European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 9

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. Full Papers

    1. Luminescent Metal Sulfonates

      Influence of Metal Cations and Coordination Modes on Luminescent Group 1 and 2 Metal Sulfonate Complexes Constructed from 4,4′-Dihydroxybiphenyl-3,3′-disulfonic Acid

      Yi-Zhe Yu, Ya-Nan Li, Zhao-Peng Deng, Zhi-Biao Zhu, Li-Hua Huo and Shan Gao

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500170

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      The self-assembly of 4,4′-dihydroxybiphenyl-3,3′-disulfonic acid with group 1 and 2 metal salts results in diverse second-coordination-sphere networks, hybrid layers, interdigitating 2D + 2D [RIGHTWARDS ARROW] 3D architectures, and 3D pillared-layered networks tuned by the metal cations and the coordination mode of the ligand.

    2. Ferrocene–Viologen Compounds

      Ferrocenyl–Bipyridinium Cations and Their Platinum Complexes Related to Viologens – Preparation, Redox Properties, and Crystal Structures

      Tomoyuki Mochida, Yusuke Funasako, Yukiko Nezu, Koji Hagiwara and Ryo Horikoshi

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500077

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      4,4′-Bipyridinium cations bearing ferrocenyl or ferrocenylphenyl substituents at the N-positions were prepared as donor–acceptor compounds. Platinum(II)-bridged diferrocene compounds were also prepared by using bipyridinium cations. These cations display multistage redox properties, and the compounds exhibit broad charge-transfer absorption bands in the range 450–800 nm.

    3. Spin-Crossover Complexes

      Effects of Big Planar Anions on the Spin Transition of a Mononuclear Manganese(III) Complex with a Hexadentate Schiff-Base Ligand

      Shi Wang, Yong-Hua Li and Wei Huang

      Article first published online: 26 MAR 2015 | DOI: 10.1002/ejic.201500024

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      Spin-crossover in d4 ions is a most rare event. Changing the size of the anion from NO3 to [Pt(mnt)2] and [Ni(dmit)2] leads to significant changes in the overall crystal packing of Mn ion-pair complexes and furthermore in the spin state of the MnIII center.

  2. Short Communications

    1. Titanium Aminophenolate Systems

      Potent Reactivity in Solubilised Oxo-Titanium Polymers

      Alastair J. Nielson and Joyce M. Waters

      Article first published online: 25 MAR 2015 | DOI: 10.1002/ejic.201403135

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      [TiO(salen)]n polymers solubilised in aldehyde solution show potent activity when ortho substituents are present on the salicylidene ligand aromatic rings. Unprecedented carbon-based chemistry is demonstrated by the formation of new ligands about the titanium centre.

  3. Full Papers

    1. Copper Selenides

      Monoclinic Copper(I) Selenide Nanocrystals and Copper(I) Selenide/Palladium Heterostructures: Synthesis, Characterization, and Surface-Enhanced Raman Scattering Performance

      Long Zhang, Shulin Zhao, Yafei Li, Yaqian Lan, Min Han, Zhihui Dai and Jianchun Bao

      Article first published online: 25 MAR 2015 | DOI: 10.1002/ejic.201500008

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      Monoclinic Cu2Se nanocrystals and Cu2Se/Pd heterostructures have been synthesized by simple and facile methods. Owing to strong synergistic effects and phase-dependent characteristics, the surface-enhanced Raman scattering performance of the Cu2Se/Pd heterostructure is superior to those of Cu2Se, Pd, CuSe/Pd, and Cu2–xSe/Pd.

    2. Hypervalent P Heterocycles

      Phenylpyrazole-Based Hypervalent Phosphorus Compounds: From Positional Isomerism to Stacking Interactions

      Alexander N. Kornev, Vyacheslav V. Sushev, Yulia S. Panova, Natalia V. Zolotareva, Evgenii V. Baranov, Georgy K. Fukin and Gleb A. Abakumov

      Article first published online: 24 MAR 2015 | DOI: 10.1002/ejic.201500102

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      The dichlorophosphino derivative of 3,5-dimethyl-1-phenyl-1H-pyrazole exists in solution as an equilibrium mixture of positional isomers. Its reduction leads to cationic diphosphines with a chloride bridge between the phosphorus atoms. The hypervalent N···P (1.774–1.885 Å) and Hal···P interactions influence the behavior in solution and the arrangement of molecules in the crystal form.

