European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 27

Early View (Online Version of Record published before inclusion in an issue)

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.686

ISI Journal Citation Reports © Ranking: 2015: 12/46 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie

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  1. Communications

    1. Phosphorescent Metallogels

      Unusual Aggregation/Gelation-Induced Phosphorescence of Propeller-Type Binuclear Platinum(II) Enantiomers

      Fei Gou, Jinghui Cheng, Xiaohong Zhang, Guangyu Shen, Xiangge Zhou and Haifeng Xiang

      Version of Record online: 30 SEP 2016 | DOI: 10.1002/ejic.201600839

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      Propeller-type binuclear PtII enantiomers without any intermolecular hydrogen bonding or Pt–Pt interaction exhibit unusual aggregation/gelation-induced phosphorescence through strong multiple intermolecular H–C, H–Pt, H–O, and H–H interactions. The intermolecular π–π stacking interactions between two enantiomers can be well tuned by their chemical structures to induce the formation of gels.

  2. Full Papers

    1. Bimetallic Schiff Base Complexes

      Bi-Compartmental Schiff-Base with Peripheral Ester Functionalization: Synthesis and Magnetic Behavior of Bimetallic Zn-Ln Complexes (Ln = Dy, Tb, Gd)

      Virginie Béreau, Hélène Bolvin, Carine Duhayon and Jean-Pascal Sutter

      Version of Record online: 30 SEP 2016 | DOI: 10.1002/ejic.201600924

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      We report a novel ester-functionalized bi-compartmental Schiff-base ligand and its dinuclear Zn-Ln complexes. The ester groups do not change the coordination environment of the Ln centers with respect to the nonfunctionalized ligand, but alter the coordination strength of the central ligand core. The Dy derivative shows slow relaxation of magnetization in zero field with an energy barrier of 96 K.

    2. Calixarene Complexes

      Self-Assembly of a Trilanthanide(III) Core Sandwiched between Two Thiacalix[4]arene Ligands

      Nobuhiko Iki, Teppei Tanaka, Shoichi Hiro-oka and Kozo Shinoda

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600762

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      Thiacalix[4]arene-p-tetrasulfonate (TCAS) and lanthanide(III) ions self-assemble to form a 3:2 Ln3TCAS2 complex, in which a tri-LnIII cluster is sandwiched between two TCAS ligands. The reaction attains equilibrium in a stepwise manner over a very long time (1–4 d). Certain amounts of minor products, including Ln1TCAS1, Ln2TCAS2, and Ln4TCAS2, are found in the final product.

  3. Corrections

    1. You have free access to this content
      Cooperative Effects in Copper Polyamidoamine Dendrimer Complexes Catalyzing the Reduction of Molecular Oxygen

      Yi-Hsuan Tang, Yen Chung Lin, Sodio C. N. Hsu, Si-Ting Liou, Hsing-Yin Chen, Kuang-Chan Hsieh, Wan-Jung Chuang, Li-Ting Chiu, Yeh-Long Chen and Chai-Lin Kao

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201601144

  4. Full Papers

    1. Lactide Polymerisation

      Zinc Chloride Complexes with Aliphatic and Aromatic Guanidine Hybrid Ligands and Their Activity in the Ring-Opening Polymerisation of d,l-Lactide

      Angela Metz, Ramona Plothe, Britta Glowacki, Andreas Koszalkowski, Michael Scheckenbach, Andreas Beringer, Thomas Rösener, Janna Michaelis de Vasconcellos, Roxana Haase, Ulrich Flörke, Alexander Hoffmann and Sonja Herres-Pawlis

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600870

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      Twelve new zinc chloride complexes with hybrid guanidine ligands are reported. The structural properties of these systems were studied intensively by means of X-ray crystallography and DFT calculations. Their activity in lactide polymerisation was correlated with their natural charges.

    2. Energetic Materials

      Energetic Materials Trends in 5- and 6-Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents

      Nipuni-Dhanesha H. Gamage, Benedikt Stiasny, Eric G. Kratz, Jörg Stierstorfer, Philip D. Martin, G. Andrés Cisneros, Thomas M. Klapötke and Charles H. Winter

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600767

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      Oxygen-rich 5- and six-membered cyclic peroxides have been prepared and fully characterized, including by X-ray crystallography, electronic structure calculations, and detailed energetic materials testing. Most compounds are highly sensitive toward impact and friction, but two compounds where X = OH have reduced sensitivities.

    3. Molecular Cages for Drug Delivery

      Self-Assembled Palladium and Platinum Coordination Cages: Photophysical Studies and Anticancer Activity

      Felix Kaiser, Andrea Schmidt, Wolfgang Heydenreuter, Philipp J. Altmann, Angela Casini, Stephan A. Sieber and Fritz E. Kühn

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600811

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      New, nontoxic, self-assembled M2L4 coordination cages are synthesized from highly fluorescent ligands. The cages are able to encapsulate the anticancer drug cisplatin and enhance its cytotoxicity towards cancer cells.

    4. Diastereomers Imitate Enantiomers

      Co-Crystallization of Half-Sandwich (RM,RC)/(SM,RC) Diastereomers in Single Crystals

      Henri Brunner, Takashi Tsuno, Michael Bodensteiner, Stefanie Gärtner, Chiemi Miyahara, Seera Ito, Takaki Kurosawa and Kazuhiro Koyama

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600962

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      The diastereomers (RFe,RC)/(SFe,RC)-[CpFe(Prophos)PPh(OMe)2]PF6 form 1:1 co-crystals with a racemate-like lattice of almost image and mirror image molecules, whereas the diastereomers (RRu,RC)/(SRu,RC)-[MeCpRu(Prophos)Cl] crystallize in a 7:93 co-crystal with a conglomerate-like lattice of almost the same molecules.

  5. Microreviews

    1. Ru Anticancer Complexes

      Thirty Years of the Drug Candidate NAMI-A and the Myths in the Field of Ruthenium Anticancer Compounds: A Personal Perspective

      Enzo Alessio

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600986

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      Almost 30 years after the discovery of NAMI-A, and after two clinical phase studies have been accomplished, the time seems to be appropriate for drawing up a balance sheet. The undemonstrated misconceptions (or myths) that, over the years, have thrived around NAMI-A and other ruthenium drug candidates are also critically addressed in detail.

  6. Communications

    1. Silylene Complexes

      Homoleptic Two-Coordinate 14-Electron Palladium and Platinum Complexes with Two Bis(guanidinato)silylene Ligands

      Johannes A. Baus, Felix M. Mück, Rüdiger Bertermann and Reinhold Tacke

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600872

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      Treatment of [PdCl2(SMe2)2] and [PtCl2(PiPr3)2] with the bis(guanidinato)silylene [iPrNC(NiPr2)NiPr]2Si leads to the homoleptic palladium and platinum complexes I and II, respectively. The almost linearly coordinated Pd0 and Pt0 complexes are 2-coordinate, 14-electron transition-metal species and represent unprecedented 4-coordinate silicon(II) compounds with SiMN3 skeletons (M = Pd, Pt).

