European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 18

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.942

ISI Journal Citation Reports © Ranking: 2014: 8/44 (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 - 72
  1. Full Papers

    1. Solid-State Transformations

      Probing Solid-State Breathing and Structural Transformations in a Series of Silver(I) Porous Coordination Polymers

      Witold M. Bloch and Christopher J. Sumby

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500647

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      Herein two new examples of an AgI porous coordination polymer that display solid-state breathing are reported. Additional transformations of these materials to non-porous 2D and 3D structures are investigated.

    2. Luminescent Silicate Nanoparticles

      Insight into CaMgSi2O6:Eu2+,Mn2+,Dy3+ Nanoprobes: Influence of Chemical Composition and Crystallinity on Persistent Red Luminescence

      Céline Rosticher, Bruno Viana, Guillaume Laurent, Patrick Le Griel and Corinne Chanéac

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500257

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      Nanoparticles of CaxMgySi2O6 doped with Eu2+, Mn2+, and Dy3+ have been prepared with a high production yield by a sol–gel method inspired by the Stöber process with the aim of improving the luminescent properties and decreasing the size of silicate-based nanoprobes. Such a study is essential to promote the emergence of these nanoprobes in the field of optical imaging.

    3. Magnetic Nanohybrids

      Synthesis of Stable Magnetic Polyaniline Nanohybrids with Pyrene as a Cross-Linker for Simultaneous Diagnosis by Magnetic Resonance Imaging and Photothermal Therapy

      Taeksu Lee, Doyeon Bang, Yeonji Park, Young Wook Chang, Byunghoon Kang, Jinyoung Kim, Jin-Suck Suh, Yong-Min Huh and Seungjoo Haam

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500283

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      Magnetic polyaniline nanoparticles (MPANs) are synthesized and show evenly mixed magnetic nanoparticles (MNPs) and polyaniline (PANI) with increased colloidal stability owing to the hydrophobic and π–π interactions between the PANI and pyrene molecules.

    4. Metal Chelating Agents

      Mercury Complexes with Tripodal Pseudopeptides Derived from D-Penicillamine Favour a HgS3 Coordination

      Anne-Solène Jullien, Christelle Gateau, Colette Lebrun and Pascale Delangle

      Article first published online: 1 JUL 2015 | DOI: 10.1002/ejic.201500421

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      Tripodal pseudopeptides anchored on a nitrilotriacetic chemical scaffold and extended with three D-penicillamine units stabilize the unusual HgS3 coordination over a large pH range in a hindered coordination environment.

    5. Sensors

      Off–On, Ratiometric, and On–Off Fluorescence Responses of Thioether-Linked Bisquinolines toward Hg2+ and Fe3+ Ions

      Yuji Mikata, Kaori Nakanishi, Fumie Nakagaki, Asako Kizu and Hideo Konno

      Article first published online: 1 JUL 2015 | DOI: 10.1002/ejic.201500220

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      The selectivity of fluorescent bisquinoline derivatives with thioether linkers for Hg2+ ions is improved by 8-quinolylmethyl tethering and increasing the number of sulfur atoms through the extension of the linker.

  2. Microreviews

    1. Mn Oxidation Catalysis

      Redox-State Dependent Ligand Exchange in Manganese-Based Oxidation Catalysis

      Shaghayegh Abdolahzadeh, Johannes W. de Boer and Wesley R. Browne

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500134

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      The role played by Mn-based complexes in controlling reactive oxygen species and in the water oxidation complex of photosystem II has inspired the design of catalysts for chemical processes such as the oxidation of organic substrates and bleaching applications. Here, the redox and pH dependence of the coordination chemistry of Mn complexes applied in oxidations with H2O2 is reviewed.

  3. Full Papers

    1. Ti and V Coordination Chemistry

      Synthesis and Characterisation of Various Diester and Triester Adducts of TiCl4

      Ben J. Blackburn, Jared H. Crane, Caroline E. Knapp, Peter Marchand, David Pugh, Ivan P. Parkin and Claire J. Carmalt

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500471

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      The synthesis of novel titanium complexes with triesters and diesters was achieved using Schlenk techniques for the purpose of ellucidating the previously unknown mechanisms at play during the industrially used Chloride Process.