    3. Bimetallic Coordination Polymers

      External-Template-Assisted Formation of Octacyanometalate-Based MV–MnII (M = W, Mo) Bimetallic Coordination Polymers with Magnetic Properties

      Jun Qian, Jingchun Hu, Hirofumi Yoshikawa, Jinfang Zhang, Kunio Awaga and Chi Zhang

      Article first published online: 24 MAR 2015 | DOI: 10.1002/ejic.201403223

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      2D coordination polymers {{[μ4-M(CN)8]2[Mn(dmf)3]2[Mn(dmf)4]}·2DMF}n (M = W, Mo) and a 1D chain compound {{[μ4-Mo(CN)8][Mn(dmf)4]2}·(ClO4)}n are constructed by external-template-assisted formation in the presence and absence of bis(benzimidazol-2′-yl)pyridine. All three compounds can be assembled into 3D supramolecular structures, and two of the compounds exhibit typical ferrimagnetic properties.

    4. Mesoporous Materials

      Facile Preparation of Ammonium Molybdophosphate/Al-MCM-41 Composite Material from Natural Clay and Its Use in Cesium Ion Adsorption

      Chunyan Sun, Feng Zhang, Xiao Wang and Fangqin Cheng

      Article first published online: 23 MAR 2015 | DOI: 10.1002/ejic.201500114

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      A composite ammonium molybdophosphate/Al-MCM-41 material is synthesized by a one-pot method with natural clay as the silica and aluminum source. A modified “liquid-phase transport” step allows the use of impure natural clay as the starting material to produce pure product without sedimentation pretreatment. The composite material is effective for the adsorption of cesium ions from brine.

    5. V-Catalyzed Oxidative Bromination

      Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

      Federica Sabuzi, Ekaterina Churakova, Pierluca Galloni, Ron Wever, Frank Hollmann, Barbara Floris and Valeria Conte

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500086

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      Catalysis of thymol bromination by vanadium derivatives is directly compared to catalysis by a V-dependent bromoperoxidase. All reactions were performed under mild and sustainable conditions with relatively inexpensive reagents. Appealing results were obtained in terms of selectivity and sustainability.

    6. Ternary Polygermanides

      Flux Crystal Growth of the Ternary Polygermanide LaPtGe2, a p-Type Metal

      Daniel E. Bugaris, Mihai Sturza, Fei Han, Jino Im, Duck Young Chung, Arthur J. Freeman and Mercouri G. Kanatzidis

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500019

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      Plate crystals of LaPtGe2 have been grown from a molten indium flux. This compound crystallizes in the CeNiSi2-type structure. Electrical resistivity, Hall effect, and thermopower measurements have shown that LaPtGe2 exhibits p-type metallic behavior, which is consistent with electronic band structure calculations.

    7. Supported Bimetallic Catalysts

      Room-Temperature Hydrogenation of Citral Catalyzed by Palladium–Silver Nanocrystals Supported on SnO2

      Shuo Wang, Rongan Shen, Zheng Chen, Jiaxi Wang, Dingsheng Wang and Yadong Li

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500057

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      We have developed two strategies to optimize Pd catalysts for the selective hydrogenation of citral and exploited a catalyst (Pd0.6Ag0.4–SnO2/C) with the best catalytic performance (the conversion of citral reached 99 %, and the selectivity was up to 96 %).

    8. Molecular Docking

      Synthesis, Crystal Structures, Molecular Docking, and Urease Inhibitory Activities of Transition-Metal Complexes with a 1,2,4-Triazolecarboxylic Acid Derived Ligand

      Yong-Peng Xu, Yue-Hu Chen, Zhi-Jian Chen, Jie Qin, Shao-Song Qian and Hai-Liang Zhu

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500050

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      Four novel crystals of copper, zinc, and iron complexes based on 1,2,4-triazole carboxylic acid derivatives were determined by single-crystal X-ray diffraction. The inhibitory activity and kinetic studies were tested in vitro against jack bean urease. The computational predications, biological evaluation, and mechanism study will help in the discovery of new urease inhibitors.

