European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 7

Early View (Online Version of Record published before inclusion in an issue)

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

ISI Journal Citation Reports © Ranking: 2013: 10/45 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie


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  1. Short Communications

    1. Cirality of Metal Complexes

      Probing Chiral Recognition of Enzyme Active Sites with Octahedral Iridium(III) Propeller Complexes

      Peter Göbel, Florian Ritterbusch, Melanie Helms, Matthias Bischof, Klaus Harms, Manfred Jung and Eric Meggers

      Article first published online: 5 MAR 2015 | DOI: 10.1002/ejic.201500087

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      Enzyme inhibiting chiral bis-cyclometalated organoiridium(III) complexes were designed to investigate the influence of the metal-centered configuration.

    2. Heterometallic Terephthalates

      Unusual Luminescence Properties of Heterometallic REE Terephthalates

      Aleksei Y. Grishko, Valentina V. Utochnikova, Aleksei A. Averin, Andrei V. Mironov and Natalia P. Kuzmina

      Article first published online: 5 MAR 2015 | DOI: 10.1002/ejic.201403071

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      The quantum yield (QY) of bimetallic terephthalates EuxM1–x(BDC)3/2(H2O)2 (M = Y, Gd; x > 0.05) remains constant (ca. 27 %) upon dilution of Eu3+ with nonluminescent Y3+ or Gd3+. This behavior, unusual for coordination compounds, is ascribed to the ability of the BDC2– environment to accumulate and transfer energy to Eu3+ ions, which sequentially emit several photons after a single excitation.

  2. Full Papers

    1. Supramolecular Interactions

      Hydrogen Bond, π–π, and CH–π Interactions Governing the Supramolecular Assembly of Some Hydrazone Ligands and Their MnII Complexes – Structural and Theoretical Interpretation

      Dipali Sadhukhan, Monami Maiti, Guillaume Pilet, Antonio Bauzá, Antonio Frontera and Samiran Mitra

      Article first published online: 5 MAR 2015 | DOI: 10.1002/ejic.201500030

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      Slight steric and electronic modifications to the ligand backbone provoke differences to the nuclearities and supramolecular architectures of three MnII complexes synthesized from two different hydrazone Schiff base ligands. For all of the compounds, the binding energies through supramolecular forces have been quantitatively estimated by DFT calculations.

  3. Corrections

    1. You have free access to this content
      Catalytic Synthesis of Bi- and Teraryls in Aqueous Medium with Palladium(II) Complexes of 2-(Pyridine-2-ylmethylsulfanyl)benzoic Acid

      Om Prakash, Hemant Joshi, Kamal Nayan Sharma, Alpesh Kumar Sharma and Ajai K. Singh

      Article first published online: 3 MAR 2015 | DOI: 10.1002/ejic.201500178

      This article corrects:
  4. Full Papers

    1. Phosphorus Nitrides

      CuPN2: Synthesis, Crystal Structure, and Electronic Properties

      Florian J. Pucher, Franziska Hummel and Wolfgang Schnick

      Article first published online: 2 MAR 2015 | DOI: 10.1002/ejic.201500009

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      CuPN2, the first known ternary Cu phosphorus nitride, has been synthesized under high-pressure high-temperature conditions. It is isostructural to LiPN2 and an indirect bandgap semiconductor as shown by DFT calculations.

    2. Phosphorescence in Platinum Chelates

      Theoretical Insight Into the Role of Triarylboron Substituents in Tetradentate Dianionic Bis(N-heterocyclic carbene) Platinum(II) Chelates – Improving the Performance of Blue Light Emission

      Li Tian, Yafei Luo, Luqiong Zhang, Ming Li, Rongxing He and Wei Shen

      Article first published online: 2 MAR 2015 | DOI: 10.1002/ejic.201403092

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      The introduction of triarylboron substituents and appropriate π-conjugation to the N-heterocyclic (NHC) ligands of PtII complexes may improve their phosphorescence efficiencies and render them good candidates for highly efficient blue emission.

    3. Magnetic Properties of Cubanes

      Synthesis, Magnetic Properties, and X-ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [MII4(HL2)4(OAc)4]

      Andreas Scheurer, Jana Korzekwa, Takayuki Nakajima, Frank Hampel, Anna Buling, Christine Derks, Manfred Neumann, Loïc Joly, Konstantin Petukhov, Klaus Gieb, Paul Müller, Karsten Kuepper and Karsten Meyer

      Article first published online: 2 MAR 2015 | DOI: 10.1002/ejic.201402988

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      Starting from 2,6-pyridinedimethanol (H2L2, 3) and metal(II) acetate tetrahydrates, divalent CoII and NiII cubanes [MII4(HL2)4(OAc)4] (4) have been synthesized through self-organization. In addition to standard methods (e.g., IR, MS, X-ray analysis), complexes 4 were also characterized by magnetometry and X-ray spectroscopic techniques, including XPS, XAS, and XMCD.

    4. Luminescent Ceramics

      Luminescence Matching with the Sensitivity Curve of the Human Eye: Optical Ceramics Mg8–xMx(BN2)2N4 with M = Al (x = 2) and M = Si (x = 1)

      Markus Ströbele, Konstantin Dolabdjian, David Enseling, Danuta Dutczak, Boriana Mihailova, Thomas Jüstel and H.-Jürgen Meyer

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403116

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      Compounds Mg8–xMx(BN2)2N4 were prepared by solid-state reaction of MgCl2, Li3(BN2), and AlN for M = Al, and of Mg3N2, BN, and Si3N4 for M = Si. Their crystal structures were refined from powder X-ray diffraction data with the space group Requation imagem for M = Al, Si, and P21/c for M = Si. Eu(II)-doped Mg8–xMx(BN2)2N4 show broad band emissions in the visible region of the spectrum (λex = 320 nm).

