European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 26

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: 10/44 (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


  1. 1 - 100
  2. 101 - 102
  1. Full Papers

    1. Ionic Liquids

      Organic–Inorganic Hybrid Membranes Based on Sulfonated Poly(ether ether ketone) and Tetrabutylphosphonium Bromide Ionic Liquid for PEM Fuel Cell Applications

      Vijay Shankar Rangasamy, Savitha Thayumanasundaram, Niels de Greef, Jin Won Seo and Jean-Pierre Locquet

      Article first published online: 19 SEP 2014 | DOI: 10.1002/ejic.201402558

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      Polymer–ionic liquid electrolyte membranes were fabricated from tetrabutylphosphonium bromide ([P4 4 4 4]Br) and sulfonated poly(ether ether ketone) (SPEEK). Their thermal, mechanical, structural and electrical properties show promise for their use in high-temperature fuel cell applications.

    2. Zn Coordination Chemistry

      The Effect of ZnII Coordination on the Addition of 2-(Aminomethyl)benzimidazole to Acrylonitrile

      Martha P. Falcón-León, Antonio R. Tapia-Benavides, Hugo Tlahuext, Carlos Galán-Vidal, Oscar R. Suarez-Castillo and Margarita Tlahuextl

      Article first published online: 19 SEP 2014 | DOI: 10.1002/ejic.201402346

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      The aza additions of 2-(aminomethyl)benzimidazole (HL) to acrylonitrile depend on pH and are not selective. However, the N[RIGHTWARDS ARROW]Zn coordination bonds in HL increase the selectivity of the aza addition to acrylonitrile because the ZnII protects the imidazolic nitrogen atoms. Moreover, the aza addition of ZnII complexes requires an aqueous medium.

    3. Metalloporphyrins

      Exploring the Effects of Axial Pseudohalide Ligands on the Photophysical and Cyclic Voltammetry Properties and Molecular Structures of MgII Tetraphenyl/porphyrin Complexes

      Khaireddine Ezzayani, Zouhour Denden, Shabir Najmudin, Cecilia Bonifácio, Eric Saint-Aman, Frédérique Loiseau and Habib Nasri

      Article first published online: 18 SEP 2014 | DOI: 10.1002/ejic.201402546

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      The [Mg(TPP)X] (TPP = tetraphenylporphyrinato; X = N3, NOC, NCS) complex ions were characterized by X-ray diffraction. The effects of the nature of the axial pseudohalide ligand X on the photophysical and redox properties of these species in dichloromethane have also been studied by cyclic voltammetry, UV/Vis spectroscopy, and fluorescence spectroscopy techniques.

    4. Lone-Pair–π Interactions

      2-Pyridylcyanoxime–NiII Clusters with Unusual Topologies: Lone-Pair–π Interactions and Magnetic Properties

      Albert Escuer, Jordi Esteban, Júlia Mayans and Mercè Font-Bardia

      Article first published online: 18 SEP 2014 | DOI: 10.1002/ejic.201402598

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      Magnetic properties and supramolecular lone-pair–π-ring interactions have been analyzed for a series of new tri- and pentanuclear nickel derivatives of the 2-pyridylcyanoximate ligand.

    5. Chiral Copper Cluster

      A Pair of Enantiopure Cubane-Type CuII4O4 Clusters: Synthesis, Structure, Chirality and Magnetism

      Ji Yin, Ting-Ting Yin, Chen Gao, Bing-Wu Wang, Yuan-Yuan Zhu, Zong-Quan Wu and Song Gao

      Article first published online: 18 SEP 2014 | DOI: 10.1002/ejic.201402608

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      A pair of enantiopure cubane-type CuII4O4 clusters was obtained from a chiral Schiff base ligand. The chirality and weak antiferromagnetic interactions within the CuII4L4 core were studied.

    6. Metal–Organic Frameworks

      Designing Near-Infrared and Visible Light Emitters by Postsynthetic Modification of Ln+3–IRMOF-3

      Reda M. Abdelhameed, Luis D. Carlos, P. Rabu, Sérgio M. Santos, Artur M. S. Silva and João Rocha

      Article first published online: 17 SEP 2014 | DOI: 10.1002/ejic.201402789

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      The postsynthetic modification of IRMOF-3 with ethyl oxalyl monochloride and ethyl acetoacetate followed by the chelation of trivalent lanthanide ions is a suitable route for the preparation of efficient near-infrared (Nd3+) and visible (Eu3+ and Tb3+) light emitters.

    7. Metallacycles

      Reactivity of a Seven-Membered Zirconacyclocumulene towards CN Multiple Bonds – Formation of Metallaheterocycles by Insertion of C≡N and C=N Groups

      Vladimir V. Burlakov, Lisanne Becker, Vyacheslav S. Bogdanov, Maxim V. Andreev, Perdita Arndt, Anke Spannenberg, Wolfgang Baumann and Uwe Rosenthal

      Article first published online: 17 SEP 2014 | DOI: 10.1002/ejic.201402618

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      Reactions of RC≡N (R = Me, Ph) and PhCH=NPh with the seven-membered zirconacyclocumulene [Cp2Zr{η4-Me3SiC4(SiMe3)–C(C2SiMe3)=CSiMe3}] (1) give five-membered cycles by insertion of CN bonds. For the nitrile with R = Me, stabilization by dimerization occurs to yield 2, whereas for R = Ph with a second nitrile, pyrimidines are formed. Compound 4 reversibly inserts CO2.

    8. Mesoporous Materials

      Synthesis of Co/Ni Unitary- or Binary-Doped CeO2 Mesoporous Nanospheres and Their Catalytic Performance for CO Oxidation

      Xiufang Liu, Lu Han, Wei Liu and Yanzhao Yang

      Article first published online: 17 SEP 2014 | DOI: 10.1002/ejic.201402570

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      Ceria, pure ceria doped with transition metal ions (Co2+, Ni2+), and Co/Ni binary-doped ceria mesoporous notched hollow nanospheres were prepared from a one-step solvothermal synthesis. The incorporation of metal ions into the ceria fluorite lattice results in higher catalytic activity. In addition, the mesoporous nanospheres can be used as an excellent support for noble metals.

    9. Peptide Conjugates

      Synthesis, Characterization of Some Ferrocenoyl Cysteine and Histidine Conjugates, and Their Interactions with Some Metal Ions

      Guo-Cheng Han, Annaleizle Ferranco, Xiao-Zhen Feng, Zhencheng Chen and Heinz-Bernhard Kraatz

      Article first published online: 17 SEP 2014 | DOI: 10.1002/ejic.201402470

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      A series of disubstituted ferrocenoyl cysteine and histidine derivatives as well as iron–sulfur cluster analogs were synthesized. According to circular dichroism (CD) spectra, all ferrocenoyl compounds have P-helical conformation. Conversely, after the addition of ZnII, the configuration for ferrocene (Fc) amino acid conjugates 6a and 6b changed from P-helical to M-helical in the 480 nm region.

    10. Phosphorescent Emitters

      Ruthenium(II) Photosensitizers with Electron-Rich Diarylamino-Functionalized 2,2′-Bipyridines and Their Application in Dye-Sensitized Solar Cells

      Qiwei Wang, Wenjun Wu, Cheuk-Lam Ho, Liqin Xue, Zhenyang Lin, Hua Li, Yih Hsing Lo and Wai-Yeung Wong

      Article first published online: 17 SEP 2014 | DOI: 10.1002/ejic.201402396

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      New ruthenium(II)-based photosensitizers with electron-rich diarylamino-2,2′-bipyridine ligands have been developed. They can be used to afford decent and reasonably stable device performance in dye-sensitized solar cells (up to 5.95 % in cosensitized cells versus 6.76 % for N719), thereby revealing the great potential of these dyes.

    11. Metallacycles

      Investigating the Formation Mechanism of Arene Ruthenium Metallacycles by NMR Spectroscopy

      Amine Garci, Gajendra Gupta, Claudio Dalvit and Bruno Therrien

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402639

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      The stereochemical properties of twelve dinuclear arene ruthenium complexes have been studied in solution by NMR spectroscopy. All complexes showed lability of the pyridyl-based ligands in solution and rapid exchange between the cis and trans isomers. The intermediate species have been identified and, thus, provided insights into the formation mechanism of arene ruthenium metalla-assemblies.

