European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 3

January 2015

Volume 2015, Issue 3

Pages 356–551

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. You have free access to this content
      Mechanistic Insights into Phenol Oxidation by a Copper(II) Complex of a Pyridine- and Amide-Containing Copolymer in an Aqueous Medium (Eur. J. Inorg. Chem. 3/2015)

      Vasiliki Lykourinou and Li-June Ming

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201590008

      Thumbnail image of graphical abstract

      The cover picture shows the two distinct pathways for phenol hydroxylation and oxidation by the copper complex of a copolymer in an aqueous medium, that is, a dinuclear and a mononuclear mechanism with H2O2 and air, respectively, as the oxidation agents. Despite the random sequence and heterogeneity of this copper–copolymer complex, the rates of catalysis achieved are comparable to or better than those of many metal complexes with well-defined structures. This copper–copolymer complex may serve as a blueprint for further design of metallopolymers with various chemical and physical properties by modification of the metal-binding ligands and the side chains. The water splash (1/125 s) and the floating leaves in the background hint the green chemistry nature of the research. Details are discussed in the article by V. Lykourinou and L.-J. Ming on p. 375 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. You have free access to this content
      Mechanistic Insights into Phenol Oxidation by a Copper(II) Complex of a Pyridine- and Amide-Containing Copolymer in an Aqueous Medium (page 356)

      Vasiliki Lykourinou and Li-June Ming

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201500015

      Thumbnail image of graphical abstract

      The easy preparation of the metallopolymers and their potential in various metal-mediated catalysis reactions will allow us to explore broad applications...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 375 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Graphical Abstract: Eur. J. Inorg. Chem. 3/2015 (pages 357–363)

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201590009

  4. News

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
  5. Masthead

    1. Top of page
    2. Cover Picture
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    4. Graphical Abstract
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    6. Masthead
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    1. Masthead: Eur. J. Inorg. Chem. 3/2015 (pages 368–369)

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201590011

  6. Short Communication

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Single-Molecule Magnets

      A Click-Functionalized Single-Molecule Magnet Based on Cobalt(II) and Its Analogous Manganese(II) and Zinc(II) Compounds (pages 370–374)

      Christian Plenk, Jasmin Krause and Eva Rentschler

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201402955

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      An azide-functionalized single-molecule magnet suitable for click reactions is reported. The solution stability of three novel building blocks containing single CoII, MnII, and ZnII metal ions is proven in great detail by using ESI-MS and NMR spectroscopy. Remarkably, alternating current susceptibility data of the six-coordinate cobalt(II) complex reveal single-molecule magnet behavior.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Masthead
    7. Short Communication
    8. Full Papers
    1. Dioxygen Activation

      Mechanistic Insights into Phenol Oxidation by a Copper(II) Complex of a Pyridine- and Amide-Containing Copolymer in an Aqueous Medium (pages 375–381)

      Vasiliki Lykourinou and Li-June Ming

      Article first published online: 7 NOV 2014 | DOI: 10.1002/ejic.201402778

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      A CuII complex of a pyridine- and amide-containing copolymer catalyzes phenol hydroxylation/oxidation in aqueous methanol at pH 8.0 and 25 °C. First-order rate accelerations by factors of 4.2 × 105 and 1.4 × 105 and deuterium kinetic isotope effects of 2.8 and 1.2, respectively, were observed with and without H2O2. The results suggest that different mechanisms apply for oxidation by O2 and H2O2.

    2. Nitridophosphates

      Sn6[P12N24] – A Sodalite-Type Nitridophosphate (pages 382–388)

      Florian J. Pucher, Constantin Frhr. von Schirnding, Franziska Hummel, Vinicius R. Celinski, Jörn Schmedt auf der Günne, Birgit Gerke, Rainer Pöttgen and Wolfgang Schnick

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201403040

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      The new pseudobinary nitridophosphate Sn6[P12N24] is synthesized and investigated. The β-cage of this compound, which crystallizes with the sodalite type of structure, is partially empty, as shown by several experimental and theoretical methods.