    5. Hydrogenase Models

      Mononuclear Iron(II) Dicarbonyls Derived from NNS Ligands – Structural Models Related to a “Pre-Acyl” Active Site of Mono-Iron (Hmd) Hydrogenase

      Keren A. Thomas Muthiah, Gummadi Durgaprasad, Zhu-Lin Xie, Owen M. Williams, Christopher Joseph, Vincent M. Lynch and Michael J. Rose

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403013

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      A series of iron(II) dicarbonyls are prepared from neutral Schiff base (NNS) ligands. These “phosphine-free” complexes are extremely temperature- and light-sensitive and somewhat like the active site of mono-[Fe] hydrogenase. The Fe(CO)2-bound methylpyridine unit in [(MeNNS)Fe(CO)2Br]+ may represent a “snapshot” of an intermediate during the biogenesis of the Fe–C(=O)acyl-containing active site.

    6. Photocatalytic Graphitic Carbon Nitride

      CdS/g-C3N4 Hybrids with Improved Photostability and Visible Light Photocatalytic Activity

      Yao Xu and Wei-De Zhang

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403193

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      Nanocomposite photocatalysts CdS/g-C3N4 with different ratios of CdS and graphitic carbon nitride are described as high-performance photocatalysts for environmental remediation. The very stable and recyclable photocatalysts exhibit greatly enhanced photocatalytic activity under visible-light irradiation. Synergistic effects between CdS and g-C3N4 led to efficient separation of charge carriers.

    7. Titanocene Reactivity

      Reactions of [Cp2Ti(η2-Me3SiC2SiMe3)] with 1,4-Bis(diphenylphosphanyl)but-2-yne: Coupling and Isomerization versus Phosphorylation

      Kai Altenburger, Fabian Reiß, Kathleen Schubert, Wolfgang Baumann, Anke Spannenberg, Perdita Arndt and Uwe Rosenthal

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201500032

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      Cuttings and Couplings: The reactions of 1,4-bis(diphenylphosphanyl)but-2-yne with [Cp2Ti(η2-Me3SiC2SiMe3)] have been investigated. An initial alkyne coupling reaction led to a metallacyclopentadiene. Thermal treatment then led to an allene complex by a 1,3-H shift in the coordinated alkyne. In addition, a highly unusual complex with a Ti–H–P bridge was obtained by phosphorylation of the alkyne.

    8. Hydrogen Bonding

      Imidazolium 1,3-Benzazaphospholide Ion Pairs with Strong C–H···N Hydrogen Bonds – Synthesis, Structures, and Reactivity

      Chengfu Pi, Xiaoling Yu and Wenjun Zheng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201500058

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      The treatment of 1H-1,3-benzazaphosphole with N-heterocyclic carbenes produces ionic species exhibiting strong charge-assisted hydrogen bonds, which further react with carbodiimide to give carbamimidoylimidazolium 1,3-benzazaphospholides. The crystal structures of the complexes indicate ion pair conformation in the solid state.

    9. Bonding in Heteroallenic Compounds

      A Model Study on Molecular Properties and Mechanistic Investigations of P=C=E14 Molecules

      Ming-Chung Li, Tsung-Wei Shih, Yu-Chi Li, Jia-Ying Ma and Ming-Der Su

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201500037

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      M06-2X computational results reveal that Mes*P=C=E14(tBu)Tip compounds contain both P=C and C=E14 double bonds in nature. Moreover, this theoretical work suggests that the smaller the atomic number of the group 14 element, E14, in the heteroallenic –P=C=E14< molecule, the more kinetically and thermodynamically stable is its heteroallenic –P=C=E14< species towards various chemical reactions.

    10. Cobalt Copolymerization Catalysts

      Amine-bis(phenolato)cobalt(II) Catalysts for the Formation of Organic Carbonates from Carbon Dioxide and Epoxides

      Marina Reiter, Peter T. Altenbuchner, Stefan Kissling, Eberhardt Herdtweck and Bernhard Rieger

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403087

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      New amine-bis(phenolato)cobalt(II) complexes were synthesized and employed in the coupling and copolymerization of carbon dioxide and epoxides. In combination with DMAP, complex 3 enabled poly(cyclohexene) carbonate generation. End-group analysis found DMAP and methoxy terminated polymer chains due to chain-transfer and the active species for CHO/CO2 copolymerization was found to be CoII.

    11. Single-Source Precursors

      [Ag{S2CNR(C2H4OH)}] as Single-Source Precursor for Ag2S – Synthesis, Decomposition Mechanism, and Deposition Studies

      Robert Mothes, Alexander Jakob, Thomas Waechtler, Stefan E. Schulz, Thomas Gessner and Heinrich Lang

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403182

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      The synthesis, thermal behavior, and decomposition mechanism of [Ag{S2CNR(C2H4OH)}] (R = Me, Bu) is discussed. Its application as a single-source spin-coating precursor for thin-film α-Ag2S fabrication is reported.