    12. Polymorphs

      Prospective Electroluminescent Hybrid Materials

      Olga B. Petrova, Roman I. Avetisov, Andew V. Khomyakov, Rasim R. Saifutyarov, Alina A. Akkuzina, Elena N. Mozhevitina, Alexandr V. Zhukov and Igor Ch. Avetissov

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402538

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      Three polymorphs of tris(8-hydroxyquinoline)boron (Bq3) were obtained by high-temperature substitution reaction. Their spectral and structural properties were investigated and showed Bq3 to be a potential blue emitter. Hybrid material (HM) films B2O3/Alq3/B2O3 on a glass substrate were made by vacuum sputtering. Laser heating of the HM film resulted in an irreversible change in its photoluminescence.

    13. Surface Functionalization

      Spatially Confined Functionalization of Transparent NiO Thin Films with a Luminescent (1,10-Phenanthroline)tris(2-thenoyltrifluoroacetonato)europium Monolayer

      Emanuele Smecca, Cristina Tudisco, Antonino E. Giuffrida, Maria R. Catalano, Adolfo Speghini, Graziella Malandrino and Guglielmo G. Condorelli

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402479

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      Anchoring of the Eu(TTA)3phen complex on MOCVD-grown NiO films is reported. The NiO surface was activated by means of a sputtering process and functionalized with a phosphonic linker, followed by the coordination of the Eu complex through a ligand-exchange reaction. The luminescent hybrid system has been proven to retain the optical properties of the Eu complex.

    14. Lanthanides

      Solvochemical Synthesis and Crystal Structure of the Fluoride-Derivatized Early Lanthanoid(III) ortho-Oxidomolybdates(VI) LnF[MoO4] (Ln = Ce–Nd)

      Tanja Schustereit, Thomas Schleid and Ingo Hartenbach

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402407

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      A new solvochemical synthesis leads to noncrystalline lanthanoid(III) fluoride oxidomolybdates(VI). After thermal treatment of the crude products, single crystals of the LnF[MoO4] series (Ln = Ce–Nd) are obtained. The crystal structures are determined, and spectroscopic measurements are performed for the crystalline samples and the noncrystalline crude product.

    15. Self-Healing Materials

      Furan-Modified Spherosilicates as Building Blocks for Self-Healing Materials

      Tom Engel and Guido Kickelbick

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402551

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      Octameric furfuryl-functionalized spherosilicates were used to prepare self-healing hybrid materials based on a reversible Diels–Alder reaction. Two different bismaleimides were used as dienophilic cross-linkers for the self-healing materials. The healing abilities are dictated by the nature of the cross-linker.

    16. Coordination Polymers

      Coordination Polymers Based on Alkylboronate Ligands: Synthesis, Characterization, and Computational Modelling

      Dorothée Berthomieu, Christel Gervais, Guillaume Renaudin, Marc Reinholdt, Saad Sene, Mark E. Smith, Christian Bonhomme and Danielle Laurencin

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402561

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      The synthesis and characterization of three new crystalline alkylboronate structures are described, together with their DFT modelling and calculations of solid-state NMR parameters and IR O–H stretching frequencies.

    17. Half-Sandwich Complexes

      Complex Formation between [(η6-p-cymene)Ru(H2O)3]2+ and Hydroxycarboxylates or their Sulfur Analogues – The Role of Thiolate Groups in Metal Ion Binding

      Dániel Hüse, Linda Bíró, János Patalenszki, Attila Csaba Bényei and Péter Buglyó

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402559

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      Although the hydroxycarboxylates L-malic acid and L-tartaric acid form mostly mononuclear complexes with [(η6-p-cymene)Ru(H2O)3]2+ and can prevent hydrolysis of the metal ion, their sulfur analogues thiolactate and thiomalate prefer to bind through bridging thiolate groups to yield highly stable dinuclear [Ru2A2]-type complexes.

    18. Sandwich Complexes

      Water-Soluble Heteronuclear [NaCuII6] Metallomacrocyclic Sandwich Complexes: Synthesis, Structure, Properties and In Vitro Biological Studies

      Ayan Patra, Santu Kumar Saha, Tamal K. Sen, Luca Carrella, Ghezai T. Musie, Anisur Rahman Khuda-Bukhsh and Manindranath Bera

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402582

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      Water-soluble heteronuclear metallomacrocyclic sandwich clusters [NaCu6(hpnbpda)3(OH)3(OH2)3](X) [H3hpnbpda = N,N′-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N′-diacetic acid; X = NO3 (1), ClO4 (2), and PF6 (3)] have been synthesized. The cytotoxicity, DNA content analysis, DNA binding and cleavage, and mechanism of possible apoptotic cell-death events in HeLa cells were performed using complex 1.

    19. Antiparasitic Metal Complexes

      Effect of the Metal Ion on the anti T. cruzi Activity and Mechanism of Action of 5-Nitrofuryl-Containing Thiosemicarbazone Metal Complexes

      Micaella Cipriani, Jeannette Toloza, Lara Bradford, Eugenia Putzu, Marisol Vieites, Estela Curbelo, Ana Isabel Tomaz, Beatriz Garat, Juan Guerrero, Jorge S. Gancheff, Juan Diego Maya, Claudio Olea Azar, Dinorah Gambino and Lucía Otero

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402614

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      Eight complexes of formula [MCl(L)(PTA)] (M = Pd or Pt, L = 5-nitrofuryl-containing thiosemicarbazone ligands, PTA = 1,3,5-triaza-7-phosphaadamantane) were obtained. Most were active in vitro against T. cruzi. The mechanism involves bioreduction and formation of free radical species. All interact with DNA in an intercalative-like manner, but this does not lead to their antichagasic activity.

  2. Short Communications

    1. Radical–Palladium Complex

      Synthesis and Properties of a Bis[(nitronyl nitroxide)-2-ide radical anion]–Palladium Complex

      Shuichi Suzuki, Hiroyuki Yokoi, Masatoshi Kozaki, Yuki Kanzaki, Daisuke Shiomi, Kazunobu Sato, Takeji Takui and Keiji Okada

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402564

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      The chemical reduction of a bis[(nitrosonium nitroxide)-2-ide]–palladium dication selectively gave two different reduced species: a stable radical cationic species featuring a nitronyl nitroxide and a nitrosonium nitroxide, and a stable diradical species composed of two nitronyl nitroxide species. The radical cation species showed spin-localization in one of nitronyl nitroxide framework, whereas the diradical species exhibited spin-delocalization with a exchange interaction of J/kB = –36 K in a singlet ground state.

    2. Ferrocenylphosphinidene Complexes

      Activation of a 1-Chlorophosphirane Complex by Aluminum Trichloride: Generation and Trapping of [Fc-P-W(CO)5] (Fc = Ferrocenyl)

      Feny Ho, Rakesh Ganguly and François Mathey

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402662

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      AlCl3 promotes the reaction of a 1-chlorophosphirane tungsten complex with thiophene and ferrocene. The 1-ferrocenylphosphirane complex is a source of [FcP-W(CO)5]; Fc = ferrocenyl.

  3. Full Papers

    1. Polyphosphides

      Structure and Vibrational Analyses of LiP15

      Nadine Eckstein, Laura-Alice Jantke, Thomas F. Fässler, János Mink, Markus Drees and Tom Nilges

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402383

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      LiP15, the most phosphorus-rich polyphosphide in the Li–P phase diagram, has been characterized by single-crystal X-ray diffraction, quantum chemical investigations and vibrational spectroscopy. It features a pronounced needlelike morphology and is extremely sensitive to mechanical stress. It crystallizes in its own structure type, which has been confirmed by XRD and quantum calculations.

    2. Conformational Analysis

      CH3N=SF2=NCH3: Structural, Conformational, and Configurational Properties in the Gaseous and in the Condensed Phases

      Norma L. Robles, Simon Parsons, Rüdiger Mews and Heinz Oberhammer

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402523

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      The structural and configurational properties of CH3–N=SF2=N–CH3 were studied by vibrational spectroscopy, quantum chemical calculations, and X-ray crystallography. Only vibrational spectroscopy shows evidence of a conformational equilibrium of the antianti form and a slightly less favored antisyn configuration. The crystalline solid at 120 K is consistent with an antianti form.

