European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 21

July 2013

Volume 2013, Issue 21

Pages 3568–3725

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. Further Masthead
    7. News
    8. Microreview
    9. Short Communications
    10. Full Papers
    1. You have free access to this content
      Analysis of the Hysteretic Behaviour of 3D Spin Crossover Compounds by Using an Ising-Like Model (Eur. J. Inorg. Chem. 21/2013)

      Daniel Chiruta, Jorge Linares, Yann Garcia, Pierre Richard Dahoo and Mihai Dimian

      Article first published online: 12 JUL 2013 | DOI: 10.1002/ejic.201390093

      Thumbnail image of graphical abstract

      The cover picture shows a thermally induced two-step spin conversion with hysteresis as reflected by the modelling of 3D spin-crossover compound [Fe(btr)3](ClO4)2, whose crystal structure is shown in the background. The importance and diversity of interactions and external factors, not only for material behaviour but also in nature, are suggested by the sphere on the right, which represents a spin-crossover molecule under pressure. This 3D object could be regarded as the eye of the scientist who modelled the emblematic modern art endless column by Constantin Brâncuşi, depicted on the left, which reflects the French-Romanian spirit that inspired this contribution. Details are discussed in the article by J. Linares, Y. Garcia et al. on p. 3601 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. Further Masthead
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    8. Microreview
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    1. You have free access to this content
      Analysis of the Hysteretic Behaviour of 3D Spin Crossover Compounds by Using an Ising-Like Model (page 3568)

      Daniel Chiruta, Jorge Linares, Yann Garcia, Pierre Richard Dahoo and Mihai Dimian

      Article first published online: 12 JUL 2013 | DOI: 10.1002/ejic.201300654

      Thumbnail image of graphical abstract

      The variety of spin-crossover behaviour exhibited by these relatively simple nanosystems has often reminded us about the inspiring beginning of Auguries of Innocence by William Blake: “To see a world in a grain of sand”....

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 3601 ff.

  3. Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 21/2013 (page 3570)

      Article first published online: 12 JUL 2013 | DOI: 10.1002/ejic.201390094

  4. Graphical Abstract

    1. Top of page
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    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. Further Masthead
    7. News
    8. Microreview
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  5. Further Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 21/2013 (page 3577)

      Article first published online: 12 JUL 2013 | DOI: 10.1002/ejic.201390096

  6. News

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  7. Microreview

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    1. Paint Drying

      The Quest for Cobalt-Free Alkyd Paint Driers (pages 3581–3591)

      Johannes W. de Boer, Philana V. Wesenhagen, Erica C. M. Wenker, Karin Maaijen, Franjo Gol, Hugh Gibbs and Ronald Hage

      Article first published online: 17 JUN 2013 | DOI: 10.1002/ejic.201300205

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      Paints containing alkyd resins need catalysts for oxidative curing. Because of the probable reclassification of the widely used cobalt carboxylates as carcinogens there is interest in alternative alkyd paint drying catalysts. Various manganese and iron paint driers with polydentate ligands have recently been reported; a particular iron-based catalyst shows good paint drying activity at low dosage.

  8. Short Communications

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    1. Uranyl Hybrids

      A Uranyl Hybrid Compound Designed from Urea-Bearing Dipropionic Acid (pages 3592–3595)

      Yu-Bo Shu, Cong Xu and Wei-Sheng Liu

      Article first published online: 17 JUN 2013 | DOI: 10.1002/ejic.201300555

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      A uranyl hybrid compound with urea-bearing dipropionic acid as a well-designed ligand is prepared. The urea group plays a role in coordination and in hydrogen-bonding interactions. The uranyl ion can be selectively complexed and precipitated by this urea-bearing ligand from alkaline spring water in the presence of competing metal ions.

