European Journal of Inorganic Chemistry

Cover image for Vol. 2012 Issue 25

September 2012

Volume 2012, Issue 25

Pages 3943–4081

  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
      An Insight into the Reversible Dissociation and Chemical Reactivity of a Sterically Encumbered Diphosphane (Eur. J. Inorg. Chem. 25/2012)

      Daniela Förster, Herbert Dilger, Fabian Ehret, Martin Nieger and Dietrich Gudat

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/ejic.201290077

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      The cover picture shows the amazingly diverse reactivity of a sterically encumbered diphosphane towards alkynes. The steric hindrance facilitates homolytic cleavage of the P–P bond: the experimentally determined dissociation energy of 79 kJ mol–1 is substantially lower than the gas-phase dissociation energies of small diphosphanes, and a substantial amount of the diphosphane dissociates even at ambient temperature into phosphanyl radicals (the double horse, which is reminiscent of the arms of the city of Stuttgart, is meant as an allegory for this process). Chemical reactions of this equilibrium mixture may either follow a radical mechanism as in the trans addition of two radicals to the triple bond of an unactivated alkyne. Alternatively, a substrate can bypass the radicals to react with the intact diphosphane, as in the unexpected ring metathesis reaction with an electron-poor alkyne. Details are discussed in the article by D. Gudat et al. on p. 3989 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
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  4. Microreview

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    5. Microreview
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    1. N-Heterocyclic Carbenes

      Studies of the Electronic Properties of N-Heterocyclic Carbene Ligands in the Context of Homogeneous Catalysis and Bioorganometallic Chemistry (pages 3955–3969)

      Anuj Kumar and Prasenjit Ghosh

      Version of Record online: 8 AUG 2012 | DOI: 10.1002/ejic.201200622

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      Towards understanding the key attributes that define the influence of N-heterocyclic carbenes on catalysis, our efforts, involving combined experimental and computational approaches, in looking into a variety of catalytic and biomedical applications of these compounds are summarized.

  5. Short Communications

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    1. Iron Oxohalide Nanotubes

      You have full text access to this OnlineOpen article
      Crystalline Iron Oxohalide Nanotube Pea Pods (pages 3971–3974)

      Iwan Zimmermann, Mats Johnsson and Sven Lidin

      Version of Record online: 30 JUL 2012 | DOI: 10.1002/ejic.201200205

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      Isostructural compounds Fe7Sb3(PO4)3O6Cl3 and Fe7Sb3(PO4)3O6Br3 are the first iron phosphates containing SbIII. Tubular Fe7(PO4)3O6X3 units (X = Cl, Br) are linked by SbO4 groups to build up a 3D framework. The Fe atoms are arranged to resemble an armchair-type (3,3) nanotube.

    2. Iridium Photosensitizers

      Cationic Iridium Complexes Coordinated with Coumarin Dyes – Sensitizers for Visible-Light-Driven Hydrogen Generation (pages 3975–3979)

      Shin-ya Takizawa, César Pérez-Bolívar, Pavel Anzenbacher Jr. and Shigeru Murata

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/ejic.201200474

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      Cationic iridium(III) complexes with Coumarin 6 ligands were prepared and used as sensitizers for visible-light-driven hydrogen generation. Intense absorption in the visible region was observed, and high turnover numbers in hydrogen generation were achieved.

      Corrected by:

      Correction: Cationic Iridium Complexes Coordinated with Coumarin Dyes – Sensitizers for Visible-Light-Driven Hydrogen Generation

      Vol. 2013, Issue 19, 3439, Version of Record online: 3 JUN 2013

    3. Microscopic Multistability

      Microscopic Origin for Multistability in a Photomagnetic CoFe Prussian Blue Analogue (pages 3980–3983)

      Julien Lejeune, Jean-Daniel Cafun, Giulia Fornasieri, Jean-Blaise Brubach, Gaëlle Creff, Pascale Roy and Anne Bleuzen

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/ejic.201200746

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      Microscopic investigation of the photoinduced and thermally populated CoIIFeIII states of the Na2Co4[Fe(CN)6]3.3·14H2O Prussian blue analogue revealed different coordination spheres for the sodium cation and evidence of a new kind of multistability.

