European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 28

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.942

ISI Journal Citation Reports © Ranking: 2014: 8/44 (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 - 55
  1. Short Communications

    1. Mixed-Valent Compounds

      Electronic Lability in a Dinuclear Cobalt–Bis(dioxolene) Complex

      Azadeh Madadi, Masumi Itazaki, Robert W. Gable, Boujemaa Moubaraki, Keith S. Murray and Colette Boskovic

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500980

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      A dinuclear cobalt complex with a bridging bis(dioxolene) ligand shows evidence for coinciding metal- and ligand-based mixed-valence, as well as a thermally stimulated spin-crossover or valence-tautomeric transition.

    2. Tetraphosphanediides

      Formation of a Carbene–Phosphinidene Adduct by NHC-Induced P–P Bond Cleavage in Sodium Tetramesityltetraphosphanediide

      Anup K. Adhikari, Toni Grell, Peter Lönnecke and Evamarie Hey-Hawkins

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500952

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      The reaction of [Na2(thf)4P4Mes4] (Mes = 2,4,6-Me3C6H2) with 1,3-dimethylimidazolin-2-ylidene (Me2Im) or the corresponding imidazolium iodide ([Me2ImH]I) leads to P–P bond cleavage and formation of the carbene–phosphinidene adduct (Me2Im)PMes.

  2. Full Papers

    1. Thermoluminescent Complexes

      Luminescent Thermochromism in a Gold(I)–Copper(I) Phosphine–Pyridine Complex

      Kelly Chen and Vincent J. Catalano

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500925

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      Simple changes to solvent coordination on Cu perturbs the emission and modifies the Au–Cu distance in a heterometallic complex. The luminescent thermochromism of an AuI–CuI phosphine–pyridine complex at 77, 298, and 343 K is also reported.

    2. Phosphaferrocene Derivatives

      The First Coordination Polymers Based on 1,3-Diphosphaferrocenes and 1,1′,2,3′,4-Pentaphosphaferrocenes

      Claudia Heindl, Sabine Reisinger, Christoph Schwarzmaier, Lena Rummel, Alexander V. Virovets, Eugenia V. Peresypkina and Manfred Scheer

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500873

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      A synthetic approach to a series of iPr-substituted phosphaferrocenes was found. Their self-assembly with CuI halides led to one- and two-dimensional polymers: 1D chains containing the 1,3-diphosphaferrocene, 1D ladderlike structures with the 1,1′,2,3′,4-pentaphosphaferrocene, and 2D meshlike networks bearing the 1,2,4-triphosphaferrocene.

    3. Diboranyl Phosphonium Cations

      Diboranyl Phosphonium Cations: Synthesis and Chemical Properties

      Sebastian Litters, Michael Ganschow, Elisabeth Kaifer and Hans-Jörg Himmel

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500861

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      Hydride abstraction from a diborane by B(C6F5)3 followed by addition of a phosphine yielded the first diboranyl phosphonium cations.

    4. Triazole NHC Complexes

      1,2,4-Triazole-Based N-Heterocyclic Carb­ene Nickel Complexes – Synthesis and Catalytic Application

      Linus P. Bheeter, Duo Wei, Vincent Dorcet, Thierry Roisnel, Prasenjit Ghosh, Jean-Baptiste Sortais and Christophe Darcel

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500852

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      Four new nickel complexes bearing 1,2,4-triazole-based N-heterocyclic carbene backbones and a cyclopentadienyl ligand are prepared, fully characterized, and evaluated in the catalytic borylation of aryl bromides with bis(pinacolato)diboron.

    5. Tetraphosphane Ligands

      Serendipitous CO- and RhI-Induced ­Coupling of Bidentate Phosphaalkenes with Expulsion of Bis(trimethylsilyl)ketene Leading to RhIII-Coordinated Dianionic Tetradentate Ligands

      Daniela Lungu, Roxana M. Bîrzoi, Christine Goers, Rainer Bartsch, Wolf-W. du Mont, Constantin Daniliuc and Peter G. Jones

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500817

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      The reaction of [RhCl(CO)(PPh3)2] with bidentate phosphaalkene ligands 1 [(Me3Si)2C=PN(R)PPh2; 1a: R = 1-Ada; 1b: R = tBu] leads, with elimination of bis(trimethylsilyl)ketene, to racemic RhIII–chloro complexes [RhCl({Ph2PN(R)P}2C(SiMe3)2)] (11a,b) each containing a dianionic η4-coordinated ligand. CO is essential for the unusual ligand coupling reaction.

    6. Titanacycles

      Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

      Florian Loose, Marc Schmidtmann, Wolfgang Saak and Rüdiger Beckhaus

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500805

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      Shake well before use: Imines and low-valent titanium fragments react to form titanaaziridines, five-membered McMurry-like coupling products, and titanadiazacyclohexene as a Michael-coupling product.

