European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 34

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

VIEW

  1. 1 - 83
  1. Communications

    1. Metallo-Supramolecular Assembly

      Hampered Subcomponent Self-Assembly Leads to an Aminal Ligand: Reactivity with Silver(I) and Copper(II)

      Jacopo Tessarolo, Alfonso Venzo, Gregorio Bottaro, Lidia Armelao and Marzio Rancan

      Version of Record online: 6 DEC 2016 | DOI: 10.1002/ejic.201601121

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      The ineffectiveness of a subcomponent self-assembly procedure leads to a new aminal ligand (L). The combination of L with AgI gives a 2D network; CuII induces decomposition and oxidation of L, which leads to an unprecedented [Cu4(pic)4(OH)2(H2O)6](ClO4)2 (Hpic = picolinic acid) tetramer.

    2. Magnetic Nanoparticles

      First-Principles Calculations and Optical Absorption Spectrum of a Light-Colored Aluminum-Substituted ε-Iron Oxide Magnet

      Tomomichi Nasu, Marie Yoshikiyo, Hiroko Tokoro, Asuka Namai and Shin-ichi Ohkoshi

      Version of Record online: 5 DEC 2016 | DOI: 10.1002/ejic.201601169

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      Periodic structure calculations of Al-substituted ε-Fe2O3 reveal that ε-Al0.5Fe1.5O3 has a wide band gap. A highly dispersed polymer solution of the ε-Al0.66Fe1.34O3 nanomagnet is prepared, and it is very light in color relative to other magnetic ferrites. Such a light-colored magnetic material should be useful for colored magnetic toners for color printing.

  2. Full Papers

    1. Zn Finger Proteins

      Cisplatin Preferentially Binds to Zinc Finger Proteins Containing C3H1 or C4 Motifs

      Siming Yuan, Xin Ding, Yang Cui, Kaiju Wei, Yuchuan Zheng and Yangzhong Liu

      Version of Record online: 5 DEC 2016 | DOI: 10.1002/ejic.201601140

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      Cisplatin selectively binds to ZFPs containing C4 or C3H motifs. MDM2-zf (C4) and PARP-1-zf2 (C3H) show a higher reactivity to cisplatin than Sp1-zf2 (C2H2). The platination of ZFPs causes the zinc release and structural perturbation of the proteins. The different reactivity of the various ZFPs may be correlated with the targeting of cisplatin in cells.

    2. Ruthenium–Arene Complexes

      Cationic Ru(η6-p-cymene) Complexes of 3-Hydroxy-4-pyr(id)ones – Lipophilic Triphenylphosphine as Co-Ligand Is Key to Highly Stable and Cytotoxic Anticancer Agents

      Shahida Parveen, Muhammad Hanif, Sanam Movassaghi, Matthew P. Sullivan, Mario Kubanik, Muhammad Ashraf Shaheen, Tilo Söhnel, Stephen M. F. Jamieson and Christian G. Hartinger

      Version of Record online: 2 DEC 2016 | DOI: 10.1002/ejic.201601163

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      Replacing the labile chlorido ligand in Ru(η6-p-cymene)[3-hydroxy-4(1H)-pyr(id)one]Cl complexes with triphenylphosphine or 1,3,5-triaza-7-phoshatricyclo[3.3.1.1]decane resulted in compounds with higher anticancer activity. The improved activity can be rationalized by higher stability in aqueous solution and in the presence of biomolecules.

  3. Communications

    1. Targeting Integrin Receptors

      Functionalization of Ruthenium(II) Terpyridine Complexes with Cyclic RGD Peptides To Target Integrin Receptors in Cancer Cells

      Eva M. Hahn, Natalia Estrada-Ortiz, Jiaying Han, Vera F. C. Ferreira, Tobias G. Kapp, João D. G. Correia, Angela Casini and Fritz E. Kühn

      Version of Record online: 2 DEC 2016 | DOI: 10.1002/ejic.201601094

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      Two terpyridine-based ruthenium(II) complexes are designed to be coupled to a cyclic peptide targeting integrin receptor αvβ3 to achieve models for targeted anticancer agents.

  4. Full Papers

    1. CN-Bridged Assemblies

      Solvatomagnetic Studies on Cyano-Bridged Bimetallic Chains Based on [Mn(cyclam)]3+ and Hexacyanometallates

      Beata Nowicka, Michał Heczko, Michał Rams, Mateusz Reczyński, Bartłomiej Gaweł, Wojciech Nitek and Barbara Sieklucka

      Version of Record online: 2 DEC 2016 | DOI: 10.1002/ejic.201601007

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      CN-bridged chains based on the [Mn(cyclam)]3+ cation and [M(CN)6]3– anions (M = Cr, Fe) show marked changes in structure and magnetic properties upon dehydration.

    2. Group 14 Bridges

      Electrochemistry of Dinuclear Organometallic [5]Trovacenyl Derivatives Bridged by Group 14 Elements (Si, Ge, Sn, Pb)

      Feng Lu and Klaus Harms

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601045

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      The electrochemistry of dinuclear [5]trovacenyl derivatives [(η7-C7H7)V(η5-C5H4)]2MR2 (2··, 3··, 4··, and 5··, M = Si, Ge, Sn, Pb; R = Me or Ph) bridged by group 14 elements (Si, Ge, Sn, and Pb) was investigated systematically by cyclic voltammetry. The results indicate that the strength of the weak intramolecular electronic communication between the two V centers is in the order of Si (2··) < Ge (3··) < Sn (4··) < Pb (5··).