    12. Layered Double Hydroxides

      On the Thermal Stability and Structures of Layered Double Hydroxides Mg1–xAlx(OH)2(NO3)x·mH2O (0.18 ≤ x ≤ 0.38)

      Anja Olafsen Sjåstad, Niels Højmark Andersen, Ponniah Vajeeston, Jayakumar Karthikeyan, Bjørnar Arstad, Arne Karlsson and Helmer Fjellvåg

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201403232

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      Structural aspects of nitrate-based layered double hydroxides Mg1–xAlx(OH)2(NO3)x·mH2O have been investigated by various experimental and theoretical methods. The main focus was on the orientation of the NO3 groups in the interlayer gallery, the reversible hydration/dehydration process and the transport of Al from octahedral to tetrahedral sites during the formation of a metastable rock salt oxide.

    13. Molybdenum Nitride Complexes

      Synthesis and Catalytic Activity of Molybdenum–Nitride Complexes Bearing Pincer Ligands

      Eriko Kinoshita, Kazuya Arashiba, Shogo Kuriyama, Aya Eizawa, Kazunari Nakajima and Yoshiaki Nishibayashi

      Article first published online: 27 FEB 2015 | DOI: 10.1002/ejic.201500017

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      Molybdenum–nitride complexes bearing pincer ligands have been designed, prepared, and characterized spectroscopically. The catalytic activities of these molybdenum–nitride complexes have been investigated in the formation of ammonia from molecular dinitrogen under ambient conditions.

  5. Short Communications

    1. Metal-Induced C–F Activation

      Lanthanoid Induced C–F Activation of All Fluorine Atoms of One CF3 Group

      Glen B. Deacon, Peter C. Junk and Daniel Werner

      Article first published online: 25 FEB 2015 | DOI: 10.1002/ejic.201500137

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      The lanthanum formamidinate complex [La(CF3Form)3] {CF3FormH = N,N′-bis(2-trifluoromethylphenyl)formamidine} readily undergoes C–F activation of all fluorine atoms of one CF3 group to give LaF3, and two isomeric polytrifluoromethylphenyl-substituted polyamidines, one containing a 1,2,3,4-tetrahydroquinazoline heterocyclic core.

  6. Full Papers

    1. Luminescent Eu Complexes

      Syntheses, Structures, and Photophysical Properties of Eu and Lu Diketonates with a Neutral Polydentate Imidazolylmethanamine Ligand

      Kristina S. Kisel, Gerald Linti, Galina L. Starova, Vladimir V. Sizov, Alexei S. Melnikov, Anatoly P. Pushkarev, Mikhail N. Bochkarev, Elena V. Grachova and Sergey P. Tunik

      Article first published online: 25 FEB 2015 | DOI: 10.1002/ejic.201403186

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      Neutral EuIII and LuIII diketonate complexes with a Schiff base NNO ligand are studied spectroscopically. The Eu complex shows red metal-centered phosphorescence with a quantum yield of ca. 80 %. An organic light-emitting device (OLED) with the Eu complex in a poly(9-vinylcarbazole) (PVK) matrix reveals electrochromism owing to variations in the efficacy of the metal-centered and matrix emission.

    2. Biomimetic Carbonate Materials

      A Cationic Polyelectrolyte-Controlled Liquid Mineral Precursor Process in the BaCO3 System

      Jianhua Zhu, Lei Huang, Mingfang Cui, Li Ma and Fabin Cao

      Article first published online: 23 FEB 2015 | DOI: 10.1002/ejic.201403153

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      A polymer-induced liquid mineral precursor (PILP) provides a general pathway towards biomimetic materials with complex morphology. In this article, we expand the conception of cationic polyelectrolyte-induced liquid precursors to other inorganic systems, such as barium carbonate. Mesocrystal fibers and a self-organized concentric ring pattern were synthesized in the mineral solution.

    3. Magnetic Nanocatalysts

      One-Step Green Synthesis of Multifunctional Fe3O4/Cu Nanocomposites toward Efficient Reduction of Organic Dyes

      Zhen-Zhen Wang, Shang-Ru Zhai, Bin Zhai and Qing-Da An

      Article first published online: 20 FEB 2015 | DOI: 10.1002/ejic.201403219

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      An Fe3O4/Cu nanocatalyst that exhibits excellent catalytic performance in the degradation of 4-nitrophenol (4-NP) (the reaction was accomplished within 4 min), rhodamine B (within 3 min), and methylene blue (within 1 min) as well as superior stability (can be reused at least five times) was successfully synthesized through a green one-step solvothermal method with ethylene glycol as reductant and reaction media.

    4. Hemilabile Ligands

      Differential Reactivity of [TpRu(κ2P,N-iPr2PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBArF4, Lithium Acetylide, and Acetylenes

      Vinay K. Singh, M. Carmen Puerta and Pedro Valerga

      Article first published online: 19 FEB 2015 | DOI: 10.1002/ejic.201500082

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      The behaviors of ruthenium complexes bearing 2-pyridyl(diisopropylphosphanyl)amine (iPr2PNHPy) or 2-pyridyl(diisopropylphosphanyl)thioether (iPr2PSPy) ligands are compared. The main emphasis is on the differential reactivity of [TpRuCl(iPr2PXPy)] (X = NH, S; Tp = trispyrazolylborate) towards NaBArF4 {BArF4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, lithium acetylide, and acetylenes.

    5. Platinum(IV) Prodrug Complexes

      Bis- and Tris(carboxylato)platinum(IV) Complexes with Mixed Am(m)ine Ligands in the trans Position Exhibiting Exceptionally High Cytotoxicity

      Björn R. Hoffmeister, Michaela Hejl, Michael A. Jakupec, Markus Galanski and Bernhard K. Keppler

      Article first published online: 19 FEB 2015 | DOI: 10.1002/ejic.201403226

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      A total of 18 bis- and tris(carboxylato)platinum(IV) complexes with am(m)ine ligands in the trans position were synthesized and characterized. Their cytotoxicity was investigated for three human cancer cell lines; the most lipophilic compounds showed promising IC50 values down to the nanomolar range.

