European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 26

September 2014

Volume 2014, Issue 26

Pages 4230–4407

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
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    8. Short Communication
    9. Short Communications
    10. Full Papers
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    1. You have free access to this content
      Synthesis and Redox Properties of PNP Pincer Complexes Based on N-Methyl-4,4′-bipyridinium (Eur. J. Inorg. Chem. 26/2014)

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

      Article first published online: 16 SEP 2014 | DOI: 10.1002/ejic.201490128

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      The cover picture shows the synthesis of novel “metalloviologens” bearing PNP pincer ligands based on N-methyl-4,4′-bipyridinium. These complexes are stable toward two steps of single electron transfer, where p-quinoid-type complexes play a key role. The rhodium complex bearing the PNP pincer ligand based on N-methyl-4,4′-bipyridinium is also found to work as a catalyst for dihydrogen production under photoinduced electron transfer conditions. Details are discussed in the article by Y. Miyake, Y. Nishibayashi et al. on p. 4273 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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      Synthesis and Redox Properties of PNP Pincer Complexes Based on N-Methyl-4,4′-bipyridinium (page 4230)

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

      Article first published online: 16 SEP 2014 | DOI: 10.1002/ejic.201402797

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      Our ultimate goal in this project is the construction of a stable redox system for efficient reduction of water and CO2 under photoirradiation...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 4273 ff.

  3. Graphical Abstract

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    1. Graphical Abstract: Eur. J. Inorg. Chem. 26/2014 (pages 4232–4237)

      Article first published online: 16 SEP 2014 | DOI: 10.1002/ejic.201490129

  4. News

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  5. Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 26/2014 (page 4242)

      Article first published online: 16 SEP 2014 | DOI: 10.1002/ejic.201490131

  6. Further Masthead

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    1. Masthead: Eur. J. Inorg. Chem. 26/2014 (page 4243)

      Article first published online: 16 SEP 2014 | DOI: 10.1002/ejic.201490132

  7. Short Communication

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    1. Macrocyclic Chromophores

      A Macrocyclic 2,2′-Bibenzimidazole Ruthenium(II) Chromophore as a Versatile Building Block for Supramolecular Devices (pages 4244–4249)

      Dieter Sorsche and Sven Rau

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402609

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      A new pH- and cation-switchable ruthenium(II) chromophore is presented. Owing to the versatility of the macrocyclic 2,2′-bibenzimidazole ligand, the complex presents itself as an attractive new building block for supramolecular arrays.

  8. Short Communications

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    1. Crystal Engineering

      Insight into Structure: Function Relationships in a Molecular Spin-Crossover Crystal, from a Related Weakly Cooperative Compound (pages 4250–4253)

      Jérôme Elhaïk, Colin A. Kilner and Malcolm A. Halcrow

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402623

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      The ClO4 salt of [FeL2]2+ {L = 2,6-bis(3-methylpyrazol-1-yl)pyridine} undergoes very gradual thermal spin-crossover. In contrast, the BF4 salt of the same complex exhibits an abrupt and structured spin-transition, with a complicated structural chemistry. The difference can be attributed to a much larger change in molecular structure between the spin states of the complex in the more cooperative BF4 salt (the weakly cooperative ClO4 salt is pictured).

    2. Mesoporous Nanoparticles

      Smart Decoration of Mesoporous TiO2 Nanospheres with Noble Metal Alloy Nanoparticles into Core–Shell, Yolk–Core–Shell, and Surface-Dispersion Morphologies (pages 4254–4257)

      Pengyu Wang, Hiroko Tooriyama, Kazuya Yokoyama, Masataka Ohtani, Haruyasu Asahara, Tomoya Konishi, Nagatoshi Nishiwaki, Masahiko Shimoda, Yoshiyuki Yamashita, Hideki Yoshikawa and Kazuya Kobiro

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402646

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      Au–Pt–Pd@TiO2, Au–Pt@TiO2, and Au@TiO2 mesoporous nanoparticles with core–shell, yolk–core–shell, and surface-dispersion morphologies are synthesized by a solvothermal method in methanol. The alloy cores of the Au–Pt–Pd@TiO2 and Au–Pt@TiO2 yolk–core–shell nanoparticles have Au@Pt–Pd and Au@Pt embedded sub-core–shell structures, respectively.