  7. Full Papers

    1. Tungsten Iodide Clusters

      Characterization of Ax[W6I14] as Key Compounds for Ligand-Substituted A2[W6I8L6] Clusters

      Thorsten Hummel, Markus Ströbele, Dominic Schmid, David Enseling, Thomas Jüstel and H.-Jürgen Meyer

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/ejic.201600926

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      Ax[W6I14] compounds with A = Na, K, Rb, or Cs are prepared from W3I12 and alkali iodides (AI) by means of solid-state reactions. All compounds can be dissolved in polar organic solvents making them valuable precursors for soluble octahedral [W6I8I6]2– cluster ions, as demonstrated for Na2[W6I8(OCH3)6]·8(CH3OH). Excitation and emission spectra of solid Na[W6I14] and Cs2[W6I14] are reported.

    2. Photocatalysis

      Copyrolysed C3N4-Ag/ZnO Ternary Heterostructure Systems for Enhanced Adsorption and Photocatalytic Degradation of Tetracycline

      Suyana Panneri, Priyanka Ganguly, Balagopal N. Nair, Abdul Azeez Peer Mohamed, Krishna Gopakumar Warrier and Unnikrishnan Nair. S. Hareesh

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/ejic.201600646

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      Combined adsorption and sunlight-induced photocatalysis by C3N4-Ag-ZnO ternary composites have been developed for the efficient degradation of tetracycline antibiotic.

  8. Communications

    1. Azaferrocene-Based Pincer Complexes

      Azaferrocene-Based PNP-Type Pincer Ligand: Synthesis of Molybdenum, Chromium, and Iron Complexes and Reactivity toward Nitrogen Fixation

      Shogo Kuriyama, Kazuya Arashiba, Kazunari Nakajima, Hiromasa Tanaka, Kazunari Yoshizawa and Yoshiaki Nishibayashi

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/ejic.201601051

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      Some transition-metal complexes, including molybdenum, chromium, and iron complexes, bearing azaferrocene-based PNP-type pincer ligands are prepared and characterized by X-ray analysis. The stoichiometric and catalytic reactivities of molybdenum–dinitrogen complexes toward nitrogen fixation are investigated in detail.

  9. Full Papers

    1. Towards Ferrocyne

      Improved Syntheses of 1,2-Disubstituted Ferrocenes

      Georg Werner and Holger Butenschön

      Version of Record online: 23 SEP 2016 | DOI: 10.1002/ejic.201600766

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      New or improved syntheses of useful 1,2-disubstituted ferrocenes are presented. These include 1,2-homo- and 1,2-heterodihaloferrocenes as well as ferrocene-1,2-dicarboxylic anhydride, which is a potential precursor for 1,2-dehydroferrocene and 2-aminoferrocenecarboxylic acid.

    2. Lithium Zincates

      Synthesis, Structure and Solution Studies on Mixed Aryl/Alkyl Lithium Zincates

      Andrew J. Roberts, Alan R. Kennedy, Ross McLellan, Stuart D. Robertson and Eva Hevia

      Version of Record online: 22 SEP 2016 | DOI: 10.1002/ejic.201601020

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      Studies on the cocomplexation of PhLi and Zn(CH2SiMe3)2 have revealed a dramatic solvent effect and intricate solution behaviours as well as unique structural motifs in zincate chemistry.

    3. Mg Hydrosilylation Catalysts

      Syntheses of Sterically Bulky Schiff-Base Magnesium Complexes and Their Application in the Hydrosilylation of Ketones

      Mengtao Ma, Xingchao Shen, Weifan Wang, Jia Li, Weiwei Yao and Lijun Zhu

      Version of Record online: 22 SEP 2016 | DOI: 10.1002/ejic.201600899

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      A series of sterically bulky Schiff-base magnesium complexes have been prepared, which could be used as catalysts for the hydrosilylation of ketones with (EtO)3SiH.

    4. Rules in Crystal Design

      Dynamic Directing Effect and Symmetric Correlation in Three pH-Modulated 1,4-Diazabicyclo[2.2.2]octane/Iodoargentate Hybrids

      Tanlai Yu, Huihui Li, Pengfei Hao, Junju Shen and Yunlong Fu

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/ejic.201600757

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      Three dabco/iodoargentate hybrids have been prepared by changing the pH. Variation of the hydrogen-bonded aggregating forms of dabco at different pH, modulation of the inorganic moiety from a [3276] cage in 1 to a [32114] cage in 2 and helical chain in 3, and their intrinsic symmetry/chiral transfer reveal unique dynamic structural directing effects and flexibility of the iodoargentate framework.

    5. Heterotrimetallic Complexes

      Heterotrimetallic CuII(L)–LnIII–MIII (M = Cr, Fe; Ln = Pr, Nd, Sm, Gd) Complexes Ranging from 0D Clusters to 1D Chains and 2D Networks: Syntheses, Structures, and Magnetism

      Hongbo Zhou, Chao Chen, Kang Wu, Yashu Liu and Xiaoping Shen

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/ejic.201600886

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      Four new heterotrimetallic CuII(L)–LnIII–MIII (M = Cr, Fe; Ln = Pr, Nd, Sm, Gd) complexes were obtained. Interestingly, the CuII(L)–LnIII–MIII unit forms new discrete hexanuclear clusters, 1D regular chains, and 2D networks, which were not found in related complexes of previous studies.

    6. Ferrocenyl Chalcogenolates

      ZnII and CdII Ferrocenechalcogenolate Complexes

      Andrew I. Wallbank, Terry P. Lebold, Aneta Borecki, Alexander M. Polgar, Blake M. Waters, Mark S. Workentin and John F. Corrigan

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/ejic.201600898

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      Zinc(II) and cadmium(II) complexes ligated with ferrocenethiolates and ferroceneselenolates are readily prepared from substituted ferrocene reagents containing trimethylsilylchalcogen moieties.

    7. Tripodal Germyl Ligands

      Platinum Complexes Bearing a Tripodal Germyl Ligand

      Roy Herrmann, Philipp Wittwer and Thomas Braun

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/ejic.201600652

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      A series of five-coordinate platinum(II) complexes bearing the tripodal germyl ligand [Ge(H)(2-C6H4PPh2)3] is reported. Their structures were studied by X-ray crystallography. The norbornyl complex [Pt(nor){Ge(2-C6H4PPh2)3}] was not formed by the reaction of norbornene with [Pt(H){Ge(2-C6H4PPh2)3}].

  10. Communications

    1. Gas Adsorption by MOFs

      High Gas Adsorption Capacity of an agw-Type Metal–Organic Framework Decorated with Methyl Groups

      Liting Du, Zhiyong Lu, Li Xu, Mengtao Ma and Jinchi Zhang

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/ejic.201600576

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      A new methyl-functionalized metal–organic framework, {Cu3(CMPEIP)2·2H2O}n {m-NB13, H3CMPEIP = 5-[(4-carboxy-2-methylphenyl)ethynyl]isophthalic acid} is synthesized and characterized. {Cu3(CMPEIP)2·2H2O}n exhibits a high BET surface area of 3215.4 m2 g–1, a large H2 uptake (1.92 wt.-% at 0.1 MPa and 77 K), and excellent CO2 storage capacity (9.24 wt.-% at 0.1 MPa and 298 K).