  7. Short Communications

    1. Lead Orthophosphates

      Three Alkali Metal Lead Orthophosphates – Syntheses, Crystal Structures and Properties of APbPO4 (A = K, Rb, Cs)

      Shengshi Huang, Qun Jing, Jian Han, Shilie Pan, Hongping Wu and Zhihua Yang

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403244

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      Three alkali metal lead orthophosphates, APbPO4 (A = K, Rb, Cs), have been synthesized by conventional solid-state reaction. They crystallize in the same space group, Pnma, but they are not all isostructural.

  8. Full Papers

    1. Dirhenium Complexes

      Triphenylguanidine-Promoted ortho-Metalation Reaction in a Triply Bonded Dirhenium System – Spectroscopic, Structural, and Computational Studies

      Suman Mallick, Mrinal Kanti Ghosh and Swarup Chattopadhyay

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403207

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      A series of ortho-metalated dirhenium complexes are prepared by reacting Re2Cl4(μ-Ph2PCH2PPh2)2 with different para-substituted triphenylguanidine ligands (HTPGR, R = H, Me, OMe) and characterized by different spectroscopic techniques and by X-ray crystallography. The complexes have similar spectral and electrochemical properties, which are consistent with the results of a theoretical study.

    2. Gold Complexes

      Customized Buchwald-Type Phosphines Bearing an “Inverted” Pyrimidinium Betaine as an Aryl Group Surrogate – Synthesis and Coordination Chemistry with Gold(I)

      Ludovik Noël-Duchesneau, Noël Lugan, Guy Lavigne, Agnès Labande and Vincent César

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403205

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      The attachment of a pyrimidinium betaine at the ortho position of one of the aryl groups of a triarylphosphine is proposed as a means to diversify the already well-documented palette of Buchwald-type phosphines. The structure of a gold complex reveals that the malonic carbon center that acts as the linker also weakly interacts with the gold center.

    3. DOTA-Based Gd Chelates

      Dinuclear DOTA-Based GdIII Chelates – Revisiting a Straightforward Strategy for Relaxivity Improvement

      André Fontes, Shima Karimi, Lothar Helm, Maxim Yulikov, Paula M. Ferreira and João P. André

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403159

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      Two DOTA-based dimeric chelators are developed, and their dinuclear GdIII chelates are studied by variable-temperature 1H nuclear magnetic relaxation dispersion (NMRD) and 17O NMR spectroscopy. The distance between the GdIII centers is determined by double electron–electron resonance and by molecular modeling. Only a model with some level of aggregation could satisfactorily explain our results.

    4. Actinide Metaphosphates

      Further Insight into Uranium and Thorium Metaphosphate Chemistry and the Effect of Nd3+ Incorporation into Uranium(IV) Metaphosphate

      Na Yu, Vladislav V. Klepov, Stefan Neumeier, Wulf Depmeier, Dirk Bosbach, Evgeny V. Suleimanov and Evgeny V. Alekseev

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403098

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      Two new polymorphic modifications of uranium metaphosphate are obtained, and their crystal structures are elucidated as well as those of previously reported thorium and uranium tetraphosphates. The uranium atoms are partially substituted by neodymium atoms in the structure of one of the uranium metaphosphates, and the substitution significantly affects the structure.

    5. Zeolitic Imidazolate Frameworks

      Controlled Synthesis of Phase-Pure Zeolitic Imidazolate Framework Co-ZIF-9

      Zafer Öztürk, Jan P. Hofmann, Martin Lutz, Matjaž Mazaj, Nataša Zabukovec Logar and Bert M. Weckhuysen

      Article first published online: 18 FEB 2015 | DOI: 10.1002/ejic.201403077

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      Phase-pure zeolitic imidazolate framework Co-ZIF-9 can be prepared by modification of the commonly used synthesis procedure through pH adjustment, which suppresses the formation of the secondary framework, cobalt formate.

    6. Heterometallic Compounds

      Osmium–Nitrosyl Oxalato-Bridged Lanthanide-Centered Pentanuclear Complexes – Synthesis, Crystal Structures and Magnetic Properties

      Anatolie Gavriluta, Nicolas Claiser, Paul-Steffen Kuhn, Ghenadie Novitchi, Jean Bernard Tommasino, Olga Iasco, Vadim Druta, Vladimir B. Arion and Dominique Luneau

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201500023

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      Coordination tilt: Depending on the size of the Ln(III) ion, osmium–nitrosyl oxalato-bridged lanthanide-centered pentanuclear complexes exhibit two different coordination numbers, 8 or 9, for the central lanthanide ion, and both numbers are observed for dysprosium.

    7. Neutral Nickel Complexes

      Electronic Structures of “Low-Valent” Neutral Complexes [NiL2]0 (S = 0; L = bpy, phen, tpy) – An Experimental and DFT Computational Study

      Mei Wang, Jason England, Thomas Weyhermüller and Karl Wieghardt

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403144

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      The electronic structures of the two series of complexes [Ni(bpy)3]n (bpy = 2,2′-bipyridine; n = 2–, 1–, ..., 3+) and [Ni(bpy)2]m (m = 1–, ..., 3+) have been studied experimentally and computationally (DFT). All octahedral species contain a NiII ion, and the reductions are strictly ligand-centered, whereas the [Ni(bpy)2]m series contains tetrahedral NiII and NiI ions.