    3. Hydroxyapatite

      Effect of Magnesium on the Solubility of Hydroxyapatite

      Quan Liu, Zhuofan Chen, Haobo Pan, Brian W. Darvell and Jukka Pekka Matinlinna

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601056

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      The mass solubility of hydroxyapatite is increased substantially and rapidly in the presence of low concentrations of magnesium ions, probably because phosphate complexation shifts the equilibrium. Thus, magnesium-deficiency osteoporosis cannot be exerted through a direct solubility effect on biological apatite, and cellular chemistry is implicated.

    4. Tetrathiafulvalene Complexes

      Structural and Physical Investigations of Coordination Complexes Involving Pyridylethylenedithio–Tetrathiafulvalene Ligands Decorated with Cyanoethylsulfanyl and Cyanoethylselanyl Moieties

      Haiet Douib, Fabrice Pointillart, Bertrand Lefeuvre, Stéphane Golhen, Olivier Cador, Boris Le Guennic, Abdelkrim Gouasmia and Lahcène Ouahab

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601241

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      Two hetero-difunctionalized ethylenedithio–tetrathiafulvalene-based ligands are designed, and their two nitrile and 4-pyridyl coordinating groups allowed the formation of both mononuclear and cyclic tetranuclear complexes involving various transition-metal ions.

    5. Structure-Activity Role of PbII Lone Pairs

      Correlating Structural Features and 207Pb NMR Parameters with the Stereochemical Activity of PbII Lone Pairs in Birefringent Pb[2,6-bis(benzimidazol-2-yl)pyridine] Complexes

      John R. Thompson, David Snider, John E. C. Wren, Scott Kroeker, Vance E. Williams and Daniel B. Leznoff

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601235

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      A set of highly birefringent Pb(bbp) [bbp = 2,6-bis(benzimidazol-2-yl)pyridine] complexes has been investigated by 207Pb solid-state NMR spectroscopy and X-ray crystallography, showing correlations between two structural distortion parameters and the 207Pb chemical shift span, which allows the relative degree of stereochemical lone-pair activity of each complex in the series to be determined.

  5. Communications

    1. Polyoxometalates

      Synthesis and Characterization of the First Nickel(II)-Centered Single-Side Tris-Functionalized Anderson-Type Polyoxomolybdate

      Nadiia I. Gumerova, Alexander Roller and Annette Rompel

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601198

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      The first single-side Tris-functionalized Anderson-type polyoxomolybdate containing a divalent heteroatom [NiII(OH)3Mo6O18(OCH2)3CNH3]3– is prepared via the presynthesized parent anion.

  6. Full Papers

    1. Compartmental Ligand Complexes

      A Series of [2+2] Schiff Base Macrocyclic Dinuclear ZnII Complexes with Rigid 1,2-Diamine and Flexible 1,8-Diamine Components

      Fei-Fan Chang, Yong Hu, Kun Zhang, Hui-Qin Chen and Wei Huang

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601057

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      Eight [2+2] Schiff base dinuclear macrocyclic ZnII complexes, bearing different rigid 1,2-diamine and flexible 1,8-diamine components, have been successfully constructed by zinc ion template-assisted syntheses.

    2. Ferrocene–Lithium Interactions

      Fe–Li Interactions in Ferrocenyllithium Compounds

      Andrea Malastová, Ján Vallo, Ambroz Almássy, Michal Pitoňák, Pavel Neogrády and Radovan Šebesta

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601114

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      Bonding interactions between the iron and lithium atoms in ferrocenyl organolithium compounds are described by quantum-chemical computational methods [DFT, MP2, and CCSD(T)].

    3. Nickel Uracil Complexes

      Synthesis and Investigation of Solid- and Solution-State Structures of Nickel(II) Complexes with 1,3-Dimethyl-5-(arylazo)-6-aminouracil

      Atanu Purkayastha, Diptanu Debnath, Subhadip Roy, Antonio Bauzá, Rupasree Choudhury, Antonio Frontera and Tarun Kumar Misra

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601021

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      Nickel(II) complexes of 1,3-dimethyl-5-(arylazo)-6-aminouracil ligands possess perfect square-planar geometry. Crystallographic and DFT studies show that N–H/π and C–H/π interactions play important roles in the stabilization of the supramolecular assembly in the solid state, whereas in solution these interactions are present in chloroform and disrupted in DMSO due to the formation of hydrogen bonds.

    4. Highly Reactive Small Molecules

      Preparation and Spectroscopic Studies of FC(O)SSCl

      Melina V. Cozzarín, Shengrui Tong, Mao-Fa Ge, Carlos O. Della Védova and Rosana M. Romano

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201600966

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      The novel FC(O)SSCl molecule has been prepared by the reaction of ClC(O)SSCl with TlCl. The more stable syn-gauche structure is in equilibrium with the less stable anti-gauche conformer. The compound was characterized by electron-impact mass spectrometry, and the vibrational and electronic properties were studied.

    5. Biferrocene in Conjugated Systems

      Functionalised Biferrocene Systems towards Molecular Electronics

      Lucy E. Wilson, Christopher Hassenrück, Rainer F. Winter, Andrew J. P. White, Tim Albrecht and Nicholas J. Long

      Version of Record online: 30 NOV 2016 | DOI: 10.1002/ejic.201601036

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      A new method for the synthesis and incorporation of biferrocenyl systems within extended conjugated systems is reported, alongside in-depth cyclic voltammetry, UV/Vis/near-infrared (NIR) spectroelectrochemistry and X-ray crystallography characterisation.

