European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 30

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


  1. 1 - 71
  1. Full Papers

    1. Reductants from Ascorbic Acid

      Mechanistic Complications Caused by Redox Equilibration: Ascorbate Reduction of a Ruthenium(III) Complex under Low Driving Force Conditions

      Olga Impert, Anna Katafias, Joanna Fenska, Marta Chrzanowska, Stanisław Koter, Carlos Dücker-Benfer and Rudi van Eldik

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/ejic.201600950

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      The reduction of cis-dichloridobispicolinatoruthenate(III) by l-ascorbic acid reveals evidence for three parallel reaction paths that turns out to be a result of the low driving force of the studied system.

    2. Catalytic Pd Pincer Complexes

      5,6- and 6,6-Membered Palladium(II) Pincer Complexes Based on Functionalized Carboxamides with Ancillary Sulfur and Nitrogen Donors

      Svetlana G. Churusova, Diana V. Aleksanyan, Andrei A. Vasil'ev, Yulia V. Nelyubina, Valentin V. Novikov, Alexander A. Pavlov, Gleb L. Denisov, Zinaida S. Klemenkova and Vladimir A. Kozlov

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/ejic.201601093

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      Multidentate ligands based on functionalized carboxamides with ancillary N or S donors readily undergo direct cyclopalladation to afford PdII pincer complexes with 5,6- or 6,6-membered fused metallocycles. The preliminary evaluation of the catalytic activities of the resulting palladocycles in the Suzuki cross-coupling allows the determination of the main structure–activity relationships.

    3. Iron Selenide Precursors

      Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr2)2N}2] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

      Nikolaos Levesanos, Wipula P. R. Liyanage, Eleftherios Ferentinos, Grigorios Raptopoulos, Patrina Paraskevopoulou, Yiannis Sanakis, Amitava Choudhury, Pericles Stavropoulos, Manashi Nath and Panayotis Kyritsis

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/ejic.201600833

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      The structural, spectroscopic, and electrochemical characterization of [Fe{(EPiPr2)2N}2] [E = S (1), Se (2)] is reported. Chemical vapor deposition (CVD) experiments with 2 afford iron selenides, including FeSe.

    4. Functionalization of Ammonia

      C–N Bond Coupling Reactions of Ammonia with Acetone Promoted by Iridium and Rhodium Complexes: Experimental and DFT Studies

      M. Pilar Betoré, Pilar García-Orduña, Fernando J. Lahoz, Miguel A. Casado, Víctor Polo and Luis A. Oro

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/ejic.201600925

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      Chloridorhodium and -iridium complexes react with ammonia in acetone to afford new species containing an amino/imino ligand formed by sequential C–N and C–C coupling, as confirmed by DFT methods.

    5. 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

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      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.

  2. 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

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      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.

  3. Full Papers

    1. Ferrocenylcatecholates

      Tin(IV) and Antimony(V) Complexes Bearing Catecholate Ligands Connected to Ferrocene – Syntheses, Molecular Structures, and Electrochemical Properties

      Svetlana V. Baryshnikova, Ekaterina V. Bellan, Andrey I. Poddel'sky, Maxim V. Arsenyev, Ivan V. Smolyaninov, Georgy K. Fukin, Alexander V. Piskunov, Nadezhda T. Berberova, Vladimir K. Cherkasov and Gleb A. Abakumov

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/ejic.201600885

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      A ferrocenyl-containing 3,5-di-tert-butylcatechol and its tin(IV) and antimony(V) derivatives are synthesized. The presence of the –CH=N–N=CH– group in the catecholato ligand results in the formation of stable complexes with anionic metal–catecholato moieties and hydraziniumylidene counterions and allows electronic interactions between the two redox-active parts of the molecule.

    2. Ti Oxo Catalysts

      A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

      Tamara A. Bazhenova, Nadezhda V. Kovaleva, Gennady V. Shilov, Galina N. Petrova and Denis A. Kuznetsov

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/ejic.201600804

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      A series of titanium(+4) catecholate complexes with different architectures has been synthesized and structurally characterized. The investigated compounds demonstrated excellent activity as catalysts for C2H2 [RIGHTWARDS ARROW] C2H4 conversion, representing a rare example of selective hydrogenation of acetylene catalyzed by a non-precious metal.

