European Journal of Inorganic Chemistry

Cover image for Vol. 2013 Issue 26

September 2013

Volume 2013, Issue 26

Pages 4528–4693

  1. Cover Picture

    1. Top of page
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    3. Cover Profile
    4. Masthead
    5. Graphical Abstract
    6. Further Masthead
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    1. You have free access to this content
      A Solid-Solution Approach to Mixed-Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks (Eur. J. Inorg. Chem. 26/2013)

      Olesia Kozachuk, Mikhail Meilikhov, Kirill Yusenko, Andreas Schneemann, Bettina Jee, Anusree V. Kuttatheyil, Marko Bertmer, Christian Sternemann, Andreas Pöppl and Roland A. Fischer

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/ejic.201390114

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      The cover picture shows correlations (linear as well as non-linear) between metal ratios and the structure and properties of materials while increasing the complexity of the framework and combining different metals in single-phased MOFs to give mixed-metal MOF solid solutions. The applied EPR spectroscopic analysis, in particular, is a powerful tool in these studies to obtain insight into the local metal structures in such complex multicomponent MOF materials and to detect intrinsic structural defects that are not observed (and not expected) in the parent monometallic MOFs. O. K. is acknowledged for designing the cover artwork. Details are discussed in the article by R. A. Fischer et al. on p. 4546 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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      A Solid-Solution Approach to Mixed-Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks (page 4528)

      Olesia Kozachuk, Mikhail Meilikhov, Kirill Yusenko, Andreas Schneemann, Bettina Jee, Anusree V. Kuttatheyil, Marko Bertmer, Christian Sternemann, Andreas Pöppl and Roland Fischer

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/ejic.201301049

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      The biggest challenge in the presented work was using various analytical methods to understand the impact of doping with a second metal (V, in particular) and reveal the organization of these frameworks at the molecular level, which defines their properties...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 4546 ff.

  3. Masthead

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    1. Aluminum Catalysts

      An Efficient Homogeneous Chloro–Aluminum–[N2O2] Catalyst for the Coupling of Epoxides with Carbon Dioxide (pages 4541–4545)

      Monica A. Fuchs, Christiane Altesleben, Thomas A. Zevaco and Eckhard Dinjus

      Version of Record online: 8 AUG 2013 | DOI: 10.1002/ejic.201300634

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      A new homogeneous aluminum catalyst based on a N2O2 ligand obtained from diethyl ethoxymethylenemalonate was used in the conversion of epoxides with carbon dioxide. Copolymerization with cyclohexene oxide led to alternating polycarbonates in the presence of a cocatalyst even at only 2 bar CO2 pressure. Propylene oxide afforded selectively the corresponding cyclic carbonate in high yields.

  8. Full Papers

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    1. Metal–Organic Frameworks

      A Solid-Solution Approach to Mixed-Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks (pages 4546–4557)

      Olesia Kozachuk, Mikhail Meilikhov, Kirill Yusenko, Andreas Schneemann, Bettina Jee, Anusree V. Kuttatheyil, Marko Bertmer, Christian Sternemann, Andreas Pöppl and Roland A. Fischer

      Version of Record online: 27 JUN 2013 | DOI: 10.1002/ejic.201300591

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      Systematic studies on the doping of [Al(OH)L]n [L = 1,4-benzenedicarboxylate (bdc) or 1,4-naphthalenedicarboxylate (ndc)] metal–organic frameworks (MOFs) with V ions to obtain [(AlOH)1–x(VO)xL]n (0 < x < 1) solid-solution materials are reported. Detailed characterization allowed us to examine the correlations between compositions and the structures and properties of the final mixed-metal materials.

    2. Microwave Synthesis

      Efficient and Rapid Synthesis of Chlorido-Bridged Half-Sandwich Complexes of Ruthenium, Rhodium, and Iridium by Microwave Heating (pages 4558–4562)

      Justus Tönnemann, Julie Risse, Zacharias Grote, Rosario Scopelliti and Kay Severin

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/ejic.201300600

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      The important organometallic starting materials [(p-cymene)RuCl2]2 and [(cyclopentadienyl)MCl2]2 (M = Ru, Rh, Ir) can be obtained by microwave heating. This methodology shortens their synthesis times from several hours to a few minutes.

    3. Uranyl Complexes

      2,2′-Bipyridine and 1,10-Phenanthroline as Coligands or Structure-Directing Agents in Uranyl–Organic Assemblies with Polycarboxylic Acids (pages 4563–4573)

      Pierre Thuéry

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/ejic.201300502

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      Seven uranyl complexes with oxalic, citraconic, 1,2,3,4-cyclobutanetetracarboxylic, citric and D-(–)-citramalic acids were obtained under hydrothermal conditions in the presence of 2,2′-bipyridine or 1,10-phenanthroline. The crystal structures evidence the different roles played by the nitrogen-containing molecules.