    3. Complex Multimetallic Structures

      Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures (pages 4258–4262)

      Grzegorz Filipczyk, Alexander Hildebrandt, Ulrike Pfaff, Marcus Korb, Tobias Rüffer and Heinrich Lang

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402659

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      A straightforward one-pot synthetic method including cyclotrimerization, C–H activation, and ring formation to novel hexaferrocenylbenzene is discussed. The electrochemical and spectro-electrochemical behavior as well as a mechanism for the formation of the title compound is reported.

    4. Cu–Radical-Supported Oxidation

      Copper(II)-Coordinated α-Azophenols: Effect of the Metal-Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity (pages 4263–4267)

      Amélie Kochem, Alexandre Carrillo, Christian Philouze, Maurice van Gastel, Amaury du Moulinet d'Hardemare and Fabrice Thomas

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402312

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      Tetrahedral distortion at the metal ion in a copper(II) complex containing tridentate ligands with a (Nquinoline,Nazo,Ophenol) donor set is tuned by the α-quinoline substituent. The CuII–phenoxyl radical species oxidizes benzyl alcohol at rate constants that are essentially independent of the distortion at the metal center.

    5. Metal–Organic Frameworks

      Development of a SO3H-Functionalized UiO-66 Metal–Organic Framework by Postsynthetic Modification and Studies of Its Catalytic Activities (pages 4268–4272)

      Yi Luan, Nannan Zheng, Yue Qi, Jie Yu and Ge Wang

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402509

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      A novel metal–organic framework UiO-66-NH2-derived Brønsted acid catalyst is synthesized by employing a postsynthetic modification strategy under mild conditions. Acetalization and benzimidazole formation are evaluated to demonstrate the high reactivity and selectivity of the nanoscaled UiO-66-NH-RSO3H catalyst.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
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    1. Pincer Ligand Complexes

      Synthesis and Redox Properties of PNP Pincer Complexes Based on N-Methyl-4,4′-bipyridinium (pages 4273–4280)

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

      Article first published online: 26 JUN 2014 | DOI: 10.1002/ejic.201402349

      Thumbnail image of graphical abstract

      We have designed and prepared a series of novel PNP pincer ligands based on N-methyl-4,4′-bipyridinium for the construction of stable complexes toward two steps of single electron transfer reactions, where p-quinoid-type complexes play a key role. The rhodium complex bearing PNP pincer ligand based on N-methyl-4,4′-bipyridinium is also found to work as a catalyst for dihydrogen production under the photoinduced electron-transfer conditions.

    2. Solar Cells

      Optimal-Temperature-Based Highly Efficient NiS Counter Electrode for Quantum-Dot-Sensitized Solar Cells (pages 4281–4286)

      Hee-Je Kim, Tae-Bin Yeo, Soo-Kyoung Kim, S. Srinivasa Rao, A. Dennyson Savariraj, K. Prabakar and Chandu V. V. M. Gopi

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402026

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      In quantum-dot-sensitized solar cells, nickel sulfide is a highly efficient catalyst by reducing the redox species that mediate the reduction of the sensitizer after electron injection. The catalytic activity of the NiS counter electrode depends on the deposition temperature. This is supported by cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements.

    3. Half-Sandwich Complexes

      (Arene)ruthenium Complexes with Imidazolin-2-imine and Imidazolidin-2-imine Ligands (pages 4287–4293)

      Justus Tönnemann, Rosario Scopelliti and Kay Severin

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402583

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      (Arene)Ru complexes with imidazolin-2-imine and imidazolidin-2-imine ligands of the general formula [(cymene)RuCl2L] are described. Photochemical activation allows the preparation of complexes in which the imines act as π ligands with tethered imine groups.

  10. Full Paper

    1. Top of page
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    1. Lewis Acids

      Poly-Boron, -Silicon, and -Gallium Lewis Acids by Hydrometallation of 1,5- and 1,8-Dialkynylanthracenes (pages 4294–4301)

      Jan-Hendrik Lamm, Jan Horstmann, Jan H. Nissen, Jan-Henrik Weddeling, Beate Neumann, Hans-Georg Stammler and Norbert W. Mitzel

      Article first published online: 25 JUL 2014 | DOI: 10.1002/ejic.201402376

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      A series of B-, Si- and Ga-containing poly-Lewis acids were synthesised by converting 1,5- and 1,8-dialkynylanthracene derivatives in hydrometallation reactions. Some of the compounds reacted with diethyl ether, which demonstrates the variable behaviour of the Lewis acidic compounds towards Lewis basic molecules.