    2. ZnO Thin Films

      Aerosol-Assisted Chemical-Vapour Deposition of Zinc Oxide from Single-Source β-Iminoesterate Precursors

      Joe A. Manzi, Caroline E. Knapp, Ivan P. Parkin and Claire J. Carmalt

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500416

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      The synthesis, isolation and characterisation of zinc β-iminoesterate precursors of the type [Zn(CH3C(NR)CHC(O)OCH2CH3)] are described, as well as their use for the first time in the aerosol-assisted chemical-vapour deposition (AACVD) of ZnO thin films at 450 °C. Results show that changing the R group on the N moiety of the precursors has a significant effect on carbon contamination in the films.

    3. Thermoelectric Nitride Materials

      Origin of Projected Excellent Thermoelectric Transport Properties in d0-Electron AMN2 (A = Sr or Ba; M = Ti, Zr, Hf) Layered Complex Metal Nitrides

      Isao Ohkubo and Takao Mori

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500350

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      d0-Electron layered complex metal nitrides (AMN2) are expected to exhibit excellent thermoelectric properties that arise from their electronic structures and small effective masses.

  4. Microreviews

    1. Phosphovanadomolybdates

      Mo-V-Phosphoric Heteropoly Acids and Their Salts: Aqueous Solution Preparation – Challenges and Perspectives

      Victor F. Odyakov, Elena G. Zhizhina, Yulia A. Rodikova and Leonid L. Gogin

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500359

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      Preliminary V2O5 activation by addition of hydrogen peroxide H2O2 allows one to obtain vanadium-containing heteropoly acid (HPA) solutions directly from V2O5, MoO3, and H3PO4 without extraneous components. Such a synthetic pathway, named a peroxide route, offers a promising ecological method for preparing valuable Mo-V-P HPAs in short reaction times on a large scale.

  5. Full Papers

    1. Dye-Sensitized Solar Cells

      Dye-Sensitized Solar Cells with Biferrocenyl Antennae Having Quinoxaline Spacers

      Ratna Chauhan, Mohammad Shahid, Manoj Trivedi, Dinesh P. Amalnerkar and Abhinav Kumar

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500488

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      Four biferrocenyl quinoxaline derivatives are synthesized and their light-harvesting properties are explored. Dyes having Cl, NO2, and COOH substituents on the spacers show the best photovoltaic performance, and this may be attributed to their ability to accept high loadings of the dye on the TiO2 surface and the long lifetime of electrons in the TiO2 conduction band.

    2. Catalase Mimics

      High Turnover Catalase Activity of a Mixed-Valence MnIIMnIII Complex with Terminal Carboxylate Donors

      Reena Singh, Matti Haukka, Christine J. McKenzie and Ebbe Nordlander

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500468

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      The neutral dimanganese(II,III) complex [Mn2(BCPMP)(OAc)2] (1) has been synthesized and characterized. Complex 1 was found to be an effective catalyst for the disproportionation of H2O2 with high catalytic rate and a turnover number of 7500, the highest turnover reported to date for a catalase mimic.

    3. Phase Transition Materials

      Reversible Phase Transitions and Dielectric Properties in [(CH3)4P]2[Cr2O7] and ­[Et4P]2[Cr3O10]

      Ping-Ping Shi, Qiong Ye, Hui-Ting Wang, Qiang Li, Da-Wei Fu and Yi Zhang

      Article first published online: 25 JUN 2015 | DOI: 10.1002/ejic.201500409

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      Tetramethylphosphonium dichromate and tetraethylphosphonium trichromate undergo reversible phase transitions accompanied by peak- and step-like dielectric anomalies, respectively. The crystal structures and results of the rotational potential energy calculations indicate that the phase-transition mechanisms are closely related to the dynamics of the dichromate and trichromate anions.