    8. Actinide Coordination Chemistry

      Synthesis and Structural Study of Tetravalent (Zr4+, Hf4+, Ce4+, Th4+, U4+) Metal Complexes with Cyclic Hydroxamic Acids

      Pawel Jewula, Jean-Claude Berthet, Jean-Claude Chambron, Yoann Rousselin, Pierre Thuéry and Michel Meyer

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403206

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      1-Hydroxypiperidine-2-one (1H, 1,2-PIPOH) is a cyclic hydroxamic acid that occurs in several siderophores as one of the three FeIII binding units. It can form neutral homoleptic complexes with tetravalent transition-metal (Zr and Hf), lanthanide (Ce), and actinide (Th and U) cations with a diversity of coordination stereochemistries ranging from the square antiprism to the dodecahedron.

    9. NHC-Based Ni Catalysts

      Asymmetric Base-Free Michael Addition at Room Temperature with Nickel-Based Bifunctional Amido-Functionalized N-Heterocyclic Carbene Catalysts

      Mitta Nageswar Rao, Meera Haridas, Manoj Kumar Gangwar, Palanisamy Rajakannu, Alok Ch. Kalita and Prasenjit Ghosh

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403224

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      A series of nickel-based chiral bifunctional catalysts with N-heterocyclic carbene ligands derived from readily available and inexpensive (1R)-(–)-menthol, (1S)-(–)pinene, and (1R)-(+)-camphor synthons successfully catalyze asymmetric base-free Michael addition reactions under ambient conditions.

    10. Thiophenolate Oxazoline Ligands

      Coordinative Flexibility of a Thiophenolate Oxazoline Ligand in Nickel(II), Palladium(II), and Platinum(II) Complexes

      Lydia M. Peschel, Christof Holzer, Ljiljana Mihajlović-Lalić, Ferdinand Belaj and Nadia C. Mösch-Zanetti

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403108

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      A series of nickel, palladium, and platinum complexes that contain a thiophenolate oxazoline ligand were prepared. The ligand coordinates preferably in a bidentate manner but shows high coordinative flexibility depending on the metal center.

  9. Short Communications

    1. Se-Containing Conjugated Systems

      Synthesis of the First Example of Selenium-Containing Platinum(II)–Alkenylarylalkynyl Complexes

      Md. Mostafizur Rahman, Muhammad Younus and Akiya Ogawa

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403194

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      A convenient way has been developed to construct selenium-containing platinum(II)–bis(alkenylarylalkynyl) complexes having two phenylseleno moieties on each alkenyl backbone (Ar = phenylene and R = ethyl for 1a/2a; Ar = phenylene and R = phenyl for 1b/2b; Ar = biphenylene and R = ethyl for 1c/2c; Ar = biphenylene and R = phenyl for 1d/2d).

  10. Full Papers

    1. Oxidase and Catalase Mimics

      Mononuclear Iron(III) Complexes as Functional Models of Catechol Oxidases and Catalases

      Elena Badetti, Blerina Gjoka, Eszter Márta Nagy, Gérald Bernardinelli, Peter E. Kündig, Cristiano Zonta and Giulia Licini

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403225

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      Amino triphenolate iron(III) complexes promote effectively, at room temperature, the aerobic auto-oxidation of 3,5-di-tert-buthylcatechol to the corresponding o-benzoquinone (oxidase mimicking) and hydrogen peroxide dismutation (catalase mimicking).

    2. Nitridosilicates

      Structural Relationship between the Mg-Containing Nitridosilicates Ca2Mg[Li4Si2N6] and Li2Ca2[Mg2Si2N6]

      Sebastian Schmiechen, Frederik Nietschke and Wolfgang Schnick

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403178

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      Novel Mg-containing nitridosilicates, namely Ca2Mg[Li4Si2N6] and Li2Ca2[Mg2Si2N6], are presented. The nitridolithosilicate Ca2Mg[Li4Si2N6] is the second example of Mg in a fourfold planar rectangular coordination with N in nitridosilicates. Li2Ca2[Mg2Si2N6] is another representative of the novel subgroup of nitridomagnesosilicates with Mg2+ in tetrahedral coordination.

    3. Pd-Catalyzed Coupling Reactions

      Suzuki Coupling Reactions Catalyzed with Palladacycles and Palladium(II) Complexes of 2-Thiophenemethylamine-Based Schiff Bases: Examples of Divergent Pathways for the Same Ligand

      Hemant Joshi, Om Prakash, Alpesh K. Sharma, Kamal Nayan Sharma and Ajai K. Singh

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403176

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      Catalysis of Suzuki coupling reactions with palladacycles (≥ 0.001 mol-%) and palladium complexes (≥ 0.01 mol-%) proceeds with and without nanoparticles.

  11. Short Communications

    1. Photoactive Porous Silicon

      Preparation of Porous Silicon by Sodiothermic Reduction of Zeolite and Photoactivation for Benzene Oxidation

      Jing-Feng Wang, Jie-Sheng Chen and Zhong-Fu Zhou

      Article first published online: 13 FEB 2015 | DOI: 10.1002/ejic.201403033

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      Porous silicon with its high specific surface, prepared by a sodiothermic reduction method using zeolite ZSM-5 as the silicon precursor, has been used as an efficient photoactivator for direct oxidation of benzene to yield phenol in H2O2 solution under visible light irradiation.