    9. Metalloenzyme Models

      Synthesis and Characterization of 4-, 5-, and 6-Coordinate Tris(1-ethyl-4-isopropylimidazolyl-κN)phosphine Cobalt(II) Complexes

      Chanel R. Easley, Jia Li, Atanu Banerjee, Manashi Panda, William W. Brennessel, Reza Loloee, Enrique Colacio and Ferman A. Chavez

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201403203

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      [Co(T1Et4iPrIP)X2] {T1Et4iPrIP = tris(1-ethyl-4-isopropylimidazolyl)phosphine; X = OTf (1), Cl (2), Br (3)}, and [Co(T1Et4iPrIP)(CH3CN)3](OTf)2 (4) are reported. Dissolution of 1 in MeCN affords 4. Reaction of 1 with Cl or Br yields 2 or 3, respectively. DFT studies indicate that 1 has the largest HOMO–LUMO gap, which suggests that the formation of 2 or 3 from 1 is primarily sterically driven.

    10. Magnetic Manganese Helices

      Pentanuclear and Octanuclear Manganese Helices

      Hiroki Sato, Momoyo Yamaguchi, Tatsuya Onuki, Mao Noguchi, Graham N. Newton, Takuya Shiga and Hiroki Oshio

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201500096

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      Pentanuclear and octanuclear manganese helices are obtained by the reactions of a multidentate polypyridine ligand with manganese nitrate and chloride. The Mn ions in the pentanuclear complex are in a mixture of +2 and +3 valence states, whereas those of the octanuclear complex are homodivalent. Both compounds show antiferromagnetic interactions.

    11. Immobilized Chiral Catalysts

      Chiral Ruthenium Catalyst Immobilized within Magnetically Retrievable Mesoporous Silica Microcapsules for Aqueous Asymmetric Transfer Hydrogenations

      Amani Zoabi, Suheir Omar and Raed Abu-Reziq

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201403212

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      We report the design of a “quasi-homogeneous” catalytic system, based on a modified Noyori Ru-TsDPEN catalyst confined within mesoporous silica-based microreactors, for the efficient asymmetric transfer hydrogenation of ketones in water. The new system demonstrates excellent reactivity and enantioselectivity characteristic of homogeneous catalysts, but can be easily recovered.

    12. Triazole-Based Coordination Polymers

      The Effects of Alkaline-Earth Counterions on the Architectures, Band-Gap Energies, and Proton Transfer of Triazole-Based Coordination Polymers

      K. S. Asha, Arthur C. Reber, Anthony F. Pedicini, Shiv N. Khanna and Sukhendu Mandal

      Article first published online: 19 MAR 2015 | DOI: 10.1002/ejic.201403162

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      The effects of alkaline-earth ions on the architectures, band-gap energies, and proton transfer of triazole-based coordination polymers are investigated.

  4. Microreviews

    1. Transition Metal NHC Catalysis

      Accessible Syntheses of Late Transition Metal (Pre)Catalysts Bearing N-Heterocyclic Carbene Ligands

      David J. Nelson

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201500061

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      Selected examples of the synthesis of useful (pre)catalysts bearing N-heterocyclic carbenes (NHCs) are discussed. All of these examples avoid the generation and isolation of free carbenes and the use of strong, sensitive bases; therefore, they are presented as useful preparative methods that can allow these catalysts to be utilised more widely.

  5. Full Papers

    1. Low Dielectric Mg-Based MOFs

      Low Dielectric Behavior of a Robust, Guest-Free Magnesium(II)–Organic Framework: A Potential Application of an Alkaline-Earth Metal Compound

      Shruti Mendiratta, Muhammad Usman, Tien-Wen Tseng, Tzuoo-Tsair Luo, Shang-Fan Lee, Li Zhao, Maw-Kuen Wu, Mandy M. Lee, Shih-Sheng Sun, Ying-Chih Lin and Kuang-Lieh Lu

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201403243

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      A 3D, robust, and low dielectric (low-κ) Mg-based MOF with a non-interpenetrated cds-type topology was prepared. Dielectric measurements revealed the κ value to be 3.33 ± 0.1 (at 100 kHz). It is evident that the incorporation of alkaline-earth metal ions in highly porous frameworks could result in materials with low-κ properties.

    2. Metal Oxo Clusters

      Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters

      Johannes Kreutzer, Michael Puchberger, Christine Artner and Ulrich Schubert

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201403209

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      Ligand exchange in Zr4O2(OOCR)12 clusters proceeds with retention of the cluster core. A new scrambling reaction is introduced for the preparation of mixed-ligand clusters.