    7. Mesoporous Microparticles

      Morphology Control, Growth Mechanism, and Enhanced Catalytic Activity of Mesoporous CeO2 Microparticles

      Jingcai Zhang, Jinxin Guo, Wei Liu, Shuping Wang, Anran Xie, Ke Tang and Yanzhao Yang

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500714

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      Mesoporous CeO2 with flowerlike and cottonlike hierarchical structures are prepared thorough a facile solvothermal strategy by using cerium glycolate as the precursor. The catalytic test results show that the final CeO2 microparticles exhibit enhanced CO conversion performance and better reduction behavior than pure ceria.

  3. Short Communications

    1. Bioinspired Catalysis

      Electrochemical and Computational Study of the Reactivity of a Diiron Azadithiolate Complex towards Protons in the Presence of Coordinating Anions

      Marc Bourrez and Frederic Gloaguen

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejic.201500675

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      The formation of an Fe–H bond is a key step in the catalysis of electrochemical hydrogen production by diiron azadithiolate models of [FeFe] hydrogenase. Tautomerization from the reduced N-protonated complexes leads to an iron–hydride intermediate. This reaction is quenched by a coordinating anion, displacing the mechanism of the catalysis to a slower side-pathway.

  4. Full Papers

    1. Phosphorane Synthesis

      Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species

      Laurence J. Taylor, Michael Bühl, Piotr Wawrzyniak, Brian A. Chalmers, J. Derek Woollins, Alexandra M. Z. Slawin, Amy L. Fuller and Petr Kilian

      Article first published online: 6 OCT 2015 | DOI: 10.1002/ejic.201500948

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      Hydride abstraction from a primary phosphine/arsine affords the first examples of secondary phosphino/arsino-phosphonium salts. Subsequent deprotonation provides a novel and high yielding route to phosphine-stabilised phosphinidene/arsinidene. These investigations indirectly support an ionic mechanism for the spontaneous dehydrogenation of the primary arsine.

    2. Ferrocene-Based NHCs

      Ferrocene-Based N-Heterocyclic Carbenes with Functionalised Benzyl Substituents

      Charlotte Thie, Clemens Bruhn and Ulrich Siemeling

      Article first published online: 6 OCT 2015 | DOI: 10.1002/ejic.201500977

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      N-Heterocyclic carbenes with a 1,1′-ferrocenylene backbone have been equipped with functionalised benzyl substituents to make them amenable as ligands for applications in the field of metallopharmaceuticals. The 77Se NMR chemical shifts of the selenourea derivatives of these NHCs demonstrate the comparatively high electrophilicity of these carbenes.

    3. Photomagnetic Materials

      Synthesis of the Single-Crystalline Form and First-Principles Calculations of Photomagnetic Copper(II) Octacyanidomolybdate(IV)

      Yoshikazu Umeta, Szymon Chorazy, Koji Nakabayashi and Shin-ichi Ohkoshi

      Article first published online: 6 OCT 2015 | DOI: 10.1002/ejic.201500823

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      A single-crystalline form of three-dimensional copper(II) octacyanidomolybdate(IV) photomagnetic material is prepared. First-principles calculations indicate that an optical transition in the visible range is a charge transfer from MoIV to CuII, and the most efficient light absorption along the [111] direction corresponds to the alignment of the cyanide bridges.

    4. Tin(IV) Coordination Polymers

      Synthesis, Characterization, and Hydrolytic Behavior of Diorganotin(IV) Coordination Polymers with Layered Structural Motifs

      Ravi Shankar, Nisha Singla, Swati Mendiratta, Gabriele Kociok-Köhn, Kieran C. Molloy and Pavletta Shestakova

      Article first published online: 5 OCT 2015 | DOI: 10.1002/ejic.201500652

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      The mixed-ligand diorganotin(IV) coordination polymers nBu2Sn[OP(O)(OH)R]OSO2Me [R = PhMe2Si(CH2)3 (1), Et3Si(CH2)3 (2)] featuring lamellar and layered structural motifs, respectively, are synthesized and structurally characterized.

    5. Ring-Opening Polymerisation

      Comparative Study of Lactide Polymerization with Lithium, Sodium, Potassium, Magnesium, Calcium, and Zinc Azo­naphthoxide Complexes

      Carlos Gallegos, Vanessa Tabernero, Marta E. G. Mosquera, Tomás Cuenca and Jesús Cano

      Article first published online: 5 OCT 2015 | DOI: 10.1002/ejic.201500818

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      Lithium, sodium, potassium, magnesium, calcium and zinc complexes stabilized by monoanionic bidentate and tridentate azonaphthoxide ligands are synthetized. Although the extremely active alkali-metal complexes follow an activated-monomer mechanism, the alkaline-earth and zinc complexes follow a coordination–insertion mechanism assisted by the ligand.