    2. Artificial Metalloenzymes

      Structural Basis for Enantioselectivity in the Transfer Hydrogenation of a Ketone Catalyzed by an Artificial Metalloenzyme (pages 3596–3600)

      Mickaël V. Cherrier, Sylvain Engilberge, Patricia Amara, Alice Chevalley, Michèle Salmain and Juan C. Fontecilla-Camps

      Article first published online: 17 JUN 2013 | DOI: 10.1002/ejic.201300592

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      A metalloenzyme consisting of a Rh-based catalytic head and a fatty acid derived tail bound to β-lactoglobulin catalyzes the asymmetric transfer hydrogenation of a ketone with an enantiomeric excess (ee). Calculations based on the crystal structure reported here show that the complex head can adopt discrete orientations, which may explain the ee.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. Further Masthead
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    8. Microreview
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    10. Full Papers
    1. 3D Spin-Crossover Systems

      Analysis of the Hysteretic Behaviour of 3D Spin Crossover Compounds by Using an Ising-Like Model (pages 3601–3608)

      Daniel Chiruta, Jorge Linares, Yann Garcia, Pierre Richard Dahoo and Mihai Dimian

      Article first published online: 24 MAY 2013 | DOI: 10.1002/ejic.201300412

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      The effects of size, pressure and interactions on 3D spin crossover systems within the framework of an Ising-like model are discussed.

    2. Ruthenium Gallylene Complexes

      N-Heterocyclic Gallylene Supported Organoruthenium Derivatives – Synthesis, Structure, and C–H Bond Cleavage (pages 3609–3615)

      Adinarayana Doddi, Ganesan Prabusankar, Christian Gemel, Manuela Winter and Roland A. Fischer

      Article first published online: 12 JUN 2013 | DOI: 10.1002/ejic.201300257

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      The reactions of low-valent six-membered β-diketiminate–gallium(I), Ga(DDP) [DPP = HC(CMeNC6H3–2,6-iPr2)2], with [Cp*Ru(μ-H)2]2 (Cp* = pentamethylcyclopentadiene) and [(η6-p-cymene)RuCl2]2 lead to [(Cp*Ru)2(μ-H)2{μ-Ga(DDP)}] (3) and[(η6-p-cymene)Ru(DDP)Ga(µ-Cl){Ga(Cl)(N{C6H3iPr2})22-CH2C4H5)}] (6), respectively. Compound 6 is a cycloruthenated product formed by an intramolecular C–H bond cleavage reaction.

    3. Zinc-Rich Ruthenium Complexes

      From AlCp*- and GaCp*-Ligated Ruthenium Hydrides to Zinc-Rich Heterometallic Complexes (pages 3616–3622)

      Mariusz Molon, Christian Gemel and Roland A. Fischer

      Article first published online: 12 JUN 2013 | DOI: 10.1002/ejic.201300317

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      Three heteroleptic ruthenium hydride complexes [Ru(PCy3)(ZnCp*)2(ZnMe)6] (Cp* = pentamethylcyclopentadienyl), [Ru(PPh3)2(ZnCp*)2(ZnMe)2(H)2], and [Ru(PCy3)2(ZnMe)22-H)4] have been synthesized and characterized by NMR and IR spectroscopy, MS analysis, single-crystal X-ray diffraction, and elemental analysis. The influence of the phosphane ligand on the product formed is discussed.

    4. Luminescent Cu(I) Clusters

      Luminescence in Functionalized Copper Thiolate Clusters – Synthesis and Structural Effects (pages 3623–3631)

      Robert Langer, Munendra Yadav, Bastian Weinert, Dieter Fenske and Olaf Fuhr

      Article first published online: 7 JUN 2013 | DOI: 10.1002/ejic.201300155

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      A series of polynuclear copper(I) thiolate clusters were synthesized and characterized by single-crystal X-ray diffraction. All of them show significant luminescence in the solid state. Intensity and wavelength of the emitted light strongly depend on the molecular structures of the compounds.