    6. Zinc Polyazides

      Binary Polyazides of Zinc

      Jonas Bresien, Holger Ott, Kati Rosenstengel, Axel Schulz, Philipp Thiele and Alexander Villinger

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201601035

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      A series of zinc azide solvates Zn(N3)2·n solvent (solvent = DMSO, n = 1, 3/2, 3; MeCN, n = 2/3), and tetraazidozincate anions [Zn(N3)4]2– as [Ph4P]+ and [PNP]+ [PNP = bis(triphenylphosphine)iminium] salts were synthesized and comprehensively characterized. The X-ray structures of all Zn(N3)2 solvates, as well as six polymorphs of [Ph4P]2[Zn(N3)4] could be determined for the first time.

    7. Metal–Organic Frameworks

      Reactivity Studies of Metal–Organic Frameworks under Vapor-Assisted Aging: Structural Interconversions and Transformations

      Panjuan Tang, Chunmei Jia, Yujie Jiang, Wei Gong, Xiaocong Cao, Junyi Yang and Wenbing Yuan

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201600907

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      Structural interconversion and transformation made easy: metal–organic frameworks (MOFs) are surprisingly reactive under vapor-assisted aging (VAG) at room temperature and can undergo various rearrangements.

    8. Photocytotoxicity

      Platinum(II) Complexes of Curcumin Showing Photocytotoxicity in Visible Light

      Koushambi Mitra, Srishti Gautam, Paturu Kondaiah and Akhil R. Chakravarty

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201601078

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      Platinum(II)–curcumin complexes having diammine or chelating amines as ligands show photocytotoxicity: in visible light the curcumin ligand dissociates, thereby generating platinum(II)–DNA crosslinking agents and curcumin as a phototoxin.

    9. Homogeneous Catalysis in Water

      Synthesis, Palladium(II) Complexes, and Catalytic Use of a Phosphanylferrocene Ligand Bearing a Guanidinium Pendant

      Ondřej Bárta, Ivana Císařová and Petr Štěpnička

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201601262

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      A phosphanylferrocene donor with a hydrophilic guanidinium substituent, Ph2PfcCH2NHC(NH)NH2·HCl (fc = ferrocene-1,1′-diyl), has been synthesized and utilized as a ligand for PdII complexes. Both the defined complexes and their in situ generated analogues were evaluated as pre-catalysts for the Suzuki–Miyaura cross-coupling of arylborates with aryl bromides in polar reaction solvents.

    10. Radiolabelling

      Rhenium Complexes Based on an N2O Tridentate Click Scaffold: From Synthesis, Structural and Theoretical Characterization to a Radiolabelling Study

      Romain Eychenne, Sihem Guizani, Jin-Hui Wang, Claude Picard, Nadia Malek, Paul-Louis Fabre, Mariusz Wolff, Barbara Machura, Nathalie Saffon, Nicolas Lepareur and Eric Benoist

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201600877

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      Novel tricarbonylrhenium complexes of the general formula [Re(CO)3(L)], in which LH is an N2O tridentate click ligand, have been prepared and fully characterized, including by X-ray crystallography and DFT calculations. The analogous [188Re(CO)3(L)] complexes were also investigated and their structures established by HPLC. This study shows the great potential of tripodal click scaffolds for 188ReI.

    11. Phthalocyanines

      Phthalocyanine Derivatives with Eight Peripheral Long-Chain n-Alkylseleno Substituents

      Philipp M. Reintanz, Robin Guthardt, Clemens Bruhn, Fabian Mohr and Ulrich Siemeling

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201601115

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      4,5-Bis(n-alkylseleno)phthalodinitriles are prepared from inexpensive starting materials by avoiding highly toxic selenols and cyanides. They are used as building blocks for alkylseleno-substituted phthalocyanine derivatives, including phthalocyaninatomanganese(III) and bis(phthalocyaninato)terbium(III) complexes.

    12. Polyoxometalates

      Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media

      Harrison A. Neal, Jennifer Szymanowski, Jeremy B. Fein, Peter C. Burns and May Nyman

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201601219

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      The transfer of uranyl capsule polyoxometalates to organic media is facile, bringing forth new solution behavior of the clusters and their encapsulated species, as well as demonstrating efficient separations.

    13. Precursors for Ge and SnO Thin Films

      N-Alkoxy Carboxamide Stabilized Tin(II) and Germanium(II) Complexes for Thin-Film Applications

      Sheby Mary George, Ji Hyeun Nam, Ga Yeon Lee, Jeong Hwan Han, Bo Keun Park, Chang Gyoun Kim, Dong Ju Jeon and Taek-Mo Chung

      Version of Record online: 29 NOV 2016 | DOI: 10.1002/ejic.201600884

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      Alkoxy-functionalized carboxamides act as excellent stabilizing ligands for germanium and tin complexes, and the physicochemical properties of these complexes prove their potential as precursors for thin-film deposition.

    14. Heteromultinuclear Assemblies

      Heterotri- and Heteropentanuclear Copper(I)–Ferrocenyl Complexes Assembled through a “Click” Strategy: A Structural, Electrochemical, and Spectroelectrochemical Investigation

      Sinja Manck, Marc Röger, Margarethe van der Meer and Biprajit Sarkar

      Version of Record online: 25 NOV 2016 | DOI: 10.1002/ejic.201601075

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      The metalloligand pyridyl–triazolyl–ferrocene derived through a “click” strategy is combined with Cu–dppf to obtain heteromultinuclear complexes containing multiple redox-active centers.