    3. Silver Coordination to π-Systems

      Synthesis and Molecular Structures of the Cationic Silver Complexes of the Polycondensed Aromatics Fluorene, Pseudorubrene, and Truxene

      Tobias Wombacher, Sabine Foro and Jörg J. Schneider

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/ejic.201600901

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      Coordination of silver(I) salts to the extended polycyclic aromatic hydrocarbon (PAH) frameworks of fluorene, truxene, and pseudorubrene (LPsrub) may occur on binding sites of local highest electron density. Clar's π-aromatic sextet rule allows the preferential coordination of AgI to these PAH molecules to be understood.

    4. Hypervalent Silicon Compounds

      Progress in the Synthesis and Bioactivity of Hexacoordinate Silicon(IV) Complexes

      Jens Henker, Julia Wirmer-Bartoschek, Lars Erik Bendel, Yonggang Xiang, Chen Fu, Klaus Harms, Harald Schwalbe and Eric Meggers

      Version of Record online: 21 OCT 2016 | DOI: 10.1002/ejic.201600953

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      (Arenediolato)bis(polypyridyl)silicon(IV) complexes were selectively functionalized through a bis-nitration/reduction/condensation protocol and investigated for their binding to DNA G-quadruplexes.

    5. Ti Imine Complexes

      Imines in the Titanium Coordination Sphere: η1-Imine Complexes as Sources of Azavinylidenes and Four-Membered Imine–Amido-N,N′ Chelates

      Florian Loose, Marc Schmidtmann, Wolfgang Saak and Rüdiger Beckhaus

      Version of Record online: 21 OCT 2016 | DOI: 10.1002/ejic.201600995

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      Octahedral (I) and trigonal-bipyramidal (II) η1-imine complexes of titanium were isolated by reactions of Schiff bases with titanium(IV) chloride and structurally characterized. By elimination of Me3SiCl from the corresponding trimethylsilylimines and titanium halides unexpected N–C coupling reactions forming new N,N′ chelates III via azavinylidenes IV occur.

    6. Distorted Porphyrins

      Optimal Size Matching and Minimal Distortion Energy: Implications for Natural Selection by the Macrocycle of the Iron Species in Heme

      Qiuhua Liu, Min Tang, Wennan Zeng, Xi Zhang, Jianxiu Wang and Zaichun Zhou

      Version of Record online: 21 OCT 2016 | DOI: 10.1002/ejic.201600883

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      The combination of a porphyrin and a metal is mainly based on optimal size matching to tune the electronic structure of the metal and to meet the need for minimal distortion energy. Crystal structures of model compounds are used to determine the core size parameters, and DFT computations are used to calculate distortion energies. Structure–energy correlations show a common principle in enzymes containing tetrapyrroles.

    7. Iron Hydride Catalysis

      Activation of CO2, CS2, and Dehydrogenation of Formic Acid Catalyzed by Iron(II) Hydride Complexes

      Lin Wang, Hongjian Sun, Zhenyu Zuo, Xiaoyan Li, Weiqin Xu, Robert Langer, Olaf Fuhr and Dieter Fenske

      Version of Record online: 21 OCT 2016 | DOI: 10.1002/ejic.201600642

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      Fluoroarylimine-stabilized iron(II) hydrides were used for the activation of CO2. Iron(II) formate was obtained either by CO2 insertion into the Fe–H bond or from the reaction of iron(II) hydride with formic acid. The dehydrogenation of formic acid was explored with iron hydrides as catalysts. An unexpected product was generated from the reaction of CS2, iron hydride, and an imine.

    8. Carbene precursors

      On Route to C4/C5 P-Bifunctional 1,3-Thiazole-Based Carbenes

      Imtiaz Begum, Gregor Schnakenburg and Rainer Streubel

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201600911

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      A PIII/PV-substituted N-heterocyclic carbene (NHC) precursor is synthesized from a PV-substituted thiazole-2-thione through a lithiation–phosphanylation sequences. The mixed substituted thiazole-2-thione is treated with elemental sulfur to afford a PV/PV homochalcogenide thiazole-2-thione, whereas the reaction with H2O2–urea adduct affords a PV/PV heterochalcogenide derivative.

    9. Indenyl Compounds

      Indenyl Compounds with Constrained Hapticity: The Effect of Strong Intramolecular Coordination

      Ondřej Mrózek, Jaromír Vinklárek, Zdeňka Růžičková and Jan Honzíček

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201601029

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      The unusual example of a low hapticity lock is reported for indenyl compounds with intramolecularly coordinated pyridine arms. The combined experimental and theoretical study reveals a high stability of η3:κN- and η3:κN,N-coordination compounds toward η3 to η5 haptotropic rearrangement.