    3. Lanthanide Nanochemistry

      A Technique to Fabricate La2O2CN2:Tb3+ Nanofibers and Nanoribbons with the Same Morphologies as the Precursors (pages 389–396)

      Xiaomin Guo, Wensheng Yu, Xiangting Dong, Jinxian Wang, Qianli Ma, Guixia Liu and Ming Yang

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201402860

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      Tb3+-doped La2O2CN2 nanofibers and nanoribbons were fabricated by cyanamidation from precursor La2O3:Tb3+ nanofibers and nanoribbons made by electrospinning. The morphologies of the final products were the same as those of their respective precursors. The La2O2CN2:Tb3+ nanostructures are tetragonal in structure with space group I4/mmm and exhibit excellent luminescence performance.

    4. Seleno- and Telluroether as Ligands

      Structural Variation in [PdX2{RE(CH2)nNMe2}] (E = Se, Te; X = Cl, OAc) Complexes: Experimental Results, Computational Analysis, and Catalytic Activity in Suzuki Coupling Reactions (pages 397–407)

      Dilip K. Paluru, Sandip Dey, Amey Wadawale, Dilip K. Maity, Nattamai Bhuvanesh and Vimal K. Jain

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201402943

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      Complexes [PdX2{RE(CH2)nNMe2}]m (X = Cl, OAc) exist in one monomeric and two dimeric forms in solution depending on E and n. Molecular structures were established by X-ray structural analyses and supported by DFT calculations. These complexes act as catalyst in Suzuki coupling reactions.

    5. Spin-Crossover Complexes

      Iron(II) Spin-Crossover Complexes with Schiff Base Like Ligands and N-Alkylimidazoles (pages 408–413)

      Stephan Schlamp, Charles Lochenie, Tobias Bauer, Rhett Kempe and Birgit Weber

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403021

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      Iron(II) spin-crossover complexes with Schiff base like equatorial ligands and alkylimidazole axial ligands are synthesised. The alkyl chain length is varied from 5 to 7 and 10 carbon atoms. The crystal structures of the C7 and C10 compounds are described. There is an increased cooperativity in spin-crossover behaviour for the compound with the longer C10 alkyl chain than for the C5 compound.

    6. Lanthanide Luminescence

      Synthesis, Stability and Sensitised Lanthanide Luminescence of Heterobimetallic d/f Terpyridine Complexes (pages 414–420)

      Evan G. Moore, Massimo Benaglia, Giacomo Bergamini and Paola Ceroni

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403100

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      The synthesis and solution properties for a series of heterobimetallic RuII–LnIII complexes are reported. These compounds demonstrate the use of a RuII bis-terpyridine unit as the sensitiser for LnIII-based near-infrared emission for the first time. Energy transfer is shown to operate through both the triplet ligand-centred and triplet metal-to-ligand charge-transfer pathways.

    7. Coupling Reactions

      Synthesis and Reactions of PdII Complexes with Aryl, Aroyl, and Iminoaroyl Ligands – Insertion of CO and RNC into the Pd–Ar Bond and Intermolecular Coupling of the Ligands (pages 421–429)

      Yuji Suzaki, Masanori Shirokawa, Takeyoshi Yagyu and Kohtaro Osakada

      Article first published online: 15 DEC 2014 | DOI: 10.1002/ejic.201402720

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      Aryl-, aroyl-, and iminoaroyl iodidopalladium(II) complexes with a 2,2′-bipyridine ligand react with AgBF4 and H2O to afford biaryls, diarylketones, and arylamides by labilization of the iodido ligand.

    8. Electrorheological Properties

      Anisotropic α-Fe2O3@TiO2 Core–Shell Nanoparticles and Their Smart Electrorheological Response (pages 430–440)

      Xiaoli Tian, Yichao Yin, Baoxiang Wang, Xianfen Song, Shuangshuang Sun, Shoushan Yu, Chuncheng Hao and Kezheng Chen

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejic.201402816

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      α-Fe2O3@TiO2 core–shell nanoparticles were synthesized by means of a controlled hydrolysis method and can be used as smart electrorheological (ER) materials. The nonspherical core–shell nanoparticles possess uniform sizes and weak magnetism. The α-Fe2O3@TiO2 ER suspension exhibits an enhanced electrorheological effect compared with that of a pure α-Fe2O3 ER suspension.

    9. Hybrid Material

      Hybrid Material Constructed from Hg(NCS)2 and 2,4,6-Tris(2-pyrimidyl)-1,3,5-triazine (TPymT): Coordination of TPymT in a 2,2′-Bipyridine-Like Mode (pages 441–446)

      Damir A. Safin, Rebecca J. Holmberg, Kevin M. N. Burgess, Koen Robeyns, David L. Bryce and Muralee Murugesu

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201402832

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      Reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with a mixture of HgCl2 and NH4NCS leads to the formation of a polymeric heteroleptic hybrid material [{[Hg(NCS)2]2TPymT}n], in which two coordination pockets of TPymT are each coordinated to two HgII cations in an unprecedented 2,2′-bipyridine-like mode.