    15. Antiproliferative Ferrocenophanes

      Side-Chain Effects on the 1-(Bis-aryl-methylidene)-[3]ferrocenophane Skeleton: Antiproliferative Activity against TNBC Cancer Cells and Comparison with the Acyclic Ferrocifen Series

      Meral Gormen, Pascal Pigeon, Yong Wang, Anne Vessières, Siden Top, Franck Martial, Christina Gros, Michael J. McGlinchey and Gérard Jaouen

      Version of Record online: 25 NOV 2016 | DOI: 10.1002/ejic.201601088

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      New [3]ferrocenophane derivatives bearing various side-chains have been synthesized and their biochemical properties studied. These complexes were found to have very strong antiproliferative effects against MDA-MB-231 breast cancer cells (IC50 = 0.05–0.39 µm).

    16. Photocatalytic Borates

      In1–xGaxBO3 (0 ≤ x ≤ 0.5) – Solvothermal Synthesis, Morphology, and Performance in Photocatalytic Water Reduction

      Yao Yang, Kai Song, Mufei Yue, Liangju Li, Rihong Cong, Wenliang Gao and Tao Yang

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201601071

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      The solvothermal method was used to prepare partial solid solutions of In1–xGaxBO3 (0 ≤ x ≤ 0.5), in which InBO3 exhibits spindlelike nanocrystallites with the optimal photocatalytic H2 evolution rate of 56.1(5) µmol h–1 g–1 at a NiOx loading of 1 wt.-%).

    17. Photocatalysis

      Helicity in Photocatalysis – Advantage or Obstacle? Studies on Silver Complexes – Synthesis, Structure, and Photocatalytic Activity

      Marta A. Fik, Maciej Kubicki, Angelika E. Odachowska, Joanna Karpińska and Violetta Patroniak

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201600809

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      The photocatalytic activities of a mononuclear AgI complex and a dinuclear AgI helicate with a Schiff base type ligand are investigated for the degradation of methylene blue and quinoline yellow as well as organic carbon in a wastewater sample.

    18. Cu Complexes for DNA Cleavage

      Oxidative DNA Cleavage Promoted by a Phenoxyl-Radical Copper(II) Complex

      Olesea Cuzan, Amélie Kochem, A. Jalila Simaan, Sylvain Bertaina, Bruno Faure, Viviane Robert, Sergiu Shova, Michel Giorgi, Michel Maffei, Marius Réglier and Maylis Orio

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201601001

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      Copper(II) complex 1 with a benzotriazole–phenolate ligand was synthesized and investigated by spectroscopic methods. Its one-electron oxidized species 1+ was generated and characterized by UV/Vis EPR spectroscopy and theoretical calculations. The capability of complex 1 for performing oxidative cleavage of DNA was evaluated in the presence of H2O2 or under aerobic conditions with ascorbate or dithiothreitol.

    19. Copper Catecholase

      Dinuclear Copper(II) Complexes with Distant Metal Centers: Weaker Donor Groups Increase Catecholase Activity

      Paulino Zerón, Michael Westphal, Peter Comba, Marcos Flores-Álamo, A. Claudia Stueckl, Carmen Leal-Cervantes, Víctor M. Ugalde-Saldívar and Laura Gasque

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201600967

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      Two dinuclear complexes with Cu···Cu distances above 7 Å display EPR spectra typical of dipole–dipole-coupled dicopper(II) complexes. The catalytic efficiency of these two compounds for catechol oxidation is the highest among a series or related complexes owing to their remarkably low Michaelis constants, which are associated to the weaker donor groups present in these ligands.

    20. Nucleoside Analogues

      Organometallic Nucleoside Analogues: Effect of Hydroxyalkyl Linker Length on Cancer Cell Line Toxicity

      Jonathan L. Kedge, Huy V. Nguyen, Zahra Khan, Louise Male, Media K. Ismail, Holly V. Roberts, Nikolas J. Hodges, Sarah L. Horswell, Youcef Mehellou and James H. R. Tucker

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201600853

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      Chiral ferrocene derivatives show distinct structure–activity relationships in their cancer cell line activities.

    21. Metals in Medicine

      Enhancing the Cytotoxic Activity of Anticancer PtIV Complexes by Introduction of Lonidamine as an Axial Ligand

      Yulia N. Nosova, Lidia S. Foteeva, Ilia V. Zenin, Timur I. Fetisov, Kirill I. Kirsanov, Marianna G. Yakubovskaya, Taisya A. Antonenko, Viktor A. Tafeenko, Leonid A. Aslanov, Anna A. Lobas, Mikhail V. Gorshkov, Markus Galanski, Bernhard K. Keppler, Andrei R. Timerbaev, Elena R. Milaeva and Alexey A. Nazarov

      Version of Record online: 23 NOV 2016 | DOI: 10.1002/ejic.201600857

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      A series of PtIV complexes with lonidamine as a ligand coordinated in axial position is reported. Lonidamine affects strongly the in vitro cytotoxic activity, lowering the IC50 values down to the nanomolar range.

    22. Metallophthalocyanines

      Coordination Polymer of Manganese(II) Phthalocyanine with 4,4′-Bipyridyl: Synthesis, Crystal Structure, and Physical Properties

      Alexey L. Litvinov, Alexey V. Kuzmin, Evgeniya I. Yudanova, Dmitri V. Konarev, Nikita R. Romanenko, Salavat S. Khasanov and Rimma N. Lyubovskaya

      Version of Record online: 22 NOV 2016 | DOI: 10.1002/ejic.201600944

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      A coordination polymer (MnIIPc·4,4′-bpy)n·(4C6H4Cl2)n of manganese(II) phthalocyanine with a pyridine-containing bidentate ligand – 4,4′-bipyridyl (4,4′-bpy) – has been obtained as single crystals. Optical and magnetic properties of the polymer have been studied.

