European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 9

March 2013

Volume 2013, Issue 9

Pages 1392–1554

  1. Cover Picture

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      Cationic and Neutral (Ar-BIAN)Copper(I) Complexes Containing Phosphane and Arsane Ancillary Ligands: Synthesis, Molecular Structure and Catalytic Behaviour in Cycloaddition Reactions of Azides and Alkynes (Eur. J. Inorg. Chem. 9/2013)

      Lidong Li, Patrícia S. Lopes, Cláudia A. Figueira, Clara S. B. Gomes, M. Teresa Duarte, Vitor Rosa, Christophe Fliedel, Teresa Avilés and Pedro T. Gomes

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/ejic.201390037

      Thumbnail image of graphical abstract

      The cover picture shows the X-ray structure of one of the (aryl-BIAN)copper(I) complexes synthesised in this work, which is reported along with a good number of other new cationic and neutral (aryl-BIAN)copper(I) complexes containing phosphane and arsane ancillary ligands. Their catalytic activity towards the azide–alkyne Huisgen cycloaddition reaction (CuAAC) was studied. The picture background represents the 25th of April Bridge, one of the icons of the city of Lisbon, but also symbolises the collaboration between the two research teams, working at different universities that are located on the two banks of the river Tejo (Tagus). Details are discussed in the article by T. Avilés, P. T. Gomes et al. on p. 1404 ff.

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      Cationic and Neutral (Ar-BIAN)Copper(I) Complexes Containing Phosphane and Arsane Ancillary Ligands: Synthesis, Molecular Structure and Catalytic Behaviour in Cycloaddition Reactions of Azides and Alkynes (page 1392)

      Lidong Li, Patrícia S. Lopes, Cláudia A. Figueira, Clara S. B. Gomes, M. Teresa Duarte, Vitor Rosa, Christophe Fliedel, Teresa Avilés and Pedro T. Gomes

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/ejic.201300207

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      The stabilisation of the active catalytic species by the donor ligands plays a very important role in this catalytic reaction...

      This and more about the story behind the cover research can be found on p. 1392.

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    1. Copper(I) Complexes

      Cationic and Neutral (Ar-BIAN)Copper(I) Complexes Containing Phosphane and Arsane Ancillary Ligands: Synthesis, Molecular Structure and Catalytic Behaviour in Cycloaddition Reactions of Azides and Alkynes (pages 1404–1417)

      Lidong Li, Patrícia S. Lopes, Cláudia A. Figueira, Clara S. B. Gomes, M. Teresa Duarte, Vitor Rosa, Christophe Fliedel, Teresa Avilés and Pedro T. Gomes

      Version of Record online: 14 JAN 2013 | DOI: 10.1002/ejic.201201211

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      The synthesis and structural characterisation of new cationic and neutral (Ar-BIAN)copper(I) [Ar-BIAN = bis(aryl)acenaphthenequinonediimine] complexes containing phosphane and arsane ancillary ligands are described. Their behaviour as catalysts for cycloaddition reactions of alkynes and azides is presented.

    2. Cluster Chemistry

      Unsymmetrically Substituted Mo3S44+ Clusters Bearing Diphosphane Ligands (pages 1418–1426)

      Ivan Sorribes, Rosa Llusar and Cristian Vicent

      Version of Record online: 23 JAN 2013 | DOI: 10.1002/ejic.201201176

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      A series of unsymmetrically substituted [Mo3S4(dmpe)3Cl3–x(dca)x]PF6 (x = 0–3) clusters that feature mixed chlorido/dicyanamido (dca) terminal ligands have been isolated. The ability to fine-tune the physicochemical properties of Mo3S44+ clusters upon stepwise dca incorporation is demonstrated.

    3. Cluster Compounds

      Synthesis and Characterization of Polynuclear Oxidobismuth Sulfonates (pages 1427–1433)

      Linda Miersch, Tobias Rüffer, Dieter Schaarschmidt, Heinrich Lang, Ralf W. Troff, Christoph A. Schalley and Michael Mehring

      Version of Record online: 29 JAN 2013 | DOI: 10.1002/ejic.201201315

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      Three soluble {Bi38O45} clusters with a nitrate/sulfonate periphery are reported, including the first example of an oxidobismuth cluster that is composed of positively and negatively charged species in the solid state. ESI-MS data is indicative of a reversible exchange of ligands.

    4. Dihydrogen Complexes

      Synthesis and Reactivity Studies of Dicationic Dihydrogen Complexes Bearing Sulfur-Donor Ligands: A Combined Experimental and Computational Study (pages 1434–1443)

      Thirumanavelan Gandhi, Subramani Rajkumar, V. Prathyusha and U. Deva Priyakumar

      Version of Record online: 1 FEB 2013 | DOI: 10.1002/ejic.201201022

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      A series of dihydrogen complexes trans-[Ru(η2-H2){SC(SR)H}(dppe)2][X][BF4] (R = CH3, X = OTf; R = C6H5CH2, X = BPh4; R = H2C=CHCH2, X = BPh4; dppe = Ph2PCH2CH2PPh2) bearing sulfur-donor ligands has been synthesized by protonation of the (alkyl dithioformate)hydrido complexes trans-[Ru(H){SC(SR)H}(dppe)2][X] by using HBF4·Et2O.