  12. Full Papers

    1. Nanoparticle–Clay Hybrids

      Formation of Cadmium Sulfide and Zinc Sulfide Mixture in the Interlayer Space of Montmorillonite

      Jirabhorn Kabilaphat, Nithima Khaorapapong, Areeporn Ontam and Makoto Ogawa

      Article first published online: 13 FEB 2015 | DOI: 10.1002/ejic.201403164

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      A mixture of CdS and ZnS was prepared in unmodified and organically modified montmorillonite. The products showed emission bands owing to both CdS and ZnS. The blueshift of absorption onsets and the increase in PL intensity were caused by the confinement effect. CdS and ZnS formed separately in different interlayer spaces (segregation).

    2. Iron(V) Reactivity

      On the Iron(V) Reactivity of an Aggressive Tail-Fluorinated Tetraamido Macrocyclic Ligand (TAML) Activator

      Qizhi Ren, Yisong Guo, Matthew R. Mills, Alexander D. Ryabov and Terrence J. Collins

      Article first published online: 12 FEB 2015 | DOI: 10.1002/ejic.201500001

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      The oxidation states of IV and V are achievable for electron-poor iron tetraamido macrocyclic ligand (TAML) activators. The corresponding oxidoiron(V) species demonstrates the highest reactivity reported so far for any TAML activator in the oxidation of thioanisole and C–H bond activations of ethylbenzene and cyclohexane.

    3. Supercapacitor Materials

      Microwave-Assisted Synthesis of Few-Layered TaTe2 and Its Application as Supercapacitor

      Disha Chakravarty, Praveen Kumar, Vaishali S. Ugale and Dattatray J. Late

      Article first published online: 12 FEB 2015 | DOI: 10.1002/ejic.201403220

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      The first experimental investigations on the use of microwave to synthesize atomically thin few-layer TaTe2 nanosheets are described. This material also shows good performance as a supercapacitor.

    4. Bioorganometallic Chemistry

      Synthesis of CpM(CO)3–DAB and –PAMAM Dendrimer Conjugates and Preliminary Evaluation of Their Biological Activity

      Wanning Hu, Jan Hoyer, Ines Neundorf, Preshendren Govender, Gregory S. Smith and Ulrich Schatzschneider

      Article first published online: 12 FEB 2015 | DOI: 10.1002/ejic.201403060

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      Dendrimers of different generation and core structure are used as carriers for bioactive organometallic half-sandwich complexes of the type CpM(CO)3 (Cp = cyclopentadienyl, M = Mn or Re). Interestingly, the most-active compounds are the first-generation dendrimer conjugates, and the influence of the metal center is much less pronounced.

    5. Ru Antitumor Agents

      Trinuclear Half-Sandwich RuII, RhIII and IrIII Polyester Organometallic Complexes: Synthesis and in vitro Evaluation as Antitumor Agents

      Andrew R. Burgoyne, Banothile C. E. Makhubela, Mervin Meyer and Gregory S. Smith

      Article first published online: 11 FEB 2015 | DOI: 10.1002/ejic.201403192

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      Polyester-containing trinuclear half-sandwich RuII, RhIII and IrIII complexes were prepared and characterised. The cytotoxicity was investigated for all compounds. Aqueous stability studies and interactions with model DNA 5′-GMP were performed for the most-active compounds.

    6. Magnetogenic Probes

      Spring-Loaded Iron(II) Complexes as Magnetogenic Probes Reporting on a Chemical Analyte in Water

      Corentin Gondrand, Fayçal Touti, Estelle Godart, Yevgen Berezhanskyy, Erwann Jeanneau, Philippe Maurin and Jens Hasserodt

      Article first published online: 11 FEB 2015 | DOI: 10.1002/ejic.201403183

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      A new low-spin iron(II) triazacyclononane-based complex, selected from four different candidates, acts as a molecular probe that turns a diamagnetic aqueous sample into a paramagnetic one as a response to a chemical analyte. The four complexes are prepared by a highly convergent synthetic protocol and give precious insights into structure–activity relationship (SAR) tendencies.

    7. Gold Complexes

      A Trinuclear AuI Complex with Different R3P–Au Centers: Synthesis, Characterization, and Synergetic Catalysis for Hydration of Phenylacetylene

      Shi-Jun Lai, Da Yang, Yong-Qi Li, Xiao-Li Zhao, Yong Lu and Ye Liu

      Article first published online: 11 FEB 2015 | DOI: 10.1002/ejic.201403150

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      A trinuclear AuI complex of 3A was synthesized and fully characterized relative to the mononuclear (1A) and dinuclear (2A) complexes. Compound 3A exhibited the best catalytic performance for hydration of phenylacetylene owing to the synergetic catalytic effect of the three R3P–Au centers, in which each Au site acted in a different way to activate the substrate molecules.

    8. Phenylphosphonate Intercalates

      Intercalates of Strontium Phenylphosphonate with Alcohols – Structure Analysis by Experimental and Molecular Modeling Methods

      Vítězslav Zima, Klára Melánová, Petr Kovář, Ludvík Beneš, Jan Svoboda, Miroslav Pospíšil and Aleš Růžička

      Article first published online: 11 FEB 2015 | DOI: 10.1002/ejic.201403069

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      Structures of alcohol intercalated strontium phenylphosphonates were suggested on the basis of a combination of single-crystal X-ray diffraction data and molecular modeling.

    9. Defect-Modulated MOFs

      Generation of Defect-Modulated Metal–Organic Frameworks by Fragmented-Linker Co-Assembly of CPO-27(M) Frameworks

      Nadia E. A. El-Gamel

      Article first published online: 11 FEB 2015 | DOI: 10.1002/ejic.201403110

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      The generation of defect-modulated metal–organic frameworks (MOFs) by stepwise doping of 2-hydroxyterephthalate (BDC-OH) into CPO-27-M (M = MgII, CoII, and NiII) frameworks is discussed. Microporous structures are generated with reasonable porosity. No significant changes to the morphologies of the frameworks are observed after the fragmented-linker doping.