    4. CO Hydrogenation

      Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B–O Bond Formation (pages 4574–4584)

      Rajkumar Jana, Subrata Chakraborty, Olivier Blacque and Heinz Berke

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300482

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      Several manganese and rhenium formyl complexes containing chelating diphosphanylborane ligands were prepared and spectroscopically characterized. Exemplary single-crystal X-ray structures revealed the possibility for intramolecular Lewis acid support of the manganese- and rhenium-bound formyl groups by intramolecular B–O bond formation for cases with appropriate chelate ring sizes.

    5. Photolysis of Selenoacetic Acids

      Formation of the Matrix-Isolated Difluoromethylselanes XCF2SeH (X = H, Cl) Through Photolysis of Selenoacetic Acids, XCF2C(O)SeH (pages 4585–4594)

      Jovanny A. Gómez Castaño, Rosana M. Romano, Helmut Beckers, Helge Willner and Carlos O. Della Védova

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300322

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      Matrix photochemistry has been successfully employed for the formation of two hitherto unknown selane molecules, HCF2SeH and ClCF2SeH, by starting from HCF2C(O)SeH and ClCF2C(O)SeH acids. The species were identified through their IR spectra, with the assistance of ab initio and DFT methods.

    6. Technetium Oxidation

      Diperoxo Pertechnetic Acid Characterized by Spectroscopic and Quantum Chemical Studies (pages 4595–4600)

      Frederic Poineau, Philippe F. Weck, Benjamin P. Burton-Pye, Eunja Kim, Lynn C. Francesconi, Alfred P. Sattelberger, Konstantin E. German and Kenneth R. Czerwinski

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300383

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      The speciation of Tc(+7) was performed in HNO3/H2O2 solutions by combined UV/Vis spectroscopic and quantum chemical calculations. Results are consistent with the presence of diperoxo pertechnetic acid.

    7. Catalytic Dipeptide Hydrolysis

      Hydrolysis of Dipeptides Catalyzed by a Zirconium(IV)-Substituted Lindqvist Type Polyoxometalate (pages 4601–4611)

      Hong Giang T. Ly, Gregory Absillis, Sneha R. Bajpe, Johan A. Martens and Tatjana N. Parac-Vogt

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/ejic.201300270

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      The hydrolysis of dipeptides in the presence of a zirconium(IV)-substituted Lindqvist type polyoxometalate was investigated. Of the dipeptides studied, His–Ser was most effectively hydrolyzed, with a first-order rate constant of 9.53 × 10–6 s–1 at pD 7.4 and 60 °C. The binding of His–Ser to the Zr complex and the effect of pH, temperature, inhibitors, and ionic strength on the rate constant were examined.

    8. Heterodimetallic Complexes

      Heterodimetallic Structures Based on Cyano-Substituted Bis(dithiolene) Complexes and Ni and Cu Cyclam Cations (pages 4612–4618)

      Ana C. Cerdeira, Dulce Belo, Sandra Rabaça, Laura C. J. Pereira, Joana T. Coutinho, Dulce Simão, Rui T. Henriques, Olivier Jeannin, Marc Fourmigué and Manuel Almeida

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/ejic.201300490

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      Heterodimetallic structures based on the combination of anionic FeIII and CuII bis(dithiolene) complexes containing nitrile groups with [M(cyclam)]2+ (M = Ni, Cu) cations display a new coordination mode of the dithiolene S atom towards the metal cyclam.

    9. Protein Binding

      Unveiling the Interaction of Vanadium Compounds with Human Serum Albumin by Using 1H STD NMR and Computational Docking Studies (pages 4619–4627)

      David M. Dias, João P. G. L. M. Rodrigues, Neuza S. Domingues, Alexandre M. J. J. Bonvin and M. Margarida C. A. Castro

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300419

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      1H STD NMR analysis complemented by HADDOCK studies have revealed that the [VO2(dmpp)(H2O)(OH)] species, resulting from the oxidation of the potential insulin mimetic VO(dmpp)2, binds preferentially to HSA site I. These findings corroborate the involvement of this serum protein in the transport of vanadium species in the blood stream and their delivery to target cells.

    10. Ruthenium Photosensitizers

      A Family of RuII Photosensitizers with High Singlet Oxygen Quantum Yield: Synthesis, Characterization, and Evaluation (pages 4628–4635)

      Eleftherios K. Pefkianakis, Dionysios Christodouleas, Dimosthenis L. Giokas, Kyriakos Papadopoulos and Georgios C. Vougioukalakis

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300431

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      A series of ruthenium complexes bearing a pyridine–quinoline hybrid ligand were synthesized and extensively characterized. The 1O2 generation quantum yield of these complexes is enhanced in comparison with that of the benchmark parent complex [Ru(bpy)3]Cl2 (bpy = 2,2′-bipyridine), and the most efficient complex outperforms the parent complex by up to two times.