  4. Short Communications

    1. Photovoltaic Materials

      Synthesis of Bulk Kesterite – A Prospective Photovoltaic Material

      Slawomir Podsiadlo, Maciej Bialoglowski, Grzegorz Matyszczak, Paulina Marek, Wojciech Gebicki, Rajmund Bacewicz, Marcin Stachowicz, Piotr Dluzewski and Krzysztof Wozniak

      Article first published online: 8 SEP 2014 | DOI: 10.1002/ejic.201402392

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      An advanced synthesis and characterization of bulk single crystals of kesterite are reported. Mixtures of powders of CuS, ZnS, and SnS2 were annealed in vacuo in quartz ampoules at 500–1100 °C to obtain free-standing single crystals of kesterite. SEM, TEM, XRD, Raman, and EXAFS measurements confirm the excellent structural properties of Cu2ZnSnS4 bulk single crystals.

  5. Full Papers

    1. Germanium Amides

      Monomeric Germanium(II) Amides Bearing β-Diketiminato Ligands: Synthesis, Structural Characterization, and Thermal Properties

      Ernesto Ballestero-Martínez, Jerzy Klosin, Bradley D. Fahlman and Leslie W. Pineda

      Article first published online: 5 SEP 2014 | DOI: 10.1002/ejic.201402594

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      Steric and electronic fine-tuning of β-diketiminate ligands led to the formation of monomeric germanium(II) amides by means of metathesis pathway. X-ray structural data show the germanium atom in a distorted-tetrahedral geometry. Thermogravimetric measurements of the Ge-based compounds suggest thermal decomposition.

    2. Bis(organoamino)phosphanes

      Reactivity of Bis(organoamino)phosphanes with Aluminum(III) Compounds: Straightforward Access to Diiminophosphinates by Means of Hydrogen-Atom Migration – An Experimental and Theoretical Study

      Jan Vrána, Roman Jambor, Aleš Růžička, Mercedes Alonso, Frank De Proft and Libor Dostál

      Article first published online: 5 SEP 2014 | DOI: 10.1002/ejic.201402554

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      The hydrogen-atom migration in the structure of bis(organoamino)phosphanes smoothly leads to a monoanionic diiminophosphinate backbone.

    3. Photodegradation

      Synthesis and Structure of [Et3NH]­[Fe(HL)2] [H3L = L-2-(3,5-Di-tert-butyl-2-hydroxybenzylamino)succinic Acid] and Its Catalytic Activity towards Efficient Photodegradation of Dyes in the Presence of H2O2

      Sohaham Dasgupta, Sanghamitra Atta, N. D. Pradeep Singh, Dibakar Deb, W. Scott Kassel and Manish Bhattacharjee

      Article first published online: 5 SEP 2014 | DOI: 10.1002/ejic.201402314

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      A new biomimetic amino acid ligand, L-2-(3,5-di-tert-butyl-2-hydroxybenzylamino)succinic acid (LH3), and its iron(III) complex, [Et3NH][Fe(LH)2], have been synthesized. The complex was structurally characterized. The complex was found to be an efficient catalyst for the environmentally friendly visible-light-mediated degradation and decolouriation of a number of dyes such as methylene blue.

    4. Rare-Earth Amidinate Complexes

      Structural and Reactivity Consequences of Reducing Steric Bulk of N,N′-Diarylformamidinates Coordinated to Lanthanoid Ions

      Glen B. Deacon, Peter C. Junk, Lauren K. Macreadie and Daniel Werner

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402653

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      A variety of rare-earth dimeric complexes of general formula [Ln(p-TolForm)3]2 [Ln = La, Ce, Nd, or Sm; p-TolForm = N,N′-bis(4-methylphenyl)formamidinate], were obtained showing unusual μ-1κ(N,N′):2κ(N,N′) formamidinate bridging. Dimer formation was metal size dependent.

    5. Dichalcogenides

      Reactions of Bis(dibenzobarrelenyl) Dichalcogenides with a Palladium(0) Complex: Unexpected Formations of Mono­nuclear Chalcogenide(dichalcogenolato)­palladium(II) Complexes and Dichalco­genahexacyclo Compounds

      Norio Nakata, Yuki Yamaguchi and Akihiko Ishii

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402518

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      Mononuclear chalcogenide(dichalcogenolato)PdII complexes were obtained by the reactions of bis(dibenzobarrelenyl) dichalcogenides with [Pd(PPh3)4] in toluene heated at reflux. The formations of these PdII complexes can be reasonably explained by the reaction of the 1,2-chalcogenapalladacycles with dichalcogenides through σ-bond metathesis.

    6. Actinides

      Theoretical Design of cis-Bis(imido)uranium Iodides – Electronic Structures and Spectroscopic Properties

      Chun-Mei Lv, Ling-Chao Pan, Qing-Jiang Pan, Yuan-Ru Guo and Hong-Xing Zhang

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402505

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      The electronic and spectroscopic properties of cis-bis(imido)uranium iodides have been explored by DFT. A mixed π(U=N) and π(Ph) character was calculated for their highest occupied molecular orbitals. Each U=N bond forms one orbital, which contributes to the bent N=U=N molecular skeleton. The delocalized character of the N=U=N unit in the corresponding trans isomer allows its linear structure.

    7. Barium Titanate Nanoparticles

      Barium Titanate Torus-Like Particles: Low-Temperature Synthesis and Formation Mechanism

      Florentina Maxim, Iuliana Poenaru, Florina Teodorescu and Speranta Tanasescu

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402497

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      This work reports the mechanism of formation of the hollow torus-like barium titanate particles by a template-free hydrothermal method with a view to evaluating the properties of these hollow perovskite oxide crystals nanomaterials.

    8. Luminescence

      Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks

      Mariela M. Nolasco, Ricardo F. Mendes, Patrícia P. Lima, Filipe A. Almeida Paz, Luís D. Carlos and João Rocha

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402492

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      The applicability of the LUMPAC software for calculations of the photoluminescence properties of metal–organic frameworks is assessed by considering three systems with a ditopic 1,4-phenylenebis(methylene)diphosphonic acid ligand and Eu3+ ions. A simple method based on the crystallographic structural subunits affords excellent agreement between the calculated and experimental photoluminescence.

    9. Nanoparticulate Thin Films

      TiO2/Eu3+ Thin Films with High Photoluminescence Emission Prepared by Electrophoretic Deposition from Nanoparticulate Sols

      Mario Borlaf, María T. Colomer, Alicia de Andrés, Fátima Cabello, Rosalia Serna and Rodrigo Moreno

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402445

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      Transparent and nanoparticulate anatase TiO2/Eu3+ thin films were obtained by electrophoretic deposition. A densification of the films occurs at a thickness above 400 nm and, concomitantly, a significant increase of the Eu3+ emission efficiency is detected. Similar values of PL efficiency to those of the xerogels (bulk material) could be achieved.

    10. Anionic Ligands

      Nickel and Copper Complexes of Pyrrolecarboxamide Ligands – Stabilization of M3+ Species and Isolation of Ni3+ Complexes

      Sushil Kumar, Megha Munjal, Jyoti Singh and Rajeev Gupta

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402361

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      NiII and CuII complexes of pyrrolecarboxamide ligands containing –H, –CH3, and –Cl substituents are presented. Chemical and electrochemical oxidation results in the isolation of Ni3+ complexes and the generation of Cu3+ species. Spectroscopic studies reveal square-planar geometries around the Ni3+ and Cu3+ ions.

    11. Gas Adsorbing Materials

      Efficient Hybrid-Type CO2 Adsorbents of Reassembled Layered Double Hydroxide 2D Nanosheets with Polyoxometalate 0D Nanoclusters

      Jayavant L. Gunjakar, In Young Kim and Seong-Ju Hwang

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402480

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      Porous nanohybrids of Mg-Al-layered double hydroxide (LDH) 2D nanosheets and polyoxometalate 0D nanoclusters are synthesized by an exfoliation–reassembling process. The resulting nanohybrid materials show promising CO2 adsorption capabilities exceeding those of pristine Mg-Al-LDH, underscoring the usefulness of the present hybridization method in optimizing gas adsorption by LDH materials.

