(NCO)4, and were structurally characterized by single-crystal X-ray diffraction and solid-state and solution NMR spectroscopy.

    12. Proton Sponges

      The First Metal Complexes of the Proton Sponge 1,8-Bis(N,N,N′,N′-tetramethylguanidino)naphthalene: Syntheses and Properties (pages 4440–4447)

      Ute Wild, Olaf Hübner, Astrid Maronna, Markus Enders, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200800677

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      Pd and Pt complexes of the proton sponge 1,8-bis(N,N,N′,N′-tetramethylguanidino)naphthalene were synthesized which exhibit unusual structural details pointing to interesting chemical properties.

    13. Red-Emitting Ru Complexes

      One-Step Synthesis of 4,4′-Dicyano-2,2′-bipyridine and Its Bis(4,4′-di-tert-butyl-2,2′-bipyridine)ruthenium(II) Complex (pages 4448–4452)

      Sebastian Losse, Helmar Görls, Robert Groarke, Johannes G. Vos and Sven Rau

      Version of Record online: 26 AUG 2008 | DOI: 10.1002/ejic.200701304

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      This report describes a new route for the synthesis of 4,4′-dicyano-2,2′-bipyridine. With the developed synthetic route we are able to obtain the ligand in a fast, economical and effective one-step synthesis with a facile workup procedure. The ability of this bipyridine derivative to serve as a chelating ligand in a ruthenium(II) complex is investigated.

    14. Tetranuclear Copper(II) Clusters

      Adipato-Bridged Copper(II) Complexes (pages 4453–4461)

      Yue-Qing Zheng, De-Yi Cheng, Jian-Li Lin, Zhi-Feng Li and Xian-Wen Wang

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800309

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      Double-semi-paddle-wheel tetranuclear copper(II) clusters are bridged as secondary building units by adipato ligands into 2D (4,4) networks. Magnetic analyses suggest that the synsyn carboxylate bridgeswithin the semi-paddle-wheel unit mediate considerate antiferromagnetic interactions, whereas the monoatomic μ2-O bridges in the middle Cu2O2 rings transmit a small ferromagnetic coupling.

    15. Hydrogen Transfer Reactions

      Mechanistic Insights into Acetophenone Transfer Hydrogenation Catalyzed by Half-Sandwich Ruthenium(II) Complexes Containing 2-(Diphenylphosphanyl)aniline – A Combined Experimental and Theoretical Study (pages 4462–4473)

      Alessia Bacchi, Marcella Balordi, Roberto Cammi, Lisa Elviri, Corrado Pelizzi, Filippo Picchioni, Vincenzo Verdolino, Kees Goubitz, René Peschar and Paolo Pelagatti

      Version of Record online: 25 AUG 2008 | DOI: 10.1002/ejic.200800509

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      Complexes of the type {Ru[(κ2P,N)PNH2](p-cymene)Cl}Y [PNH2 = 2-(diphenyphosphanyl)aniline, Y = Cl, PF6, BF4, BPh4, and TfO] promote the reduction of acetophenone through Noyori's bifunctional mechanism, as evidenced by MS (ESI) and DFT calculations, and the inertness of the complex {Ru[(κ2P,N)PNMe2](p-cymene)Cl}Cl avoid of N–H functionalities.

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