    4. A Near-IR Light Switch

      Shining a New Light on an Old Game – An OsII-Based Near-IR Light Switch (pages 3984–3988)

      Emanuela Trovato, Maria Letizia Di Pietro and Fausto Puntoriero

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/ejic.201200787

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      The first example of an [Os(tpy)2]-like species able to intercalate into DNA, a new OsII complex, was fully characterized. It exhibits an absorption spectrum that extends to 800 nm and is able to behave as a real OFF-ON near-IR DNA light switch (see picture).

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. P–P Bond Reactivity

      An Insight into the Reversible Dissociation and Chemical Reactivity of a Sterically Encumbered Diphosphane (pages 3989–3994)

      Daniela Förster, Herbert Dilger, Fabian Ehret, Martin Nieger and Dietrich Gudat

      Version of Record online: 6 JUL 2012 | DOI: 10.1002/ejic.201200633

      Thumbnail image of graphical abstract

      The tendency of sterically encumbered diphosphanes to dissociate at room temperature into phosphanyl radicals is explained by a low P–P bond enthalpy of 79 kJ mol–1. Still, reactions with alkynes do not necessarily proceed as radical additions to the triple bond but may proceed by direct attack of the diphosphane at the alkyne, yielding unexpected ring metathesis products with intact P–P bonds.

    2. Weak Noncovalent Interactions

      Complexes of Zinc(II) with N-Imidazolyl- and N-Pyrazolylpyrimidine Donor Ligands: Synthesis, Crystal Structures, and Theoretical Study (pages 3995–4003)

      Pablo Cañellas, Marta Torres, Antonio Bauzá, María M. Cánaves, Kika Sánchez, María I. Cabra, Angel García-Raso, Juan J. Fiol, Pere M. Deyà, Elies Molins, Ignasi Mata and Antonio Frontera

      Version of Record online: 25 JUL 2012 | DOI: 10.1002/ejic.201200379

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      A combined experimental and theoretical study of ZnII complexes with imidazolyl- and pyrazolylpyrimidine ligands is reported. Three new complexes were characterized by means of X-ray crystallography, and the relevant noncovalent interactions observed in the solid state were analyzed by using high-level ab initio calculations.

    3. Coordination Compounds

      Spectroscopy and Photophysics in Cyclometalated RuII–Bis(bipyridyl) Complexes (pages 4004–4011)

      Maria L. Muro-Small, James E. Yarnell, Catherine E. McCusker and Felix N. Castellano

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/ejic.201200460

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      Cyclometalated RuII coordination compounds of the general formula [Ru(bpy)2(C∧N)]PF6 {C∧N = 2-phenylpyridine (1), 2-(2,4-difluorophenyl)pyridine (2), 2-(4-methoxyphenyl)-5-methylpyridine (3), benzo[h]quinoline (4); bpy = 2,2′-bipyridine} have been synthesized, structurally and electrochemically characterized, and examined with spectroscopic techniques including ultrafast transient absorption.

    4. Transition-Metal Complexes

      2,3,4,5-Tetraphenylbiphenyl-Containing CuI/ReI Complexes: Synthesis, Property Analysis and Theoretical Studies (pages 4012–4019)

      Quan Xiang, Xin Sun, Guoyu Zhu, Haiying Sun, Yuchun Wan, Zhenjun Si and Qian Duan

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/ejic.201200276

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      We have used the diimine Ph6PyMz to synthesize the two transition-metal complexes [Cu(Ph6PyMz)(DPEphos)]BF4 and [RePh6PyMz(CO)3Br], which mainly gave 3LLCT emission in CH2Cl2 solution and pure 3MLCT emission in the solid state. This different photophysical behavior has mainly been attributed to the higher freedom of Ph6PyMz.

    5. Cryptate Complexes

      Cryptate Complexes with the Potential for CO2 Activation: Quantum Chemical Predictions and Synthetic Efforts (pages 4020–4028)

      Alexander Fuchs, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel

      Version of Record online: 1 AUG 2012 | DOI: 10.1002/ejic.201200072

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      Quantum chemical calculations demonstrate the potential of cryptate complexes for CO2 activation. Experiments on the way to an experimental realization and their difficulties are discussed.

