European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 21

July 2016

Volume 2016, Issue 21

Pages 3365–3523

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. News
    5. Communications
    6. Full Papers
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      Front Cover: Sulfur versus Dioxygen: Dinuclear (Trisulfido)copper Complexes (Eur. J. Inorg. Chem. 21/2016) (page 3365)

      Miriam Wern, Tobias Hoppe, Jonathan Becker, Stefan Zahn, Doreen Mollenhauer and Siegfried Schindler

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201670211

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      The cover picture shows elemental sulfur in the crater of the volcano on the Vulcano island, Italy (photograph courtesy of Christopher Schmidt, Marburg). Sulfur is one of the few elements that can be found in its elemental form in nature. It is quite likely that sulfur was a key element for the evolution of life. A macrocylic copper(I) complex with the ligand tet b (= rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) can easily react with elemental sulfur to form a dinuclear product complex with a bridging trisulfido ligand. Details are discussed in the article by S. Schindler et al. on p. 3384 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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    3. Cover Profile
    4. News
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      Sulfur versus Dioxygen: Dinuclear (Trisulfido)copper Complexes (page 3366)

      Miriam Wern, Tobias Hoppe, Jonathan Becker, Stefan Zahn, Doreen Mollenhauer and Siegfried Schindler

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/ejic.201600831

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      It was quite surprising that sulfido ligands can be easily substituted with peroxido ligands in the reaction of copper sulfido complexes with dioxygen…

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 3384 ff.

  3. News

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    2. Cover Picture
    3. Cover Profile
    4. News
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  4. Communications

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    1. Hydrogen-Storage Materials

      Intracell Hydrogen Adsorption–Transmission in a Co2P Solid Hydrogen-Storage Material (pages 3371–3375)

      Di Bao, Peng Gao, Chenliang Li, Guoxun Wu, Yanbo Wang, Yujin Chen, Han Zhou and Piaoping Yang

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600345

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      An intracell Kubas-enhanced adsorption mechanism for improving the hydrogen-storage capacity of Co2P has been described for the first time.

    2. Metal–Boron Complexes

      Silylosmium Anions for the Synthesis of Borylosmium(II) Complexes by Salt Elimination (pages 3376–3379)

      Holger Braunschweig, Marc-André Légaré, Alexander Matler and Benedikt Wennemann

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600262

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      Osmium anionic complexes, K[(PMe3)Os(CO)3(SiR3)] (R = Me, Et), are synthesized by deprotonation of the corresponding metal hydrides. The nucleophilicity of these compounds is demonstrated through the reaction of K[(PMe3)Os(CO)3(SiMe3)] with Cl2BDur and Br2BDur (Dur = 2,3,5,6-tetramethylphenyl) to give haloboryl complexes through a salt elimination process that is unprecedented for Os–B chemistry.

    3. Silver Sulfide Clusters

      Octanuclear Silver Sulfide Cluster [Ag88-S)(µ-mimt)12](NO3)6 Containing the First Thione-Stabilized Ag8 Cube Caging a Sulfide Anion (pages 3380–3383)

      Yali Shen, Shuzhen Liu, Peipei Sun, Chunying Tang and Dingxian Jia

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600643

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      The first thione-protected silver sulfide cluster [Ag88-S)(mimt)12](NO3)6 (mimt = 4-methyl-1,3-imidazolidine-2-thione) is synthesized by gradual S2– release from Na2S2O3 in solution. The cluster contains an octanuclear Ag8 cube that cages an S2– ion at the center, and the shell is stabilized by 12 µ2-mimt ligands bridging two Ag atoms to form the cubic edges.

  5. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. News
    5. Communications
    6. Full Papers
    1. Trisulfido Ligands

      Sulfur versus Dioxygen: Dinuclear (Trisulfido)copper Complexes (pages 3384–3388)

      Miriam Wern, Tobias Hoppe, Jonathan Becker, Stefan Zahn, Doreen Mollenhauer and Siegfried Schindler

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/ejic.201600614

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      The first examples of structurally characterized (trisulfido)copper complexes (with ligands tmpa and tet b) have been synthesized and characterized. Reactivity studies and DFT calculations were performed with these complexes.

    2. Electrostatic Properties of NHCs

      Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts (pages 3389–3395)

      Hannes Buhl, Kathrin Verlinden, Christian Ganter, Sladjana B. Novaković and Goran A. Bogdanović

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600292

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      High-resolution X-ray diffraction experiments (100 K) have been used to investigate and quantitatively compare the electron density distribution in two carbene adducts of selenium.

    3. Carbon Dioxide Reforming

      One-Pot Synthesis of Ordered Mesoporous NiSiAl Oxides for Catalyzing CO2 Reforming of CH4 (pages 3396–3404)

      Xianmei Xiang, Huahua Zhao, Jian Yang, Jun Zhao, Liang Yan, Huanling Song and Lingjun Chou

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600463

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      Ordered mesoporous NiSiAl oxide is prepared by an improved evaporation-induced self-assembly strategy. The silica doping improves the retention of ordered mesopores and the amorphous NiAl phase; this permits the uniform dispersion of the active Ni nanoparticles and, thus, decreases the amount of deposited carbon and improves the catalytic stability for the CO2 reforming of CH4.

