European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 22

August 2014

Volume 2014, Issue 22

Pages 3442–3618

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. You have free access to this content
      Detailed Geometric and Electronic Structures of a One-Electron-Oxidized Ni Salophen Complex and Its Amido Derivatives (Eur. J. Inorg. Chem. 22/2014)

      Laureline Lecarme, Linus Chiang, Christian Philouze, Olivier Jarjayes, Tim Storr and Fabrice Thomas

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201490106

      Thumbnail image of graphical abstract

      The cover picture shows the correlation between the low-energy near-infrared absorption spectrum and the spin density in three radical complexes. The crystal structure of one is shown at the bottom right. Mountains that surround the cities of Grenoble and Vancouver fit nicely into the background of the near-infrared curves. Details are discussed in the article by T. Storr, F. Thomas et al. on p. 3479 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. Graphical Abstract
    5. News
    6. Masthead
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. You have free access to this content
      Detailed Geometric and Electronic Structures of a One-Electron-Oxidized Ni Salophen Complex and Its Amido Derivatives (page 3442)

      Laureline Lecarme, Linus Chiang, Christian Philouze, Olivier Jarjayes, Tim Storr and Fabrice Thomas

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402643

      Thumbnail image of graphical abstract

      The biggest surprise in this work was the non-innocence of the aromatic bridge in mediating the electronic communication between the phenolate and phenoxyl rings...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 3479 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Further Masthead
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    1. Graphical Abstract: Eur. J. Inorg. Chem. 22/2014 (pages 3444–3449)

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201490107

  4. News

    1. Top of page
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    3. Cover Profile
    4. Graphical Abstract
    5. News
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  5. Masthead

    1. Top of page
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    1. Masthead: Eur. J. Inorg. Chem. 22/2014 (page 3454)

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201490109

  6. Further Masthead

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    5. News
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    1. Masthead: Eur. J. Inorg. Chem. 22/2014 (page 3455)

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201490110

  7. Short Communications

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. Isomerization

      Reductive Behavior of [Fe2(CO)42-dmpe){μ-(SCH2)2NBn}]: Effect of Symmetrization on the Rotated Conformation in FeI-FeI Models of [2Fe]H Subsite of [Fe-Fe]­H2ases (pages 3456–3461)

      Luca De Gioia, Catherine Elleouet, Sabrina Munery, François Y. Pétillon, Philippe Schollhammer, Jean Talarmin and Giuseppe Zampella

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402335

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      Electrosynthesis, through an electron-transfer-catalyzed process, and structural characterization of the symmetrical complex [Fe2(CO)4(μ-dmpe){μ-(SCH2)2NBn}] [dmpe = 1,2-bis(dimethylphosphino)ethane] afford straight experimental evidence that desymmetrization is required to promote an inverted pyramidal conformation in this class of model compounds of the [2Fe]H subsite of [Fe-Fe]H2ases.

    2. Click Chemistry

      A Luminescent Ruthenium Azide Complex as a Substrate for Copper-Catalyzed Click Reactions (pages 3462–3466)

      Anne Kroll, Katharina Monczak, Dieter Sorsche and Sven Rau

      Article first published online: 3 JUL 2014 | DOI: 10.1002/ejic.201402395

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      A new azide-functionalized 2,2′-bipyridine and its polypyridyl–ruthenium(II) complex are both suitable for click reactions. The substitution has a minor effect on the photophysical properties of the complex. Hence, the presented azide complex is a promising building block for the straightforward synthesis of a variety of photoactive click derivatives.

    3. Borate–Phosphates

      The Effect of the Ratio of [M/(B+P)] on the Configuration of Anionic Groups: Synthesis of the Borate–Phosphate LiPb4(BO3)(PO4)2 (pages 3467–3473)

      Shengshi Huang, Hongwei Yu, Jian Han, Shilie Pan, Qun Jing, Ying Wang, Lingyun Dong, Hongping Wu, Zhihua Yang and Xian Wang

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402389

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      Statistical analysis and experiments results show that regulating the [M/(B+P)] ratio is an effective strategy to synthesize borate–phosphates. Guided by this idea, the first example in the Li2O–PbO–B2O3–P2O5 system, LiPb4(BO3)(PO4)2, is synthesized. More interesting, it possesses a 3D structure with a corrugated 2D layer of [B2Pb8O18] that is further connected by a [LiP2O8] chain.