    11. High-Temperature Chemistry

      Synthesis, Vaporization and Thermodynamic Properties of Superfine Nd2Hf2O7 and Gd2Hf2O7 (pages 4636–4644)

      Vladimir G. Sevastyanov, Elizaveta P. Simonenko, Nikolay P. Simonenko, Valentina L. Stolyarova, Sergey I. Lopatin and Nikolay T. Kuznetsov

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300253

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      Finely dispersed powders of Nd2Hf2O7 and Gd2Hf2O7 were synthesized, their temperature agglomeration processes at different conditions were examined, and special features of the vaporization process in the temperature range 2100–2750 K were investigated by high-temperature mass spectrometry. Some thermodynamic properties were also determined.

    12. Cage Compounds

      Synthesis and Coordination of the Cagelike Siloxane Compounds E2{(SiMe2)2O}3 (E = As, Sb, Bi) (pages 4645–4653)

      Christian Bimbös, Maximilian Jost, Carsten von Hänisch and Klaus Harms

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300479

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      We describe the synthesis of the cagelike siloxane compounds E2{(SiMe2)2O}3 for the heavy homologues of the pnictides. Investigations on the coordination of the compounds show the effects of the adduct strength on the major structural parameters of the cage frameworks.

    13. Mesoionic Compounds

      A PdII Complex Bearing a Benzimidazole-Derived Ligand with Potentially “Mesoionic and Remote” Character and Its Catalytic Activity (pages 4654–4661)

      Han Vinh Huynh, Hong Lee Ong, Jan C. Bernhammer and Gilles Frison

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300334

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      The oxidative addition of Pd0 to a C2-protected 5-bromobenzimidazolium salt affords a complex of an unprecedented and formally neutral benzimidazole-derived ligand (bimy). DFT calculations indicate that the bimy ligand bridges the gap between neutral mesoionic and anionic aryl ligands. The catalytic activity of the complex in the Sonogashira reaction has been studied.

    14. Blue-Emitting Phosphors

      Luminescent Properties of RbSrPO4:Eu2+ Phosphors for Near-UV-Based White-Light-Emitting Diodes (pages 4662–4666)

      Dong Kyun Yim, Hee Jo Song, Hee-Suk Roh, Seung-Joo Kim, Byung Suh Han, Yun-Ho Jin, Hyun-Seon Hong, Dong-Wan Kim and Kug Sun Hong

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300457

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      The crystal structure of the phosphate-based host matrix RbSrPO4 is investigated by Rietveld refinement for the first time. The photoluminescence properties of Eu2+-doped RbSrPO4 are explored, and the results indicate that this phosphor has potential for use in near-UV-based white-light-emitting diodes.

    15. Energetic Compounds

      Advanced Open-Chain Nitramines as Energetic Materials: Heterocyclic-Substituted 1,3-Dichloro-2-nitrazapropane (pages 4667–4678)

      Thomas M. Klapötke, Alexander Penger, Carolin Pflüger, Jörg Stierstorfer and Muhamed Sućeska

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300382

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      The synthesis of advanced open-chain nitramines by nucleophilic substitution reactions with potassium salts of amino and/or nitro substituted 1,2,4-triazoles, imidazoles and pyrazoles on 1,3-dichloronitrazapropane yields neutral energetic materials. The energetic compounds were characterized in detail as secondary explosives. Interesting trends in safety and performance values were explored.

    16. M–Malonate Complexes

      MII–Malonate Complexes (M = Mg, Cu, Ni and Co) Characterized by Layered Structures: Experimental Observation, Hirshfeld Surface Analysis and Theoretical Study (pages 4679–4685)

      Monojit Mitra, Saikat Kumar Seth, Somnath Ray Choudhury, Prankrishna Manna, Amrita Das, Madeleine Helliwell, Antonio Bauzá, Antonio Frontera and Subrata Mukhopadhyay

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/ejic.201300459

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      Protonated 4-aminopyridine enforces a layered structure in the MgII–malonate complex, thereby resembling related complexes with Co and Ni as the metal centre. However, the related Cu complex adopts a polymeric structure. A DFT study provides an explanation for these experimental findings.

    17. Layered Double Hydroxides

      Structure of the Chloride- and Bromide-Intercalated Layered Double Hydroxides of Li and Al – Interplay of Coulombic and Hydrogen-Bonding Interactions in the Interlayer Gallery (pages 4686–4693)

      Supreeth Nagendran and P. Vishnu Kamath

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300451

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      A change in the ambient humidity alters the packing of the atoms in the interlayer gallery of [LixAl(OH)3]Xx·yH2O (X = Br, Cl; y ≈ 1/2, 2/3) layered double hydroxides. Thereby, the degree of hydration changes without a significant change in the basal spacing.

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