  11. Full Papers

    1. Organophosphorus Chemistry

      C-Silyl-N,N-dialkyl-N′-arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

      Anatoliy Marchenko, Georgyi Koidan, Anastasiya Hurieva, Yurii Vlasenko and Aleksandr Kostyuk

      Version of Record online: 20 SEP 2016 | DOI: 10.1002/ejic.201600803

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      A convenient preparative method for the synthesis of C-silyl-N,N-dialkyl-N′-arylformamidines was developed. These derivatives were employed as nucleophiles in reactions with phosphorus(III) chlorides to afford phosphanes that feature one or two formamidine substituents. We were unable to introduce three formamidine substituents into the final product.

    2. Metal–Organic Frameworks

      Three-Dimensional Co- and Mn-MOFs Containing a C2h-Symmetric Terphenyl-3,3′-dicarboxylate Linker and Their Magnetic Properties

      Hyun-Chul Kim, Ja-Min Gu, Youngmee Kim, Do Nam Lee and Seong Huh

      Version of Record online: 20 SEP 2016 | DOI: 10.1002/ejic.201600645

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      Two new magnetically active, isostructural 3D MOFs of general formula [M(3,3′-tpdc)(dmf)] (M = CoII, MnII; 3,3′-tpdc = terphenyl-3,3′-dicarboxylate) have been prepared by employing the C2h-symmetric 3,3′-tpdc bridging ligand. Their gas sorption and magnetic properties have been investigated.

    3. Ferrocene-Peptides

      Exploring Structure–Activity Relationships in Synthetic Antimicrobial Peptides (synAMPs) by a Ferrocene Scan

      Jack C. Slootweg, Pascal Prochnow, Sandra Bobersky, Julia E. Bandow and Nils Metzler-Nolte

      Version of Record online: 20 SEP 2016 | DOI: 10.1002/ejic.201600799

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      A library of ferrocene-substituted antimicrobials with one, two, or even three ferrocene residues in lieu of a tryptophan residue have been synthesized. The most potent compound shows a 16-fold increased activity over the parent, metal-free (RW)3 peptide against the A. baumannii bacteria. A four-fold increase in activity was even observed against a multi-resistant S. aureus MRSA strain.

    4. Aerobic Oxidation

      Superparamagnetic Core–Shell Metal–Organic Framework Fe3O4/Cu3(btc)2 Microspheres and Their Catalytic Activity in the Aerobic Oxidation of Alcohols and Olefins

      Jie Li, Hongyi Gao, Li Tan, Yi Luan and Mu Yang

      Version of Record online: 19 SEP 2016 | DOI: 10.1002/ejic.201600761

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      Core–shell metal–organic framework Fe3O4/Cu3(btc)2 microspheres have been successfully synthesized by a one-step solvothermal method and a subsequent layer-by-layer strategy. The superparamagnetic heterogeneous catalyst exhibits efficient activity and high selectivity in the aerobic oxidation of alcohols and the epoxidation of olefins. The catalyst shows excellent recyclability.

    5. Emissive Cu(I) Complexes

      Prolonging the Emissive Lifetimes of Copper(I) Complexes with 3MLCT and 3(π–π*) State Equilibria – A Fluorene Moiety as an “Energy Reservoir”

      Cheng Yi, Shengxian Xu, Jinglan Wang, Feng Zhao, Hongying Xia and Yibo Wang

      Version of Record online: 19 SEP 2016 | DOI: 10.1002/ejic.201600607

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      A fluorene group is used as a triplet energy reservoir to extend the excited-state lifetime of the emissive triplet metal-to-ligand charge-transfer (3MLCT) state of a CuI complex. The excited-state lifetime of the complex with a fluorene moiety (τ = 51.2 µs) is almost four times that of the parent complex (τ = 13.8 µs).

    6. Coordinated Carbon Disulfide

      Reactivity of CS2 – Syntheses and Structures of Transition-Metal Species with Dithioformate and Methanedithiolate Ligands

      Chokkapu Eswara Rao, Subrat Kumar Barik, K. Yuvaraj, K. Bakthavachalam, Thierry Roisnel, Vincent Dorcet, Jean-François Halet and Sundargopal Ghosh

      Version of Record online: 15 SEP 2016 | DOI: 10.1002/ejic.201600823

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      We report the syntheses and structures of the CS2-inserted group 6 transition-metal complexes [(η5-C5Me5M)(η2-S2CH2)(η3-S2CH)] (M = Mo, W) and the cis and trans isomers of the (sulfido)molybdenum complex [(η5-C5Me5Mo)2(µ-S2CH2S)2] (Cp* = η5-C5Me5)

    7. Thin-Film Coordination Polymers

      Band Gaps and Photocurrent Responses of Bulk and Thin-Film Coordination Polymers Based on 3,6-Di(1H-imidazol-1-yl)-9H-carbazole

      Jiang Ping Meng, Yun Gong and Jian Hua Lin

      Version of Record online: 15 SEP 2016 | DOI: 10.1002/ejic.201600916

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      From a rigid N-donor ligand, two coordination polymers (CPs) are synthesized. The CdII CP 1 has a 2D structure, and thin-film 1 is obtained by physical exfoliation. The CuI CP 2 possesses a narrower band gap and a higher photocurrent density under visible light than those of 1. Thin-film 1 shows more active electrochemical behavior and enhanced photoresponse relative to those of bulk 1.

    8. Catalytic Asymmetric Hydrogenation

      A Ferrocene-Based Phosphane/Borane Frustrated Lewis Pair for Asymmetric Imine Reduction

      Ke-Yin Ye, Xiaowu Wang, Constantin G. Daniliuc, Gerald Kehr and Gerhard Erker

      Version of Record online: 15 SEP 2016 | DOI: 10.1002/ejic.201600834

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      Asymmetric imine hydrogenation with a ferrocene-based frustrated Lewis pair catalyst was achieved with up to 69 % ee.

  12. Communications

    1. Lanthanide–Actinide Separation

      Unprecedented Increase in Affinity for EuIII over AmIII through Silica Grafting of a Carbamoylmethylphosphine Oxide-Calix[4]arene Site

      Erin M. May, Andrew Solovyov, Yijun Guo, Andriy Drapailo, Yury Matveev, Vitaly Kalchenko, Heino Nitsche and Alexander Katz

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600946

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      A grafted CMPO-calix[4]arene site on silica demonstrates affinity for EuIII over AmIII, which is unique when compared with a more flexible propoxy-tethered CMPO-calix[4]arene site as well as all previously reported CMPO-calix[4]arene ligands. The results highlight the importance of rigidity when anchoring sites for cation recognition on solid surfaces.

  13. Full Papers

    1. Unsymmetrical Diphosphines

      Group 11 Metal Complexes with Unsymmetrical Bifunctional Ferrocene Ligands

      Yu-Jun Shi, Antonio Laguna, M. Dolores Villacampa and M. Concepción Gimeno

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600929

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      Group 11 metal complexes with asymmetric bidentate phosphine–amine and diphosphine ligands are synthesized. These ligands have rich coordination chemistry and adopt monodentate or bidentate chelating or bridging coordination modes. Heterodimetallic complexes are also prepared.

    2. Ferrocene-Based SAMs

      The Interaction of 1,1′-Diphosphaferrocenes with Gold: Molecular Coordination Chemistry and Adsorption on Solid Substrates

      Michél Liebscher, Clemens Bruhn, Ulrich Siemeling, Joe Baio, Hao Lu and Tobias Weidner

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600892

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      The binding behaviour of 1,1′-diphosphaferrocenes with gold has been studied in molecular and surface coordination chemistry using pristine 1,1′-diphosphaferrocene and five congeners bearing up to eight alkyl or aryl substituents. Self-assembled monolayers (SAMs) and molecular AuI complexes exhibiting unprecedented intermetallic interactions are described.