    10. 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

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      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).

    11. Cytotoxic Complexes

      Synthesis and in vitro Toxicity of d-Glucose and d-Fructose Conjugated Curcumin–Ruthenium Complexes

      Michael Pröhl, Tanja Bus, Justyna A. Czaplewska, Anja Traeger, Michael Deicke, Henning Weiss, Wolfgang Weigand, Ulrich S. Schubert and Michael Gottschaldt

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201600801

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      Bis(demethoxy)curcumin (BDC) ligands conjugated with sugar moieties (d-fructose, d-glucose) by a triazol group reacted with Ru(bpy)2Cl2 to form the corresponding complexes. Cytotoxicity assays confirmed that sugar-decorated compounds showed reduction in cell viability for liver-cancerous cells HepG2, whereas the sugar-free complex showed increased toxicity for breast cancer cells MDA-MB-231.

    12. 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

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      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.

    13. Fluorescent Sensors

      An Off–On–Off Fluorescent Sensor for pH Windows Based on the 13aneN4–Zn2+ System

      Valeria Amendola, Greta Bergamaschi, Giacomo Dacarro, Franck Denat, Frederic Boschetti, Maria Nikolantonaki, Regis Gougeon, Giulia D'Alessio, Anne-Sophie Viaux, Lucie Bertheau, Stéphane Guyot, Nicolas Sok and Piersandro Pallavicini

      Version of Record online: 19 OCT 2016 | DOI: 10.1002/ejic.201600749

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      A 13aneN4 macrocycle functionalized with a fluorophore at a C atom of its backbone behaves as an off–on–off fluorescent pH sensor in the presence of Zn2+ ions, and the on window corresponds to the biologically relevant 6.5–7.5 pH range

    14. Supramolecular Chemistry

      Nonconventional Supramolecular Self-Assemblies of Zinc(II)–Salphen Building Blocks

      Thomas Groizard, Samia Kahlal, Vincent Dorcet, Thierry Roisnel, Christian Bruneau, Jean-François Halet and Rafael Gramage-Doria

      Version of Record online: 18 OCT 2016 | DOI: 10.1002/ejic.201600866

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      Weak interactions involving hydrogen bonding and unprecedented oxygen···oxygen interactions are responsible for the self-assembly of zinc(II)–salphen building blocks into dimeric supramolecular structures. Such an unexpected rearrangement is established unambiguously by a combination of experimental and theoretical studies.

    15. Donor–Acceptor Systems

      Dyads and Triads Based on Phenothiazine, Bis(terpyridine)ruthenium(II) Complexes, and Fullerene

      Kevin Barthelmes, Andreas Winter and Ulrich S. Schubert

      Version of Record online: 17 OCT 2016 | DOI: 10.1002/ejic.201600793

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      A series of bis(terpyridine) [bis(tpy)] ruthenium(II) complexes containing phenothiazine and fullerene moieties were prepared. The distance between both moieties was varied by different bridging units. The structures were analyzed regarding their photophysical and electrochemical properties and compared with reference complexes that do not contain the fullerene moiety.

    16. 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

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      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.

    17. 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

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      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.

    18. Iridium Blue Emitters

      Molecular Engineering of Iridium Blue Emitters Using Aryl N-Heterocyclic Carbene Ligands

      Sadig Aghazada, Aron J. Huckaba, Antonio Pertegas, Azin Babaei, Giulia Grancini, Iwan Zimmermann, Henk Bolink and Mohammad Khaja Nazeeruddin

      Version of Record online: 11 OCT 2016 | DOI: 10.1002/ejic.201600971

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      NHCs have been investigated as ligands in [Ir(dfppy)2L] complexes [dfppy = 2-(2′,4′-difluorophenyl)pyridine]. By using arylNHC ligands of different electron-accepting and -donating strengths, the energy levels of the celebrated [FIrPic] were destabilized while maintaining blue emission. Blue OLEDs incorporating these emitters show efficiencies up to 3.2 % and turn-on voltages as low as 2.7 V. [FIrPic] = Ir(dfppy)2pic; pic = 2-picolinate.