    10. Anticancer Osmium Complexes

      Antimicrobial and Antitumor Activity of Enantiopure Pybox–Osmium Complexes

      Estefanía Menéndez-Pedregal, Ángel Manteca, Jesús Sánchez, J. Díez, M. Pilar Gamasa and Elena Lastra

      Article first published online: 9 FEB 2015 | DOI: 10.1002/ejic.201403173

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      The antiproliferative activities of new water-soluble osmium(II) complexes against microbes and tumor cell lines are studied. The IC50 value for trans-[OsCl2{(S,S)-iPr-pybox}(1-PhCH2-PTA)][Br] {(S,S)-iPr-pybox = 2,6-bis[4′(S)-isopropyloxazolin-2′-yl]pyridine, PTA = 1,3,5-triaza-7-phosphatricyclo[,7]decane} against HeLa cells is 2.7 ± 0.3 μM.

    11. Conformational Isomerization

      Al3+-Ion-Triggered Conformational Isomerization of a Rhodamine B Derivative Evidenced by a Fluorescence Signal – A Crystallographic Proof

      Buddhadeb Sen, Siddhartha Pal, Samya Banerjee, Somenath Lohar and Pabitra Chattopadhyay

      Article first published online: 9 FEB 2015 | DOI: 10.1002/ejic.201403091

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      A noncytotoxic rhodamine B anisaldehyde hydrazone exhibits an aluminium-ion-induced cis (L) to trans (L′) conformational isomerization with respect to the xanthene moiety through a rotation about a N–N bond; the change is signaled by a red fluorescence response.

    12. Dendrimer-Stabilized Nanoparticles

      Alkynyl-Functionalized Imidazolium for “Click” Dendrimer Functionalisation and Palladium Nanoparticle Stabilization

      Christophe Deraedt, Martin d'Halluin, Stephanie Lesturgez, Lionel Salmon, Graziella Goglio, Jaime Ruiz and Didier Astruc

      Article first published online: 9 FEB 2015 | DOI: 10.1002/ejic.201403045

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      An imidazolium salt containing an alkynyl group was synthesized in three steps in order to functionalize nanomaterials by means of CuAAC and Sonogashira reactions. For instance, a nona-azido dendritic core could be “clicked” with the alkynyl-containing imidazolium salt. The resulting dendrimer allows the stabilization of palladium nanoparticles that are active in the Suzuki–Miyaura cross-coupling reaction.

    13. Ternary Phosphide Tellurides

      Homogeneity Range of the Zirconium Phosphide Telluride Zr2+xPTe2 and the High-Temperature Phase Transformation to Zr2PTe

      Tanja Scholz and Peer Schmidt

      Article first published online: 9 FEB 2015 | DOI: 10.1002/ejic.201403043

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      Zr2PTe2 decomposes along a homogeneity range up to Zr2.5PTe2 by partial filling of the van der Waals gap in the Bi2STe2 structure type. In the consecutive high-temperature decomposition step, “Zr2PTe” is formed. The new phase adopts the structural motif of the binary phases ZrTe and ZrTe2 and tolerates a deficit in the cation position and a mixed occupation of the anions (Zr1.95P0.84Te1.16).

  13. Short Communications

    1. Rare-Earth Imido Complexes

      Rare-Earth Metal Complexes with Terminal Imido Ligands

      Dorothea Schädle, Melanie Meermann-Zimmermann, Christoph Schädle, Cäcilia Maichle-Mössmer and Reiner Anwander

      Article first published online: 9 FEB 2015 | DOI: 10.1002/ejic.201500045

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      Lewis base induced methane elimination converts [(TptBu,Me)Ln(Me)(NHAr)] into mono-rare-earth metal imide complexes [(TptBu,Me)Ln(=NAr)(DMAP)]; terminal Ln=N bond formation is promoted by the superbulky ancillary TptBu,Me and corroborated by very short Ln–N bond lengths and almost linear Ln–N–C(aryl) bond angles (see structure; C gray, H white, N green, B pink, Lu magenta, F yellow green).

  14. Full Papers

    1. Photodynamic Therapy

      Mitochondria-Targeting Photocytotoxic Ferrocenyl Conjugates of N-Alkylpyridinium Salts

      Babu Balaji, Babita Balakrishnan, Sravanakumar Perumalla, Anjali A. Karande and Akhil R. Chakravarty

      Article first published online: 5 FEB 2015 | DOI: 10.1002/ejic.201403118

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      A ferrocenyl conjugate of an N-butylpyridinium salt with a pendant triphenylphosphonium moiety shows specific mitochondrial localization and remarkable visible-light-induced photocytotoxicity in HeLa cancer cells and is less toxic in normal 3T3 cells. The photoinduced cell death follows a mitochondria-mediated apoptotic pathway.

    2. Photocatalytic Dye Degradation

      Fabrication of Single-Layer Graphitic Carbon Nitride and Coupled Systems for the Photocatalytic Degradation of Dyes under Visible-Light Irradiation

      Xinshan Rong, Fengxian Qiu, Hao Zhao, Jie Yan, Xiaolu Zhu and Dongya Yang

      Article first published online: 5 FEB 2015 | DOI: 10.1002/ejic.201403141

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      A visible-light-responsive and environmentally friendly photocatalyst has potential applications in the removal of dyes from wastewater. The synergic effect of single-layer graphitic carbon nitride (g-C3N4) and CdS can effectively separate and transfer photoexcited carriers and is proposed to be responsible for the enhancement of the photocatalytic activity.