    3. Cobalt Nitrides

      Synthesis of Metastable Co4N, Co3N, Co2N, and CoO0.74N0.24 from a Single Azide Precursor and Intermediates in CoBr2 Ammonolysis

      Marc Widenmeyer, Larysa Shlyk, Nils Becker, Richard Dronskowski, Elke Meissner and Rainer Niewa

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600684

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      Starting from a single metastable azide precursor, we have established a new synthesis route towards metastable Co4N, Co3N, Co2N, and oxide nitride CoO0.74N0.24 by systematic variation of the reaction parameters. High-quality samples granted access to a deeper insight into the magnetic behavior of such phases.

    4. Alkynyl(amino)carbene Complexes

      Growing the Molecular Architecture at Alkynyl(amino)carbene Ligands in Diiron µ-Aminocarbyne Complexes

      Fabio Marchetti, Stefano Zacchini and Valerio Zanotti

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600736

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      Diiron complexes containing a bridging aminocarbyne and a terminal alkynyl(amino)carbene ligand undergo selective addition of nucleophiles to the alkynyl moiety to yield a variety of structural motifs.

  14. Communications

    1. Polysilathianes

      [SiSxHy]n – Perhydridopolysilathianes: Cross-Linked Thio Analogues of Polysiloxanes

      Maik Gerwig, Marcus Schwarz, Erica Brendler and Edwin Kroke

      Version of Record online: 13 SEP 2016 | DOI: 10.1002/ejic.201600988

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      Perhydridopolysilathianes consisting of D-, T-, and Q-units are formed upon transsilylation reactions involving silane dismutation. The products are mesoporous with a surface area of 187 m2 g–1.

  15. Full Papers

    1. Single-Ion Magnets

      Single-Ion Magnets Based on Mononuclear Cobalt(II) Complexes with Sulfadiazine

      Cristian Villa-Pérez, Itziar Oyarzabal, Gustavo A. Echeverría, Gloria C. Valencia-Uribe, José M. Seco and Delia B. Soria

      Version of Record online: 12 SEP 2016 | DOI: 10.1002/ejic.201600777

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      Two monomeric cobalt complexes, Co(SDZ)2bpy and Co(SDZ)2(6MQ)2 (SDZ = sulfadiazine, bpy = 2,2′-bipyridine, and 6MQ = 6-methoxyquinoline), have been prepared and characterized. X-ray diffraction studies indicate that in both compounds SDZ acts as a bidentate ligand coordinating through the sulfonamide and the pyrimidine N atoms. The complexes show slow relaxation of the magnetization below 9 and 6 K.

    2. Dioxygen Activation

      Hand in Hand: Experimental and Theoretical Investigations into the Reactions of Copper(I) Mono- and Bis(guanidine) Complexes with Dioxygen

      Alexander Hoffmann, Miriam Wern, Tobias Hoppe, Matthias Witte, Roxana Haase, Patricia Liebhäuser, Jörg Glatthaar, Sonja Herres-Pawlis and Siegfried Schindler

      Version of Record online: 12 SEP 2016 | DOI: 10.1002/ejic.201600906

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      The reactions of mono- and bis(guanidine)copper complexes with dioxygen to form bis-µ-oxido complexes have been investigated in detail by means of low-temperature stopped-flow measurements and DFT calculations.

    3. Non-Innocent Ligands

      Hexaethyltripyrrindione (H3Et6tpd): A Non-Innocent Ligand Forming Stable Radical Complexes with Divalent Transition-Metal Ions

      Stefanie Bahnmüller, Jacqueline Plotzitzka, Dirk Baabe, Birte Cordes, Dirk Menzel, Katharina Schartz, Peter Schweyen, Richard Wicht and Martin Bröring

      Version of Record online: 7 SEP 2016 | DOI: 10.1002/ejic.201600934

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      Radical dianionic is the best electronic description of biomimetic tripyrrindione ligands in the ground state of their complexes with divalent ions of nickel, copper, and palladium. The ligand acquires radical character directly upon aerobic metalation and is reminiscent of the antioxidant role of biological tripyrrindiones (the so-called biopyrrins, e.g., uroerythrin) in living systems.

  16. Communications

    1. Oxygen-Atom Transfer

      A Palladium(II) Peroxido Complex Supported by the Smallest Steric N-Heterocyclic Carbene, IMe = 1,3-Dimethylimidazole-2-ylidene, and Its Reactivity by Oxygen-Atom Transfer

      Eunsung Lee, Dae Young Bae, Sungho Park, Allen G. Oliver, Yonghwi Kim and Dmitry V. Yandulov

      Version of Record online: 7 SEP 2016 | DOI: 10.1002/ejic.201601019

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      PdII2-O2)(IMe)2 (IMe = 1,3-dimethylimidazole-2-ylidene), which is used extensively in computational studies as a standard product of Pd0 oxygenation, is synthesized and its oxygen-atom transfer reactivity studied. Thermolysis of the complex leads to the formation of 1,3-dimethylimidazol-2-one (IMeO), and its reaction with PPh3 and (Me3Si)2 results in Ph3PO and (Me3Si)2O, respectively.

  17. Full Papers

    1. Metallacyclobutenones

      Intramolecular Cycloaddition in the (Diyne)iridium Complexes [Cp*Ir(CO)(η2-ArC≡CC≡CAr)]: An Experimental and Computational Study

      Yongjia Li and Weng Kee Leong

      Version of Record online: 6 SEP 2016 | DOI: 10.1002/ejic.201600579

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      The diyne species [Cp*Ir(CO)(η2-ArC≡CC≡CAr)] undergoes intramolecular cycloaddition in the presence of two-electron donor ligands to afford iridacyclobutenone complexes. Kinetic measurements and a computational study suggest that the reaction proceeds through an alkyne insertion reaction followed by rate-limiting ligand association.

    2. Luminescent Complexes

      Asymmetrical 1,3-Bis(heteroazolyl)benzene Platinum Complexes with Tunable Second-Order Non-Linear Optical Properties

      Tung T. Dang, Jean-François Soulé, Henri Doucet, Mohamed Ali Benmensour, Abdou Boucekkine, Alessia Colombo, Claudia Dragonetti, Stefania Righetto, Denis Jacquemin, Julien Boixel and Véronique Guerchais

      Version of Record online: 6 SEP 2016 | DOI: 10.1002/ejic.201600675

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      A new series of cyclometallated platinum(II) complexes bearing an asymmetrical 1,3-bis(heteroazolyl)benzene ligand have been prepared. The N^C^N pro-ligands were synthesized by a two-step procedure that includes a Pd-catalysed C–H bond-activation reaction. All the complexes exhibit green luminescence at room temperature and a strong NLO response that can be tuned by ligand design.