    4. Metalloligands

      Close Correlation between Metal Oxidation States and Molecular Structures in a Cobalt–Gold Multinuclear Coordination System with Mixed D-Penicillaminate and Tripodal Triphosphine (pages 3474–3478)

      Yuji Hashimoto, Nobuto Yoshinari, Natsuko Matsushita and Takumi Konno

      Article first published online: 7 JUL 2014 | DOI: 10.1002/ejic.201402531

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      [Au3(tdme)(D-pen)3]3–, which possesses D-penicillaminate (D-pen) arms connected by a 1,1,1-tris[(diphenylphosphino)methyl]ethane (tdme) backbone, is designed and synthesized. This metalloligand adopts two coordination modes (bridging/chelating) coupled with two oxidation states of the binding cobalt ions (+II/+III), which leads to the formation of air-stable CoII3AuI6 and CoIIIAuI3.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Further Masthead
    8. Short Communications
    9. Full Papers
    1. Radical Complexes

      Detailed Geometric and Electronic Structures of a One-Electron-Oxidized Ni Salophen Complex and Its Amido Derivatives (pages 3479–3487)

      Laureline Lecarme, Linus Chiang, Christian Philouze, Olivier Jarjayes, Tim Storr and Fabrice Thomas

      Article first published online: 5 JUN 2014 | DOI: 10.1002/ejic.201402265

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      The radical complexes depicted feature a near-IR (NIR) transition. Time-dependent DFT (TD-DFT) calculations reveal that its origin differs and strongly depends on the linker between the central ring and the phenol rings. Depending on the linker, it is an intervalence charge transfer (IVCT) transition, an intraligand charge transfer (LLCT), or acquires ligand-to-metal charge transfer (LMCT) character.

    2. Coordination Polymers

      Structures and Magnetic Properties of Manganese(II) Compounds Based on Chains with Simultaneous Carboxylate and Pseudohalide Bridges (pages 3488–3498)

      Guang-Mei Zhuang, Xiu-Bing Li, Yan-Qing Wen, Chun-Yan Tian and En-Qing Gao

      Article first published online: 25 JUN 2014 | DOI: 10.1002/ejic.201402287

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      Various zwitterionic carboxylate ligands lead to 1D, 2D and 3D MnII coordination polymers based on distinct chains with mixed carboxylate and pseudo-halide (azide or cyanate) bridges. Magneto-structural correlations are discussed.

    3. Dinitrosyliron Complexes

      New Members of a Class of Monomeric {Fe(NO)2}10 Dinitrosyliron Complexes and a Dimeric {Fe(NO)2}10–{Fe(NO)2}10 Dinitrosyliron Complex (pages 3499–3509)

      Feng-Chun Lo, Yi-Chieh Ho, Po-Ya Chang, Gene-Hsiang Lee, Ting-Shen Kuo, Jeng-Lung Chen and Chien-Hong Chen

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402370

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      The countercation functions to modulate the formation of monomeric {Fe(NO)2}10 dinitrosyliron complex (DNIC) 4 or dimeric {Fe(NO)2}10–{Fe(NO)2}10 DNIC 5, which is demonstrated upon reduction of {Fe(NO)2}9 DNICs [cation][(NO)2Fe(SC6H4-o-NH2)2] (6) {cation = K-18-crown-6-ether (6a), [PPh4] (6b)}.

    4. Heterometallic Complexes

      Trinuclear Early/Late-Transition-Metal Thiolate Complexes (pages 3510–3520)

      Andreas Eichhöfer, Vasyl Andrushko, Tilmann Bodenstein and Karin Fink

      Article first published online: 1 JUL 2014 | DOI: 10.1002/ejic.201402069

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      The paper presents the synthesis, structural characterisation, magnetic and optical properties, along with an analysis by quantum chemical calculations of a heterometallic vanadium(II)/cobalt(II) as well as a vanadium(II)/nickel(II) thiolato complex.