    10. Vanadium Photo-cytotoxic Agents

      Remarkable Selectivity and Photo-Cytotoxicity of an Oxidovanadium(IV) Complex of Curcumin in Visible Light (pages 447–457)

      Samya Banerjee, Akanksha Dixit, Anjali A. Karande and Akhil R. Chakravarty

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejic.201402884

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      A curcumin oxidovanadium(IV) complex of pyphen is a potent metal-based cytotoxin capable of inducing remarkable ROS-mediated apoptotic photo-cytotoxicity triggered by visible light (400–700 nm). This toxicity is selective for HeLa and MCF-7 cancer cells relative to 3T3 control cells and is absent in the absence of light.

    11. Scorpionato Halide Complexes

      Scorpionato Halide Complexes [(TpPh,Me)Ni–X] [X = Cl, Br, I; TpPh,Me = Hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate]: Structures, Spectroscopy, and Pyrazole Adducts (pages 458–467)

      Tapash Deb, Caitlin M. Anderson, Huaibo Ma, Jeffrey L. Petersen, Victor G. Young Jr. and Michael P. Jensen

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejic.201402897

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      Pseudotetrahedral scorpionato halide complexes [(TpPh,Me)Ni–X] [X = Cl, Br, I; TpPh,Me = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] and pentacoordinate pyrazole adducts [(TpPh,Me)Ni(HPzPh,Me)(X)] (X = Cl, I) were synthesized, characterized by X-ray crystallography and spectroscopy, and simulated by density functional calculations. Analyses of the structures, spectroscopy, and bonding are discussed with respect to the different halides.

    12. Porphyrins

      Five-Coordinate Indium(III) Porphyrins with Hydroxy and Carboxy BODIPY as Axial Ligands: Synthesis, Characterization and Photophysical Studies (pages 468–477)

      Manas K. Panda, Theodore Lazarides, Georgios Charalambidis, Vasilis Nikolaou and Athanassios G. Coutsolelos

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejic.201402902

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      A comparative study of a new five-coordinate indium(III) porphyrin containing BODIPY as the axial ligand that binds through two different modes: a phenolate and benzoate mode is presented. Both dyad hybrid materials are fully characterized and studied by photophysical experiments.

    13. Hybrid Iodoargentates

      Different Contributions of Aliphatic and Conjugated Organic Cations to Both the Crystal and Electronic Structures: Three Hybrid Iodoargentates Showing Two Isomers of the (AgI2) Chain (pages 478–487)

      Guang-Ning Liu, Le-Le Liu, Ya-Nan Chu, Yi-Qiang Sun, Zhen-Wei Zhang and Cuncheng Li

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejic.201402919

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      Three new hybrid iodoargentates that show two isomers of 1D (AgI2) anionic chains have been synthesized under solvothermal conditions. Studies indicate that aliphatic and conjugated organic cations have different contributions to both the crystal and electronic structures.

    14. Polyoxometalates

      Three Polyoxometalate-Based Coordination Polymers Constructed from the Same Dimetallic Cyclic Building Block (pages 488–493)

      Min Gu, Yuanhang Ren, Yichen Hu, Min Tang, Zuping Kong, Bin Yue and Heyong He

      Article first published online: 15 DEC 2014 | DOI: 10.1002/ejic.201402938

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      Three polyoxometalate-based (POM-based) coordination polymers containing a similar type of building block, [M2(3-bpo)2(C5H4NCOOH)2]4+ [M = Cu, Co, Ni; 3-bpo = 2,5-bis(3-pyridyl)-1,3,4-oxadiazole], are hydrothermally synthesized. These polymers are characterized, and their electrochemical behaviors are studied by cyclic voltammetry.