    3. Ferrocenyl Allylamines

      Synthesis and Reactivity of Ferrocenyl-Substituted Allylamine Derivatives

      Rafika Bouchene, Jean-Claude Daran, Sofiane Bouacida and Eric Manoury

      Version of Record online: 6 SEP 2016 | DOI: 10.1002/ejic.201600860

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      [(2-Ferrocenylvinyl)methyl]trimethylammonium iodide (4) was obtained in high yields in two steps from commercially available compounds and used to transfer the ferrocene-containing allyl group to various amines. By controlling reaction conditions, the selectivity of the reaction could be efficiently modified towards linear or branched ferrocenyl-substituted allylamine isomers.

    4. Protic NHC Ligands

      Formation of NH,NR N-Heterocyclic Carbene Complexes through Mercuration of Mono-N-substituted Benzimidazoles

      Ming-Hung Yu, Hsueh-Hui Yang, Abbas Raja Naziruddin, Shanker Kanne, Bo-Han Wang, Fu-Chen Liu, Ivan J. B. Lin and Gene-Hsiang Lee

      Version of Record online: 5 SEP 2016 | DOI: 10.1002/ejic.201600759

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      The reactions of N-substituted benzimidazoles (R-Bim) with Hg(OAc)2 in the presence of NaBr produces N- and C-bound 12-membered mercuramacrocycles [Hg4(R-Bim)4Br4] [R = Me, pyridyl (Py), Bn]. The further protonation of these mercuramacrocycles with HBF4·OEt2 produced NH,NR N-heterocyclic carbene (NHC) complexes [(R-BimH)2Hg][BF4]2.

    5. Oxygen Atom Transfer

      Dioxidomolybdenum(VI) Complexes of Tripodal Tetradentate Ligands for Catalytic Oxygen Atom Transfer between Benzoin and Dimethyl Sulfoxide and for Oxidation of Pyrogallol

      Mannar R. Maurya, Bhawna Uprety and Fernando Avecilla

      Version of Record online: 5 SEP 2016 | DOI: 10.1002/ejic.201600694

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      Dioxidomolybdenum(VI) complexes of tripodal tetradentate ligands are isolated. Their characterization and use as catalysts for oxygen atom transfer between dimethyl sulfoxide (DMSO) and benzoin as well as the oxidation of pyrogallol are reported.

    6. Dimensionality of MOFs

      Thermal and Magnetic Diversity in the Behaviour of the CuII-bdc-bpa System: 1D, 2D and Interpenetrated 3D Frameworks

      Laura Bravo-García, Gotzone Barandika, Arkaitz Fidalgo-Marijuan, Begoña Bazan, Miren Karmele Urtiaga, Luis Lezama and María Isabel Arriortua

      Version of Record online: 5 SEP 2016 | DOI: 10.1002/ejic.201600683

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      The combination of 1,2-bis(4-pyridyl)ethane and 1,3-benzenedicarboxylate ligands has led to three new CuII-based networks with different dimensionalities, namely the 1D [Cu(m-bdc)(bpa)0.5(H2O)dmf]·0.5H2O, the 2D [Cu6(m-bdc)6(bpa)6(dmf)3]·8dmf and the 3D [Cu4(m-bdc)4(bpa)2dmf]·dmf (bdc = 1,3-benzenedicarboxylate, bpa = 1,2-bis(4-pyridyl)ethane).

    7. Porphrinoids

      Siamese-Twin Porphyrins: Variation of Two meso-Aryl Groups

      Oliver Mitevski, Sebastian Dechert, Christian Brückner and Franc Meyer

      Version of Record online: 5 SEP 2016 | DOI: 10.1002/ejic.201600714

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      The electronic and structural effects of the variation of two of the peripheral meso-aryl groups of Siamese-twin porphyrins are small to negligible, but because of solubility and crystallinity modulations, the new derivatives have multiple benefits.

  18. Communications

    1. f-Block Hydrides

      Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C5Me4SiMe3)2(H)(thf)

      Owen T. Summerscales, Enrique R. Batista, Brian L. Scott, Marianne P. Wilkerson and Andrew D. Sutton

      Version of Record online: 1 SEP 2016 | DOI: 10.1002/ejic.201600737

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      The cerium tuck-in metallocene Ce(C5H4SiMe3)(C5H4SiMe2CH2-)(thf) was synthesized and shown to reversibly form a terminal hydride species Ce(C5H4SiMe3)2(H)(thf) upon reaction with H2. This new hydride is a catalyst in H/D exchange reactions between with both sp3-CH and sp2-CH bonds, and for the hydrogenation of unsaturated alkene bonds.

  19. Full Papers

    1. Ba Lewis–Base Adducts

      Synthesis of Lewis Base Adducts of Barium Bis[bis(trimethylsilyl)amide]

      Christoph Müller, Sven Krieck, Helmar Görls and Matthias Westerhausen

      Version of Record online: 1 SEP 2016 | DOI: 10.1002/ejic.201600561

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      Transmetallation of distillable tin(II) bis[bis(trimethylsilyl)amide] with barium metal guarantees the isolation of highly pure barium bis[bis(trimethylsilyl)amide] with diverse coligands depending on the solvent.

    2. Anticancer Complexes

      Water-Soluble Platinum(II) Complexes Featuring 2-Alkyl-2H-tetrazol-5-ylacetic Acids: Synthesis, Characterization, and Antiproliferative Activity

      Elena A. Popova, Tatiyana V. Serebryanskaya, Stanislav I. Selivanov, Matti Haukka, Taras L. Panikorovsky, Vladislav V. Gurzhiy, Ingo Ott, Rostislav E. Trifonov and Vadim Yu. Kukushkin

      Version of Record online: 1 SEP 2016 | DOI: 10.1002/ejic.201600626

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      Water-soluble platinum(II) complexes featuring 2-alkyl-2H-tetrazol-5-ylacetic acids have been synthesized and characterized. The generation of the tetrazole-based complexes in solution (1 m DCl in D2O, 25 °C) was studied by 1H NMR spectroscopy and HPLC-MS. Antiproliferative activity of the new tetrazole-containing platinum(II) complexes is discussed.

    3. Ionic Liquids

      Chiral and Redox-Active Room-Temperature Ionic Liquids Based on Ferrocene and l-Proline

      Carola B. Bouvet and Harald Krautscheid

      Version of Record online: 1 SEP 2016 | DOI: 10.1002/ejic.201600585

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      The syntheses of the first ferrocene- and pyrrolidinium-based room-temperature ionic liquids (RTILs) linked through ester bridges are reported. The RTILs are reversibly redox-active through the FeII metal center as well as chiral and thermally stable up to 263 °C.

    4. Luminescent Europium Complexes

      pH-Controlled Luminescence Turn-On Behaviour of a Water-Soluble Europium-Based Molecular Complex

      Debal Kanti Singha, Prakash Majee, Sudip Kumar Mondal and Partha Mahata

      Version of Record online: 1 SEP 2016 | DOI: 10.1002/ejic.201600535

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      A water-soluble molecular europium complex with acidic functional sites has been synthesized by the hydrothermal technique and a simple solvent-evaporation method. The structure of the complex has been confirmed by single-crystal X-ray diffraction studies. The complex shows pH-dependent luminescence turn-on behaviour and completely reversible luminescence response in the range of pH 2–6.