    23. Metal–Organic Framework Catalysts

      Zinc(II) and Copper(II) Metal–Organic Frameworks Constructed from a Terphenyl-4,4′′-dicarboxylic Acid Derivative: Synthesis, Structure, and Catalytic Application in the Cyanosilylation of Aldehydes

      Anirban Karmakar, Anup Paul, Guilherme M. D. M. Rúbio, M. Fátima C. Guedes da Silva and Armando J. L. Pombeiro

      Version of Record online: 22 NOV 2016 | DOI: 10.1002/ejic.201600902

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      Metal–organic frameworks of ZnII and CuII act as recyclable heterogeneous catalysts for the cyanosilylation of aldehydes at room temperature.

    24. Water Oxidation

      Catalytic Water-Oxidation Activity of a Weakly Coupled Binuclear Ruthenium Polypyridyl Complex

      Tiago A. Matias, Ana P. Mangoni, Sergio H. Toma, Francisca N. Rein, Reginaldo C. Rocha, Henrique E. Toma and Koiti Araki

      Version of Record online: 22 NOV 2016 | DOI: 10.1002/ejic.201600889

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      A weakly coupled binuclear complex shows a rate constant for oxygen evolution that is up to 20 times larger than that of the analogous mononuclear complex, which indicates a major role of the second site on the catalytic activity.

    25. Ferrocenyl Receptors

      Synthesis of Diferrocenyl Hydrazone–Enone Receptor Molecules – Electronic Communication, Metal Binding, and DFT Study

      Sasmita Mishra, Smriti Dewangan, Santanab Giri, Shaikh M. Mobin and Saurav Chatterjee

      Version of Record online: 21 NOV 2016 | DOI: 10.1002/ejic.201601072

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      Four diferrocenyl hydrazone–enone compounds are synthesized by a two-step reaction involving 1,1′-diacetylferrocene, hydrazides, and ferrocenecarboxaldehyde. The compounds show unique structural features, metal-ion-sensing properties, and distinct electronic-communication behavior.

    26. Group V Chemistry

      Structural and Electronic Properties of Fluoride Complexes of NbV, TaV, and PaV: The Influence of Relativistic Effects on Group V Elements

      Richard E. Wilson, Stéphanie De Sio and Valerie Vallet

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/ejic.201600981

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      A comparative study of fluoride complexes of Nb, Ta, and their pseudo-homologue protactinium with use of synchrotron-based X-ray absorption spectroscopy and quantum chemical calculations reveals various seemingly nonperiodic chemistries. Computational results demonstrate that this “nonperiodic” behavior is due to the increasing influence of relativistic effects as Z increases from Nb to Pa.

    27. 3d-5d Magnetic Complexes

      Heterobimetallic Oxalate-Bridged MIIReIV (M = Zn, Cu, Ni, Co and Mn) Complexes Incorporating Bis(3,5-dimethylpyrazol-1-yl)methane: Synthesis and Magneto-Structural Studies

      Izabela Gryca, Joanna Palion-Gazda, Barbara Machura, Mateusz Penkala, Francesc Lloret and Miguel Julve

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/ejic.201601004

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      A magneto-structural study of oxalato-bridged ReIV–MII complexes shows the occurrence of intramolecular ferro- (M = Cu, Ni and Co) and antiferromagnetic interactions (M = Mn) that coexist with large zero-field splitting effects (M = Zn, Cu, Ni, Co and Mn).

    28. Palladium Catalysts

      Oxidative Cleavage of Styrenes Catalyzed by a PdII Complex of an 8-Hydroxyquinolinonate Ligand

      Hong-Ming Jhong, Yi-Hung Liu, Shie-Ming Peng and Shiuh-Tzung Liu

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/ejic.201600951

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      A dimeric PdII complex with an 8-(pyridin-2-ylmethoxy)hydroxyquinolinonate ligand was prepared and characterized. This complex is a good catalyst for the oxidative cleavage of styrenes in the presence of CuCl2 as cocatalyst.

    29. Gold(I) Complexes

      Gold(I) Complexes [N{(C3F7)C(Dipp)N}2]AuL (L = Ethylene, tert-Butyl Isocyanide, Tetrahydrothiophene, Triphenylphosphine) and Different Triazapentadienyl Ligand Coordination Modes

      Shreeyukta Singh, Guocang Wang, James X. Mao, Jaime A. Flores, Xiaodi Kou, Charles Campana, Peter Kroll and H. V. Rasika Dias

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/ejic.201600878

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      The triazapentadienyl ligand adopts diverse coordination modes as it stabilizes gold(I) bonded to carbon, phosphorus and sulfur based donors.

  7. Communications

    1. Antiparasitic Ferrocene Compounds

      Evaluation of Ferrocenyl-Containing Benzothiazoles as Potential Antiplasmodial Agents

      Muneebah Adams, Carmen de Kock, Peter J. Smith, Kelly Chibale and Gregory S. Smith

      Version of Record online: 17 NOV 2016 | DOI: 10.1002/ejic.201601000

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      Ferrocenyl-containing benzothiazoles with amine side-chains, both organosilane and carbon analogues, were screened for their antiplasmodial activity against chloroquine-sensitive (NF54) and chloroquine-resistant (Dd2) strains of P. falciparum. They showed activities in the low micromolar range.