    5. Digallium Compounds

      Treatment of the Digallium Compound R2Ga–GaR2 [R = CH(SiMe3)2] with Functionalized Dicarboxylic Acids: Macrocycles, Hydrogen Bonding, and Sulfur–Sulfur Closed-Shell Interactions (pages 3521–3526)

      Werner Uhl, Christina Stefaniak, Alexander Hepp and Jutta Kösters

      Article first published online: 26 JUN 2014 | DOI: 10.1002/ejic.201402172

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      Ga–Ga bonds act as effective templates for the generation of macrocyclic compounds with dicarboxylato spacer ligands in the bridging positions. Hydrogen bonds or sulfur–sulfur closed-shell interactions were observed with functionalized amino or dithio spacer ligands.

    6. Molecular Magnetism

      Tetranuclear [Mn2Co2], [Mn2Fe2], and [Mn2Mn2] Complexes with Defective Double-Cubane Cores and Phenoxo and Oxo Bridges: Syntheses, Crystal Structures, and Electronic Properties (pages 3527–3535)

      Pijush Malpaharia, Koushik Pramanik, Jean-Pierre Costes, Jean-Pierre Tuchagues, Brian Moulton, Michael J. Zaworotko, Babulal Das and Swapan K. Chandra

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402191

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      The syntheses, crystal structures, and electronic properties of three tetranuclear [Mn2Co2], [Mn2Fe2], and [Mn2Mn2] compounds are described. These complexes possess defective double-cubane [Mn2M2O2]8+ cores and are interesting examples that show how small structural changes in molecule-based magnetic compounds can strongly affect the overall electronic properties.

    7. Antitumor Agents

      Substitution-Modulated Anticancer Activity of Half-Sandwich Ruthenium(II) Complexes with Heterocyclic Ancillary Ligands (pages 3536–3546)

      Raja Mitra and Ashoka G. Samuelson

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402205

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      The substituents of aromatic heterocyclic ancillary ligands controls the anticancer activity of bioorganometallic half-sandwich ruthenium complexes. The chloro- and bromo-substituted complexes are less potent than the fluoro-substituted complexes.

    8. Actinide Complexation

      The Role of Residual Charges in the Interaction between NpO2+ and Th4+ Cations: Spectrophotometric and Computational Studies (pages 3547–3554)

      Parveen Kumar Verma, Priyanath Pathak, Arunasis Bhattacharyya, Dattaprasad Ravaji Prabhu, Tapan Kumar Ghanty and Prasanta Kumar Mohapatra

      Article first published online: 30 JUN 2014 | DOI: 10.1002/ejic.201402211

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      Spectrophotometric studies have been carried out in order to understand the thermodynamics of the interaction of the NpO2+ cation with Th4+ at varying nitric acid and thorium concentrations. This interaction appears to be both exothermic and endothermic depending on the nitric acid concentration. DFT calculations suggest that the NpO2+–Th4+ interaction is stronger than that of the NpO2+–UO22+ pair.

    9. Mixed-Valent Compounds

      Coexistence of Localized and Itinerant Electrons in the Double-Perovskite Ba2Fe2/3Mo4/3O6 (pages 3555–3563)

      Carlos A. López, Martín E. Saleta, José C. Pedregosa, Rodolfo D. Sánchez, José A. Alonso and María T. Fernández-Díaz

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402241

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      A double-perovskite Ba2Fe2/3Mo4/3O6 with Fe/Mo (1:2 ratio) mixed valence states was obtained. From a synthesis under reducing conditions we have stabilized the coexistence of itinerant (associated with Mo) and localized (associated with Fe) electrons. This coexistence of electrons leads to non-negligible magnetoresistance properties.

    10. Synthetic Nitrogen Fixation

      (Dinitrogen)molybdenum Complexes Supported by Asymmetric Silicon-Centered Tripod Ligands: Steric and Electronic Influences on the Coordination of Mono- and Diphosphine Coligands (pages 3564–3571)

      Henning Broda, Jan Krahmer and Felix Tuczek

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402273

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      A synthetic route to silicon-centered mixed dialkylphosphine/diarylphosphine tripod ligands has been established leading to nine new Mo–N2 complexes. The resulting structures and the activation of the coordinated N2 ligands are discussed with respect to steric and electronic effects.

