European Journal of Inorganic Chemistry

Cover image for European Journal of Inorganic Chemistry

Special Issue: Modern Coordination Chemistry and Its Impact for Meeting Global Challenges (Cluster Issue)

October 2012

Volume 2012, Issue 29

Pages 4519–4757

Issue edited by: Debbie Crans, Franc Meyer

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Microreviews
    8. Short Communications
    9. Full Papers
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      Copper(I)-Dioxygen Reactivity in a Sterically Demanding Tripodal Tetradentate tren Ligand: Formation and Reactivity of a Mononuclear Copper(II) End-On Superoxo Complex (Eur. J. Inorg. Chem. 29/2012)

      Yuki Kobayashi, Kei Ohkubo, Takashi Nomura, Minoru Kubo, Nobutaka Fujieda, Hideki Sugimoto, Shunichi Fukuzumi, Kei Goto, Takashi Ogura and Shinobu Itoh

      Version of Record online: 2 OCT 2012 | DOI: 10.1002/ejic.201290089

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      The front cover picture shows a core image of the mononuclear copper(II) end-on superoxo complex generated by using the HIPT3tren ligand. The characteristic absorption spectrum exhibiting an intense LMCT band at 434 nm together with broad and intense absorption bands in the visible to near-IR region is also included. Details are discussed in the Short Communication by S. Itoh et al. on p. 4574 ff.

  2. Editorials

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Microreviews
    8. Short Communications
    9. Full Papers
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      Coordination Chemistry (page 4519)

      Karen Hindson

      Version of Record online: 2 OCT 2012 | DOI: 10.1002/ejic.201290090

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  3. Back Cover

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Microreviews
    8. Short Communications
    9. Full Papers
    1. You have free access to this content
      Reshaping Rubrene by Controlled Reduction with Alkali Metals (Eur. J. Inorg. Chem. 29/2012)

      Alexander V. Zabula, Natalie J. Sumner, Alexander S. Filatov, Sarah N. Spisak, Vladimir M. Grigoryants and Marina A. Petrukhina

      Version of Record online: 2 OCT 2012 | DOI: 10.1002/ejic.201290092

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      The back cover picture shows the deformation of a polycyclic core of rubrene upon stepwise electron acquisition as well as the binding versatility of the resulting polyaromatic anions towards alkali metal ions. The supramolecular aggregates of rubrene have been studied in the solid state and in solution by a combination of X-ray diffraction and spectroscopic techniques. Details are discussed in the article by M. Petrukhina et al. on p. 4675 ff.

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Microreviews
    8. Short Communications
    9. Full Papers
  5. News

    1. Top of page
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    5. Graphical Abstract
    6. News
    7. Microreviews
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    9. Full Papers
  6. Microreviews

    1. Top of page
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    1. Phosphinidene–Phosphane Chemistry

      Coordination-Like Chemistry of Phosphinidenes by Phosphanes (pages 4539–4549)

      John D. Protasiewicz

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/ejic.201200273

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      The coordination chemistry of neutral phosphane adducts of phosphinidenes (phosphanylidene-σ4-phosphoranes, also known as phospha-Wittig reagents, RP=PR3) is reviewed.

    2. Europium(II) Chemistry

      Developments in the Coordination Chemistry of Europium(II) (pages 4550–4563)

      Joel Garcia and Matthew J. Allen

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/ejic.201200159

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      This review describes Eu2+-containing complexes reported in the 21st century with focus on the synthesis, reactivity, and application of these complexes.

  7. Short Communications

    1. Top of page
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    1. Heterodimetallic Complexes

      Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)-Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System (pages 4565–4569)

      Florian Heims, Valeriu Mereacre, Antonella Ciancetta, Stefan Mebs, Annie K. Powell, Claudio Greco and Kallol Ray

      Version of Record online: 23 MAY 2012 | DOI: 10.1002/ejic.201200156

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      The synthesis of a new asymmetric dinucleating ligand FloH, designed with two sets of metal ion binding groups suited to selective complexation, is reported. The site-directed generation of a heterodinuclear FeIIICuII complex is performed in highyield and purity by using FloH.