    5. Pd-Based Catalysts

      MoII Cluster Complex-Based Coordination Polymer as an Efficient Heterogeneous Catalyst in the Suzuki–Miyaura Coupling Reaction

      Daniel Bůžek, Jan Hynek, Monika Kučeráková, Kaplan Kirakci, Jan Demel and Kamil Lang

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600704

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      A novel hexanuclear molybdenum cluster, bearing six phosphine terminal ligands, has been synthesized and its single-crystal structure was determined. The combination of the cluster with PdII centers formed a coordination polymer that displayed high catalytic activity in the Suzuki–Miyaura coupling reaction.

    6. Copper Phosphonates

      The Dimeric Pyramidal Cu2O6(H2O)2 Unit – A Structural Invariant of a Homologous Series of Copper-Layered Phosphonates

      Clarisse Bloyet, Mélissa Roger, Jean-Michel Rueff, Bernard Raveau, Jean-François Lohier, Guillaume Rogez and Paul-Alain Jaffrès

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600613

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      The layered copper phosphonates Cu(H2O)PO3R and [Cu2(H2O)2(O3P–R–PO3)] form a large structural family characterized by the presence of condensed dimeric pyramidal Cu2O6(H2O)2 units. Two new members of this family with R = C6H4F and C4H4S are synthesized. These hybrids exhibit antiferromagnetic interactions between the copper ions that obey the Bleaney–Bowers law.

  20. Communications

    1. Boranes

      Extended Sandwich Molecules Displaying Direct Metal–Metal Bonds

      Subrat Kumar Barik, Monojit Ghosal Chowdhury, Susmita De, Pattiyil Parameswaran and Sundargopal Ghosh

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600888

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      Treatment of [Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) with Li[BH3(SePh)] at room temperature leads to a dimetala analogue of hexaborane(10), nido-[(Cp*Ir)(µ-SePh)2Ir{(Cp*Ir)SePh}B4H8], and in an effort to synthesize the Rh analogue under similar reaction conditions, arachno-[{(Cp*Rh)(µ-SePh)3}Rh(µ-SePh)B3H6], a rhodium analogue of tetraboarane(10), is isolated.

  21. Full Papers

    1. Mesomorphic Assemblies

      Induction of Mesomorphism through Supramolecular Assembly in Metal Coordination Compounds of “salphen”-Type Schiff Bases: Photoluminescence and Solvatochromism

      Sutapa Chakraborty, Paritosh Mondal, S. Krishna Prasad, D. S. Shankar Rao and Chira R. Bhattacharjee

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600513

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      The effects of metal coordination (M = VO2+, Ni2+, Cu2+ and Zn2+) on mesomorphism and photophysical properties of a new series of salphen ligands have been investigated. The NiII and ZnII complexes show columnar oblique and columnar rectangular phases, respectively, the latter being stable down to room temperature thus affording room temperature mesomorphism. Further, the axial vacant coordination sites in the square-planar ZnII and the square-pyramidal VO(IV) centers facilitate solvatochromism, with the former exhibiting formation of aggregates or monomers in solvents of different coordinating ability.

    2. Magneto-Chemotherapy

      Superparamagnetic Gadolinium Ferrite Nanoparticles with Controllable Curie Temperature – Cancer Theranostics for MR-Imaging-Guided Magneto-Chemotherapy

      Nanasaheb D. Thorat, Raghvendra A. Bohara, Syed A. M. Tofail, Zeid Abdullah Alothman, Muhammad J. A. Shiddiky, Md. Shahriar A Hossain, Yusuke Yamauchi and Kevin C.-W. Wu*

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600706

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      A polyol approach is reported for the easy preparation of low-Curie-temperature (TC) gadolinium-doped iron oxide nanoparticles (GdIO NPs) for targeted magnetic hyperthermia and chemotherapy coupled with T1T2 dual-model magnetic resonance (MR) imaging (where T1 and T2 are the longitudinal and transverse relaxation times, respectively).

  22. Communications

    1. Cyclometallation

      Phenyl vs. Ferrocenyl Cyclometallation Selectivity: Diastereoselective Synthesis of an Enantiopure Iridacycle

      Ross A. Arthurs, Peter N. Horton, Simon J. Coles and Christopher J. Richards

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/ejic.201600904

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      Imines containing both ferrocenyl and phenyl groups undergo selective phenyl C–H activation on cycloiridation with [Cp*IrCl2]2 and NaOAc in CH2Cl2. This was applied to the diastereoselective synthesis of an enantiopure iridacycle of configuration SC,RIr,E.

  23. Full Papers

    1. Phosphate Minerals

      Determination of the Solubility of Rhabdophanes LnPO4·0.667H2O (Ln = La to Dy)

      Clémence Gausse, Stéphanie Szenknect, Dan Wen Qin, Adel Mesbah, Nicolas Clavier, Stefan Neumeier, Dirk Bosbach and Nicolas Dacheux

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600517

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      Solubility experiments are used to determine the thermodynamic properties of the LnPO4·0.667H2O (Ln = La–Dy) rhabdophanes and demonstrate the reversibility of the equilibrium. The variation of the solubility with the ionic radius of the lanthanide is determined. The stability domain of rhabdophanes is more constrained than that of monazites.

    2. Zintl Phases

      Zintl Phases K4–xNaxSi4 (1 ≤ x ≤ 2.2) and K7NaSi8: Synthesis, Crystal Structures, and Solid-State NMR Spectroscopic Investigations

      Lavinia M. Scherf, Oliver Pecher, Kent J. Griffith, Frank Haarmann, Clare P. Grey and Thomas F. Fässler

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600735

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      New Zintl Phases: K4–xNaxSi4 (1 ≤ x ≤ 2.2) and K7NaSi8 are the first representatives of the K–Na–Si system. Both compounds contain tetrahedral [Si4]4– clusters that are isolated in K4–xNaxSi4 and connected to form linear [Na(Si4)2]7– dimers in K7NaSi8. Solid-state NMR studies coupled with quantum mechanical calculations revealed anisotropic chemical bonding in K7NaSi8.

    3. Tin Chalcogenide Precursors

      Tin(IV) Chalcogenide Complexes: Single Source Precursors for SnS, SnSe and SnTe Nanoparticle Synthesis

      Joseph R. Thompson, Ibbi Y. Ahmet, Andrew L. Johnson and Gabriele Kociok-Köhn

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600790

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      A family tin(IV) bis-HMDS complexes bearing chalcogenide ligands have been synthesized and characterized. Selected complexes have been assessed for their utility in the formation of nanoparticles. Analysis (PXRD, SEM and EDS) showed formation of SnSe and SnTe respectively.

    4. Copper(I) Complexes

      You have full text access to this OnlineOpen article
      Homo- and Heteroleptic Copper(I) Complexes with Diazabutadiene Ligands: Synthesis, Solution- and Solid-State Structural Studies

      Benjamin Zelenay, Roberto Frutos-Pedreño, Jordi Markalain-Barta, Esmeralda Vega-Isa, Andrew J. P. White and Silvia Díez-González

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600620

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      The preparation of novel copper(I) complexes with aliphatic diazabutadiene (DAB) ligands is reported. [Cu(DABR)2](BF4), [Cu(DABR)(NCMe)4](BF4) and [CuCl(DABR)] are easily synthesised and air-stable. These complexes, which remain scarce in the literature, were fully characterised, and their behaviour both in the solid state as well as in solution has been studied by means of X-ray crystallography and UV/Vis spectroscopy.