    12. Energetic Ionic Salts

      Synthesis and Characterization of the Nitrophenol Energetic Ionic Salts of 5,6,7,8-Tetrahydrotetrazolo[1,5-b][1,2,4]triazine

      Jin-Ting Wu, Jian-Guo Zhang, Xin Yin, Piao He and Tong-Lai Zhang

      Article first published online: 1 SEP 2014 | DOI: 10.1002/ejic.201402337

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      Three nitrogen-rich energetic salts of 5,6,7,8-tetrahydrotetrazolo[1,5-b][1,2,4]triazine (TZTN) have been prepared and characterized by single-crystal X-ray diffraction analysis. The salts exhibit excellent detonation performance and combine good thermal stabilities with acceptable sensitivities.

    13. Schiff-Base Complexes

      Main-Chain Oligomers from NiII- and CuII-Centered Unsymmetrical N2O2 Schiff-Base Complexes: Synthesis and Spectral, Structural, and Second-Order Nonlinear Optical Properties

      Salvador Celedón, Vincent Dorcet, Thierry Roisnel, Anu Singh, Isabelle Ledoux-Rak, Jean-René Hamon, David Carrillo and Carolina Manzur

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402469

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      The esterification of binuclear phenol and carboxylic acid functionalized ferrocenyl-containing metal-centered Schiff-base complexes (M = Ni, Cu) in the presence of N,N′-dicyclohexylcarbodiimide and dmap afforded their corresponding main-chain oligomers. They are formed of approximately six monomeric units, are redox active, and exhibit good thermal stability and high second-order NLO responses.

    14. Trimetallic Ag Complexes

      Triangular [Ag3]3+ Complexes Supported by Picolyl-Substituted N-Heterocyclic Carbene Ligands

      Lyndsay B. Munro and Vincent J. Catalano

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402483

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      A series of 12 picolyl-substituted benzimidazolylidene- and imidazolinylidene-based N-heterocyclic carbene ligands have been prepared. Eleven underwent complexation with AgI to form trimetallic complexes with short AgI–AgI metal–metal separations. In solution, all but one of these complexes are dynamic and dissociate and exchange ligands.

    15. Mechanism of Palladium Catalysis

      Mechanistic Insights into the PdII-Catalyzed Chemoselective N-Demethylation vs. Cyclometalation Reactivity Pathways in 1-Aryl-N,N-dimethylethanamines

      Jeanette See Leng Yap, Yi Ding, Xiang-Yuan Yang, Jonathan Wong, Yongxin Li, Sumod A. Pullarkat and Pak-Hing Leung

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402547

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      Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of one isomer with PdII ions generated the ortho-metalated complex, whilst the other isomer resulted in the unexpected chemoselective C–N bond cleavage to afford the corresponding secondary amine.

    16. Ambiphilic Ligands

      Synthesis, Structures and Coordination Chemistry of Singly Bridged Phosphane-Boranes with Coordinately Unsaturated Platinum Group Metals

      Victoria K. Greenacre, Melvyn B. Ansell, S. Mark Roe and Ian R. Crossley

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402649

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      The synthesis and characterisation of a range of singly bridged phosphane-boranes is described. Their coordination complexes with co-ordinately unsaturated platinum group metals demonstrate a propensity for adopting structures with pendant borane moieties occupying distal positions.

    17. Spin-Crossover Complexes

      Unusual Solvent Dependence of a Molecule-Based FeII Macrocyclic Spin-Crossover Complex

      Hongfeng Wang, Chiara Sinito, Abdellah Kaiba, José Sanchez Costa, Cédric Desplanches, Philippe Dagault, Philippe Guionneau, Jean-François Létard, Philippe Negrier and Denise Mondieig

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402666

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      The solvent dependence of spin-crossover behavior and metastability of the FeII complex [FeL222N3O2(CN)2]·H2O were investigated. Compared with the pristine and the dehydrated complex, the rehydrated complex shows enhanced metastability and an increased spin-transition temperature. This solvent dependence indicates new possibilities to improve metastability toward further applications.

    18. Coordination Chemistry

      Evolution of the Coordination-Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with N,N′-Double-Armed Diaza-Crown Ethers: Experimental and Theoretical Approaches

      Katalin Selmeczi, Jean-Pierre Joly, Mustapha Allali, Violeta Yeguas, Bernard Henry and Manuel Ruiz-Lopez

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402432

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      Symmetric versus asymmetric octahedral coordination geometry changes were observed for Cu2+, Ni2+, and Zn2+ complexes of a N,N′-triazolyl-biarmed diaza[18]crown-6 macrocycle. Quantum chemical calculations at the DFT level confirmed these observations and allowed us to interpret them in terms of covalent or noncovalent metal–ligand interactions.

    19. Solid-State Structures

      New Lithium-Containing Pnictides with 1-D Infinite Chains of Supertetrahedral Clusters: Synthesis, Crystal and Electronic Structure of Ba4Li2Cd3Pn6 (Pn = P, As and Sb)

      Julien P. A. Makongo, Tae-Soo You, Hua He, Nian-Tzu Suen and Svilen Bobev

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402434

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      Three new Zintl phases have been synthesized for the first time, and their crystal structures have been established by single-crystal X-ray diffraction. They crystallize with their own-structure type in the orthorhombic space group Cmcm (Pearson code oC60) and their crystal structure is based on one-dimensional infinite chains of supertetrahedral clusters, [Cd4Pn10].

    20. Catalytic Networks

      Two-Dimensional {Co3+–Co2+} and {Fe3+–Co2+} Networks and Their Heterogeneous Catalytic Activities

      Sumit Srivastava, Manvender Singh Dagur and Rajeev Gupta

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402375

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      Reusable two-dimensional {Co3+–Co2+} and {Fe3+–Co2+} networks heterogeneously catalyze Knoevenagel condensation and cyanation reactions of assorted aldehydes owing to the kinetic lability and Lewis acidity of the secondary Co2+ ions.

  6. Short Communications

    1. Magnetic Anisotropy in Dy Complexes

      An Ionic Dysprosium Complex Made of a Hexanuclear Dy6 Cationic Cluster and a Mononuclear Dy Anionic Unit

      Jean-Pierre Costes and Carine Duhayon

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402622

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      A novel hydrazide ligand allows the preparation of an ionic species made of a cationic hexanuclear Dy6 cluster and an anionic mononuclear Dy unit, which corresponds to the 2,4M6–1 + 1(0) motif observed for the first time with Ln ions.

    2. Ruthenium Sensitizers

      Efficient Ruthenium Sensitizer with a Terpyridine Ligand Having a Hexylthiophene Unit for Dye-Sensitized Solar Cells: Effects of the Substituent Position on the Solar Cell Performance

      Hironobu Ozawa, Takahiro Kuroda, Shohei Harada and Hironori Arakawa

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402530

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      A novel ruthenium sensitizer with a terpyridine ligand having a hexylthiophene unit at the 4-position (TUS-38) has been synthesized, and the dye-sensitized solar cell with TUS-38 showed a 10.6 % conversion efficiency under AM 1.5 (100 mW/cm2) irradiation.

  7. Microreviews

    1. Molecular Catalysts

      Chromophores, Fluorophores and Robust Ancillary Ligands for Molecular Catalysts: 1,3-Bis(2-pyridylimino)isoindolines

      Désirée C. Sauer, Rebecca L. Melen, Matthias Kruck and Lutz H. Gade

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402595

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      This microreview focuses on the development of 1,3-bis(2-pyridylimino)isoindolines (BPI) from their synthesis over half a century ago through to their current diverse applications in organic, inorganic and materials chemistry.

  8. Short Communications

    1. Borylene Insertion

      Unprecedented Borylene Insertion into a C–N Bond

      Rajendra S. Ghadwal, Christian J. Schürmann, Felix Engelhardt and Christian Steinmetzger

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402750

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      Formation of a boryl-functionalized NHO 6 as a dimer suggests the involvement of a borylene insertion into a C–N bond. The parent borylene (R = H) follows a completely different route in which hydrogen abstraction and intermolecular B–B coupling events seem operative to afford a diborane (7) stabilized by an NHC.

  9. Full Papers

    1. Asymmetric Strecker Reaction

      Chiral MnIII–salalen and –salan Complexes Derived from (S)-Pyrrolidin-2-yl­methanamine and Their Catalytic Activity in the Asymmetric Strecker Reaction

      Pramod Kumar, S. Saravanan, Noor-ul Hasan Khan, Firasat Hussain and Surendra Singh

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402548

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      Chiral MnIII–salalen and –salan complexes have been synthesized and used as a catalyst for the asymmetric Strecker reaction. These complexes were characterized by elemental analysis, FTIR and UV/Vis spectroscopy, exact mass determination and single-crystal XRD. The catalyst 9a catalysed the Strecker reactions of a range of substrates with moderate enantioselectivity of the corresponding products.