    5. Supramolecular Assemblies

      Coordination of Pentacyclohexanocucurbit[5]uril with Alkali Metal Ions and Supramolecular Self-Assembly in the Absence and Presence of Inorganic Anions (pages 3632–3640)

      Jing-Xu Hu, Ying-Feng Hu, Xin Xiao, Yun-Qian Zhang, Zhu Tao, Sai-Feng Xue, Jing-Xin Liu and Qian-Jiang Zhu

      Article first published online: 23 MAY 2013 | DOI: 10.1002/ejic.201300158

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      To find new coordination and supramolecular assemblies, the structure inducer anions [ZnCl4]2– and [CdCl4]2– were introduced into alkali metal/pentacyclohexanocucurbit[5]uril (alkali-PCyHQ[5]) systems. These anions did not show the typical “honeycomb effect”, but played the role of linkers in the construction of alkali-PCyHQ[5]-based supramolecular chains.

    6. Dissociative–Associative Transition

      A Kinetic Study on the Substitution for Acetonitrile at the trans-to-μ-Oxido Sites in a Bis(μ-acetato)(μ-oxido)diruthenium(III) Dipositive Complex: Dissociative–Associative Transition of the Activation Mode for the Substitution of Pyridine Derivatives (pages 3641–3650)

      Yohei Ido, Kiyoshi Sakaguchi, Minako Tasei, Suguru Minami, Hiroki Sawamoto, Takashi Fujihara and Akira Nagasawa

      Article first published online: 12 JUN 2013 | DOI: 10.1002/ejic.201300173

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      The CH3CN/CD3CN exchange at the trans-to-oxido sites in the bis(μ-acetato)(μ-oxido)diruthenium(III) complex cation takes place in CD3CN through a dissociative or dissociative–interchange mechanism. The activation mode of the substitution of pyridine derivatives (Rpy) for coordinated CH3CN in CH3CN shifts from a dissociative interchange to an associative interchange, depending on the electron-donating ability of Rpy.

    7. Cytotoxic Metal Complexes

      Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives – Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies (pages 3651–3658)

      Telma F. S. Silva, Piotr Smoleński, Luísa M. D. R. S. Martins, M. Fátima C. Guedes da Silva, Alexandra R. Fernandes, Daniel Luis, Ana Silva, Susana Santos, Pedro M. Borralho, Cecília M. P. Rodrigues and Armando J. L. Pombeiro

      Article first published online: 5 JUN 2013 | DOI: 10.1002/ejic.201300197

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      Cobalt and zinc compounds with 1,3,5-triaza-7-phosphaadamantane (PTA) derivatives and/or 1,10-phenanthroline-5,6-dione (DION) have been synthesized, characterized and screened against several human tumour cell lines. The DION-containing compounds exhibit specificity for the human fibroblast.

    8. Methane Oxidation

      Cobalt-Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen (pages 3659–3663)

      Thomas Strassner, Sebastian Ahrens, Michael Muehlhofer, Dominik Munz and Alexander Zeller

      Article first published online: 2 JUL 2013 | DOI: 10.1002/ejic.201300213

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      The selective cobalt-catalyzed oxidation of methane to methyl trifluoroacetate by dioxygen has been studied in detail. The catalytic activities of different cobalt precatalysts were investigated, with cobalt(II) nitrate proving to be the most efficient. The effects of solvent, reaction time, temperature, and catalyst loading have been studied.

    9. Olefin Epoxidation

      Dioxidomolybdenum(VI) Complexes Containing Ligands with the Bipyrrolidine Backbone as Efficient Catalysts for Olefin Epoxidation (pages 3664–3670)

      Ramasamy Mayilmurugan, Pedro Traar, Jörg A. Schachner, Manuel Volpe and Nadia C. Mösch-Zanetti

      Article first published online: 6 JUN 2013 | DOI: 10.1002/ejic.201300258

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      The cis-α isomers of dioxidomolybdenum complexes with a chiral backbone exhibit higher catalytic epoxidation activity than the related cis-β complexes.