    2. Oscillation Reactions

      A Vanadium-Based Chemical Oscillator: Identification of Chemical Species Responsible for the Redox Reaction and Construction of a Simplified Model (pages 4570–4573)

      Kan Kanamori, Hiroshi Kataoka and Seiichi Matsugo

      Version of Record online: 16 MAY 2012 | DOI: 10.1002/ejic.201200148

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      Products derived from indole in a vanadium-based oscillation solution were identified to be 3,3-dichloro-2-oxoindole and isatin. Peroxo species such as CHCl2OO· and CHCl2OOH were found to play a key role in the construction of the chemical oscillation system. A skeletal model for the oscillation reaction is proposed.

    3. Superoxo Complexes

      Copper(I)-Dioxygen Reactivity in a Sterically Demanding Tripodal Tetradentate tren Ligand: Formation and Reactivity of a Mononuclear Copper(II) End-On Superoxo Complex (pages 4574–4578)

      Yuki Kobayashi, Kei Ohkubo, Takashi Nomura, Minoru Kubo, Nobutaka Fujieda, Hideki Sugimoto, Shunichi Fukuzumi, Kei Goto, Takashi Ogura and Shinobu Itoh

      Version of Record online: 13 APR 2012 | DOI: 10.1002/ejic.201200177

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      Copper(I)-dioxygen reactivity has been examined by using a sterically demanding tripodal tetradentate ligand HIPT3tren. Low-temperature oxygenation of the copper(I) complex afforded a mononuclear copper(II) end-on superoxo complex 1 with a singlet ground state. The O2-binding process as well as the reactivity of 1 toward external substrates has been examined kinetically.

    4. Tungsten Nitride Nanoparticles

      Synthesis of WN(NMe2)3 as a Precursor for the Deposition of WNx Nanospheres (pages 4579–4584)

      K. Randall McClain, Christopher O'Donohue, Zhiwei Shi, Amy V. Walker, Khalil A. Abboud, Tim Anderson and Lisa McElwee-White

      Version of Record online: 13 JUL 2012 | DOI: 10.1002/ejic.201200254

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      The WNx precursor WN(NMe2)3 was synthesized from WN(OtBu)3 and Zr(NMe2)4 in good yield by using an amide/alkoxide exchange reaction. Benzene solutions of WN(NMe2)3 were utilized in an AACVD reactor to produce nanospheres of WNx on a silicon substrate at temperatures as low as 75 °C.

  8. Full Papers

    1. Top of page
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    3. Editorials
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    5. Graphical Abstract
    6. News
    7. Microreviews
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    1. Vanadyl Complexes

      Organo-Phosph(on/in)ate-Bridged Dimers of Vanadium(IV) Complexes with the Kläui Ligand: Synthesis and Characterization (pages 4585–4592)

      Xavier Riart-Ferrer, Alexander E. Anderson, Brandon M. Nelson, Fei Hao and Craig C. McLauchlan

      Version of Record online: 1 JUN 2012 | DOI: 10.1002/ejic.201200160

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      A series of dinuclear organophosphorus-bridged vanadyl complexes have been synthesized; their spectral and magnetic properties are reported.

    2. Coordination Polymers and Dimers

      Structural Variations in Copper(II) Complexes of a Bitopic Bis(pyrazolyl)methane Ligand (pages 4593–4604)

      Daniel L. Reger, Andrea E. Pascui and Mark D. Smith

      Version of Record online: 25 MAY 2012 | DOI: 10.1002/ejic.201200118

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      The bitopic ligand p-[CH(pz)2]2C6H4 (Lp) forms two types of complexes with Cu(BF4)2·3H2O: coordination polymers of the formula [Cu(μ-Lp)(solvent)]2+ and dinuclear [Cu2(μ-Lp)(solvent)6]4+, where the copper(II) ions are in a square pyramidal geometry and are oriented in an anti conformation. Hydrogen bonding interactions organize the supramolecular structures.