    6. Rearrangement and Autocatalysis

      Mechanism Involving Hydrogen Sulfite Ions, Chlorite Ions, and Hypochlorous Acid as Key Intermediates of the Autocatalytic Chlorine Dioxide–Thiourea Dioxide Reaction

      Ying Hu, Attila K. Horváth, Sasa Duan, György Csekő, Sergei V. Makarov and Qingyu Gao

      Article first published online: 5 OCT 2015 | DOI: 10.1002/ejic.201500654

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      The sigmoidal decay of ClO2 in the thiourea–ClO2 reaction is explained by a chain mechanism including HSO3 ions, HOCl, and ClO2 ions as key short-lived intermediates. The mechanism incorporates the recently discovered slow rearrangement of thiourea dioxide, which is necessarily involved in each reaction in aqueous solutions.

  5. Short Communications

    1. Supramolecular Chemistry

      Supramolecular Assembly of Metal-Organic Tubes Constructed from the Ditopic Heteroscorpionate Ligand (4-NH2C6H4)­CHpz2 (pz = Pyrazol-1-yl) and Silver(I)

      James R. Gardinier, Jeewantha S. Hewage, Justin Hoffman, Sergey V. Lindeman, Derek E. Williams and Natalia B. Shustova

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejic.201500844

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      Silver(I) complexes of a new heteroditopic heteroscorpionate have a proclivity for forming tubular assemblies with the aid of weak charge-assisted hydrogen-bonding interactions.

  6. Full Papers

    1. Zeolites

      Influence of Synthesis Conditions on the Mesopore Distribution and Morphology Control of Hierarchical ZSM-5 Zeolites Synthesized by Double-Acyloxy Organosilane Surfactants

      Jiaji Han and Dongliang Liu

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejic.201500735

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      Hierarchical ZSM-5 zeolites were synthesized by using a novel type of double-acyloxy organosilane surfactant and the influence of the synthesis conditions and alkyl chain length on the mesopore distribution and morphology control were studied.

    2. Silver Macrocyclic Catalysts

      Organometallic Reactivity of [Silver(I)­(Pyridine-Containing Ligand)] Complexes Relevant to Catalysis

      Tommaso Pedrazzini, Paolo Pirovano, Monica Dell'Acqua, Fabio Ragaini, Pasquale Illiano, Piero Macchi, Giorgio Abbiati and Alessandro Caselli

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejic.201500771

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      Chiral pyridine-containing macrocyclic ligands were employed to form stable silver(I) cationic complexes, [AgI(Pc-L*)], which were fully characterized, along with a study of their organometallic reactivity and structure elucidation, both in the solid state and in solution, by different NMR spectroscopic techniques, including 2D exchange spectroscopy (EXSY).

    3. Carbon Dioxide Insertion

      Synthesis and Characterization of Chloro- and Alkyliron Complexes with N-Donor Ligands and Their Reactivity towards CO2

      Cristina E. Roth, Angela Dibenedetto and Michele Aresta

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejic.201500657

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      Iron(II) compounds bearing N-donor ligands are synthesized, and their reactivity towards carbon dioxide is studied. This leads to the isolation and characterization of a carbamato derivative (3) and a dicarboxylato species (5).

    4. Fe PNP Pincer Complexes

      FeII Carbonyl Complexes Featuring Small to Bulky PNP Pincer Ligands – Facile Substitution of κ2P,N-Bound PNP Ligands by Carbon Monoxide

      Mathias Glatz, Christian Holzhacker, Bernhard Bichler, Matthias Mastalir, Berthold Stöger, Kurt Mereiter, Matthias Weil, Luis F. Veiros, Nadia C. Mösch-Zanetti and Karl Kirchner

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejic.201500646

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      Complexes trans- and cis-[Fe(κ3P,N,P-PNP)(CO)Cl2] bearing PNP ligands in which a pyridine ring and PR2 moieties are connected through NH, N-alkyl, or N-aryl linkers are prepared. For small PNP ligands, the treatment of [Fe(κ3P,N,P-PNP)(κ2P,N-PNP)Cl]+ with CO liberates the κ2-P,N-bound PNP ligand and affords the desired [Fe(κ3P,N,P-PNP)(CO)Cl2] complexes.

    5. Ir Double Perovskites

      Crystal and Magnetic Structure of Sr2BIrO6 (B = Sc, Ti, Fe, Co, In) in the Framework of Multivalent Iridium Double Perovskites

      Paula Kayser, Jose A. Alonso, Federico J. Mompeán, Maria Retuerto, Mark Croft, Alexander Ignatov and Maria T. Fernández-Díaz

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejic.201500569

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      Selected members of the Sr2BIrO6 family, containing cations of different nature and Ir with oxidation states 4+, 5+ and 6+, have been obtained under synthesis conditions carefully chosen to select the required iridium valence. Additionally, the influence of the Mn+ radius on the internal parameters, obtained from an X-ray neutron powder diffraction (NPD) analysis, is discussed.