    2. Heterogeneous Catalysis

      The Nature of the Active Site in Ziegler–Natta Olefin Polymerization Catalysis Systems – A Computational Investigation

      Jugal Kumawat, Virendra Kumar Gupta and Kumar Vanka

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402180

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      The nature of the active site in Ziegler–Natta heterogeneous catalysis systems has been explored with density functional theory (DFT). New insights include the understanding that donor coordination to the metal center can lead to an increase in the molecular weight of the polymer. The role of AlEt3 as a possible donor has also been investigated.

  10. Short Communications

    1. Redox-Active Ligands

      Electrochemical Implication of a Hydrogen-Bonded Imidazole on a Redox-Active-Bound Phenolate Group

      Sanae El Ghachtouli, Benedikt Lassalle-Kaiser, Régis Guillot and Ally Aukauloo

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402140

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      We report the synthesis and crystallographic structures of zinc complexes with a pentadentate N4O ligand with an imidazole group placed in the ortho position of the phenol group. Furthermore, we describe the influence of the outer-sphere imidazole fragment on the electrochemical behavior of the redox-active-bound phenolate ligand.

  11. Full Papers

    1. Janus-Head NHC Ligands

      Mono- and Hetero-Dinuclear Complexes of Janus-Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers

      Paresh Kumar Majhi, Spencer C. Serin, Gregor Schnakenburg, Derek P. Gates and Rainer Streubel

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402440

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      A family of hybrid ligands composed of hard phosphine oxides and soft N-heterocyclic carbene donor sites have been employed to synthesize [M(cod)Cl(NHCP)] complexes I, which were further converted into the corresponding dicarbonyl complexes in order to study their donor properties. The advantage of backbone phosphinoyl groups was exploited to generate hetero-dinuclear TiIV, RhI complexes 10a,a′.

    2. Polyoxometalates

      Synthesis of Metforminium(2+) Decavanadates – Crystal Structures and Solid-State Characterization

      Irma Sánchez-Lombardo, Eduardo Sánchez-Lara, Aarón Pérez-Benítez, Ángel Mendoza, Sylvain Bernès and Enrique González-Vergara

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402277

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      The synthesis, solid-state characterization, and X-ray analyses of three new metforminium(2+) decavanadates are presented. The compositions and stabilities of the three hydrates are strongly modified by the stoichiometry of the reaction and the presence or absence of ammonium cations.

    3. Enzyme Models

      A Nickel-Containing Model System of Acireductone Dioxygenases that Utilizes a C(1)-H Acireductone Substrate

      Caleb J. Allpress and Lisa M. Berreau

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402254

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      A NiII complex of a protected C(1)-H acireductone ligand can be deprotected by using NaOCH3 in the presence of O2 to give oxidative aliphatic C–C bond-cleavage products akin to those produced by the NiII-containing acireductone dioxygenase enzyme.

    4. Biosensing

      Properties of an Indium Tin Oxide Electrode Modified by a Laser Nanostructured Thin Au Film for Biosensing

      Katarzyna Grochowska, Katarzyna Siuzdak and Gerard Śliwiński

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402485

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      Thin Au films on ITO that were stepwise patterned by means of nanosecond UV laser pulses transformed into semi-regular nanoparticle arrays. The modified electrode showed enhanced activity towards ferricyanide redox systems as well as glucose, and can be considered for the production of a non-enzymatic biosensor.

    5. Multinuclear Complexes

      Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers

      Takayuki Nakajima, Keiko Seto, Andreas Scheurer, Bunsho Kure, Takashi Kajiwara, Tomoaki Tanase, Masahiro Mikuriya and Hiroshi Sakiyama

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402536

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      Unsymmetrical amine-diol ligands are suitable for the assembly of homo- and heterometallic tetranuclear {M4O6} complexes. 1D coordination polymers are formed by linking the tetranuclear nickel and cobalt complexes with a diol linker ▪▪((<=Author: the size of the graphic for the table of contents had to be reduced for technical reasons))▪▪.

    6. Metalloenzyme IR Markers

      Mid- and Far-Infrared Marker Bands of the Metal Coordination Sites of the Histidine Side Chains in the Protein Cu,Zn-Superoxide Dismutase

      Bertrand Xerri, Hugo Petitjean, François Dupeyrat, Jean-Pierre Flament, Alain Lorphelin, Claude Vidaud, Catherine Berthomieu and Dorothée Berthomieu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402263

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      The metal–histidine vibrations of the Cu,Zn-superoxide dismutase enzyme are analyzed by mid- and far-infrared difference spectroscopy. The histidine metal–ligand markers are analyzed and assigned from a combination of experimental and computational data. The contributions of the histidine modes are identified through additional data collected and calculated for labelled samples.

    7. Cation Structures

      Protonated Digermane, Distannane, and Diplumbane: Can They Be Made in the Laboratory?

      Yundong Guo, Yanjun Hao, Hui Wang, Yaoming Xie and Henry F. Schaefer III

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402510

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      Similarly to C2H7+ and Si2H7+, the Ge2H7+, Sn2H7+, and Pb2H7+ cations are predicted to be energetically favorable to varying degrees, and they appear to have different low-lying structures.

  12. Microreviews

    1. Vapochromic Materials

      Vapochromic Platinum(II) Complexes: Crystal Engineering toward Intelligent Sensing Devices

      Atsushi Kobayashi and Masako Kato

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402315

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      Square-planar platinum(II) complexes that exhibit intense changes in luminescence and color based on metallophilic interactions are promising vapochromic materials. In an effort to generate highly sensitive and selective vapor responses, various PtII complexes have been developed by utilizing different intra- and intermolecular interactions.

  13. Full Papers

    1. Inclusion Compounds

      Synthesis, Characterisation and Antiproliferative Studies of Allyl(dicarbonyl)(cyclopentadienyl)molybdenum Complexes and Cyclodextrin Inclusion Compounds

      Susana S. Braga, Vijaya Mokal, Filipe A. Almeida Paz, Martyn Pillinger, Ana F. Branco, Vilma A. Sardão, Cátia V. Diogo, Paulo J. Oliveira, Maria P. M. Marques, Carlos C. Romão and Isabel S. Gonçalves

      Article first published online: 19 AUG 2014 | DOI: 10.1002/ejic.201402540

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      The crystal structure of [(η5-C5H4–COOH)Mo(CO)23-C3H5)] (1) is presented. Both 1 and its phenylalanine derivative were included into β-cyclodextrin (CD) and per-O-methylated β-CD (TRIMEB). Overall, the inclusion contributed to a higher and more specific action on tumour cells, thereby lowering deleterious effects on a healthy myoblast line.

    2. Copper Catalysis

      Tetranuclear Copper(II) Complexes with Macrocyclic and Open-Chain Disiloxane Ligands as Catalyst Precursors for Hydrocarboxylation and Oxidation of Alkanes and 1-Phenylethanol

      Mirela-Fernanda Zaltariov, Mihaela Alexandru, Maria Cazacu, Sergiu Shova, Ghenadie Novitchi, Cyrille Train, Anatolie Dobrov, Marina V. Kirillova, Elisabete C. B. A. Alegria, Armando J. L. Pombeiro and Vladimir B. Arion

      Article first published online: 18 AUG 2014 | DOI: 10.1002/ejic.201402578

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      Two new tetranuclear copper(II) complexes act as homogeneous catalyst precursors for the single-pot hydrocarboxylation of a variety of linear and cyclic Cn (n = 5–8) alkanes into the corresponding Cn+1 carboxylic acids, peroxidative oxidation of cyclohexane, and solvent-free microwave-assisted oxidation of 1-phenylethanol.

  14. Microreviews

    1. Metallo Amino Acids

      Redox and Photochemistry of Bis(terpyridine)ruthenium(II) Amino Acids and Their Amide Conjugates – from Understanding to Applications

      Aaron Breivogel, Christoph Kreitner and Katja Heinze

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402466

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      Ruthenium(II) amino acid [Ru(4′-tpy-COOH)(4′-tpy-NH2)]2+ interacts with photons, electrons, and/or protons, to lead to phosphorescence, oxidative and reductive chemistry, acid/base chemistry, proton-coupled electron transfer, photoinduced reductive and oxidative electron transfer, excited-state proton transfer, and energy transfer. Applications include light-emitting electrochemical and dye-sensitized solar cells.