    3. Electronic Structures

      Electronic Structures of the Electron Transfer Series [M(bpy)3]n, [M(tpy)2]n, and [Fe(tbpy)3]n (M = Fe, Ru; n = 3+, 2+, 1+, 0, 1–): A Mössbauer Spectroscopic and DFT Study (pages 4605–4621)

      Jason England, Christopher C. Scarborough, Thomas Weyhermüller, Stephen Sproules and Karl Wieghardt

      Version of Record online: 6 JUN 2012 | DOI: 10.1002/ejic.201200232

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      The electronic structures of [M(tpy)2]n, [M(bpy)3]n, and [Fe(tbpy)3]n (M = Fe, Ru; n = 1+, 0, 1–) have been investigated and assigned. They all contain divalent metal centers, with the excess electrons localized on the ligands. Furthermore, the metal ions are all low spin (S = 0), except in [Fe(tpy)2]0/1–, where they are high spin (S = 2).

    4. Sequential Ligand Oxidations

      Sequential Phenolate Oxidations in Octahedral Cobalt(III) Complexes with [N2O3] Ligands (pages 4622–4631)

      Marco M. Allard, Fernando R. Xavier, Mary Jane Heeg, H. Bernhard Schlegel and Cláudio N. Verani

      Version of Record online: 22 JUN 2012 | DOI: 10.1002/ejic.201200171

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      Octahedral cobalt(III) complexes coordinated to [N2O3] ligands and MeOH display apparently similar structural, spectroscopic and redox properties. Two compounds behave as electron reservoirs with four reversible 1-electron ligand-based oxidations and one metal-based reduction. In spite of these similarities, subtle geometric and electronic differences lead to distinctive oxidative sequences.

    5. Mixed-Valent Ru Complexes

      Mono- and Dinuclear Ruthenium(II)–1,6,7,12-Tetraazaperylene Complexes of N,N′-Dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (pages 4632–4643)

      Thomas Brietzke, Wulfhard Mickler, Alexandra Kelling, Uwe Schilde, Hans-Jörg Krüger and Hans-Jürgen Holdt

      Version of Record online: 24 AUG 2012 | DOI: 10.1002/ejic.201200667

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      Dinuclear complex [{Ru(L-N4Me2)}2(μ-tape)]4+, containing 1,6,7,12-tetraazaperylene (tape) as bridging ligand and N,N′-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) as auxiliary ligand, shows a high degree of electronic interaction between the two Ru centers. For the mixed-valent state RuIII/II, the comproportionation constant, Kc, is 8.9 × 106, and there is an NIR IVCT band at 2472 nm.

    6. Redox Reactions

      Redox Activity in a Vanadium(V)–o-Dioxolene Complex Is Modulated by Protonation State As Indicated by 51V Solid-State NMR Spectroscopy and Density Functional Theory (pages 4644–4651)

      Pabitra B. Chatterjee, Olga Goncharov-Zapata, Guangjin Hou, Olga Dmitrenko, Tatyana Polenova and Debbie C. Crans

      Version of Record online: 19 SEP 2012 | DOI: 10.1002/ejic.201200259

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      The properties of an innocent vanadium(V) complex, [VO(gsal)(HCat)], were investigated by 51V solid-state magic angle spinning NMR spectroscopy and density functional theory. The upfield isotropic chemical shift and large negative chemical shift anisotropy observed in the solid state are consistent with the results of the DFT calculations; both indicate that the compound is redox-inactive.

    7. CN-Bridged Coordination Polymers

      Trimetallic [M3(dpa)4]2+ Complexes (M = Co, Ni) as Building Blocks for Cyano-Bridged Coordination Polymers (pages 4652–4660)

      Jingfang Wang, Andrew Ozarowski, Kirill Kovnir, Corey M. Thompson, Alexander A. Yaroslavtsev, Roman V. Chernikov, Naresh S. Dalal and Michael Shatruk

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/ejic.201200274

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      Trimetallic complexes M3(dpa)4Cl2 react with hexacyanometalates to afford CN-bridged coordination polymers with extended 2D structures. Partial or complete electron transfer between the trimetallic units and [Fe(CN)6]3– takes place upon the formation of the compounds.