    19. Desulfurization

      Zinc-Substituted Polyoxotungstate@amino-MIL-101(Al) – An Efficient Catalyst for the Sustainable Desulfurization of Model and Real Diesels

      Diana Julião, Ana C. Gomes, Martyn Pillinger, Rita Valença, Jorge C. Ribeiro, Baltazar de Castro, Isabel S. Gonçalves, Luís Cunha Silva and Salete S. Balula

      Version of Record online: 11 OCT 2016 | DOI: 10.1002/ejic.201600442

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      Two different synthetic approaches are studied for the encapsulation of a zinc-substituted polyoxotungstate in an amino-functionalized metal–organic framework (MOF). A composite prepared by a one-pot method is an efficient, recyclable catalyst for the oxidative desulfurization of a model diesel with an ionic liquid as an extractant and H2O2 as an oxidant.

    20. Polyoxometalates

      Tuning the Selectivity and Reactivity of Metal-Substituted Polyoxometalates as Artificial Proteases by Varying the Nature of the Embedded Lewis Acid Metal Ion

      Annelies Sap, Leentje Van Tichelen, Anneleen Mortier, Paul Proost and Tatjana N. Parac-Vogt

      Version of Record online: 11 OCT 2016 | DOI: 10.1002/ejic.201601098

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      The nature of the embedded Lewis acid metal ion in metal-substituted polyoxometalates plays a key role in directing the selectivity of cleavage during the hydrolysis of cytochrome c.

  4. Communications

    1. Metal–Organic Cages

      Capturing Hydrophobic Trifluoroiodomethane in Water into an M4L6 Cage

      Chandan Giri, Prasit Kumar Sahoo, Kari Rissanen and Prasenjit Mal

      Version of Record online: 10 OCT 2016 | DOI: 10.1002/ejic.201600990

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      Under ambient conditions, a hydrophobic effect is the key factor for the near-quantitative encapsulation of gaseous trifluoroiodomethane (CF3I) by a metal–organic supramolecular anionic cage in water.

  5. Microreviews

    1. Silver Sulfide Nanostructures

      Universal Approach to the Synthesis of Silver Sulfide in the Forms of Nanopowders, Quantum Dots, Core-Shell Nanoparticles, and Heteronanostructures

      Stanislav I. Sadovnikov and Aleksandr I. Gusev

      Version of Record online: 7 OCT 2016 | DOI: 10.1002/ejic.201600881

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      All forms of nanostructured silver sulfide can be prepared by a universal, simple, and environmentally friendly method based on hydrochemical bath deposition.

  6. Full Papers

    1. Magnetic Mn Monomers

      A Facile Synthetic Route to a Family of MnIII Monomers and Their Structural, Magnetic and Spectroscopic Studies

      Edel Houton, Brian Kelly, Sergio Sanz, Eric J. L. McInnes, David Collison, Euan K. Brechin, Anne-Laure Barra, Alan G. Ryder and Leigh F. Jones

      Version of Record online: 7 OCT 2016 | DOI: 10.1002/ejic.201601124

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      We report a rapid and facile route to the synthesis of a family of MnIII monomers of general formula [MnIIIF3(H2O)(L1–6)]. Magnetic susceptibility and magnetisation experiments along with multi-frequency/high-field EPR spectroscopy were employed to elucidate anisotropic D tensors. The terminal Mn–F vibrational stretches have been probed using Raman spectroscopy.

    2. 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

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      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.

  7. 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

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      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.

  8. 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

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      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.

  9. Communications

    1. Photosensors

      CLICK 'n' Sleep: Light-Switch Behavior of Triazole-Containing Tris(bipyridyl)ruthenium Complexes

      Markus Braumüller, Magdalena Staniszewska, Julien Guthmuller and Sven Rau

      Version of Record online: 6 OCT 2016 | DOI: 10.1002/ejic.201600964

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      The effect of a triazole moiety on the luminescence intensity of corresponding ruthenium complexes is discussed. The presence of a triazole moiety leads to enhanced sensitivity of the emissive properties towards solvent properties or apparent proton concentration. The increase of the water content always leads to a significantly lower emission intensity at high water contents. Based on theoretical investigations light-driven charge transfer involving the triazole is proposed as rational explanation. This study shows a very important limitation for the application of CLICK chemistry for the implementation of such ruthenium complexes for water splitting catalysis or sensing.

  10. Full Papers

    1. Molybdenum Clusters

      Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study

      Tomás F. Beltrán, Vicent S. Safont and Rosa Llusar

      Version of Record online: 5 OCT 2016 | DOI: 10.1002/ejic.201600586

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      Gas-phase fragmentation of the trimetallic aminophosphine Mo3S4 cluster occurs through the sequential loss of three HX molecules to afford unsaturated molybdenum/imine Mo=NH species. DFT calculations show that mechanism A is energetically favored.