    4. Polyoxometalates

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      Photophysical Characterization and Recognition Behaviour of a Bis(dansylated) Polyoxometalate (pages 3405–3410)

      Mauro Carraro, Giacomo Bergamini, Michele Di Lauro, Gloria Modugno, Massimo Baroncini, Paola Ceroni and Marcella Bonchio

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600636

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      A bis(dansylated) polyoxotungstate has been characterized to highlight the photophysical interplay between its two functional domains: a tweezer-like motif, defined by the dansyl units, and the polyanionic inorganic scaffold. The two subunits shape a ditopic receptor, being able to interact with lanthanide ions and with cationic organic chromophores, which trigger different spectral and morphological responses

    5. MOF Sensors

      Microporous Metal–Organic Frameworks Based on Zinc Clusters and Their Fluorescence Enhancements towards Acetone and Chloroform (pages 3411–3416)

      Kangcai Wang, Zhien Lin, Shi Huang, Jie Sun and Qinghua Zhang

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600184

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      Two fluorescent metal–organic frameworks constructed with d10-configured metal clusters (i.e., Zn3 and Zn7O2) and organic carboxylic acid ligands (i.e., 1,4-dicarboxybenzene and 1,4-naphthalenedicarboxylic acid) are synthesized. They show interesting fluorescence enhancement effects towards acetone and chloroform, respectively.

    6. Phosphorus Heterocycles

      One-Pot Synthesis of Phosphanylbis(N-arylglycines) and Spontaneous Diastereoselective Lactamization of P-Alkyl Derivatives To Form Five-Membered P,N-Heterocyclic Amino Acids (pages 3417–3422)

      Joanna Lach, Gottfried J. Palm, Peter G. Jones and Joachim W. Heinicke

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600202

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      PhPH2 reacts with glyoxylic acid hydrate and a primary aniline (1:2:2) in Et2O to afford a rac/meso-mixture of corresponding phosphanyl-bis(glycine) 1. Under the same mild conditions, more P-basic primary alkylphosphanes CyPH2 and iBuPH2, undergo diastereoselective lactamization affording phosphaproline derivatives 2 and 3; the structure of 2 was amenable to X-ray crystallography.

    7. Synthesis of Mononuclear Complexes

      Making Use of Obstacles: Alternative Synthetic Approaches towards Osmium(II)-Based Photochemical Molecular Devices (pages 3423–3428)

      Johannes Habermehl, Dieter Sorsche, Petra Murszat and Sven Rau

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600239

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      Two synthetic pathways lead to a red-light-absorbing mononuclear osmium complex incorporating a potential bridging ligand. In situ reduction of an OsIII precursor leads to facile access to the target compound owing to virtual dilution.

    8. Organotin Compounds

      23- and 27-Membered Macrocyclic Diorganotin(IV) Bis-dithiocarbamates: Synthesis, Spectroscopic Characterization, DFT Calculations, and Physicochemical Analysis as Anion Receptors (pages 3429–3440)

      María G. Vasquez-Ríos, Viviana Reyes-Márquez, Herbert Höpfl, Aaron Torres-Huerta, Jorge Guerrero-Álvarez, Mario Sánchez, Irán F. Hernández-Ahuactzi, Karen Ochoa-Lara, Arturo Jiménez-Sánchez and Rosa Santillán

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600254

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      Organotin-based macrocycles suitable for the selective recognition of fluoride and acetate have been structurally modified at three different sites to explore the effects of variations of the molecular configuration and conformation.

    9. Nonplanar Hemes

      Spin Modulation in Highly Distorted FeIII Porphyrinates by Using Axial Coordination and Their π-Cation Radicals (pages 3441–3453)

      Dipankar Sahoo, Tapas Guchhait and Sankar Prasad Rath

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600255

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      A series of five-coordinate FeIII octaaryltetraphenylporphyrins with varying axial ligand field strength and their 1 e-oxidized complexes have been synthesized and characterized. The molecular structures and their spectroscopic properties including metal spins have been scrutinized.

    10. Metalloenzyme Electrode

      Anchoring Cytochrome b562 on a Gold Nanoparticle by a Heme–Heme Pocket Interaction (pages 3454–3459)

      Akira Onoda, Tomoaki Taniguchi, Nozomu Inoue, Ayumi Kamii and Takashi Hayashi

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600301

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      Gold nanoparticles were immobilized on a gold electrode surface. Apocytochrome b562 was then immobilized on the surface of the AuNP-modified electrode through a heme–heme pocket interaction. The hemoprotein-immobilized electrode exhibited a ten-fold enhanced electrochemical response relative to the protein immobilized directly on the gold electrode.