    5. Tetranuclear Copper Complexes

      Tetranuclear Copper Azido Complex of 4,5-Diazafluoren-9-one (pages 1444–1450)

      B. Kishore Babu, A. R. Biju, Sailaja Sunkari, M. V. Rajasekharan and J. -P. Tuchagues

      Version of Record online: 23 JAN 2013 | DOI: 10.1002/ejic.201201057

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      The propensity of 4,5-diazafluoren-9-one to chelate through one short and one long bond allows the formation of an azide-bridged tetranuclear CuII complex, which crystallises as a molecular mixture of two distortion isomers of the open bicubane type. Ferromagnetic interactions dominate in both isomers.

    6. Heterometallic Co and Li Siloxides

      Linear Heterometallic Co3Li2 and Co4Li2 Siloxides: Precursors for the Plasma Synthesis of Adsorbent Materials (pages 1451–1457)

      Sophie Ehle, Volker Brüser, Volker Lorenz, Cristian G. Hrib, Katja Saulich, Siegfried Müller, Antje Quade and Frank T. Edelmann

      Version of Record online: 3 JAN 2013 | DOI: 10.1002/ejic.201201060

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      Linear heterometallic Co3Li2 and Co4Li2 arrays, (thf)Co[Co{μ-(Ph2SiO)2O}{(μ-Cl)2Li(thf)2}]2 (5) and [Co2(μ-Cy7Si7O12)(μ-OSiMe3)(μ-Cl){Li(thf)2}2]2 (6), were prepared and characterized. Plasma treatment of 5 was found to activate the surface by creating –C–O, –C=O, and –COO functionalities. An initial study revealed promising formaldehyde adsorption properties for the plasma-treated material 5a.

    7. Cu Complexes in Oxidation Catalysis

      Copper(II) Complexes with Schiff Bases Containing a Disiloxane Unit: Synthesis, Structure, Bonding Features and Catalytic Activity for Aerobic Oxidation of Benzyl Alcohol (pages 1458–1474)

      Alina Soroceanu, Maria Cazacu, Sergiu Shova, Constantin Turta, Jozef Kožíšek, Marian Gall, Martin Breza, Peter Rapta, Tatiana C. O. Mac Leod, Armando J. L. Pombeiro, Joshua Telser, Anatolie A. Dobrov and Vladimir B. Arion

      Version of Record online: 4 FEB 2013 | DOI: 10.1002/ejic.201201080

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      New copper(II) Schiff base complexes with a 12-membered central chelate ring, bearing the disiloxane moiety displaying a “shoulder yoke effect”, have been prepared and act as catalyst precursors for the aerobic oxidation of benzyl alcohol to benzaldehyde mediated by the TEMPO radical, reaching yields and TONs up to 99 % and 990, respectively, under mild conditions (50 °C; MeCN/H2O, 1:1).

    8. Polyoxometalate Hybrids

      Color-Tunable Luminescent Films Based on the Hybrid Assemblies of [EuW10O36]9–, Bis(N-methylacridinium) Nitrate, and Layered Double Hydroxide (pages 1475–1480)

      Zhenzhen Han, Ying Guo, Ryo Tsunashima and Yu-Fei Song

      Version of Record online: 28 JAN 2013 | DOI: 10.1002/ejic.201201135

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      Luminescent ultrathin films (UTFs) based on the hybrid assemblies of Na9[EuW10O36]·32H2O (EuW10), the photoactive organic molecule of bis(N-methylacridinium) nitrate (BNMA), and exfoliated Mg2Al-LDH (layered double hydroxide) have been fabricated successfully. The alternative intercalation of EuW10 and BNMA into LDHs results in well-ordered UTFs with tunable color and orientation effect.

    9. Gas Sensors

      Inkjet-Printed Nanoscaled CuO for Miniaturized Gas-Sensing Devices (pages 1481–1487)

      Mikhail Pashchanka, Ravi M. Prasad, Rudolf C. Hoffmann, Aleksander Gurlo and Jörg J. Schneider

      Version of Record online: 3 JAN 2013 | DOI: 10.1002/ejic.201201152

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      Printed nanoscaled cupric oxide (CuO) tracks with a line width of 100–150 μm were fabricated by inkjet printing using a molecular Schiff base copper complex as the sole precursor for ink formulation. Gas-sensing studies at temperatures of 200 and 250 °C showed a sensitivity in the upper ppm level towards CO and H2 of the nanoscaled CuO obtained from the molecular Cu precursor after calcination.