    3. Zinc Sulfonate Rectangles

      Molecular Rectangles with Rod-Shaped Disulfonic Acids

      Christina Zitzer, Thomas W. T. Muesmann, Karina Hunfeld, Jens Christoffers and Mathias S. Wickleder

      Article first published online: 18 MAR 2015 | DOI: 10.1002/ejic.201403171

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      Rod-shaped disulfonic acids are suitable for the construction of zinc-based molecular rectangles. These rectangles form flexible lattices that incorporate solvent molecules. The removal of the solvent molecules leads to disulfonates of astonishingly high thermal stability, in strong contrast to the behavior of comparable polycarboxylates.

    4. Ni-Based Sonogashira Catalysts

      Modulating Sonogashira Cross-Coupling Reactivity in Four-Coordinate Nickel Complexes by Using Geometric Control

      Anette Petuker, Christian Merten and Ulf-Peter Apfel

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500148

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      Two tripodal phosphines CH3E(CH2PPh2)3 (E = C, Si) are applied as ligands in Ni-catalyzed cross-coupling reactions; various coordination modes at the Ni center can be achieved. For the first time, experimental evidence is provided to prove that tetrahedral instead of planar (PR3)2NiCl2 moieties are required to perform effective Sonogashira coupling reactions.

    5. Polymerization Catalysts

      Oxide-Bridged Heterobimetallic Aluminum/Zirconium Catalysts for Ethylene Polymerization

      Cédric Boulho, Harmen S. Zijlstra and Sjoerd Harder

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500123

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      The targeted synthesis of a new bimetallic aluminum/zirconium species with remaining Lewis acidity on aluminum gives a dimeric Al–O–Zr complex. In the presence of methylalumoxane, this μ-oxo complex is able to activate ethylene to produce polyethylene with high activity.

  6. Short Communications

    1. Donor-Stabilized Silylenes

      Thermally Stable Four-Coordinate Silicon(IV) Complexes with an Si=N Double Bond and an SiN3El Skeleton (El = O, S, Se, Te)

      Felix M. Mück, Anna Ulmer, Johannes A. Baus, Christian Burschka and Reinhold Tacke

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500083

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      The donor-stabilized silylene 1 reacts with N2O and PhElElPh (El = S, Se, Te) to form the respective silicon(IV) complexes 25 with an Si=N double bond. Compounds 25 were structurally characterized by crystal structure analyses and NMR spectroscopic studies in the solid state and in solution

  7. Microreviews

    1. Methandiide Ligands

      Carbene Complexes Based on Dilithium Methandiides

      Viktoria H. Gessner, Julia Becker and Kai-Stephan Feichtner

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500051

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      Methandiide ligands give access to carbene complexes with unique electronic properties. The metal–carbon interactions in these complexes cover a range of bonding situations and allow the isolation of complexes with metals from the whole periodic table. We focus on the latest developments in methandiide chemistry and give an overview of the preparation and electronic structures of these complexes.

  8. Full Papers

    1. Main-Group Coordination Chemistry

      Germanium(II) and Tin(II) Halide Complexes Containing the Triimido Sulfur(VI) Phosphanyl Ligand

      Elena Carl and Dietmar Stalke

      Article first published online: 17 MAR 2015 | DOI: 10.1002/ejic.201500074

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      The P-functionalized triimido sulfur ligand [(NtBu)3SCH2PPh2] can be used without ligand scrambling to stabilize synthetically useful group 14 metal(II) halides. It chelates the metal through two S-bound imido nitrogen atoms only. The additional coordination site is provided by the phosphorus atom; although with germanium the P side-arm is pendant, it forms a long-range interaction with tin.

    2. Hydrodesufurization

      Niobium–Containing Lindqvist Isopolyanions [NbxW6–xO19](2+x)– Used as Precursors for Hydrodesulfurization Catalysts with Isomerization Properties

      Karolina Bouadjadja-Rohan, Christine Lancelot, Michel Fournier, Audrey Bonduelle-Skrzypczak, Antoine Hugon, Olivier Mentré and Carole Lamonier

      Article first published online: 13 MAR 2015 | DOI: 10.1002/ejic.201403160

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      [NbxW6–xO19](2+x)– Lindqvist type isopolyanions were synthesized and characterized to prepared NbWNi-based alumina-supported hydrodesulfurization catalysts. Nb-containing catalysts showed improved CC6 isomerization properties under HDS conditions (H2 pressure and H2S presence) compared to those of a reference NiW catalyst related to the acid properties induced by niobium.