    15. Bioinorganic Chemistry

      Biomimetic Hydroxylation Catalysis Through Self-Assembly of a Bis(pyrazolyl)methane Copper–Peroxo Complex (pages 494–502)

      Claudia Wilfer, Patricia Liebhäuser, Hannes Erdmann, Alexander Hoffmann and Sonja Herres-Pawlis

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201402957

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      Herein, we present four new bis(pyrazolyl)methane–copper complexes. Furthermore, we studied the self-assembly of a peroxo–dicopper species with catalytic hydroxylation activity of phenols by UV/Vis spectroscopy. The donor competition between pyrazolyl and pyridinyl units as well as the UV transitions of the tyrosinase model have been investigated by density functional theory.

    16. Isomerism

      Computational Insights into the Isomerism of Hexacoordinate Metal–Sarcophagine Complexes: The Relationship between Structure and Stability (pages 503–511)

      Andrés G. Algarra

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejic.201402984

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      The relative stability of the isomers of {M(NR3)2sar}2+ (M = CoIII, CoII, CuII; R = H, Me; sar = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) was studied by means of DFT calculations. Further combination of distortion/interaction analysis and shape maps revealed its relationship with the degree of distortion with respect to the ideal octahedron, which is ultimately dictated by the metal.

    17. Ternary Semiconductor Precursors

      1,2-Dithiooxalato-Bridged Heterobimetallic Complexes as Single-Source Precursors for Ternary Metal Sulfide Semiconductors (pages 512–519)

      Mathias Nowotny, Sabine Foro, Silvio Heinschke, Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201402990

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      Bimetallic single-source precursor complexes for ternary metal sulfide semiconductors are presented. The 1,2-dithiooxalato ligand serves as a linker, complexation site, and molcular source of sulfur in the formation of CuInS2 nanoparticles.

    18. Pd-Catalyzed C–C Coupling Reactions

      Catalytic Synthesis of Bi- and Teraryls in Aqueous Medium with Palladium(II) Complexes of 2-(Pyridine-2-ylmethylsulfanyl)benzoic Acid (pages 520–526)

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

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201403003

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      Complexes [PdCl2L1] [1, L1 = 2-(pyridine-2-ylmethyl)sulfanylbenzoic acid] and [Pd(L2-H)2] (2, L2-H = 2-pyridin-2-yl-benzo[b]thiophen-3-ol) catalyze Suzuki coupling (1 in water) reactions to form bi- and teraryls. L2 forms by an unprecedented cyclization of L1. Pd nanoparticles (NPs) generated in situ play a role in the catalysis, which is a combination of homogeneous and heterogeneous processes.

    19. Borates

      Structure, Thermal Behavior, and Vibrational Spectroscopy of the Silver Borate AgB3O5 (pages 527–533)

      Gerhard Sohr, Viktoria Falkowski, Michael Schauperl, Klaus R. Liedl and Hubert Huppertz

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201403006

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      During investigations of the Ag–B–O system, we found the light-stable, non-centrosymmetric silver borate AgB3O5. It is built from corner-sharing BO3 and BO4 groups, which form a three-dimensional structure. Three BO4 tetrahedra share a common, threefold-coordinated oxygen atom in bands that are interconnected by the BO3 groups.

    20. Low-Coordinate Carbene Complexes

      1,8-Disubstituted Xanthylidene-Based Remote Carbenes: Photolytic Generation and Isolation of Low-Coordinate Palladium(II) Complex (pages 534–541)

      Shun Sugawara, Manabu Abe, Yoshihisa Fujiwara, Masayuki Wakioka, Fumiyuki Ozawa and Yohsuke Yamamoto

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201403017

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      The photolysis-induced formation of 1,8-disubstituted xanthylidene-based remote carbenes from tosylhydrazone lithium salts has been investigated. The 1,8-unsubstituted carbene was found to be kinetically more reactive than the parent xanthylidene. Oxidative addition of palladium(0) to the chloride precursor facilitated the isolation of a low-coordinate 14-electron palladium(II)–carbene complex.

    21. Luminescent Ionic Liquids

      Structures and Properties of Luminescent Pentanitratoeuropate(III) Ionic Liquids (pages 542–551)

      Ying Zhao, Ling He, Ning Tang, Song Qin, Guo-Hong Tao and Fu-Xin Liang

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403018

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      A series of luminescent ionic liquids based on pentanitratoeuropate (III) anions are synthesized and characterized. These complexes exhibit high thermostability and a wide liquidus range. The 10-coordinate [Eu(NO3)5]2– anion has a highly symmetric trigonal-bipyramidal structure. Complexes 16 exhibit bright red luminescence with narrow-band and intense emission of high colorimetric purity.

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