  8. Full Papers

    1. Bioconjugation

      Propargyl-Substituted Thiocarbamoylbenzamidines of Technetium and Rhenium: Steps towards Bioconjugation with Use of Click Chemistry

      Juan Daniel Castillo Gomez, Adelheid Hagenbach and Ulrich Abram

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201601039

      Thumbnail image of graphical abstract

      Ligands with propargyl-substituted thiocarbamoylbenzamidines form stable complexes with {99TcO}3+ and {ReO}3+ cores. Prototype Click coupling products with benzylazide confirm the suitability of such units for orthogonal couplings. Successful conjugation of the rhenium compound with the peptide angiotensin-II was performed and represents a proof-of-principle solution for ongoing experiments with 99mTc.

  9. Microreviews

    1. Metal-Containing Pharmacophores

      Metal-Containing Pharmacophores in Molecularly Targeted Anticancer Therapies and Diagnostics

      Mu Yang and Ulrich Bierbach

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201601149

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      Metal-containing pharmaceuticals have a long history of applications in cytotoxic chemotherapies. Treatment of malignant disease in the postgenomic era has long moved beyond the use of indiscriminate cell poisons. Inorganic elements are now beginning to play exciting new roles in the design of smarter, molecularly targeted therapeutic agents and diagnostics.

  10. Full Papers

    1. Polyoxometalates

      Diversity of Polyoxometalate-Based Copper Compounds Obtained from the Same Reaction System

      Halyna I. Buvailo, Valeriya G. Makhankova, Vladimir N. Kokozay, Igor V. Zatovsky, Irina V. Omelchenko, Svitlana V. Shishkina, Piotr Zabierowski, Dariusz Matoga and Julia Jezierska

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201600976

      Thumbnail image of graphical abstract

      Four compounds based on P/Mo Strandberg and P/Mo/V Keggin anions are obtained under mild conditions. The nature of the products depends substantially on the V reagent. The use of Cu0 or its salts both led to identical compounds. The complexes demonstrate promising electrocatalytic activity and rapid dye adsorption.

    2. Photolabile Ru Prodrugs

      Photolabile Ruthenium(II)–Purine Complexes: Phototoxicity, DNA Binding, and Light-Triggered Drug Release

      Hazel Chan, Joy B. Ghrayche, Jianhua Wei and Anna K. Renfrew

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201601137

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      Photolabile ruthenium complexes can cage a biologically active ligand and release it when irradiated with visible light. We present a series of complexes for light-activated delivery of the anticancer agent 6-mercaptopurine. Several complexes are able to release 6-mercaptopurine on irradiation with visible light and exhibit photoselective DNA binding or toxicity towards MCF-7 breast cancer cells.

    3. Drug–Dendrimer Conjugates

      Low-Generation Polyamidoamine Dendrimers as Drug Carriers for Platinum(IV) Complexes

      Nadine S. Sommerfeld, Michaela Hejl, Matthias H. M. Klose, Ekaterina Schreiber-Brynzak, Andrea Bileck, Samuel M. Meier, Christopher Gerner, Michael A. Jakupec, Markus Galanski and Bernhard K. Keppler

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201601205

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      An unsymmetrically carboxylated platinum(IV) analogue of oxaliplatin is coupled to generation two (G-2) and four (G-4) polyamidoamine (PAMAM) dendrimers. The platinum–dendrimer complexes showed load- and size-dependent potency with IC50 values down to the low-nanomolar range, in contrast to the rather moderate activity of the free platinum(IV) compound.

  11. Communications

    1. Silver(II) Compounds

      Efficient Electrosynthesis of AgIISO4: A Powerful Oxidizer and Narrow Band Gap Semiconductor

      Piotr Połczyński, Tomasz E. Gilewski, Jakub Gawraczyński, Mariana Derzsi, Piotr Jerzy Leszczyński, Wojciech Gadomski, Zoran Mazej, Rafał Jurczakowski and Wojciech Grochala

      Version of Record online: 15 NOV 2016 | DOI: 10.1002/ejic.201601183

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      Silver(II) sulfate is synthesized on a 20 g scale by using electrosynthesis and avoiding fluorinated precursors; a product of excellent crystallinity is obtained in up to 75 % yield. As shown by impedance spectroscopy and confirmed by theoretical calculations, bulk AgIISO4 is a narrow band gap semiconductor with a fundamental band gap comparable to that of silicon (≈1.0 eV at –50 °C).

  12. Full Papers

    1. Sulfur–Sulfur Bonds

      The Key Heterolysis Selectivity of Divalent Sulfur–Sulfur Bonds for a Unified Mechanistic Scheme in the Thiosulfatolysis and Sulfitolysis of the Pentathionate Ion

      Chen Ji, Xiangdong Yan, Changwei Pan, Fengpeng Lv and Qingyu Gao

      Version of Record online: 11 NOV 2016 | DOI: 10.1002/ejic.201600991

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      The selective heterolytic cleavages of sulfur–sulfur bonds are essential mechanistic steps for nucleophilic attacks on pentathionate and higher spolythionate ions containing inequivalent divalent sulfur atoms.

    2. Hydrazone Ligands

      Zinc(II) Complexes of N,N-Di(2-picolyl)hydrazones

      David N. Barsoum, Lawrence Kyeremeh-Mensah, Quinton J. Meisner, Ronald J. Clark, Eric Masson and Lei Zhu

      Version of Record online: 9 NOV 2016 | DOI: 10.1002/ejic.201601066

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      N,N-Di(2-picolyl)hydrazone (DPH) ligands are capable of binding metal ions in two coordination modes that anchor on either the sp3 amino or the sp2 imino nitrogen atom, depending on the nature of the hydrazone moiety.