    3. Organostannylenes

      On the Reactivity of RSnCl and RSiMe3 {R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2} towards BF3·OEt2: Competing Lewis Acidities

      Michael Wagner, Michael Lutter, Christina Dietz, Marc H. Prosenc and Klaus Jurkschat

      Article first published online: 11 MAR 2015 | DOI: 10.1002/ejic.201500014

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      The reactions of boron trifluoride with the organostannylene RSnCl {R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2} and the organosilane RSiMe3 provided the corresponding 1:1 and 1:2 complexes, respectively, through the formation of P=O[RIGHTWARDS ARROW]B interactions. The experimental results are supported by DFT calculations.

    4. Photodegradation of Dyes

      Synthesis of Two Coordination Polymer Photocatalysts and Significant Enhancement of Their Catalytic Photodegradation Activity by Doping with Co2+ Ions

      Duan-Xiu Li, Zhi-Gang Ren, David J. Young and Jian-Ping Lang

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201500069

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      Two coordination polymers are prepared, and their catalytic activity for the photodegradation of rhodamine B (RhB) is enhanced by doping with Co2+ ions.

    5. Chiral Complexes for Oxidations

      Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand

      Maria Lucia Perrone, Eliana Lo Presti, Simone Dell'Acqua, Enrico Monzani, Laura Santagostini and Luigi Casella

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201500046

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      A dinuclear copper(II) complex derived from a chiral hexadentate nitrogen ligand is reported as a new catalyst for asymmetric oxidations. For biogenic catechols as model substrates, the best enantioselectivity is obtained in the oxidation of the methyl esters of L-/D-Dopa, for which 70 % ee is obtained in favor of the L enantiomer.

    6. Photochemical Linkage Isomerism

      Evidence for Photochemical Linkage Isomerism of the Phenylazo Ligand in M(CO)2(N2Ph)(PPh3)2 Cations (M = Fe and Ru)

      Wyatt A. Thornley and Thomas E. Bitterwolf

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201403211

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      Frozen-matrix photolysis studies of M(CO)2(N2Ph)(PPh3)2 cations (M = Fe and Ru) have revealed end-on/side-on photochemical linkage isomerism of the phenylazo ligand. The previously reported solvent-dependent vibrational bands of the Ru(CO)2(N2Ph)(PPh3)2 cation have now been identified as an equilibrium between the two linkage isomers.

    7. Silica Nanowires

      Synthesis, Structure, and Optical Properties of SiO2:Eu3+ Nanowires

      Hui Zhang, Ye Sheng, Xiuqing Zhou, Jie Chen, Zhan Shi, Xuechun Xu and Haifeng Zou

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201403204

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      SiO2:Eu3+ nanowires are prepared by a solvothermal method followed by subsequent calcination and acid washing processes. A possible formation mechanism is proposed in detail. In the solvothermal process, ethylenediamine (EDA) bridges between Zn ions and SiO2:Eu3+ nanowires by coordination and hydrogen bonding.

    8. Functional Coordination Polymers

      Structural Influencing Factors on ZnII/CdII Coordination Polymers Based on Tri-pyridyl-bis-amide: Assembly, Structures, Fluorescent Sensing and Selective Photocatalysis

      Xiu-Li Wang, Nai-Li Chen, Guo-Cheng Liu, Hong-Yan Lin and Ju-Wen Zhang

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201403177

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      Fourteen new ZnII/CdII coordination polymers based on tri-pyridyl-bis-amide were hydrothermally synthesized and characterized, which show photocatalytic activity and selectivity for the degradation of organic dyes. The fluorescent selectivity of these compounds makes them promising candidates as fluorescent sensor materials.

    9. Vanadium Phosphates

      Analysis and Prediction of Stacking Sequences in Intercalated Lamellar Vanadium Phosphates

      Romain Gautier, Yoann Fourré, Eric Furet, Régis Gautier and Eric Le Fur

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201403210

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      Stacking sequences of intercalated lamellar vanadium phosphates have been analyzed by DFT calculations. The relative shifts of layers have been predicted and confirmed by single-crystal X-ray diffraction for Cd(VOPO4)2·4H2O.