    11. Nanoborides

      A Size-Dependent Analysis of the Structural, Surface, Colloidal, and Thermal Properties of Ti1–xB2 (x = 0.03–0.08) Nanoparticles (pages 3460–3468)

      Bürgehan Terlan, Aleksandr A. Levin, Felix Börrnert, Julian Zeisner, Vladislav Kataev, Marcus Schmidt and Alexander Eychmüller

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600315

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      We report the size-dependent structural, surface, colloidal, and thermal properties of the well-known refractory material titanium diboride prepared at the nanoscale by a size-controlled inorganic molten-salt technique.

    12. Nickel Nanoparticle Catalysts

      Nickel Nanoparticles Supported on CMK-3 with Enhanced Catalytic Performance for Hydrogenation of Carbonyl Compounds (pages 3469–3473)

      Daeho Kim, Hyuntae Kang, Hyesu Park, Sungkyun Park, Ji Chan Park and Kang Hyun Park

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600318

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      Ni/CMK-3 was prepared by incorporating Ni particles formed inside the pores of CMK-3 by impregnation of nickel nitrate and subsequent hydrogen reduction. The prepared Ni/CMK-3 has a large surface area and a very small nickel nanoparticle size (1 nm) with the aim of achieving high performance in catalytic hydrogenation reactions.

    13. Separation of Lanthanides

      A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides (pages 3474–3479)

      Alexander S. Ivanov and Vyacheslav S. Bryantsev

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600319

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      We report an approach based on quantum chemical calculations that achieves high accuracy in predicting aqueous-phase selectivity across the lanthanide series. Quantitative agreement with experiment demonstrates the potential of the method for accelerated computer-aided discovery of superior ligands for selective lanthanide ion complexation.

    14. Anticancer Complexes

      Iridium(III) Complexes of Terpyridine- and Terpyridine-Analogous Ligands Bearing Sugar Residues and Their in vitro Activity (pages 3480–3488)

      Aram Prokop, Justyna A. Czaplewska, Mara Clausen, Marcel König, Andreas Wild, Rico Thorwirth, Benjamin Schulze, Krzysztof Babiuch, David Pretzel, Ulrich S. Schubert and Michael Gottschaldt

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600325

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      A series of terpyridine and terpyridine-analogous ligands bearing sugar moieties attached by different glycosidic bonds and their IrIII complexes was synthesized and characterized. Studies on cell viability, selectivity, drug resistance in vitro, and the apoptosis mechanism were performed. The results revealed enhanced activity of a complex bearing acetylated thioglucose.

    15. C–C Coupling

      2,5-Norbornadiene C–C Coupling Reactions Mediated by Iridium Complexes (pages 3489–3499)

      M. Pilar Betoré, Miguel A. Casado, Pilar García-Orduña, Fernando J. Lahoz, Víctor Polo and Luis A. Oro

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600336

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      Five- and seven-membered iridacycles have been prepared by sequential C–C bond-forming reactions between 2,5-norbornadiene molecules.

    16. Vanadates

      Vanadium Polyoxoanions within Coordination Polymers Based on a Macrocyclic Nickel Complex: Structural Diversities and Single-Crystal to Single-Crystal Transformation (pages 3500–3505)

      Guang-Chuan Ou, Xian-You Yuan, Zhi-Zhang Li, Wen-Yi Li, Fei Zeng, Ji-Hua Deng and Di-Chang Zhong

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600284

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      Five coordination polymers have been constructed from a macrocyclic NiII complex and vanadium polyoxoanions. The vanadium polyoxoanions assume diverse structures, namely the [V16O42]n4n sheet, [V6O18]6– ring, [VO3]nn chain, [VO3]nn sheet, and [V10O29]n8n chain. Electrochemical measurements indicate that two of the coordination polymers are potential catalysts for water splitting.

    17. Bimetallic Frameworks

      Rational Design of Two-Dimensional Bimetallic Wave Structures from Zigzag Chains via Site-Specific Coordination around the 2,6-Naphthalenediphosphonic Acid Motif (pages 3506–3512)

      Aysun Bulut, Yunus Zorlu, Michael Wörle, Salih Paşa, Hüseyin Kurt, Jon Zubieta, Jens Beckmann and Gündoğ Yücesan

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600309

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      The preparation of one-, two-, and three-dimensional metal–organophosphonate frameworks from a V-shaped molecular precursor is reported.

    18. Metathesis Catalysts

      Remarkable Ability of the Benzylidene Ligand To Control Initiation of Hoveyda–Grubbs Metathesis Catalysts (pages 3513–3523)

      Tymoteusz Basak, Krzysztof Grudzień and Michał Barbasiewicz

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600435

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      Initiation of Hoveyda–Grubbs metathesis catalysts requires opening of the chelate ring, followed by ligand exchange in the initial turnover of the metathesis cycle. Our studies reveal that substitution at the 6-position of the benzylidene ring influences the latter process and shifts the complexes to the latent systems (Mes = 2,4,6-trimethylphenyl).

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