  6. Short Communications

    1. Heterobimetallic Polycarbene Complexes

      Trinuclear Heterobimetallic Complexes by Stepwise Metalation of a Macrocyclic Tetraimidazolium Salt

      Christian Schulte to Brinke and F. Ekkehardt Hahn

      Article first published online: 25 JUN 2015 | DOI: 10.1002/ejic.201500519

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      The selective stepwise metalation of a rigid macrocyclic tetraimidazolium salt gives rise to trinuclear heterobimetallic tetracarbene complexes (AuI/RhIII2, AuI/IrIII2, AuI/RuII2) with M···M distances of less than 5.5 Å in the solid state.

  7. Full Papers

    1. Near-Infrared Dyes

      Azadipyrromethene-Based Near-Infrared Dyes: Effect of Thienylethynyl Substitution at the Distal and Proximal Phenyl Groups

      Cassie M. Daddario, Qi Han, Matthias Zeller and Geneviève Sauvé

      Article first published online: 25 JUN 2015 | DOI: 10.1002/ejic.201500348

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      Azadipyrromethene ligands substituted with thienylethynyl substituents at the distal or proximal phenyl groups were synthesized and coordinated with BF2+ and ZnII. Thienylethynyl substitutions redshift the absorption spectra of the dyes, with a larger shift for proximal substitution. Substitutions also stabilize the anions, and the placement of the thienylethynyl groups do not affect the reduction potentials.

    2. Nitrato Coordination Modes

      A Range of Nitrato Coordination Modes in NiII Complexes with the Versatile Ligand 1,8-Bis(2-pyridyl)-3,6-dithiaoctane: Structural, Spectroscopic, Electrochemical, and Theoretical Studies

      Vanessa Ramírez-Delgado, Luis Felipe Hernández-Ayala, Juan Carlos García-Ramos, Marcos Flores-Alamo, Rodrigo Galindo-Murillo, Lena Ruiz-Azuara and Luis Ortiz-Frade

      Article first published online: 25 JUN 2015 | DOI: 10.1002/ejic.201500335

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      In this work we report a series of complexes of nickel with the ligand 1,8-bis(2-pyridyl)-3,6-dithiaoctane (pdto) and NO3 moieties coordinated or as counterion, with different electrochemical and spectroscopic responses. Theoretical studies were carried out to explain these changes.

    3. Layered Borates

      Ba2B6O11, a Member of the BaO-B2O3 Family, Featuring a Layer Framework

      Lili Liu, Yun Yang, Xiaoyu Dong, Chen Lei, Shujuan Han and Shilie Pan

      Article first published online: 24 JUN 2015 | DOI: 10.1002/ejic.201500399

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      Ba2B6O11, a new centrosymmetric barium borate, features a layered structure and a wide transmission range from 240 to 2600 nm.

  8. Short Communications

    1. Glycerodendrimers

      Platinum Nanoparticles Stabilized by Glycerodendrimers: Synthesis and Application to the Hydrogenation of α,β-Unsaturated Ketones under Mild Conditions

      Bérengère Menot, Lionel Salmon and Sandrine Bouquillon

      Article first published online: 24 JUN 2015 | DOI: 10.1002/ejic.201500530

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      Pt nanoparticles are stabilized by glycerodendrimers (GD) and used (and recycled) for the reduction of α,β-unsaturated ketones to saturated ketones at room temperature in water under H2 (101.3 kPa).

  9. Full Papers

    1. Bimodal MRI Agents

      Magnetofluorescent Nanoaggregates Incorporating Terbium(III) Complexes as Potential Bimodal Agents for Magnetic Resonance and Optical Imaging

      Michael Harris, Sophie Carron, Luce Vander Elst, Sophie Laurent and Tatjana N. Parac-Vogt

      Article first published online: 23 JUN 2015 | DOI: 10.1002/ejic.201500310

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      Magnetofluorescent nanoaggregates incorporating amphiphilic terbium(III) complexes are created and their potential as bimodal agents for magnetic resonance and optical imaging are examined.