    10. Molybdenum Sulfide Clusters

      Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

      David Recatalá, Rosa Llusar, Francisco Galindo, Konstantin A. Brylev and Artem L. Gushchin

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201403228

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      Coordination of diimine ligands to a Mo3S7 cluster afforded complexes of the formula Mo3S7X4(diimine) (X = Cl or Br). The clusters with the novel imidazophenanthroline ligand IPDOP are luminescent and have moderate quantum yields. Furthermore, interaction of the NH group of IPDOP with several anions (F, AcO, and OH) resulted in a remarkable shift of the emission spectrum to longer wavelengths.

    11. Palladium–Carbene Precatalysts

      PEPPSI-Effect on Suzuki–Miyaura Reactions Using 4,5-Dicyano-1,3-dimesitylimidazol-2-ylidene-Palladium Complexes: A Comparison between trans-Ligands

      Heiko Baier, Alexandra Kelling and Hans-Jürgen Holdt

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201500010

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      Four PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) complexes 1215, bearing different 3-substituted pyridines, were prepared and used as precatalysts in Suzuki–Miyaura reactions with 20 aryl bromides and three aryl chlorides. The catalytic activities of 1215 were compared to those of complexes 4 and 5, recently presented by our group.

    12. Layered Chalcogenides

      Exfoliation of Bulk Inorganic Layered Materials into Nanosheets by the Rapid Quenching Method and Their Electrochemical Performance

      Disha Chakravarty and Dattatray J. Late

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201500039

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      We have synthesized layered materials of MoS2, WS2, MoSe2, and WSe2 by the rapid quenching method and investigated their electrochemical performance.

    13. Iodoargentate Hybrids

      Solvent-Dependent Iodoargentate Hybrids: Syntheses, Structural Diversity, Thermochromism, and Photocatalysis

      Tanlai Yu, Junju Shen, Yilin Wang and Yunlong Fu

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201500049

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      Four iodoargentate hybrids are fabricated through reaction of the same reactants in different solvent systems. The solvent impacts the aggregation modes of the cationic species, which consequently directs the formation of anionic frameworks. These hybrids display excellent photocatalytic properties for the degradation of rhodamine B, and 4 displays low-temperature reversible thermochromism.

    14. Chiral Molecular Conductors

      Chiral Radical-Cation Salts of BEDT-TTF Containing a Single Enantiomer of Tris(oxalato)aluminate(III) and -chromate(III)

      Lee Martin, Hiroki Akutsu, Peter N. Horton, Michael B. Hursthouse, Ross W. Harrington and William Clegg

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201500092

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      The use of a chiral electrolyte has produced two new chiral radical-cation salts of BEDT-TTF from racemic ammonium tris(oxalato)aluminate(III) and -chromate. One of the salts has a non-stoichiometric composition of 0.11 electrons per molecule doped to the band-insulating donor layer.

  9. Short Communications

    1. Fuctionalization of NHC Ligands

      A Chemoselective and Modular Post-Synthetic Multi-Functionalization of NHC–Platinum Complexes

      Georges Dahm, Etienne Borré, Gilles Guichard and Stéphane Bellemin-Laponnaz

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201500116

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      We report oxime ligation in combination with metal ligand exchange as a novel orthogonal and practical approach to the multi-functionalization of NHC–platinum complexes.

  10. Full Papers

    1. Small Molecule Sensing

      Facile Synthesis of ZnO–Reduced Graphene Oxide Nanocomposites for NO2 Gas Sensing Applications

      Nagesh Kumar, Arvind Kumar Srivastava, Hari Shankar Patel, Bipin Kumar Gupta and Ghanshyam Das Varma

      Article first published online: 6 MAR 2015 | DOI: 10.1002/ejic.201403172

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      A facile route for the synthesis of zinc oxide–reduced graphene oxide nanocomposites has been achieved for NO2 gas sensing applications.

  11. 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.

  12. 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.

    2. 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.

    3. 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.

    4. 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.

    5. 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).

    6. 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.

    7. 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.

    8. 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.

    9. 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.

    10. 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.

    11. 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.

    12. 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.

    13. 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.

    14. 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.

    15. 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.

    16. 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.

    17. 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.

    18. 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.

    19. 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.

    20. 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.

    21. 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.

    22. 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).

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