    6. Design of CORMs

      Synthesis and Assessment of CO-Release Capacity of Manganese Carbonyl Complexes Derived from Rigid α-Diimine ­Ligands of Varied Complexity

      Jorge Jimenez, Indranil Chakraborty and Pradip K. Mascharak

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejic.201500816

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      The rates of CO photorelease from MnI carbonyl complexes based on rigid α-diimine ligands are quite similar to one another despite significant variations in the ligand frameworks.

    7. Phosphaalkene Complexes

      Iridium(I) Complexes Bearing a Noninnocent PNP-Pincer-Type Phosphaalkene ­Ligand: Catalytic Application in the Base-Free N-Alkylation of Amines with Alcohols

      Yung-Hung Chang, Ippei Tanigawa, Hiro-omi Taguchi, Katsuhiko Takeuchi and Fumiyuki Ozawa

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejic.201500900

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      PNP-pincer-type phosphaalkene complexes of IrI bearing a dearomatized pyridine ring have been found to catalyze the dehydration/condensation of amines with alcohols under base-free conditions to afford N-alkylated amines and imines in high yields. The product selectivity can be controlled by the choice of auxiliary ligands (L) as well as the reaction conditions.

    8. Au Nanoparticle Catalysts

      Design and Synthesis of an Au@MIL-53(NH2) Catalyst for a One-Pot Aerobic Oxidation/Knoevenagel Condensation Reaction

      Yue Qi, Yi Luan, Xiong Peng, Ming Yang, Junying Hou and Ge Wang

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejic.201500808

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      Highly dispersed Au nanoparticles (NPs) were deposited on an amino-functionalized Al-based MIL-53 metal–organic framework by a facile adsorption/reduction strategy. A one-pot aerobic alcohol oxidation/Knoevenagel condensation reaction cascade was developed by taking advantage of the Au0 NPs and NH2 groups of the resulting bifunctional Au@MIL-53(NH2) catalyst.

    9. Electrochromic Complexes

      A Comparative Study of the Redox-­Induced Linkage Isomerization of Ruthenium and Osmium Complexes

      Huifang Li, Lisheng Zhang, Min Ye and Xiaolin Fan

      Article first published online: 25 SEP 2015 | DOI: 10.1002/ejic.201500666

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      Intramolecular S[RIGHTWARDS ARROW]O isomerization is more favorable in ruthenium complexes than in osmium complexes with the same coordinated ligands. Moreover, it is observed that S[RIGHTWARDS ARROW]O isomerization is preferred if the number of methylene units between the sulfoxide group and the pyridine ring in the ancillary ligand is increased. bpy = 2,2-bipyridine; pySO = 2-[(isopropylsulfinyl)methyl]pyridine; pyESO = 2-[2-(isopropylsulfinyl)ethyl]pyridine; pyPSO = 2-[3-(isopropylsulfinyl)propyl]pyridine.

    10. Germylenes

      From a Germylene to an “Inorganic Adamantane”: [{Ge4(μ-O)2(μ-OH)4}{W(CO)5}4]·4THF

      Philipp Kitschke, Lutz Mertens, Tobias Rüffer, Heinrich Lang, Alexander A. Auer and Michael Mehring

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejic.201500761

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      Germylene 1 and [W(CO)5(thf)] gave rise to 2, a transition-metal complex of a germanium(II) hydroxido oxido cluster, after hydrolysis. Germylene 1 is monomeric in solution at ambient temperature but forms dimers at low temperatures in solution and in the solid state. Cluster 2 has an adamantane-like structure based on a Ge4O2(OH)4 core, thus complementing the series of “inorganic adamantanes”.

    11. Copper(II) Halide Complexes

      Stabilization of CuII–I Bonds Using 2-Benzoylpyridine Thiosemicarbazones – Synthesis, Structure, Spectroscopy, Fluo­rescence, and Cyclic Voltammetry

      Shikha Indoria, Tarlok S. Lobana, Deep Singh, Sangita Kumari, Parveen Kumari, Tanu Bala, Ajar Kamal, Amanpreet K. Jassal, Isabel García Santos, Alfonso Castineiras and Jerry P. Jasinski

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejic.201500618

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      The direct reactions of N1-substituted 2-benzoylpyridine thiosemicarbazones [(C6H5)(C5H4N)C2=N3–N2H–C(=S)–N1HR] with copper(I) halides form square-planar or square-pyramidal paramagnetic complexes with CuII–I, CuII–Br, and CuII–Cl bonds through proton-coupled electron transfer. For R = Et, complexes 46 are obtained.