    5. Diastereoselective Synthesis

      Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquinolines

      Julien Roger, Sylviane Royer, Hélène Cattey, Aleksandr Savateev, Radomyr V. Smaliy, Aleksandr N. Kostyuk and Jean-Cyrille Hierso

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600502

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      The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero/polycyclic groups on the phosphorus atom is reported together with their characterization by X-ray analysis and NMR spectroscopy. In combination with AgF, these ferrocenyl diphosphanes allow the selective fluorination of 2-chloroquinoline derivatives, whereas palladium is highly deleterious.

    6. Electrocatalytic Ni Complexes

      You have full text access to this OnlineOpen article
      Nickel Complexes of Pyridine-Functionalized N-Heterocyclic Carbenes: Syntheses, Structures, and Activity in Electrocatalytic Hydrogen Production

      Siyuan Luo, Maxime A. Siegler and Elisabeth Bouwman

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600917

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      Pyridine-functionalized Ni-NHC complexes have been prepared and characterized by various methods. The complex having the most planar coordination geometry appeared to have the highest catalytic efficiency for proton reduction in DMF (ic/ip = 50, kobs = 490 s–1 at 0.1 V/s) using acetic acid as the proton source.

    7. Upconversion

      A Ru(bipyridine)3[PF6]2 Complex with a Rhodamine Unit – Synthesis, Photophysical Properties, and Application in Acid-Controllable Triplet–Triplet Annihilation Upconversion

      Xiaoneng Cui, Jianzhang Zhao, Ahmet Karatay, Halime Gul Yaglioglu, Mustafa Hayvali and Betül Küçüköz

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600755

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      A ruthenium(II) tris(bipyridine)–rhodamine triad is prepared, and the switching of the triplet excited state is studied through steady-state and time-resolved transient spectroscopy and electrochemistry. The switch mechanism is based on the acid-activated spirolactam[RIGHTWARDS ARROW]open-amide transformation of the rhodamine moiety.

    8. Lanthanide Square Grids

      Tetranuclear Lanthanide(III) Complexes Containing a Square-Grid Core: Synthesis, Structure, and Magnetism

      Sourav Biswas, Sourav Das, Sakiat Hossain, Arun Kumar Bar, Jean-Pascal Sutter and Vadapalli Chandrasekhar

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600744

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      The reactions of multidentate aroyl hydrazone based ligands (LH4) with Ln(NO3)3 in the presence of triethylamine has afforded a series of tetranuclear complexes [Ln4(LH2)42-OH)4]·xCH3OH·yH2O (Ln = Dy3+, x = 2, y = 2; Ln = Tb3+, x = 4, y = 5; Ln = Ho3+, x = 0, y = 13; Ln = Er3+, x = 4, y = 6). Detailed analysis of the magnetic data revealed that the Dy3+ analogue is a single-molecule magnet.

    9. Electron-Transfer

      Preparation, Characterization, Redox, and Photoinduced Electron-Transfer Properties of the NIR-Absorbing N-Ferrocenyl-2-pyridone BODIPYs

      Yuriy V. Zatsikha, Natalia O. Didukh, Tanner Blesener, Mathew P. Kayser, Yuriy P. Kovtun, David A. Blank and Victor N. Nemykin

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600855

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      Mono- and di-(N-ferrocenyl-2-pyridone)-containing BODIPYs were prepared and characterized by a variety of spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods

    10. Spin-Crossover Nanomaterials

      Resin-Assisted Constructive Synthesis of Spin-Crossover Nanorod Arrays

      Yu-Xia Wang, Dan Qiu, Zhi-Hua Li, Zhi-Guo Gu, Xuehong Ren and Zaijun Li

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600774

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      Spin-crossover nanorod arrays are synthesized by using cation-exchange polymer resin beads as templates. The nucleation and growth mechanism of the nanorod arrays is explained, and the spin-crossover phenomenon is preserved well in the nanostructured materials.

    11. Ferrocene-Fused Phospholes

      Enantioselective Synthesis of Ferrocene- or Cymantrene-Fused Planar-Chiral Phospholes

      Hao Hu, Wei-Yi Wu, Tamotsu Takahashi, Kazuhiro Yoshida and Masamichi Ogasawara

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600875

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      The enantioselective synthesis of planar-chiral ferrocene- or cymantrene-fused phospholes (S)-1a and (S)-1b was achieved. The asymmetric introduced of bromo and (Z)-2-bromovinyl groups at the 1- and 2-positions in (S)-6 followed by the cyclization with PhPBr2 provided (S)-1. The structure of (S)-1a was determined by X-ray crystallography, and derivatization of (S)-1a was examined.

  24. Communications

    1. C–H Activation

      Gold(I)-Catalyzed Reaction of Ferrocene and Propargylic Esters: Synthesis of Functionalized Ferrocene Derivatives

      Enol López, Tatiana Suárez, Alfredo Ballesteros and Luis A. López

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600836

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      The Au-catalyzed reaction of ferrocene with propargylic esters provides ferrocene derivatives featuring a functionalized vinyl moiety through initial 1,2-acyloxy rearrangement with generation of a gold carbene intermediate and subsequent electrophilic aromatic substitution. This method demonstrates the potential of carbene intermediates in the C–H bond functionalization of ferrocene.

    2. Phosphorus Hybrid Polymers

      You have full text access to this OnlineOpen article
      The Diphosphorus Complex [Cp2Mo2(CO)42-P2)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers

      Mehdi Elsayed Moussa, Bianca Attenberger, Martin Fleischmann, Andrea Schreiner and Manfred Scheer

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600895

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      A three-component reaction of the diphosphorus complex [Cp2Mo2(CO)42-P2)] (Cp = C5H5), Ag[BF4], and 2,2′-bipyrimidine yielded two novel 2D hybrid polymers. One represents a 2D organometallic-organic coordination polymer, while the other is a unique 2D organometallic-inorganic-organic coordination polymer.

    3. Ferrocene Receptors

      A Halogen Bonding 1,3-Disubstituted Ferrocene Receptor for Recognition and Redox Sensing of Azide

      Jason Y. C. Lim and Paul D. Beer

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600805

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      The first halogen bonding redox-active ferrocene receptor that binds and electrochemically senses azide selectively in solution is reported, which shows greatly improved sensitivity and discrimination compared to its hydrogen bonding analogue.

  25. Full Papers

    1. Ir Complexes for Imine Reduction

      Iridium(III) Complexes Bearing Chelating Bis-NHC Ligands and Their Application in the Catalytic Reduction of Imines

      Francisco Aznarez, Manuel Iglesias, Alexander Hepp, Benjamin Veit, Pablo J. Sanz Miguel, Luis A. Oro, Guo-Xin Jin and F. Ekkehardt Hahn

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600922

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      Iridium(III) complexes 4 and 5 bearing C^C bis-carbene chelating ligands composed of a classical NHC and an anionic imidazolylato donor were obtained from imidazolium/imidazole compounds and [{Cp*IrCl(µ-Cl)}2] in the presence of NaOAc. Complexes 4 and 5 are moderately active catalysts in the reduction of various imines with dihydrogen.