    6. Coordination Polymers

      Synthesis, Structures, and Magnetic Properties of Three 3D Coordination Polymers Based on M4O4 Cubanes (M = MnII, FeII, CoII) (pages 4029–4035)

      Chong-Bin Tian, Hua-Bin Zhang, Yan Peng, Yun-En Xie, Ping Lin, Zhi-Hua Li and Shao-Wu Du

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/ejic.201200353

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      Three new isostructural coordination polymers constructed by M4O4 cubane cores (M = MnII, FeII, CoII) and nic (Hnic = nicotinic acid) bridges have been synthesized and characterized. The manganese compound shows antiferromagnetic coupling between adjacent MnII ions in the cubane, whereas the iron and cobalt compounds exhibit antiferromagnetic and ferromagnetic interactions within the cubanes.

    7. (Thiosemicarbazone)metal Complexes

      Complex-Formation Ability of Salicylaldehyde Thiosemicarbazone towards ZnII, CuII, FeII, FeIII and GaIII Ions (pages 4036–4047)

      Éva A. Enyedy, Éva Zsigó, Nóra V. Nagy, Christian R. Kowol, Alexander Roller, Bernhard K. Keppler and Tamás Kiss

      Version of Record online: 23 JUL 2012 | DOI: 10.1002/ejic.201200360

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      The stability and stoichiometry of salicylaldehyde thiosemicarbazone complexes formed with various metal ions have been studied by means of pH potentiometry in partially aqueous solution combined with UV/Vis, EPR, 1H NMR spectroscopy and fluorimetry. Speciations are compared to those of analogous α(N)-pyridyl thiosemicarbazones.

    8. Organometallic Compounds

      Luminescent AuI–CuI Triphosphane Clusters That Contain Extended Linear Arylacetylenes (pages 4048–4056)

      Julia R. Shakirova, Elena V. Grachova, Anna A. Melekhova, Dmitrii V. Krupenya, Vladislav V. Gurzhiy, Antti J. Karttunen, Igor O. Koshevoy, Alexei S. Melnikov and Sergey P. Tunik

      Version of Record online: 23 JUL 2012 | DOI: 10.1002/ejic.201200362

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      A series of polynuclear AuI–CuI complexes based on triphosphane and polyaromatic alkynyl ligands have been synthesized. All compounds obtained display dual singlet–triplet emission that originates from metal-perturbed intraligand and “intracore” transitions with a weak contribution from the gold centers in the latter case. Photophysical data were verified by quantum chemical calculations.

    9. Bis-Ylide Ligands

      Bis-Ylide Ligands from Acyclic Proximal Diphosphonium Precursors (pages 4057–4064)

      Carine Maaliki, Mohammed Abdalilah, Cécile Barthes, Carine Duhayon, Yves Canac and Remi Chauvin

      Version of Record online: 24 JUL 2012 | DOI: 10.1002/ejic.201200407

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      Although disubstituted o-phenylene-diphosphonium bis-ylides cannot be generated by double deprotonation, a m-phenylene isomer could and was used as a chelating electron-rich C2 ligand in a rhodium(I) complex.

    10. Tuning Luminescence

      Tuning the Electronics of Phosphorescent, Amide-Functionalized, Cyclometalated IrIII Complexes: Syntheses, Structures, Spectroscopy and Theoretical Studies (pages 4065–4075)

      Jack D. Routledge, Andrew J. Hallett, James A. Platts, Peter N. Horton, Simon J. Coles and Simon J. A. Pope

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/ejic.201200647

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      The synthesis and characterization of a series of cationic cyclometalated IrIII complexes is described. The complexes are adorned with amide substituents of varied electronic character. The resultant influence of these groups upon the photophysical properties of the complexes are discussed in detail through experimental and theoretical approaches.

    11. Octadecahedral Nanoparticles

      Preparation and Properties of Octadecahedral α-Fe2O3 Nanoparticles Enclosed by {104} and {112} Facets (pages 4076–4081)

      Zhong Liu, Baoliang Lv, Dong Wu, Yuhan Sun and Yao Xu

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/ejic.201200140

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      Octadecahedral α-Fe2O3 nanoparticles with exposed {112} and {104} facets have been hydrothermally synthesized in the presence of formamide. The amount of {112} facets sequentially increases with a decrease in the amount of {104} facets in the presence of formamide, and the evolution of these morphologies gives rise to different coercivities and sensing capabilities toward H2O2.

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