  11. Full Papers

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    1. Ate Complexes

      Divalent Transition Metal Silylamide Ate Complexes (pages 4302–4309)

      Sonja N. König, David Schneider, Cäcilia Maichle-Mössmer, Benjamin M. Day, Richard A. Layfield and Reiner Anwander

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402557

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      Donor-free and tetrahydrofuran-coordinated (thf-coordinated) ate complexes of the type (thf)x(AM)M(NR2)3 (x = 0, 1; AM = Li, Na; M = Fe, Cr, Co, Mn) have been synthesized and characterized. The implications of ion size and donor-solvent coordination on the solid-state structures are discussed.

    2. Blue Emitters

      Synthesis, Structure, and Photophysical Properties of Blue-Emitting Zinc(II) Complexes with 3-Aryl-Substituted 1-Pyridylimidazo[1,5-a]pyridine Ligands (pages 4310–4319)

      G. Attilio Ardizzoia, Stefano Brenna, Sara Durini, Bruno Therrien and Mattia Veronelli

      Article first published online: 28 JUL 2014 | DOI: 10.1002/ejic.201402415

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      Zinc(II) complexes containing N,N-bidentate 3-aryl-substituted 1-pyridylimidazo[1,5-a]pyridine ligands show blue emission in the solid state with absolute photoluminescent quantum yields (ΦPL) of up to 0.40. The different emission properties of the complexes are related to the presence of intermolecular O–H···N hydrogen bonds.

    3. Magnetic Properties

      Electronic and Magnetic Properties of a Gadolinium(III) Schiff Base Complex (pages 4320–4325)

      Apoorva Upadhyay, Chinmoy Das, Muralidharan Shanmugam, Stuart K. Langley, Keith S. Murray and Maheswaran Shanmugam

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402219

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      A monomeric GdIII Schiff base complex was isolated and its electronic and magnetic properties were investigated in detail. From variable-temperature X-band dilution studies, we conclude that magnetic anisotropy arises in this complex due to low symmetry around GdIII provided by the ligand field.

    4. Cluster Compounds

      Coordination Cluster Analogues of the High-Spin [Mn19] System with Functionalized 2,6-Bis(hydroxymethyl)phenol Ligands (pages 4326–4334)

      Samir Mameri, Ayuk M. Ako, Fatma Yesil, Marcel Hibert, Yanhua Lan, Christopher E. Anson and Annie K. Powell

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402327

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      The robustness of the inorganic {MnIII12MnII74-O)8} core of Mn19 systems with variously functionalized encapsulating ligands is demonstrated by the invariance of the record S = 83/2 spin state. Chemical modification aimed towards attaching the molecule to various substrates does not interfere with the electronic structure.

    5. Univalent Gallium Complexes

      σ- or π-Coordination? Complexes of Univalent Gallium Salts with Aromatic Nitrogen Bases (pages 4335–4341)

      Martin R. Lichtenthaler, Florian Stahl, Daniel Kratzert, Boumahdi Benkmil, Hermann A. Wegner and Ingo Krossing

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402360

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      Upon interaction of [Ga(C6H5F)2]+[Al(ORF)4] with pyrazine or 2,6-di-tert-butyl-4-methylpyridine, σ-coordination prevails. Thus, these two aromatic nitrogen bases function as Lewis bases, yielding homoleptic and mixed N-donor complexes or coordination polymers of gallium(I).

    6. Iron Phosphonate

      A Direct Three-Component Reaction for the Isolation of a Nonanuclear Iron(III) Phosphonate (pages 4342–4348)

      Joydeb Goura, Junjie Liu, Paul Goddard and Vadapalli Chandrasekhar

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402371

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      The reaction of anhydrous ferric chloride with cyclopentylphosphonic acid and pivalic acid in the presence of triethylamine at room temperature afforded a nonanuclear iron(III) phosphonate. It possesses a cage structure with a distorted icosahedral core. Mössbauer studies confirm high-spin FeIII, whereas magnetic measurements suggest strong antiferromagnetic couplings between the Fe3+ ions.