    12. Fluorinated Scorpionates

      Third-Generation Scorpionates [RBpz3] – How Influential Is the Nondonor Substituent R?

      Hannes Vitze, Michael Bolte, Hans-Wolfram Lerner and Matthias Wagner

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejic.201500801

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      Cyclic voltammetry, IR spectroscopy, and X-ray crystallography are employed with selected complexes of (C6F5Bpz3) and (C6H5Bpz3) (pz = pyrazol-1-yl) to reveal differences in the electronic structures and crystal packings of fluorinated and non-fluorinated species.

    13. Nitrile–Oxime Coupling

      Highly Reactive NiII-Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

      Elena V. Andrusenko, Evgeniy V. Kabin, Alexander S. Novikov, Nadezhda A. Bokach, Galina L. Starova, Andrey A. Zolotarev and Vadim Yu. Kukushkin

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejic.201500693

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      Conventional nitriles and dialkylcyanamides display different reactivity in NiII/oxime-mediated reactions. Whereas nitriles RCN react with NiII/ketoxime systems to afford (1,3,5-triazapentadiene)NiII species, formed by postulated nitrile–oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide–oxime coupling products or a Busch-type complex.

    14. Molecular Conductors

      A Methyl-Substituted Thiophene–Tetra­thiafulvalene Donor and Its Salts

      Rafaela A. L. Silva, Isabel C. Santos, Elsa B. Lopes, Sandra Rabaça, Sergi Galindo, Marta Mas-Torrent, Concepció Rovira, Manuel Almeida and Dulce Belo

      Article first published online: 22 SEP 2015 | DOI: 10.1002/ejic.201500806

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      α-Methyldithiophene–tetrathiafulvalene has lower oxidation potentials than the unsubstituted analogue and shows a mobility of 4 × 10–4 cm2 V–1 s–1 if used as a semiconductor in an organic field-effect transistor. Two charge-transfer salts are obtained by electrocrystallization; they present unusual stoichiometries and interesting crystal structures that are modulated by the donor's methyl group.

    15. Luminescent Borates

      Host-Sensitized Photoluminescence and Coordination Environment Evolution in Ba6(Bi1–xTbx)9B79O138 (0 ≤ x ≤ 1)

      Qiaoqi Li, Rihong Cong, Wenliang Gao and Tao Yang

      Article first published online: 21 SEP 2015 | DOI: 10.1002/ejic.201500622

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      Host-sensitized photoluminescence was confirmed in Ba6(Bi1–xTbx)9B79O138 (0 ≤ x ≤ 1), which originates from the highly efficient Bi3+-to-Tb3+ energy transfer. An evolution of the coordination environments of the Bi3+/Tb3+ sites was observed to be correlated with the variation of the ratio of cyan/green [defined as I(5D4[RIGHTWARDS ARROW]7F6)/I(5D4[RIGHTWARDS ARROW]7F5) of Tb3+].

    16. Fluorescent Boron(III) Complexes

      Fluorescent Boron Complexes of 25-Oxa­smaragdyrins Containing Axial Silyloxy Groups

      Emandi Ganapathi, Tamal Chatterjee and Mangalampalli Ravikanth

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejic.201500718

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      The synthesis, structures and properties of highly fluorescent BIII complexes of 25-oxasmaragdyrins containing axial silyloxy groups are described. The presence of silyloxy groups as axial ligands on boron in BIII-smaragdyrin complexes results in hypsochromic shifts in absorption and emission bands, in enhancement in the fluorescent yields and in the macrocycles become electron-rich.

    17. Ru Porphyrin Complexes

      Comparative Study of the Catalytic Amination of Benzylic C–H Bonds Promoted by Ru(TPP)(py)2 and Ru(TPP)(CO)

      Gabriele Manca, Carlo Mealli, Daniela Maria Carminati, Daniela Intrieri and Emma Gallo

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejic.201500656

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      The catalytic activity of Ru(TPP)(py)2 (2) (TPP = dianion of tetraphenylporphyrin, py = pyridine) in the amination of C–H bonds by organic azides (RN3) was experimentally compared to that of Ru(TPP)(CO) (1). A computational analysis corroborates similar radical mechanisms with a triplet imido intermediate, in spite of the electronic differences of the apical ligands.

    18. Photocatalysts

      Electrospun TiO2 Nanofibers Surface-Loaded with Ag Nanoparticles as a Sensitizer and Their Enhanced Effect in Photocatalytic Applications

      Li Zhang, Lei Wang, Yuan Wei, Mingyue Zhang, Haifeng Jiang, Jianing Li, Shu Li and Junfeng Li

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejic.201500609

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      TiO2 is a high-performance catalyst for photocatalytic degradation and hydrogen evolution. However, its wide band gap and the fast recombination of the photogenerated electron–hole pairs limit its applications. Ag nanoparticles are loaded onto TiO2 nanofibers by photoreduction to enhance the photocatalytic efficiency of the catalyst. The optimum Ag loading is 5 %.