    3. Molybdenum Reduction Chemistry

      Synthesis and Structures of Mono- and Dinuclear Molybdenum Complexes with Reduced α-Diimine Ligands

      Yanxia Zhao, Yurong Xue, Wenhua Xu, Ji-Hu Su, Biao Wu and Xiao-Juan Yang

      Version of Record online: 9 NOV 2016 | DOI: 10.1002/ejic.201600999

      Thumbnail image of graphical abstract

      A series of molybdenum complexes, including two Mo≡Mo triple-bond, one Mo–Mo single-bond, and one mononuclear compound, with dianionic α-diimine ligands HL2– and different oxidation states of molybdenum centers (+3, +4, or +5), have been synthesized and characterized.

    4. Thermoelectric Materials

      Tuning Crystal Structures and Thermoelectric Properties through Al Doping in ReSi1.75

      Fei Wang, Igor Veremchuk and Sven Lidin

      Version of Record online: 9 NOV 2016 | DOI: 10.1002/ejic.201600792

      Thumbnail image of graphical abstract

      Aluminium doping into ReSi1.75 renders an incommensurate composite crystal structure that has been solved for the first time by the superspace method. In comparison with ReSi1.75 with no doping, this doped incommensurate phase exhibits significantly improved thermoelectric properties.

    5. Ferrocenyl Ligands

      1,1′-Bis(pyrazol-4-yl)ferrocenes: Potential Clip Ligands and Their Supramolecular Structures

      Mattia Veronelli, Sebastian Dechert, Anne Schober, Serhiy Demeshko and Franc Meyer

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/ejic.201600644

      Thumbnail image of graphical abstract

      Supramolecular double deckers of the common pyrazolate-based [M(µ-pz)]3 metallomacrocycles (M = CuI, AgI, AuI; pz = pyrazolate) are assembled from ferrocene derivatives with two C-4-appended pyrazole rings. The ferrocene/pyrazole proligands H2RL form dimeric or trimeric supramolecular aggregates through intermolecular NH···N hydrogen bonds, both in the solid state and in solution.

    6. Ferrocenyl(thio)ureas

      Solution Conformation and Self-Assembly of Ferrocenyl(thio)ureas

      Kristina Hanauer, Minh Thu Pham, Christoph Förster and Katja Heinze

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/ejic.201600918

      Thumbnail image of graphical abstract

      Assembly processes of (thio)ureas are fundamental in anion sensing, supramolecular chemistry, and crystal engineering. The interplay of monomer conformation and hydrogen bonding, including nonclassical hydrogen bonds to iron(II), for the self-assembly of redox-active N,N′-disubstituted ferrocenyl(thio)ureas is elucidated. The impact of oxidation of 16 on conformation and assembly is discussed.

    7. 1,1′-Bis(phosphino)ferrocene Ligands

      Late Transition Metal Compounds with 1,1′-Bis(phosphino)ferrocene Ligands

      Sage F. Hartlaub, Nicole K. Lauricella, Catherine N. Ryczek, Aliza G. Furneaux, Jon D. Melton, Nicholas A. Piro, W. S. Kassel and Chip Nataro

      Version of Record online: 25 OCT 2016 | DOI: 10.1002/ejic.201601099

      Thumbnail image of graphical abstract

      Zinc compounds containing 1,1′-bis(phosphino)ferrocene ligands and several phosphine chalcogenide derivatives are prepared, and most are characterized by X-ray crystallography. The removal of a chlorido ligand from [(AuCl)2{1,1′-bis(phosphino)ferrocene}] results in the formation of [Au2(µ-Cl){1,1′-bis(phosphino)ferrocene}]+ species, which contain weak Au–Au interactions.

  13. Communications

    1. Noncovalent Bonding Interactions

      Ferrocene–Triazole Combination as a Benchmark for the Electrochemical Detection of Noncovalent Halogen-Bonding Interactions

      Fabiola Zapata, Antonio Caballero and Pedro Molina

      Version of Record online: 25 OCT 2016 | DOI: 10.1002/ejic.201600838

      Thumbnail image of graphical abstract

      A triferrocene–bis(iodotriazole) was synthesized. Its electrochemical sensing properties were studied by observing the cathodic shifts of the redox peaks in the presence of several oxoanions.

  14. Full Papers

    1. Ferrocene-Bridged Ligands

      Transition-Metal Complexes with Ferrocene-Bridged Bis(imidazolin-2-imine) and Bis(diaminocyclopropenimine) Ligands

      Kristof Jess, Dirk Baabe, Matthias Freytag, Peter G. Jones and Matthias Tamm

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201600841

      Thumbnail image of graphical abstract

      A ferrocene-based bis(imidazolin-2-imine) ligand was used for the synthesis of MCl2 salts (M = Mn–Zn). Its FeCl2 complex was oxidized and both complexes were characterized by Mössbauer spectroscopy, SQUID magnetometry, and X-ray diffraction. A trimetallic PdII complex was obtained with a ferrocene-based bis(cyclopropenimine).

    2. Chiral Lanthanide Complexes

      Homoleptic Chiral Benzamidinate Complexes of Rare-Earth Elements: Synthesis, Structure, Luminescence, and Magnetism

      Meng He, Zhi Chen, Eufemio Moreno Pineda, Xue Liu, Elisabeth Bouwman, Mario Ruben and Peter W. Roesky

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201600851

      Thumbnail image of graphical abstract

      A series of enantiomerically pure homoleptic rare-earth metal amidinate complexes [Ln{(S)-NEBA}3] {(S)-NEBA = (S,S)-N,N′-bis[1-(2-naphthyl)ethyl]benzamidinate; Ln = Y, Sm, Tb, Dy, Er, Yb, Lu} is reported. The luminescence and magnetic properties of some selected compounds were investigated.