  15. Full Papers

    1. Nanoparticles

      Defining the Structural Parameters of Tri­azole Ligands in the Templated Synthesis of Silver Nanoparticles

      Heba A. Kashmery, Alasdair W. Clark, Ruggero Dondi, Andrew J. Fallows, Paul M. Cullis and Glenn A. Burley

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402593

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      Control of both the size and shape of silver nanoparticles (AgNPs) can be achieved using triazole sugar ligands and the Tollens' reagent [Ag(NH3)2OH] as the silver source. Higher affinity for AgI results in smaller AgNPs, whereas ligands with lower affinity for AgI form larger AgNPs in which the size can be tuned according to the reaction conditions.

    2. Cluster Compounds

      You have full text access to this OnlineOpen article
      Mixed-Metal Oxo Clusters Structurally Derived from Ti6O4(OR)8(OOCR′)8

      Christine Artner, Ayse Koyun, Matthias Czakler and Ulrich Schubert

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402499

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      Fe/Ti, Zn/Ti, Cd/Ti, Ca/Ti, and Sr/Ti mixed-metal oxo clusters were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures can be traced back to that of Ti6O4(OR)8(OOCR′)8 clusters and the structural variations to the different ionic radii and coordination numbers.

    3. Energetic Materials

      Contributions to the Chemistry of N-Methylnitramine: Crystal Structure, Synthesis of Nitrogen-Rich Salts, and Reactions towards 2-Nitro-2-azapropyl Derivatives

      Marcos A. Kettner, Thomas M. Klapötke, Thomas G. Müller and Muhamed Sućeska

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402441

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      The hitherto unknown crystal structure of N-methylnitramine has been determined. Its Mannich product with formaldehyde was treated with 2-nitro-2-azapropyl isocyanate or water to provide products that were characterized as energetic materials and compared to currently used explosives.

    4. Composite Structures

      Optical and Electrooptical Properties of Porous-Silicon/Conjugated-Polymer Composite Structures

      Amit Nahor, Itai Shalev, Amir Sa'ar and Shlomo Yitzchaik

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402450

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      An organic–inorganic hybrid structure consisting of porous silicon and nanowires of poly(N-vinylcarbazole) (PVK) exhibits optical behavior of the PVK nanowires, which is unique when compared with the bulk material. Furthermore, a simple method to control the band alignment between type-I and type-II is demonstrated. Our results enable a variety of applications and electrooptical characteristics.

    5. Spin-State Energetics

      You have full text access to this OnlineOpen article
      Spin-State Energetics of FeII Complexes – The Continuing Voyage Through the Density Functional Minefield (pages 4573–4580)

      Benjamin J. Houghton and Robert J. Deeth

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402253

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      Calculating the absolute spin-state energies of metal complexes is a challenge for quantum chemistry. Computing trends is easier, but caution is required. Not all functionals perform equally, and even for the good ones, there are generally outliers. Despite significant progress, the “universal functional” remains elusive.

    6. Luminescent Complexes

      o-Oxazolinyl- and o-Thiazolinylphenol as Antennae in Luminescent EuIII and TbIII Complexes

      Sebastiaan Akerboom, E. Tom Hazenberg, Ireen Schrader, Sarah F. Verbeek, Ilpo Mutikainen, Wen Tian Fu and Elisabeth Bouwman

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402447

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      Complexes of europium(III) and terbium(III) using the ligands 2-(4,5-dihydro-1,3-oxazol-2-yl)phenol and 2-(4,5-dihydro-1,3-thiazol-2-yl)phenol have been prepared with M/L ratios of 1:3 and 1:4; five of these compounds show bright luminescence upon excitation by near-UV radiation. Crystallisation from DMSO resulted in the formation of CO3-containing octanuclear complexes.

    7. Blue Phosphorescence

      Towards Deep-Blue Phosphorescence: Molecular Design, Synthesis and Theoretical Study of Iridium Complexes with Cyclometalating 2-Phenyl-2H-[1,2,3]tri­azole Ligands

      Yinping Zhao, Jia Tang, Houyu Zhang and Yuguang Ma

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402399

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      Two blue-emitting iridium complexes with cyclometalating 2-phenyl-2H-[1,2,3]triazole ligands were synthesized and characterized. The two complexes both show strong deep-blue emission at 77 K, but no emission at room temperature. Calculations suggest that this lack of emmission might be caused by distorted excited state structures of the complexes.

    8. Rhodium

      Synthesis and Characterization of Cationic Synphos-Rhodium Complexes

      Antje Meißner, Hans-Joachim Drexler, Sonja Keller, Carmen Selle, Virginie Ratovelomanana-Vidal and Detlef Heller

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402324

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      Several types of cationic Rh complexes generated under reaction conditions starting from the precursor [Rh(Synphos)(diolefin)]BF4 were identified by NMR spectroscopy. Furthermore, six of these species were characterized by X-ray analysis for the first time; this includes the active species [Rh(Synphos)(acetone)2]BF4 as well as deactivating arene complex [Rh(Synphos)(methyl-η6-benzene)]BF4.

    9. Isomerization

      A Differential Scanning Calorimetry and Theoretical Study on the Isomerization of trans-[Co(cyclam)(ONO)2]X (X = PF6, ClO4)

      Abbas Eslami, Nahid Hasani and Saeed Yeganegi

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402174

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      The thermal linkage isomerization of the title compounds in the solid state was studied by differential scanning calorimetry (DSC). The observed exothermic DSC peak of the dinitrito isomer was resolved into two peaks that correspond to two isomerization stages. A comparative experimental and DFT study was performed on the thermodynamics and kinetics of the dinitrito to dinitro isomerization.

    10. Diselenaphospholanes

      Reactions of 1,3,2-Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and -iridium Dichloride

      Bernd Wrackmeyer, Elena V. Klimkina and Wolfgang Milius

      Article first published online: 12 AUG 2014 | DOI: 10.1002/ejic.201402486

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      Borane reagents as well as Cp*MCl2 (Cp* = pentamethylcyclopentadienyl; M = Rh, Ir) react with 1,3,2-diselenaphospholanes by the formation of adducts, followed by ring insertion, and finally by exchange.

    11. Uranyl–Organic Frameworks

      Uranyl Ion Complexes with trans-3-(3-Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework

      Pierre Thuéry and Jack Harrowfield

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402556

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      The heterofunctional pro-ligand trans-3-(3-pyridyl)acrylic acid was used to build a uranyl–copper(II) heterometallic complex, in which the preferential bonding of the two cations reflects hard and soft affinities and which crystallizes as a 3D framework. The crystal structure of a new 1D homometallic uranyl complex with the same ligand is also described.

    12. C–H Activation

      Rationalizing and Disrupting Fluxional Processes in Agostically Stabilized 14-Electron Alkyliridium Hydride Complexes

      Nicholas Phillips, Lucinda Treasure, Nicholas H. Rees, Rémi Tirfoin, John E. McGrady and Simon Aldridge

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402516

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      By NMR spectroscopy and DFT methods, the mechanism of fluxional exchange in cationic bis(NHC) IrIII systems with an agostic C–H bond and cis-alkyl/hydride ligands is shown to feature an oxidative pathway. Related nonfluxional systems can be “trapped” by the addition of two-electron donors (L), and their stability to C–H reductive elimination can be tuned through the π-acceptor properties of L.

    13. Solar Cells

      Triphenylamine-Substituted Metalloporphyrins for Solution-Processed Bulk Heterojunction Solar Cells: The Effect of the Central Metal Ion on Device Performance

      Yunan Zhang, Shitong Zhang, Liang Yao, Leiqiang Qin, Li Nian, Zengqi Xie, Bing Yang, Linlin Liu and Yuguang Ma

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402427

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      Porphyrins with enhanced solubility and intermolecular interactions have been developed by incorporating the flexible and strong electron-donating triphenylamine substituent. Furthermore, different metal(II) ions have been introduced to the porphyrin and applied in organic photovoltaics to study the effects of the central metal ions on device performance.