    8. Copper Siloxides

      Copper(I) Siloxides – Aggregated Solid-State Structures, Cu–Cu Interactions and Dynamic Solution Behavior (pages 4661–4668)

      Fabian Schax, Christian Limberg and Clemens Mügge

      Version of Record online: 25 JUN 2012 | DOI: 10.1002/ejic.201200294

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      The Cu4O4 unit is a recurring structural motif that is assembled from siloxane-diolate/CuI systems. These systems are remarkably flexible in solution, also with regards to the length of the siloxane backbone and fragmentation.

    9. Dipeptide–Pd Conjugates

      Molecular Structures of Dipeptide–Palladium(II) Conjugated Complexes (pages 4669–4674)

      Toshiyuki Moriuchi, Kunihiro Morimoto, Yuki Sakamoto and Toshikazu Hirao

      Version of Record online: 31 MAY 2012 | DOI: 10.1002/ejic.201200155

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      A dipeptide–PdII conjugated complex with an ancillary acetonitrile ligand was designed and studied as a metalloreceptor. Exchange of the labile acetonitrile ligand with 4-aminopyridine resulted in a complex exhibiting emission at λmax = 652 nm in the solid state. Each preorganized helical molecule was found to be packed in a right-handed helical-like molecular arrangement.

    10. Anionic Ligand Coordination

      Reshaping Rubrene by Controlled Reduction with Alkali Metals (pages 4675–4683)

      Alexander V. Zabula, Natalie J. Sumner, Alexander S. Filatov, Sarah N. Spisak, Vladimir M. Grigoryants and Marina A. Petrukhina

      Version of Record online: 4 MAY 2012 | DOI: 10.1002/ejic.201200164

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      Mono-, di- and tetraanions of rubrene have been prepared by a stepwise alkali-metal reduction. The geometries of charged rubrene anions and their supramolecular aggregation with alkali-metal ions in the solid state and solution are discussed based on single-crystal X-ray diffraction studies, ESR and multinuclear NMR spectroscopy.

    11. Supramolecular Catalysis

      Supramolecular Hybrid Bidentate Ligands in Asymmetric Hydrogenation (pages 4684–4693)

      Rosalba Bellini and Joost N. H. Reek

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/ejic.201200549

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      The performance of a new class of supramolecular hybrid bidentate ligands was investigated in rhodium-catalysed asymmetric hydrogenation. After optimisation of the reaction conditions, the scope of these ligands was explored in the asymmetric hydrogenation of various prochiral olefins. Higher activity and selectivity was obtained with the supramolecular catalysts than the nontemplated analogues.

    12. Multicomponent Reactions

      Zn-Mediated Synthesis of 3-Substituted Indoles Using a Three-Component Reaction Approach (pages 4694–4700)

      Daniele Anselmo, Eduardo C. Escudero-Adán, Marta Martínez Belmonte and Arjan W. Kleij

      Version of Record online: 3 MAY 2012 | DOI: 10.1002/ejic.201200150

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      The Zn(salphen)-mediated synthesis of 3-substituted indoles by using a multicomponent reaction approach is reported. The reaction parameters were investigated and the selectivity for the 3-CR product was examined under various conditions. Selectivity for the target compound is significantly compromised by side-product formation due to in situ reaction of the intermediate species with malononitrile, which affords N-heterocyclic structures.

    13. Soft Scorpionate Ligands

      Copper Complexes with a Hybrid Scorpionate Ligand Containing Pyridazine-3-thione (pages 4701–4707)

      Gernot Nuss, Anja Ozwirk, Bastian N. Harum, Gerald Saischek, Ferdinand Belaj and Nadia C. Mösch-Zanetti

      Version of Record online: 2 MAY 2012 | DOI: 10.1002/ejic.201200158

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      A new hybrid scorpionate ligand, Na[HB(mim)2(PntBu)] (Na[PnBm]), containing the methimazole and pyridazine moieties was prepared. Reaction of the ligand with CuCl and phosphane donors gave complexes [Cu{PnBm}(PR3)] (R = cyclohexyl 1, phenyl 2), whereas without phosphane donors dimeric complex [Cu{PnBm}]2 (3) was formed. The fluxional behavior was further investigated by theoretical calculations.