  7. Microreviews

    1. Carboboration

      1,1-Carboboration Through Activation of Silicon–Carbon and Tin–Carbon Bonds

      Bernd Wrackmeyer and Ezzat Khan

      Article first published online: 17 SEP 2015 | DOI: 10.1002/ejic.201500727

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      Triorganoboranes activate Sn–C(sp) or Si–C(sp) bonds, leading to inter- and intramolecular 1,1-carboboration reactions. The zwitterionic intermediates were characterized in the solid state and in solution. Many new silicon heterocycles are accessible by combining 1,2-hydroboration and 1,1-carboboration.

  8. Full Papers

    1. Luminescent Heterometallic Complexes

      Influence of the Crystal Structure on the Luminescence Properties of Mixed Eu,La–(1,10-Phenanthroline) Complexes

      Ting-Hai Yang, Lianshe Fu, Rute A. S. Ferreira, Mariela M. Nolasco, João Rocha, Luís D. Carlos and Fa-Nian Shi

      Article first published online: 17 SEP 2015 | DOI: 10.1002/ejic.201500611

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      A series of europium Eu- and La-doped complexes with two different crystal structures were synthesized in aqueous solution by using different Eu/La ratios. Eu/La ≥ 5:5 afforded a Eu(phen)2(NO3)3 structure (phen = 1,10-phenanthroline), while Eu/La ≤ 3:7 resulted in the formation of a {[La(phen)2(H2O)2(NO3)2](NO3)·2(phen)(H2O)} structure.

    2. N,N>-Chelating Ligands

      3-(Pyridin-2-yl)imidazo[1,5-a]pyridine (Pyridylindolizine) as Ligand in Complexes of Transition and Main-Group Metals

      Celedonio M. Álvarez, Lucía Álvarez-Miguel, Raúl García-Rodríguez, Jose M. Martín-Álvarez and Daniel Miguel

      Article first published online: 17 SEP 2015 | DOI: 10.1002/ejic.201500776

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      Thorough screening confirms the potential of the now easily available 3-(pyridin-2-yl)imidazo[1,5-a]pyridine (Py-indz) ligand in the preparation of complexes with transition and main-group metallic centers in very different environments.

    3. Dendrimers

      Cooperative Effects in Copper Polyamido­amine Dendrimer Complexes Catalyzing the Reduction of Molecular Oxygen

      Yi-Hsuan Tang, Yen Chung Lin, Sodio C. N. Hsu, Si-Ting Liou, Hsing-Yin Chen, Kuang-Chan Hsieh, Wan-Jung Chuang, Li-Ting Chiu, Yeh-Long Chen and Chai-Lin Kao

      Article first published online: 14 SEP 2015 | DOI: 10.1002/ejic.201500540

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      Generation-dependent cooperation is observed in O2 reduction by Cu2+ complexes of pyridine-modified polyamidoamine (PAMAM) dendrimers. Spectrophotometric titrations suggest the existence of bicopper active centers in the fifth- and sixth-generation (G5 and G6) analogs, which was further confirmed by the same reaction with catechol as a reductant and kojic acid titration experiments.

    4. Photoredox-Active Ru Complexes

      Towards Ruthenium-Based Building Blocks for CuAAC Click Reactions: Challenges in Generating Ruthenium(II) Poly­pyridine Alkynes

      Natalia Zabarska, Dieter Sorsche, Frank W. Heinemann, Susanne Glump and Sven Rau

      Article first published online: 14 SEP 2015 | DOI: 10.1002/ejic.201500630

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      For the coordination reaction of alkyne-bipyridines with Ru(bpy)2Cl2 unexpected side reactions take place, forming a RuII–CO species and methyl-bipyridine. Here we give a detailed mechanism of the side reactions and an adequate workup procedure to obtain a pure alkyne-substituted ruthenium(II) polypyridine complex, which is the intended product.

    5. Heterocyclic Phosphanes and Boranes

      The Reaction between Diazadienes and Element Tribromides EBr3 (E = P, B) Revisited: Metal-Free Synthesis of Halogenated N-Heterocyclic Phosphanes and Boranes

      Dirk Herrmannsdörfer, Manuel Kaaz, Oliver Puntigam, Johannes Bender, Martin Nieger and Dietrich Gudat

      Article first published online: 14 SEP 2015 | DOI: 10.1002/ejic.201500834

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      The reaction of diazadienes with EBr3 may follow two different pathways to yield either 2-bromo- or 2,4-dibromo-substituted N-heterocyclic products. DFT studies were used to provide a mechanistic explanation for the diverse behaviour, which also allows to understand the differing reactivity of ECl3 and EBr3 towards diazadienes. The usability of the “metal-free” syntheses is demonstrated in selected examples.