    7. Bridged Complexes

      Synthesis of Trinuclear Heterobimetallic Cyanido-Bridged Complexes from the Reaction of [MnI(CN)(CO)(tBuNC)4] with Transition-Metal Chlorides (pages 4349–4356)

      Kathi Carl, Anke Sterzik, Helmar Görls and Wolfgang Imhof

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402398

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      The reaction of [Mn(CN)(CO)(tBuNC)4] with transition-metal chlorides led to the formation of cyanide-bridged trinuclear coordination compounds. If CuII or FeII was used as the central metal atom, intramolecular electron transfer (M = Cu, Fe) and disproportionation processes (M = Fe) were observed and investigated by UV/Vis and EPR spectroscopy and X-ray crystallography.

    8. Ligand Design

      Aminoalkyl-1,1-bis(phosphinic acids): Stability, Acid–Base, and Coordination Properties (pages 4357–4368)

      Tomáš David, Soňa Procházková, Jan Kotek, Vojtěch Kubíček, Petr Hermann and Ivan Lukeš

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402420

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      Four geminal bisphosphinates were synthesized, and their acid–base properties and coordination behaviour with Cu2+, Zn2+ and Ni2+ ions were studied. The compounds show lower amine basicity and complex stability constants than those of analogous bisphosphonates. In the solid-state structures of the Ca2+ and Cu2+ complexes, the bisphosphinates are coordinated in O,O′-chelating mode.

    9. Palladium Catalysis

      Palladium Nanoparticles Stabilized by Glycodendrimers and Their Application in Catalysis (pages 4369–4375)

      Sylvain Gatard, Lionel Salmon, Christophe Deraedt, Jaime Ruiz, Didier Astruc and Sandrine Bouquillon

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402457

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      Small and monodisperse glycodendrimer-stabilized palladium nanoparticles (PdDSNs) were prepared from low concentrations of metal precursor in the presence of NaBH4. PdDSNs were characterized by transmission electron microscopy (TEM) and their catalytic activities evaluated for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 and for Suzuki–Miyaura C–C coupling.

    10. Pseudorotaxane Synthesis

      Thiacrown Ethers with Oxygen and Sulfur for Coordination: Formation of the Pd and Pt Complexes and Pseudorotaxane with Dialkylammonium (pages 4376–4384)

      Hiroyuki Nagai, Yuji Suzaki and Kohtaro Osakada

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402465

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      Mono-, di-, tri-, and tetrathiacrown ethers form pseudorotaxanes with dialkylammonium salts and transition-metal complexes with palladium(II) and platinum(II). The pseudorotaxanes of di- and tetrathiacrown ethers undergo decomplexation/complexation cycles by competitive metal coordination with PdCl2.

    11. Metal–Organic Frameworks

      One-Pot Multiple Metal–Organic Framework Formation: Concomitant Generation of Structural Isomers or of Drastically Distinct Materials (pages 4385–4393)

      Achareeya Cheansirisomboon, Jorge Salinas-Uber, Chiara Massera, Olivier Roubeau, Sujittra Youngme and Patrick Gamez

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402475

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      The (solvothermal) reactions to produce MOFs may lead to the simultaneous generation of multiple solid materials, for instance, structural isomers or even radically different compounds.

    12. Sila-Galbanones

      Sila-α-galbanone and Analogues: Synthesis and Olfactory Characterization of Silicon-Containing Derivatives of the Galbanum Odorant α-Galbanone (pages 4394–4407)

      Steffen Dörrich, Anna Ulmer, Christoph Mahler, Christian Burschka, Johannes A. Baus, Reinhold Tacke, An Chai, Changming Ding, Yue Zou, Gerhard Brunner, Andreas Goeke and Philip Kraft

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402597

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      Sila-α-galbanone, sila-α-spirogalbanone, and sila-nor-α-galbanone (sila-analogues of α-galbanone, α-spirogalbanone, and nor-α-galbanone) were synthesized starting from Me2SiCl2, (CH2=CH)2SiCl2, and Me2(CH2=CH)SiCl, respectively. These sila-analogues proved to be less volatile and thus more tenacious than the parent carbon compounds while also providing insight into structure–odor correlations.

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