    2. Mixed Donor Ligands

      Homo- and Heterodinuclear Rh and Ir Complexes Supported by SNn Mixed-Donor Ligands (n = 2–4). Stereochemistry and Coordination-Site-Exchange Reactions of Cp*M (M = Rh, Ir) Units

      Takayuki Nakajima, Yuki Kawasaki, Bunsho Kure and Tomoaki Tanase

      Version of Record online: 29 AUG 2016 | DOI: 10.1002/ejic.201600722

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      Coordination-site exchange reactions of Cp*M (M = Rh, Ir) fragments occurred in homo- and heterodinuclear RhIII and IrIII complexes supported by a SN2 Ligand.

    3. Photodynamic Therapy

      Evaluation of Perylene Bisimide-Based RuII and IrIII Complexes as Photosensitizers for Photodynamic Therapy

      Cristina Mari, Huaiyi Huang, Riccardo Rubbiani, Marcus Schulze, Frank Würthner, Hui Chao and Gilles Gasser

      Version of Record online: 16 AUG 2016 | DOI: 10.1002/ejic.201600516

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      The biological activity of a RuII polypyridyl complex 1 and an IrIII organometallic complex 2 on four cell lines is presented. Although the cytotoxicity of 1 did not improve significantly upon light irradiation, 2 reached nanomolar IC50 values on all the cell lines tested when activated with 420 nm light in low doses.

    4. Ferrocene Peptides

      Synthesis and Conformational Study of Monosubstituted Aminoferrocene-Based Peptides Bearing Homo- and Heterochiral Pro-Ala Sequences

      Mojca Čakić Semenčić, Ivan Kodrin, Lidija Barišić, Marko Nuskol and Anton Meden

      Version of Record online: 16 AUG 2016 | DOI: 10.1002/ejic.201600648

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      The synthesis and conformational analysis of monosubstituted aminoferrocene-based peptides bearing a Pro-Ala sequence indicate the potential fine tuning of the conformational properties by variation of the chirality of the constituent amino acids.

    5. Entatic State Models

      Implications of Guanidine Substitution on Copper Complexes as Entatic-State Models

      Alexander Hoffmann, Julia Stanek, Benjamin Dicke, Laurens Peters, Benjamin Grimm-Lebsanft, Alina Wetzel, Anton Jesser, Matthias Bauer, Manuel Gnida, Wolfram Meyer-Klaucke, Michael Rübhausen and Sonja Herres-Pawlis

      Version of Record online: 11 AUG 2016 | DOI: 10.1002/ejic.201600655

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      A series of guanidine–quinoline copper complexes reveals that subtle influences such as the change in guanidine substitution have a large impact on the coordination distortion between tetrahedral and square-planar environments and the role of these complexes as entatic-state models.

    6. Cyanidometallates

      Alternative Synthetic Route to Potassium Octacyanidoniobate(IV) and Its Molybdenum Congener

      Gabriela Handzlik, Michał Magott, Barbara Sieklucka and Dawid Pinkowicz

      Version of Record online: 9 AUG 2016 | DOI: 10.1002/ejic.201600669

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      A novel alternative synthetic route for octacyanidoniobate(IV) and octacyanidomolybdate(IV) are reported. The preparation of both complexes is significantly improved in terms of simplicity, preparation time, yield and purity.

    7. Structure Determination in Solution

      Discrimination of Octahedral versus Trigonal Bipyramidal Coordination Geometries of Homogeneous TiIV, VV, and MoVI Amino Triphenolate Complexes through Nitroxyl Radical Units

      Elena Badetti, Vega Lloveras, Francesco Romano, Rosalia Di Lorenzo, Jaume Veciana, José Vidal-Gancedo, Cristiano Zonta and Giulia Licini

      Version of Record online: 6 AUG 2016 | DOI: 10.1002/ejic.201600649

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      A new stable radical-containing ligand and the corresponding VV, TiIV, and MoVI complexes have been synthesized and studied by electron paramagnetic resonance (EPR) spectroscopy. In these systems, dipolar interactions among the organic radicals are strongly dependent on the geometry assumed in solution.

    8. Spin-Crossover Complexes

      Magnetic Bistability in Macrocycle-Based FeII Spin-Crossover Complexes: Counter Ion and Solvent Effects

      Eric Milin, Bouabdellah Benaicha, Fatima El Hajj, Véronique Patinec, Smail Triki, Mathieu Marchivie, Carlos J. Gómez-García and Sébastien Pillet

      Version of Record online: 6 AUG 2016 | DOI: 10.1002/ejic.201600660

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      A new series of FeII spin-crossover complexes based on an N-functionalized macrocycle ligand have been prepared and fully characterized. One exhibits magnetic bistability with a 9 K wide hysteresis loop (136–145 K) and the other two show either an abrupt (T1/2 = 83 K) or gradual (T1/2 = 150 K) transition without hysteresis. The different behaviour can be explained by intermolecular interactions.

    9. Fluorido Complexes

      Rhodium and Iridium Fluorido and Bifluorido Complexes Derived from Peroxido Precursors

      Hanna Baumgarth, Gregor Meier, Thomas Braun and Beatrice Braun-Cula

      Version of Record online: 29 JUL 2016 | DOI: 10.1002/ejic.201600682

      Thumbnail image of graphical abstract

      The rhodium and iridium fluorido bifluorido complexes trans-[M(4-C5F4N)(F)(FHF)(CNtBu)(PR3)2] (M = Rh, R = Et; M = Ir, R = iPr) have been synthesized from the peroxido precursors by using HF sources. Abstraction of the coordinated HF by base gave the difluorido complexes trans-[M(4-C5F4N)(F)2(CNtBu)(PR3)2] (M = Rh, R = Et; M = Ir, R = iPr).

    10. Confocal Microscopy Imaging

      Substitution of Metallocenes with [2.2]Paracyclophane to Enable Confocal Microscopy Imaging in Living Cells

      Joanna Skiba, Claudia Schmidt, Petra Lippmann, Philipp Ensslen, Hans-Achim Wagenknecht, Rafał Czerwieniec, Fabian Brandl, Ingo Ott, Tytus Bernaś, Barbara Krawczyk, Dominik Szczukocki and Konrad Kowalski

      Version of Record online: 13 JUL 2016 | DOI: 10.1002/ejic.201600281

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      The biodistribution of metallocenyl uracil–pyrenes is investigated through an indirect approach that exploits the structural similarities of metallocenyl and [2.2]paracyclophanyl groups. Confocal microscopy of a [2.2]paracyclophane uracil–pyrene shows its accumulation in the membranes, cytoplasm, and mitochondria. A similar biodistribution pattern is postulated for the metallocenyl congeners.

    11. Palladium Catalysts

      Synthesis of Phosphanylferrocenecarboxamides Bearing Guanidinium Substituents and Their Application in the Palladium-Catalyzed Cross-Coupling of Boronic Acids with Acyl Chlorides

      Hana Charvátová, Ivana Císařová and Petr Štěpnička

      Version of Record online: 6 JUL 2016 | DOI: 10.1002/ejic.201600461

      Thumbnail image of graphical abstract

      Phosphanylferrocene ligands 1 and 2 bearing guanidinium pendants have been prepared and utilized as donors in PdII complexes and in the Pd-catalyzed cross-coupling of arylboronic acids with benzoyl chlorides to give benzophenones. Consistently better results were achieved with ligand 2 possessing an extended alkylguanidinium moiety appended to the phosphanylferrocene unit through an amide moiety.

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