    14. Solid-Phase Synthesis

      Mechanochemical Synthesis of SiO44–-Substituted Hydroxyapatite, Part II – Reaction Mechanism, Structure, and Substitution Limit

      Natalya Bulina, Marina Chaikina, Andrey Andreev, Olga Lapina, Arcady Ishchenko, Igor Prosanov, Konstantin Gerasimov and Leonid Solovyov

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402246

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      Silicate-substituted hydroxyapatite powders containing different amounts of silicon have been synthesized by the mechanochemical method. Several apatite crystal structures that differ by the position of the hydroxy groups have been identified.

    15. 3D Nanoarchitectures

      Synthesis of Urchin-Like FeF2 Nanoarchitectures and Their Conversion into Three-Dimensional Urchin-Like Mesoporous α-Fe2O3 Nanoarchitectures for Methane Activation

      Bing Dong, Hengqiang Zhang, Aiguo Kong, Yingying Kong, Fan Yang and Yongkui Shan

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402152

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      Novel urchin-like FeF2 nanoarchitectures have been fabricated by an unconventional nonhomogeneous ionic liquid/diphenyl ether solvothermal method and converted into 3D urchin-like mesoporous α-Fe2O3 nanoarchitectures by solid-state thermal annealing. The α-Fe2O3 nanoarchitectures exhibit good catalytic properties in methane activation reactions.

    16. Solid-Phase Synthesis

      Mechanochemical Synthesis of SiO44–-Substituted Hydroxyapatite, Part I – Kinetics of Interaction between the Components

      Marina Chaikina, Natalya Bulina, Arcady Ishchenko and Igor Prosanov

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402247

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      The kinetics of the dry mechanochemical synthesis of hydroxyapatite modified by SiO44– ions is studied. From the first seconds of mechanical activation, the initial Ca(H2PO4)2·H2O partially reacts with CaO to form CaHPO4 (interior of the nanoparticles); the nanoparticle shell is Ca(H2PO4)2·H2O, and the material located near the nanoparticles is a mechanical mixture of the initial components.

    17. Ruthenium Complexes

      [Ge(H)(2-C6H4PPh2)3] as Ligand Precursor at Ruthenium: Formation and Reactivity of [Ru(Cl){Ge(2-C6H4PPh2)3}]

      Roy Herrmann, Thomas Braun and Stefan Mebs

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402256

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      The ruthenium complex [Ru(Cl){Ge(2-C6H4PPh2)3}] can be converted into the dihydrogen complex [Ru{Ge(2-C6H4PPh2)3}(H)(H2)] on treatment with KH in a dihydrogen atmosphere. A reaction of [Ru{Ge(2-C6H4PPh2)3}(H)(H2)] with hydrazine led to its catalytic disproportionation to give ammonia and the ammonia complex [Ru{Ge(2-C6H4PPh2)3}(H)(NH3)].

    18. Pincer Complexes

      Microwave-Assisted C–C and C–S Couplings Catalysed by Organometallic Pd-SCS or Coordination Ni-SNS Pincer Complexes

      Manuel Basauri-Molina, Simón Hernández-Ortega and David Morales-Morales

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402571

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      A series of SCS-PdII and SNS-NiII pincer compounds of the type [PdCl{C6H3-2,6-(CH2SR)2}] and [NiCl2{C5H3N-2,6-(CH2SR)2}] {R = tBu, sBu, iBu} were synthesized and used as efficient catalysts in C–C Suzuki–Miyaura and C–S thiolation cross-coupling reactions.

    19. Crystal Growth Study

      Syntheses and Solid-State Structures of Et2SbTeEt and Et2BiTeEt

      Stefan Heimann, Andreas Kuczkowski, Dieter Bläser, Christoph Wölper, Rebekka Haack, Georg Jansen and Stephan Schulz

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402471

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      Single crystals of Et2M–TeEt (M = Sb 1, Bi 2) as well as tBu3Sb (3) were grown by using an IR-laser-assisted technique. Compounds 1 and 2 form short intermolecular E···Te interactions in the solid state, which were further investigated with dispersion-corrected density functional theory.

    20. Bioinorganic Chemistry

      BOX Ligands in Biomimetic Copper-Mediated Dioxygen Activation: A Hemocyanin Model

      Adam Walli, Sebastian Dechert, Matthias Bauer, Serhiy Demeshko and Franc Meyer

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402378

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      A series of bis(oxazoline)-copper(I) complexes reversibly bind dioxygen to yield biomimetic μ-η22-peroxo-dicopper(II) species, which represent new functional hemocyanin models. Their kinetics of formation have been studied under cryo conditions, and the complexes have been isolated as surprisingly stable solids. All were investigated by a variety of methods, both in solution and in the solid state.

  16. Microreviews

    1. Coordination Geometry

      Trigonal Bipyramidal or Square Pyramidal Coordination Geometry? Investigating the Most Potent Geometry for Vanadium Phosphatase Inhibitors

      Debbie C. Crans, Michael L. Tarlton and Craig C. McLauchlan

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402306

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      In this microreview, we analyze the five-coordinate geometries (an important factor in phosphoryl group transfer) for a range of VO4X coordination spheres with regard to their structure, considered as square pyramidal or trigonal bipyramidal geometries. We demonstrate that actual differences between the coordination environments are very small and presumably less critical than generally anticipated.

  17. Full Papers

    1. Silver Clusters

      Synthesis of Atomically Precise Silver Clusters by Using the Miscibility Principle

      Atanu Ghosh and Thalappil Pradeep

      Article first published online: 28 JUL 2014 | DOI: 10.1002/ejic.201402587

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      Silver and gold clusters have been synthesized by using the miscibility principle of solvents. Three solvents, that is, water, methanol, and toluene (or chloroform) have been used to synthesize different silver clusters by this method without phase-transfer agents. Separate regions of the phase diagram (a, b, c, and d) produce distinctly different clusters from the same reactant compositions.

    2. Nanostructures

      Photoinduced Topological Transformation in Mesoscopic Inorganic Nanoparticles: Application as a UV Sensor

      Santu Das, Preethi Thomas and Soumyajit Roy

      Article first published online: 22 JUL 2014 | DOI: 10.1002/ejic.201402297

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      Irradiation of ammonium heptamolybdate tetrahydrate soft-oxometalate (SOM) nanorods with UV light leads to their topological transformation into molybdenum blue SOM nanospheres. This transformation is accompanied by a colour change from colourless to blue, which can be exploited for UV sensing. Thus, when a particular threshold amount of UV irradiation is absorbed, the nanorods change colour.

    3. Copper Catalysts

      Polynuclear Copper(II) Complexes as Catalysts for the Peroxidative Oxidation of Cyclohexane in a Room-Temperature Ionic Liquid

      Raja Jlassi, Ana P. C. Ribeiro, M. Fátima C. Guedes da Silva, Kamran T. Mahmudov, Maximilian N. Kopylovich, Tatiana B. Anisimova, Houcine Naïli, Gonçalo A. O. Tiago and Armando J. L. Pombeiro

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402352

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      Multinuclear CuII complexes with a catalytic metal centre and an acid functionality catalyze the peroxidative oxidation of cyclohexane in acid-free water/air/CH3CN or ionic liquid media.

  18. Microreviews

    1. Silver(I) Cyanoximates

      Synthesis, Properties, and Applications of Light-Insensitive Silver(I) Cyanoximates

      Nikolay Gerasimchuk

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402251

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      Twelve coordination polymers of silver(I) cyanoximates of composition AgL were found to be very stable towards visible light. Three areas of potential practical relevance of these unusual complexes have emerged. The chemical, structural, technological, and biological aspects of the applications of these compounds are reviewed.

    2. Heterometallic Complexes

      Polynuclear Heterometallic Complexes from Metal Powders: The “Direct Synthesis” Approach

      Dmytro S. Nesterov, Oksana V. Nesterova, Vladimir N. Kokozay and Armando J. L. Pombeiro

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402266

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      In this review we summarize our experience in the field of the “direct synthesis” of polynuclear heterometallic complexes, covering preparative and structural aspects as well as applications of the compounds obtained.

    3. Stimuli-Responsive Materials

      Stimuli-Responsive Dynamic Gold Complexes

      Csaba Jobbágy and Andrea Deák

      Article first published online: 10 JUL 2014 | DOI: 10.1002/ejic.201402249

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      A general overview on stimuli-responsive gold(I) and gold–heterometal derivatives is presented with a special focus on the impact of noncovalent interactions on molecular structures, packing patterns and solid-state properties. Representative examples with thermo-, mechano- and vapochromic luminescence, vapochromism and gas sorption properties have been selected.