    3. Spin Relaxation

      Teaching Ferrocenium How to Relax: A Systematic Study on Spin–Lattice Relaxation Processes in tert-Butyl-Substituted Ferrocenium Derivatives

      Matthias Reiners, Dirk Baabe, Peter Schweyen, Matthias Freytag, Peter G. Jones and Marc D. Walter

      Version of Record online: 12 OCT 2016 | DOI: 10.1002/ejic.201600873

      Thumbnail image of graphical abstract

      A series of sterically encumbered ferrocenium derivatives exhibit unusually slow paramagnetic relaxation on the 57Fe Mössbauer time scale. The trends established for the spin–spin and spin–lattice (Orbach and Raman) relaxation parameters correlate well with the observations from electron paramagnetic resonance (EPR) spectroscopy and solid-state magnetic susceptibility studies for these compounds.

    4. Valence Tautomers

      Oxidized Styrylruthenium–Ferrocene Conjugates: From Valence Localization to Valence Tautomerism

      Christopher Hassenrück, Philipp Mücke, Johanna Scheck, Serhiy Demeshko and Rainer F. Winter

      Version of Record online: 11 OCT 2016 | DOI: 10.1002/ejic.201600776

      Thumbnail image of graphical abstract

      The radical cations of the title complexes exists as two equilibrating valence tautomers in which the unipositive charge is either concentrated at the ferrocenyl site or delocalized over the styrylruthenium entity.

    5. Ferrocenylphosphanes

      Planar-Chiral Secondary Ferrocenylphosphanes

      Souvik Pandey, Menyhárt B. Sárosi, Peter Lönnecke and Evamarie Hey-Hawkins

      Version of Record online: 6 OCT 2016 | DOI: 10.1002/ejic.201600935

      Thumbnail image of graphical abstract

      An efficient way to obtain diastereomerically pure chiral secondary ferrocenylphosphane derivatives derived from Ugi's amine is described. The formation of amine–borane or phosphane–borane adducts was studied by 11B and 31P NMR spectroscopy. A theoretical study was performed to understand the tendency toward borane adduct formation.

  15. Communications

    1. CNC Pincer Ligands

      A Rigid CNC Pincer Ligand Acting as a Tripodal Cp Analogue

      Eva Jürgens and Doris Kunz

      Version of Record online: 6 OCT 2016 | DOI: 10.1002/ejic.201601008

      Thumbnail image of graphical abstract

      X-ray structure analysis reveals the unexpected facial coordination mode of a rigid CNC pincer ligand. The red title complex is obtained by reaction of the respective Li pincer complex with [Ru(NCCH3)3(Cp*)]PF6.

  16. Full Papers

    1. Ferrocenyl Ethers

      Multi-Ferrocenyl Aryl Ethers – Applying Nucleophilic Aromatic Substitution Reactions to Aryl Fluorides

      Marcus Korb and Heinrich Lang

      Version of Record online: 6 OCT 2016 | DOI: 10.1002/ejic.201600850

      Thumbnail image of graphical abstract

      The reaction of ferrocenol with aryl fluorides resulted in the formation of single- and up to penta-ferrocenyloxy-substituted benzenes, depending on the number of fluorine atoms in the starting material. Electrochemical investigations revealed separated redox events for each ferrocenyl group.

  17. Microreviews

    1. Ferrocenes

      Why is Ferrocene so Exceptional?

      Didier Astruc

      Version of Record online: 5 OCT 2016 | DOI: 10.1002/ejic.201600983

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      The most remarkable properties of ferrocene and its structure and chemistry are emphasized, from historical aspects to recent trends, in an overview justifying why it is such an exceptional tool in asymmetric catalysis, electron-transfer processes, sensing, molecular engineering, opto-electronics, materials science and medicine.

  18. Full Papers

    1. Sandwich Compounds

      Multiferrocenyl Cobalt-Based Sandwich Compounds

      Grzegorz Filipczyk, Steve W. Lehrich, Alexander Hildebrandt, Tobias Rüffer, Dieter Schaarschmidt, Marcus Korb and Heinrich Lang

      Version of Record online: 5 OCT 2016 | DOI: 10.1002/ejic.201600848

      Thumbnail image of graphical abstract

      Treatment of FcC≡C–C≡CFc with Co(η5-C5H5)(CO)2 afforded eleven multiferrocenyl sandwich complexes. The synthesis, characterization, and (spectro)electrochemistry are discussed.

    2. 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

      Thumbnail image of graphical abstract

      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.

  19. 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

      Thumbnail image of graphical abstract

      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.

  20. 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

      Thumbnail image of graphical abstract

      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. 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

      Thumbnail image of graphical abstract

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

    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

      Thumbnail image of graphical abstract

      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. 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

      Thumbnail image of graphical abstract

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

    5. 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

      Thumbnail image of graphical abstract

      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.

    6. 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

      Thumbnail image of graphical abstract

      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.

    7. 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

      Thumbnail image of graphical abstract

      [(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.

  21. 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

      Thumbnail image of graphical abstract

      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.

  22. Full Papers

    1. 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

      Thumbnail image of graphical abstract

      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.

    2. 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

      Thumbnail image of graphical abstract

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

    3. 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

      Thumbnail image of graphical abstract

      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.

  23. 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

      Thumbnail image of graphical abstract

      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. 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

      Thumbnail image of graphical abstract

      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.

  24. Full Papers

    1. 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

      Thumbnail image of graphical abstract

      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.

    2. 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

      Thumbnail image of graphical abstract

      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.

    3. 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

      Thumbnail image of graphical abstract

      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.

    4. 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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