    3. Lanthanide-Nitronyl Nitroxide Chains

      Slow Magnetic Relaxation in Pseudo-One-Dimensional 2p-4f Chains Involving π–π Interactions

      Juanjuan Wang, Mei Zhu, Cun Li, Junqing Zhang and Licun Li

      Article first published online: 5 FEB 2015 | DOI: 10.1002/ejic.201403184

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      Two lanthanide nitronyl nitroxide complexes with pseudo-one-dimensional chain structures have been obtained. The DyIII complex shows slow relaxation of magnetization, and this represents a new strategy toward Ln–radical single-chain magnets (SCMs).

    4. Noble Gas Chemistry

      [XeF5]+/Metal and [XeF5]+/Non-Metal Mixed-Cation Salts of Hexafluoridoantimonate(V)

      Zoran Mazej and Evgeny Goreshnik

      Article first published online: 5 FEB 2015 | DOI: 10.1002/ejic.201500028

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      NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3] are the first examples of [XeF5]+/metal and [XeF5]+/non-metal mixed-cation compounds. The crystal structure of NO2XeF5(SbF6)2 is composed of [NO2]+ and [XeF5]+ cations and [SbF6] anions. In the crystal structure of XeF5[Cu(SbF6)3] the [XeF5]+ cations are located in cavities present in the tridimensional framework made up of CuF6 and SbF6 octahedra sharing joint apexes.

    5. C=C Bond Cleavage

      Complexation of Tetrakis(acetato)chloridodiruthenium with Naphthyridine-2,7-dicarboxylate – Characterization and Catalytic Activity

      Chia-Han Lee, Cai-Ling Wu, Shao-An Hua, Yi-Hung Liu, Shie-Ming Peng and Shiuh-Tzung Liu

      Article first published online: 3 FEB 2015 | DOI: 10.1002/ejic.201403156

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      The reaction of calcium naphthyridine-2,7-dicarboxylate (Cadcnp) with Ru2(OAc)4Cl provides Ca[Ru2(dcnp)(OAc)3]2 as the exclusive product. The complex is catalytically active for the oxidative cleavage of olefins in aqueous media.

    6. Sensors for Explosives

      A Eu-Doped Y-Based Luminescent Metal–Organic Framework as a Highly Efficient Sensor for Nitroaromatic Explosives

      Debal Kanti Singha, Prakash Majee, Sudip Kumar Mondal and Partha Mahata

      Article first published online: 3 FEB 2015 | DOI: 10.1002/ejic.201403097

      Thumbnail image of graphical abstract

      The luminescence of a three-dimensional metal–organic framework (MOF) with aromatic-ligand-sensitized Eu3+ activators is useful for sensing trace amounts of nitroaromatic explosives in solution through the quenching phenomenon.

    7. 3D Manganese Frameworks

      Synthesis, Structure and Magnetic Properties of a 3D Manganese(II) Framework Featuring a Heptanodal Topology and Tube-in-Tube Dihelical Chains

      Zilu Chen, Lixia Quan, Long Liu, Yifei Wang, Huahong Zou and Fupei Liang

      Article first published online: 3 FEB 2015 | DOI: 10.1002/ejic.201403093

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      The decomposition reaction of a Schiff base drives the formation of a rare 3D MnII framework, which features a heptanodal topology and alternately arranged tube-in-tube dihelical chains with opposite chiralities, as well as spin-canted and metamagnetic behavior.

    8. NO Decomposition

      Fundamental Aspects of Rare Earth Oxides­ Affecting Direct NO Decomposition Catalysis

      Soichiro Tsujimoto, Toshiyuki Masui and Nobuhito Imanaka

      Article first published online: 3 FEB 2015 | DOI: 10.1002/ejic.201403061

      Thumbnail image of graphical abstract

      Among four fundamental factors (crystal structure, lattice parameters, particle morphology, and the density of basic sites), crystal structure is the aspect that most significantly affects direct NO decomposition activities of rare earth oxides (REOs), and the density of basic sites ranks second in importance to crystal structure.

    9. Energetic Materials

      Ionic Ferrocene-Based Burning-Rate Catalysts with Polycyano Anions: Synthesis, Structural Characterization, Migration, and Catalytic Effects During Combustion

      Xuelin Liu, Jizhen Li, Fuqiang Bi, Weiqiang Zhang, Guofang Zhang and Ziwei Gao

      Article first published online: 30 JAN 2015 | DOI: 10.1002/ejic.201403023

      Thumbnail image of graphical abstract

      Fifteen polycyano-based ionic ferrocene compounds were prepared and structurally characterized. The compounds exhibit low migration tendency and highly catalytic effects on thermal decomposition of ammonium perchlorate (AP), hexogen (RDX), and octogen (HMX).

  15. Short Communications

    1. Manganese Clusters

      A Mn6 Cluster inside a Mn10 Wheel: Characterization of a Mn16-Oximate Complex Resulting from a Tetrazole-2-pyridylketoneoximate Ligand

      Laura Alcazar, Mercè Font-Bardia and Albert Escuer

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejic.201403128

      Thumbnail image of graphical abstract

      Tetrazole-2-pyridylketoneoximate, obtained by in situ cyclization of 2-pyridylcyanoximate and azide, was characterized in a Mn16 complex with an unprecedented topology formed by one hexanuclear {MnII2MnIII4} unit coordinated perpendicularly to a decametallic {MnII6MnIII2MnIV2} wheel.


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