    10. Pentacoordinated Silicon

      Cocrystallising Rotamers of a Pentacoordinate Silicon Complex with a Chiral Aminodiol Ligand (pages 1488–1492)

      Sebastian Schlecht, Maik Finze, Rüdiger Bertermann, Walter Frank, Anke Domann and Manfred Braun

      Version of Record online: 25 JAN 2013 | DOI: 10.1002/ejic.201201173

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      The interconversion of turnstile rotamers at silicon, readily occurring in solution, is frozen in the solid state. Therein, the pentacoordinate complexes featuring a homochiral backbone are reported as the first examples of cocrystallising rotamers at silicon.

    11. Silica Nanoparticles

      Radioactive Europium-Chelate-Based Silica Nanoparticles as a Probe for Stability, Incorporation Efficiency and Trace Analysis (pages 1493–1498)

      Nicolas Wartenberg, Olivier Raccurt, Elodie Bourgeat-Lami, Daniel Imbert and Marinella Mazzanti

      Version of Record online: 24 JAN 2013 | DOI: 10.1002/ejic.201201189

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      Two luminescent terbium and europium lanthanide chelates were efficiently embedded into silica nanoparticles by using a reverse microemulsion process without covalent bonding. Efficiency and stability were investigated with an effective method based on a γ-emitting europium (152) radioactive probe.

    12. Ditopic Complexes

      Synthesis, Structure and Catalytic Properties of Dinuclear MoVI Complexes with Ditopic Diaminotetraphenols (pages 1499–1508)

      Antti Riisiö, Ari Lehtonen, Mikko M. Hänninen and Reijo Sillanpää

      Version of Record online: 31 JAN 2013 | DOI: 10.1002/ejic.201201234

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      A one-pot reaction of ditopic diaminotetraphenols with [MoO2(acac)2] (acac = acetylacetonate) produces novel dinuclear MoVI complexes with structural diversity. The complexes show good catalytic performance and selectivity in alcohol oxidation and moderate performance and good selectivity in epoxidation.

    13. Energetic Materials Research

      The 1,3-Diamino-1,2,3-triazolium Cation: A Highly Energetic Moiety (pages 1509–1517)

      Thomas M. Klapötke, Davin G. Piercey and Jörg Stierstorfer

      Version of Record online: 29 JAN 2013 | DOI: 10.1002/ejic.201201237

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      An energetic cation with a high heat of formation was prepared by the amination of 1-amino-1,2,3-triazole. The 1,3-diamino-1,2,3-triazolium cation obtained shows performances comparable to, or better than, the triaminoguanidinium cation commonly used in energetic salts.

    14. Minor Actinides

      Local and Electronic Structure of Americium-Bearing PuO2 (pages 1518–1524)

      Damien Prieur, Ursula Carvajal-Nunez, Tonya Vitova and Joseph Somers

      Version of Record online: 28 JAN 2013 | DOI: 10.1002/ejic.201201294

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      Coupling XRD and X-ray absorption spectroscopy techniques have shown that a biphasic fluorite Am-bearing PuO2 material is obtained following sintering in moisturized Ar/H2. Heating of this sample in air ensured the formation of a substoichiometric fluorte Pu+IV0.80Am+III/+IV0.20O1.98 solid solution.

    15. Lewis Acid–Base Adducts

      Lewis Acid–Base Adducts of 1-Mesityl- and 1-Chloro-2,3,4,5-tetraphenylborole (pages 1525–1530)

      Holger Braunschweig, Ching-Wen Chiu, Daniela Gamon, Katrin Gruß, Christian Hörl, Thomas Kupfer, Krzysztof Radacki and Johannes Wahler

      Version of Record online: 29 JAN 2013 | DOI: 10.1002/ejic.201201383

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      Lewis acid–base adducts of boroles can be useful precursors for chemical derivatization of the borole system. This paper covers the synthesis of a series of borole-derived Lewis acid–base adducts as well as a brief comparison of the relative Lewis acidity of 1-mesityl-2,3,4,5-tetraphenylborole and 1,2,3,4,5-pentaphenylborole.

    16. Nanostructured Metal Sulfides

      Influence of the Morphology of Lithiated Copper(I) Sulfides with the Formal Composition “Li2Cu4S3” on Their Stability in Electrochemical Cycling (pages 1531–1540)

      Andreas Eichhöfer, Heino Sommer, Vasyl Andrushko, Sylvio Indris and Sharali Malik

      Version of Record online: 23 JAN 2013 | DOI: 10.1002/ejic.201201099

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      Upon prolonged electrochemical cycling, the capacity of nanostructured and porous “Li2Cu4S3” fades much faster than that of a compact material with the same composition.

    17. Ketoiminate Complexes

      Synthesis and Characterization of Zinc Ketoiminate and Zinc Alkoxide–/Phenoxide–Ketoiminate Complexes (pages 1541–1554)

      Carlo Di Iulio, Mathew Middleton, Gabriele Kociok-Köhn, Matthew D. Jones and Andrew L. Johnson

      Version of Record online: 31 JAN 2013 | DOI: 10.1002/ejic.201201114

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      A family of zinc ketoiminate, zinc phenoxide–ketoiminate and zinc alkoxide–ketoiminate complexes have been synthesized and characterized; their ability to polymerize rac-lactide both in solution and in the melt are also described.

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