  11. 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.

  12. 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

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      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. CO-RMs

      Photoactivated Functionizable Tetracarbonyl(phenylpyridine)manganese(I) Complexes as CO-Releasing Molecules: A Direct Suzuki–Miyaura Cross-Coupling on a Thermally Stable CO-RM

      Jonathan S. Ward, Joshua T. W. Bray, Benjamin J. Aucott, Conrad Wagner, Natalie E. Pridmore, Adrian C. Whitwood, James W. B. Moir, Jason M. Lynam and Ian J. S. Fairlamb

      Version of Record online: 5 OCT 2016 | DOI: 10.1002/ejic.201600775

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      Photoactivated CO-releasing molecules have been traditionally irradiated using a TLC lamp. In this paper the use of LEDs close to the sample is reported. This gives efficient CO release compared to a TLC lamp. The complex shown releases CO efficiently and can be functionalised further with a Suzuki reaction.

    3. Zinc Porphyrins

      Synthesis, Electronic Spectroscopy, Cyclic Voltammetry, Photophysics, Electrical Properties and X-ray Molecular Structures of meso-{Tetrakis[4-(benzoyloxy)phenyl]porphyrinato}zinc(II) Complexes with Aza Ligands

      Soumaya Nasri, Imen Zahou, Ilona Turowska-Tyrk, Thierry Roisnel, Fredérique Loiseau, Eric Saint-Amant and Habib Nasri

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/ejic.201600575

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      The synthesis of the new meso-porphyrin tetrakis[4-(benzoyloxy)phenyl]porphyrin (H2TPBP), the [Zn(TPBP)] starting material, and the 4-diazabicyclo[2.2.2]octane, pyrazine, 4,4′-bipyridine, 4,4′-diaminodiphenylmethane, and 4-cyanopyridine zinc(II) complexes with H2TPBP are described. These species are characterized by spectroscopy, cyclic voltammetry, and single-crystal X-ray diffractometry.

    4. Magnetic Ln Clusters

      Two Discrete Ln12 Shelf-Shaped Clusters: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation

      Yi-Ming Li, Wei-Wei Kuang, Li-Li Zhu, Yun Xu and Pei-Pei Yang

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/ejic.201600556

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      Two discrete Ln12 clusters with four-layer triangular shelf-shaped structures have been constructed by using 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol as a ligand. The Gd12 cluster acts as a cryogenic magnetic refrigerant with –ΔSm = 30.99 J kg–1 K–1 for H = 7 T at T = 4 K, whereas the Dy12 cluster exhibits weak slow magnetic relaxation.

    5. Silyl–Substituted Carbanions

      Unexpected Formation and Crystal Structure of the Highly Symmetric Carbanion [C(SiCl3)3]

      Uwe Böhme, Maik Gerwig, Franziska Gründler, Erica Brendler and Edwin Kroke

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/ejic.201600763

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      Disproportionation of Si2Cl6 in the presence of [nBu4N]Cl in halogenated solvents yields the compound [nBu4N][C(SiCl3)3]. X-ray structure analysis proves the existence of a highly symmetric carbanion, which is stabilized by three trichlorosilyl groups.

    6. Energetic MOFs

      A 3D CuII-Based Energetic MOF: Synthesis, Structure, and Energetic Performance

      Qi Yang, Xiaxia Song, Guowei Zhao, Guoli Yang, Langlei Yang, Qing Wei, Gang Xie, Sanping Chen and Shengli Gao

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/ejic.201600814

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      A new energetic MOF, [Cu2(to)(dns)(H2O)]n (1; H2to = 1,2,4-triazol-5-one, H2dns = 3,5-dinitrosalicylic acid), has been synthesized and characterized. The superior density, thermostability, insensitivity, and detonation properties of 1 might be due to the coordination of the nitro group as well as its compact 3D framework.

    7. 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.

    8. 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.

    9. 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.

    10. 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.

    11. 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.

    12. 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.

  13. 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.

  14. 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.

    3. 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.

    4. 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.

    5. 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.

    6. 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.

    7. 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.

    8. 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.

    9. 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.

    10. 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.

  15. 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.

  16. 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

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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.

    2. 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.

    3. 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

    4. 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.

  17. 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. 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.

  18. 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

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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.

    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

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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.

    3. 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.

    4. 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.

    5. 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.

    6. 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

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      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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