    11. Redox Chemistry

      Experimental and DFT/Time-Dependent DFT Studies on Neutral and One-Electron-Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (PdII, PtII) Derivatives (pages 3572–3581)

      Maria Pia Donzello, Giorgia De Mori, Elisa Viola, David Futur, Zhen Fu, Corrado Rizzoli, Luisa Mannina, Enrico Bodo, Maria Luisa Astolfi, Claudio Ercolani and Karl M. Kadish

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402282

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      6,7-Dicyano-2,3-di(2-pyridyl)quinoxaline, [(CN)2Py2Qx], its mononuclear complex [(CN)2Py2QxPtCl2] and the 2,3-dicyanopyrazine compounds [(CN)2Py2Pyz] and its PtII complex [(CN)2Py2PyzPtCl2], carrying 2-pyridyl rings were studied as neutral and mononegatively charged species by electrochemical and UV/Vis spectral measurements. The obtained data were interpreted by DFT/time-dependent DFT studies.

    12. Tellurenyl Chloride Adducts

      A Facile Route for Stabilizing Highly Reactive ArTeCl Species Through the Formation of T-Shaped Tellurenyl Chloride Adducts: quasi-Planar Zwitterionic [HPy*]TeCl2 and [HPm*]TeCl2; Py* = 2-pyridyl, Pm* = 2-(4,6-dimethyl)pyrimidyl (pages 3582–3586)

      Victor N. Khrustalev, Zhanna V. Matsulevich, Julia M. Lukiyanova, Rinat R. Aysin, Alexander S. Peregudov, Larissa A. Leites and Alexander V. Borisov

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402294

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      Two new stable T-shaped tellurenyl chloride adducts, [HPy*]TeCl2 (1) and [HPm*]TeCl2 (2) [Py* = 2-pyridyl, Pm* = 2-(4,6-dimethyl)pyrimidyl], act as close analogs of highly unstable monomeric Py*TeCl and Pm*TeCl. The quasi-planar zwitterionic structures of 1 and 2 were studied by experimental and theoretical methods. Thus, a novel facile route to stabilize highly reactive Ar*TeCl species (Ar* = N-functionalized aryl) by addition of an HCl molecule has been demonstrated.

    13. Spin Crossover

      Spin-State-Dependent Properties of an Iron(III) Hydrogenase Mimic (pages 3587–3599)

      Eileen Edler and Matthias Stein

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402295

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      A pentacoordinate FeIII complex shows spin-state-dependent features, for example, its structural parameters and the torsional profile of the axial ligand. The intermediate state is confirmed to be the ground state, but the ordering of spin states is dependent on the c3 parameter in hybrid DFT functionals. Thermodynamic analysis suggests that this compound is a possible spin-crossover complex.

    14. Palladium Complexes

      Alternative Synthetic Methods for PEPPSI-Type Palladium Complexes (pages 3600–3607)

      Kerry-Ann Green, Paul T. Maragh, Kamaluddin Abdur-Rashid, Alan J. Lough and Tara P. Dasgupta

      Article first published online: 25 JUN 2014 | DOI: 10.1002/ejic.201402317

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      Several PEPPSI-type complexes (PEPPSI = pyridine-enhanced precatalyst preparation stabilization and initiation) were successfully prepared in good yields by a new synthetic method involving hydrohalides of pyridine, azolium salts and palladium bisacetylacetonate.

    15. Photoelectrochemical Cells

      Synthesis and Photoelectrochemical Properties of Efficient Photoanodes Built from Fe2O3/NiO Heterostructures (pages 3608–3613)

      Weiqiang Fan, Chao Zhang, Hongye Bai, Xiaoqiang Yu and Weidong Shi

      Article first published online: 2 JUL 2014 | DOI: 10.1002/ejic.201402416

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      New Fe2O3/NiO heterostructures have been successfully synthesized. Variation of the quantity of NiO can significantly affect their microstructures and photoelectrochemical properties.

    16. Tetrametallaborane Clusters

      The Buildup of Eight-Vertex Tetrametallaborane Clusters: Bisdisphenoidal versus Tetracapped Tetrahedral Structures (pages 3614–3618)

      Alexandru Lupan and R. Bruce King

      Article first published online: 2 JUL 2014 | DOI: 10.1002/ejic.201402363

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      Density functional theory predicts the experimentally known bisdisphenoidal structure for Cp4M4B4H4 (M = Co, Ni) but a tetracapped tetrahedral structure for Cp4Fe4B4H4. Addition of BH units to Cp4M4 or Cp4M4B2H2 to give Cp4M4B4H4 is predicted to be highly exothermic for all three metals.

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