    10. Guanidines

      Redox Reactions Between Guanidine Electron Donors and Silver Dicyanamide: Synthesis of C,N Material Precursors and Coordination Polymers (pages 3671–3679)

      Benjamin Eberle, Hendrik Herrmann, Elisabeth Kaifer and Hans-Jörg Himmel

      Article first published online: 7 JUN 2013 | DOI: 10.1002/ejic.201300267

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      Competition and interplay between redox and coordination reactions in mixtures of redox-active guanidines and silver dicyanamide lead to new precursors of C,N materials and coordination polymers.

    11. Selenium Chemistry

      Modeling the Glutathione Peroxidase-Like Activity of a Cyclic Seleninate by DFT and Solvent-Assisted Proton Exchange (pages 3680–3688)

      Craig A. Bayse and Kristine N. Ortwine

      Article first published online: 12 JUN 2013 | DOI: 10.1002/ejic.201300279

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      Despite their toxicity, organoselenium compounds are important for their potential application in disease prevention. The antioxidant activity of a small organoselenium compound is investigated by DFT and explicit solvation models that facilitate proton exchange.

    12. Coordination Chemistry

      Di- and Trinuclear Zinc and Cobalt Complexes and Their Reactivity towards Dioxygen (pages 3689–3698)

      Inke Siewert, Malte Sietzen, Sebastian Dechert and Serhiy Demeshko

      Article first published online: 17 JUN 2013 | DOI: 10.1002/ejic.201300287

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      Herein, we report the synthesis of a new ligand with two adjacent pyrazole–pyridine units and its dinuclear cobalt(II) and zinc complexes as well as a trinuclear zinc complex. The reactivity of these complexes with dioxygen is investigated.

    13. Ring-Opening Polymerization

      Neutral and Cationic N-Heterocyclic Carbene Zinc Adducts and the BnOH/Zn(C6F5)2 Binary Mixture – Characterization and Use in the Ring-Opening Polymerization of β-Butyrolactone, Lactide, and Trimethylene Carbonate (pages 3699–3709)

      Gilles Schnee, Christophe Fliedel, Teresa Avilés and Samuel Dagorne

      Article first published online: 4 JUN 2013 | DOI: 10.1002/ejic.201300292

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      A variety of new N-heterocyclic carbene (NHC) organozinc adducts are synthesized and characterized, among which are the first examples of NHC-stabilized zinc organocations. The NHC–Zn(C6F5)2 adducts and BnOH/Zn(C6F5)2 are effective ring-opening polymerization (ROP) initiators of cyclic esters/carbonates under mild conditions.

    14. Iron-Catalyzed OH Substitution

      Iron-Catalyzed Ferrocenylmethanol OH Substitution by S, N, P, and C Nucleophiles (pages 3710–3718)

      Rita Mazzoni, Mauro Salmi, Stefano Zacchini and Valerio Zanotti

      Article first published online: 19 JUN 2013 | DOI: 10.1002/ejic.201300239

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      Direct substitution of the OH group in ferrocenylmethanol by S, N, P, and C nucleophiles containing an active hydrogen atom (thiols, aromatic amines, diphenylphosphane, furan, pyrrole, indole) can be accomplished by use of the iron catalyst [Fe(CO)2(Cp)][OTf] (Cp = cyclopentadienyl, OTf = SO3CF3).

    15. Mesoporous Structures

      Three-Dimensional Network Mesoporous Nanostructured α-Manganese Dioxide with High Supercapacitive Performance: Facile, Environmental and Large-Scale Synthesis (pages 3719–3725)

      Li-Li Yu, Jun-Jie Zhu and Jing-Tai Zhao

      Article first published online: 10 JUN 2013 | DOI: 10.1002/ejic.201300265

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      Three-dimensional network mesoporous nanostructured α-MnO2 with a high specific surface area and narrow pore size distribution has been fabricated in high yields without a template at room temperature.

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