    6. Bismuth Drugs

      Powerful Antibacterial Activity of Phenyl-Thiolatobismuth(III) Complexes Derived from Oxadiazolethiones

      Ahmad Luqman, Victoria L. Blair, Rajini Brammananth, Paul K. Crellin, Ross L. Coppel and Philip C. Andrews

      Article first published online: 11 SEP 2015 | DOI: 10.1002/ejic.201500795

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      Seven heteroleptic thiolatobismuth(III) complexes [BiPh(X-PTOT)2] derived from a series of 5-substituted phenylthiazole oxadiazolethiones [X-PTOT(H)] provide powerful antibacterial action against the multi-resistant bacteria MRSA and VRE.

    7. Linkage NO Isomers

      Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light-Induced Linkage NO Isomers in [RuNO(NO2)2­(pyridine)2OH]

      Gennadiy A. Kostin, Alexander O. Borodin, Artem A. Mikhailov, Natalia V. Kuratieva, Boris A. Kolesov, Denis P. Pishchur, Theo Woike and Dominik Schaniel

      Article first published online: 11 SEP 2015 | DOI: 10.1002/ejic.201500702

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      Through photocrystallography, IR spectroscopy, and Raman spectroscopy, a light-induced isonitrosyl linkage isomer (MS1) is detected and refined in fac-[RuNO(NO2)2Py2OH]; after irradiation at λ = 445 nm, the population of MS1 is ca. 66–75 %. The infrared and Raman spectra reveal the downshift of the ν(NO), ν(Ru–NO), and δ(Ru–N–O) vibrations by 120–150 cm–1.

    8. Pt Antitumor Complexes

      Effects of Buffers and pH on the Reaction of a trans-Platinum Complex with 5′-Guanosine Monophosphate

      Chan Li, Yi Ding, Lanjun Cheng, Yuchuan Zheng, Einar Sletten and Yangzhong Liu

      Article first published online: 11 SEP 2015 | DOI: 10.1002/ejic.201500728

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      The reaction of an anti-tumor trans-platinum agent with GMP is influenced by buffer at physiological concentrations. Carbonate buffer reacts with trans-EE and significantly reduces the platination of GMP, whereas the reaction of phosphate buffer has much less of an effect.

    9. Charge Recombination in DSSCs

      Isomer Dependence of Efficiency and Charge Recombination in Dye-Sensitized Solar Cells Using Ru Complex Dyes Bearing Halogen Substituents

      Nina Chadwick, D. Kishore Kumar, Aruna Ivaturi, Benjamin A. Grew, Hari M. Upadhyaya, Lesley J. Yellowlees and Neil Robertson

      Article first published online: 11 SEP 2015 | DOI: 10.1002/ejic.201500633

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      Changing the position (from 4,4′ to 5,5′) along with the nature of the halogen (F, Cl, or Br) substituents affects the electronic and spectroscopic properties of the Ru(H2-dcbpy)(N,N′-Y2-bpy)(NCS)2 dyes as well as the recombination rates at the TiO2-dyes-I/I3 interface hence affecting the performance of the dyes in DSSCs.

    10. Host–Guest Chemistry

      Highly Selective and Sensitive Detection of Picric Acid Explosive by a Bisporphyrin Cleft: Synergistic Effects of Encapsulation, Efficient Electron Transfer, and Hydrogen Bonding

      Pritam Mondal and Sankar Prasad Rath

      Article first published online: 11 SEP 2015 | DOI: 10.1002/ejic.201500645

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      An efficient host–guest complexation leads to rapid, highly selective, and efficient detection of picric acid (PA) in the presence of other nitroaromatics in solution as well as in the solid phase.

    11. Pd Chalcogenide Nanoparticles

      Pyrazole-Stabilized Dinuclear Palladium(II) Chalcogenolates Formed by Oxidative Addition of Bis[2-(4-bromopyrazol-1-yl)ethyl] Dichalcogenides to Palladium(II) – Tailoring of Pd–S/Se Nanoparticles

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

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejic.201500529

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      The thermolyses of chalcogenolato-bridged dinuclear PdII complexes of pyrazole-based thiolates and selenolates in 1:1 mixtures of oleic acid (OA) and 1-octadecene (ODE) afford Pd17Se15, Pd4S, and Pd16S7 + PdS nanoparticles (NPs).