  19. Short Communications

    1. Electron-Transfer Reactions

      Electron-Transfer Rate Enhancements in Nanosized Waterpools

      Bret B. Lorenz, Debbie C. Crans and Michael D. Johnson

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402307

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      The kinetics of electron-transfer reactions between metal complexes and ascorbic acid (vitamin C) are reported in both aqueous media and in nanosized water droplets formed in microemulsions. Rate-constant enhancements of up to two orders of magnitude are reported.

  20. Full Papers

    1. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization

      Andrónico Neira-Carrillo, Fabian Luengo-Ponce, Patricio Vásquez-Quitral, Mehrdad Yazdani-Pedram, María Soledad Fernández, Helmut Cölfen and José Luis Arias

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402063

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      Sulfonated and fluorescent polymethylsiloxanes (SO3H-PMS) were synthesized and used as additives for in vitro calcium oxalate (CaOx) crystallization. The strong modifying capacity of SO3HPMS on CaOx morphologies and CaOx monohydrate (COM) and CaOx dihydrate (COD) crystal types was demonstrated. Fluorescent CaOx crystals were also produced by the inclusion of SO3H-PMS into the CaOx matrix.

    2. Macroions

      Self-Assembly of Subnanometer-Scaled Polyhedral Oligomeric Silsesquioxane (POSS) Macroions in Dilute Solution

      Jing Zhou, Panchao Yin, Lang Hu, Fadi Haso and Tianbo Liu

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402237

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      Two oppositely charged polyhedral oligomeric silsesquioxane (POSS) macroions with identical charge and similar sizes can self-assemble into blackberry-type supramolecular structures in dilute solution. This transition from simple macroions to assemblies can be regulated by the solvent polarity.

    3. Nickel Hydride Electrocatalysts

      A NiII–Bis(diphosphine)–Hydride Complex Containing Proton Relays – Structural Characterization and Electrocatalytic Studies

      Parthapratim Das, Ryan M. Stolley, Edwin F. van der Eide and Monte L. Helm

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402250

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      A new member of the [Ni(PR2NR′2)2]2+ family of electrocatalysts is reported. Complex [Ni(PiPr2NPh2)2]2+ is an electrocatalyst for proton reduction to form H2. Additionally, we have isolated and structurally characterized the NiII–hydride [HNi(PiPr2NPh2)2]+.

  21. Microreviews

    1. Dinuclear Technetium Complexes

      A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

      Frederic Poineau, Paul M. Forster, Tanya K. Todorova, Erik V. Johnstone, William M. Kerlin, Laura Gagliardi, Kenneth R. Czerwinski and Alfred P. Sattelberger

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402340

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      This review covers the metal–metal bond chemistry of dinuclear technetium complexes published in the period 2005–2014. The preparation, solid-state and electronic structures, and spectroscopic properties of (nBu4N)2Tc2X8, Tc2(O2CCH3)4X2, Tc2(O2CCH3)2Cl4, cesium salts of Tc2X83–, and Tc2X4(PMe3)4 (X = Cl, Br) are presented.

  22. Full Papers

    1. Cycloruthenated Complexes

      Cycloruthenation of N-(Naphthyl)salicyl­aldimine and Related Ligands: Utilization of the Ru–C Bond in Catalytic Transfer Hydrogenation

      Jayita Dutta, Michael G. Richmond and Samaresh Bhattacharya

      Article first published online: 17 JUN 2014 | DOI: 10.1002/ejic.201402236

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      N-(Naphthyl)-4-R-salicylaldimines (R = OCH3, H, Cl; H2L1–H2L3) and 2-hydroxy-N-(naphthyl)naphthaldimine (H2L4) react with [Ru(PPh3)2(CO)2Cl2], undergoing C–H bond activation at the peri position, to afford complexes of the type [Ru(PPh3)2(L)(CO)] (L = L1L4), which can efficiently catalyze the transfer hydrogenation of carbonyl compounds.

    2. Nickel Nanoparticles

      A Neutral 1D Coordination Polymer Constructed from the NiII Complex of the N-Phosphorylated Thiourea PhNHC(S)­NHP­(O)(OPh)2 and Pyrazine: A Single-Source Precursor for Nickel Nanoparticles

      Maria G. Babashkina, Damir A. Safin, Koen Robeyns and Yann Garcia

      Article first published online: 3 JUN 2014 | DOI: 10.1002/ejic.201402278

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      Interaction of [Ni{PhNHC(S)NP(O)(OPh)2}2] with pyrazine (pz) yielded the 1:1 coordination polymer [NiL2pz]n, in which the coordination mode of L changed unexpectedly from 1,3-N,S- to 1,5-O,S-[NiL2pz]n dissolved in tri-n-octylphosphine (TOP) is decomposed in hot hexadecylamine to give TOP-capped face-centered cubic Ni nanoparticles with an average particle size of 17(2) nm.

    3. POM-Tethered Diblock Copolymers

      Supramolecular Assemblies of Polyoxometalate-Tethered Diblock Copolymers with Tunable Sizes in N-Methyl-2-pyrrolidone/Toluene Mixed Solvents

      Fadi Haso, Ruixin Wang, Panchao Yin, Jing Zhou, Lu Jin, Zhonghua Peng and Tianbo Liu

      Article first published online: 27 MAY 2014 | DOI: 10.1002/ejic.201402201

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      Rod–coil diblock copolymers, consisting of poly(3-hexylthiophene-2,5-diyl) as the rod block and a POM tethered to a polystyrene derivative as the coil block, self-assemble into vesicles in polar solvents. The vesicle size can be controlled by changing the solvent polarity. A transition to reverse vesicles with controllable size is achieved when the solvent is relatively nonpolar.

    4. Single-Molecule Magnets

      Slow Magnetic Relaxation in a Redox-Active Tetrathiafulvalene-Based Ferromagnetic Dysprosium Complex

      Fabrice Pointillart, Stéphane Golhen, Olivier Cador and Lahcène Ouahab

      Article first published online: 14 MAY 2014 | DOI: 10.1002/ejic.201402181

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      The dinuclear coordination complex [Dy(tta)2(L1)(L2)]2·2(CH2Cl2) [tta = 2-thenoyltrifluoroacetonate, L1 and L2 = tetrathiafulvalene (TTF) ligands] shows significant ferromagnetic interactions between both DyIII ions. Owing to the two different TTF ligands, the molecule is a multiredox system. It also displays single-molecule magnetic behaviour with the Ising ground state MJ = ±15/2.

  23. Short Communications

    1. Organometallic Gold Compounds

      New Gold(I) Organometallic Compounds with Biological Activity in Cancer Cells

      Benoît Bertrand, Andreia de Almeida, Evelien P. M. van der Burgt, Michel Picquet, Anna Citta, Alessandra Folda, Maria Pia Rigobello, Pierre Le Gendre, Ewen Bodio and Angela Casini

      Article first published online: 13 MAY 2014 | DOI: 10.1002/ejic.201402248

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      Organometallic N-heterocyclic carbene gold(I) complexes bearing a fluorescent coumarin ligand are synthesized, and their antiproliferative effects in normal and tumor cells in vitro are studied. Their biological properties may be due to inhibition of thioredoxin reductases. Fluorescence confocal microscopy allows the uptake of the compounds in cancer cells to be observed.

  24. Full Papers

    1. Coordination Chemistry

      Cyanido-Bearing Cobalt(II/III) Metalloligands – Synthesis, Crystal Structure, and Magnetic Properties

      Maria-Gabriela Alexandru, Diana Visinescu, Nadia Marino, Giovanni De Munno, Julia Vallejo, Francesc Lloret and Miguel Julve

      Article first published online: 9 MAY 2014 | DOI: 10.1002/ejic.201402190

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      Three diamagnetic CoIII complexes PPh4[Co(L)(CN)4] [L = ethylenediamine (en), 1; 2-(aminomethyl)pyridine (ampy), 2; 1,10-phenanthroline (phen), 3] and one CoII complex PPh4[Co(dmphen)(CN)3] (4, dmphen = 2,9-dimethyl-1,10-phenanthroline) were obtained and characterized by single-crystal XRD and FTIR spectroscopy. Complex 4 forms weakly antiferromagnetically coupled CoII···CoII supramolecular dimers.


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