    14. Acceptor–Donor–Acceptor Complexes

      Lanthanide-Based Dinuclear Complexes Involving an o-Quinone–Tetrathiafulvalene–o-Quinone Bridging Ligand: X-ray Structures, Magnetic and Photophysical Properties (pages 4708–4718)

      Fabrice Pointillart, Viacheslav Kuropatov, Alexander Mitin, Olivier Maury, Yann Le Gal, Stéphane Golhen, Olivier Cador, Vladimir Cherkasov and Lahcène Ouahab

      Version of Record online: 24 APR 2012 | DOI: 10.1002/ejic.201200121

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      YbIII luminescence of the paramagnetic dinuclear complex [Yb2(hfac)6(L)] (L = 4,4′,7,7′-tetra-tert-butyl-2,2′-bi-1,3-benzodithiole-5,5′,6,6′-tetrone) is induced by the lowest-energy irradiation (13335 cm–1) for the sensitisation of near-infrared emissive lanthanides.

    15. DNA Cleavage

      Design and Synthesis of a Functional Derivative of the Triazinium Cation and Its Rhodium Complex that Shows Photoinduced DNA Cleavage Activity and Photocytotoxicity (pages 4719–4727)

      Pradip Ghosh, Mominul Sinan, Debojyoti Lahiri, Sovan Roy and Sreebrata Goswami

      Version of Record online: 25 MAY 2012 | DOI: 10.1002/ejic.201200054

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      The design and synthesis of an intensely blue rhodium(III) complex, which appears to be a promising photochemotherapeutic agent, is described.

    16. Bioinspired Zinc Complexes

      Zinc Complexes of a Bioinspired Binucleating Ligand Platform – Equilibria in Solution and Structures in the Solid State (pages 4728–4738)

      Simone Wöckel, Joanna Gałęzowska, Sebastian Dechert, Wolfram Meyer-Klaucke, Ebbe Nordlander and Franc Meyer

      Version of Record online: 26 JUL 2012 | DOI: 10.1002/ejic.201200269

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      A bioinspired bis(tetradentate) pyrazolate-bridged ligand forms various zinc(II) complexes of different nuclearity in aqueous solution, depending on pH. A detailed picture of the multitude of species and their dynamic equilibria was obtained from the combination of potentiometry, NMR and EXAFS spectroscopy, ESI mass spectrometry, and X-ray diffraction.

    17. Dicopper Complexes

      pH-Dependent Imidazolato Bridge Formation in Dicopper Complexes: Magnetic, Electrochemical, and Catalytic Repercussions (pages 4739–4749)

      Inés Monte-Pérez, Ana M. Sosa, Sylvain Bernès, Núria Aliaga-Alcalde, Víctor M. Ugalde-Saldívar and Laura Gasque

      Version of Record online: 29 MAY 2012 | DOI: 10.1002/ejic.201200167

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      The dicopper complexes of two dinucleating ligands undergo a strong antiferromagnetic coupling upon formation of an imidazolato bridge. UV/Vis and EPR spectroscopy as well as electrochemical studies confirmed the potentiometric solution speciation.

    18. Enzyme Models

      Photoinitiated Dioxygenase-Type Reactivity of Open-Shell 3d Divalent Metal Flavonolato Complexes (pages 4750–4757)

      Katarzyna Grubel, Amy R. Marts, Samuel M. Greer, David L. Tierney, Caleb J. Allpress, Stacey N. Anderson, Brynna J. Laughlin, Rhett C. Smith, Atta M. Arif and Lisa M. Berreau

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/ejic.201200212

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      UV irradiation of 3-hydroxyflavonolato complexes of dn metal ions under aerobic conditions results in oxidative carbon–carbon bond cleavage and the formation of O-benzoylsalicylato complexes and CO under stoichiometric or catalytic conditions. These results show that a variety of metal ions promote light-induced flavonoloxidation and CO release under mildconditions.

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