    12. Hybrid Composite Catalysts

      Bioinspired Nanoparticle-Assembly Route to a Hybrid Scaffold: Designing a Robust Heterogeneous Catalyst for Asymmetric Dihydroxylation of Olefins

      Nagaraju Shilpa, Joydeb Manna and Rohit Kumar Rana

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejic.201500711

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      A bioinspired hybrid design based on the biosilica nanostructure allows chemical transformations with entrapped osmium species enabling superior catalytic activity, stability and reusability in the asymmetric dihydroxylation of olefins.

    13. Ir Complexes with High NLO Activity

      A Family of IrIII Complexes with High Nonlinear Optical Response and Their Potential Use in Light-Emitting Devices

      Iván González, Diego Cortés-Arriagada, Paulina Dreyse, Luis Sanhueza-Vega, Isabelle Ledoux-Rak, Daniel Andrade, Iván Brito, Alejandro Toro-Labbé, Marco Soto-Arriaza, Stefano Caramori and Bárbara Loeb

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejic.201500505

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      The synthesis and photophysical analysis of a series of IrIII complexes was performed. The complexes show nonlinear optics activity, and appear to have potential as efficient emitters for light electrochemical cells.

    14. Redox-Active Ligands

      Combined Oxidation, Deprotonation, and Metal Coordination of a Redox-Active Guanidine Ligand

      Ute Wild, Elisabeth Kaifer, Hubert Wadepohl and Hans-Jörg Himmel

      Article first published online: 8 SEP 2015 | DOI: 10.1002/ejic.201500597

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      The synthesis and reactivity of the guanidino-functionalized aromatic compound 1,2,4,5-tetrakis(N,N′-dicyclohexylguanidino)benzene are reported. Its reaction with [{PdCl(C3H5)}2] resulted in a coupled oxidation, deprotonation, and coordination process that led directly to a hexanuclear palladium complex.

    15. MRI Contrast Agents

      PEGylated DOTA-AHA-Based GdIII Chelates: A Relaxometric Study

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

      Article first published online: 4 SEP 2015 | DOI: 10.1002/ejic.201500688

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      Three PEGylated derivatives of DOTA-AHA with different molecular weights are prepared, and their GdIII chelates are studied by variable-temperature 1H nuclear magnetic relaxation dispersion (NMRD) and 17O NMR spectroscopy. The isomeric M/m ratio is determined by a 1H NMR study of several LnIII chelates of DOTA-A(PEG750)HA to shed light on the relaxometric behavior of the GdIII chelates.

    16. Role of Chalcogen Donor Atoms

      On the Role of Chalcogen Donor Atoms in Diimine-Dichalcogenolate PtII SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?

      Anna Pintus, M. Carla Aragoni, Francesco Isaia, Vito Lippolis, Dominique Lorcy, Alexandra M. Z. Slawin, J. Derek Woollins and Massimiliano Arca

      Article first published online: 31 AUG 2015 | DOI: 10.1002/ejic.201500777

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      The effect of replacing sulfur with selenium as the donor atoms in the class of SONLO chromophores [Pt(NN)(EE)] (EE = N-methyl-2-thioxothiazoline-4,5-dichalcogenolate; NN = bipy, phen) was investigated by comparatively investigating their UV/Vis spectroscopic, electrochemical, and SONLO properties.

  9. Correspondence

    1. Sensors for Iron Ions

      Key Considerations for Sensing FeII and FeIII in Aqueous Media

      Shawn C. Burdette

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500566

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      Recently, Ghosh et al. reported on the fluorescent response of N-(2-aminoethyl)naphthalen-1-amine toward FeII, FeIII, and HgII (K. Ghosh, S. Rathi, P. Gupta, P. Vashisth, V. Pruthi, Eur. J. Inorg. Chem. 2015, 311), concluding that metal binding to the diamine chelator leads to chelation-induced quenching; however, the experimental protocols are incompatible with the aqueous chemistry of FeIII.

  10. Short Communications

    1. Terminal Phosphinidenes

      The Reaction of Terminal Phosphinidene Complexes [RP–W(CO)5] with Vinylbor­onic Acids: Cycloaddition vs. P–C Bond Formation

      Yong Xiang Ng and François Mathey

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500594

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      Terminal phosphinidene complexes react with vinylboronic acid to give the expected phosphirane complexes, but the addition of K3PO4 changes the course of the reaction, and secondary vinylphosphine complexes are obtained instead.

  11. Full Papers

    1. Phosphacyclobutadiene Complexes

      Cobalt(I) and Nickel(II) Complexes of Bis(1,3-diphosphacyclobutadiene) Sandwich Anions

      Christian Rödl and Robert Wolf

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500583

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      Dinuclear diphosphacyclobutadiene complexes have been synthesized by transmetalating the thallium(I) salt [Tl(thf)2{Co(P2C2tBu2)2}] with organometallic cobalt(I) and nickel(II) halides. The structural, spectroscopic, and redox properties of two new bimetallic complexes are presented, and their electronic structures are analyzed by DFT calculations.


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