    2. Spin Crossover

      Spin-Crossover Nano- and Micrometric Rod-Shaped Particles Synthesized in Homogeneous Acid Media

      Haonan Peng, Gábor Molnár, Lionel Salmon and Azzedine Bousseksou

      Article first published online: 23 JUN 2015 | DOI: 10.1002/ejic.201500486

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      Various sizes of spin-crossover (SCO) nano- and micrometric rod-shaped particles have been synthesized in homogeneous acid media. The complete characterization of the samples revealed a correlation between the size of the particles and their composition. The SCO properties were investigated by optical, magnetic, and Mössbauer measurements.

  10. Short Communications

    1. Frustrated Lewis Pair Adducts

      Extremely Facile Transformations of Tris(3,5-dimethylpyrazolyl)borate: a Bidentate Nitrogen Ligand and a C2-Chiral Cation

      Marzieh Daryanavard, David Armstrong, Alan J. Lough and Ulrich Fekl

      Article first published online: 23 JUN 2015 | DOI: 10.1002/ejic.201500424

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      Although aryldiazonium cations have been known for a very long time, they are still good for surprises. Aryldiazonium cations ArN2+ react with hydridotris(3,5-dimethylpyrazolyl)borate (commonly used as a ligand) to remove a hydride and to form short-lived intermediate tris(3,5-dimethylpyrazolyl)borane, which is trapped as the acetone adduct. If 2 equiv. of ArN2+ are used, 3,5-dimethylpyrazolate will additionally be abstracted, followed by acetone trapping.

  11. Full Papers

    1. Osmium Phosphors

      Quantum Chemical Investigation on Phosphine-Functionalized Charge-Neutral Osmium(II) Complexes Bearing Bidentate/Tetradentate Pyridylpyrazolate-Based Ligands

      Yuqi Liu, Godefroid Gahungu, Xiaobo Sun, Ying Wang and Zhijian Wu

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500329

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      A series of charge-neutral OsII complexes with bidentate/tetradentate pyridylpyrazolate-based ligands are investigated by changing the monodentate PR3 ligands. DFT and time-dependent DFT calculations show that the PR3 ligand plays an important role in controlling the photophysical and phosphorescence properties of these OsII complexes.

    2. Coordination Polymers

      Syntheses, Structures, and Characteristics of Six Coordination Polymers Based on 1,4-Bis(imidazol-1-yl)benzene and Isophthalates Containing Coordination-Inert Substituents

      Xiaoju Li, Yanqing Su, Xinxiong Li, Guangchao Ma and Qidan Ling

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500281

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      Six metal-organic coordination polymers have been constructed from 5-hydroxyisophthalate or 5-methoxyisophthalate and rigid 1,4-bis(imidazol-1-yl)benzene. The coordination-inert hydroxy and methoxy substituents of 5-substituted isophthalates and the directional hydrogen bonds exerted important effects on the structures and properties of the coordination polymers.

    3. Oxidovanadium Complexes

      Crystal Structure, Antioxidant Properties and Characteristics in Aqueous Solutions of the Oxidovanadium(IV) Complex [VO(IDA)phen]·2H2O

      Joanna Pranczk, Dagmara Jacewicz, Dariusz Wyrzykowski, Andrzej Wojtczak, Aleksandra Tesmar and Lech Chmurzyński

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500272

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      The crystal structure of the oxidovanadium(IV) complex [VO(IDA)(phen)]·2H2O (IDA = iminodiacetate, phen = 1,10-phenanthroline) was determined. Potentiometric titrations and kinetic measurements based on stopped-flow methods allowed the stability of the complex to be determined in aqueous solution. The antioxidant activity of VO(IDA)phen towards superoxide and organic radicals was investigated.

    4. Tungstenvanadates

      A Keggin-Type Structure Expanded by an Eight-Membered Ring of Alternating Edge-Sharing VO5 and VO6 Polyhedra: Solvothermal Synthesis, Crystal Structure, and Magnetic Properties

      Maren Rasmussen, Christian Näther, Jan van Leusen, Paul Kögerler and Wolfgang Bensch

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500286

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      A mixed-valent polyoxidotungstovanadate featuring a central Keggin fragment encapsulated by an eight-membered ring consisting of edge-sharing VO5 and VO6 polyhedra was solvothermally synthesized at pH ≈ 12.

    5. Porous Metalorganic Frameworks

      Synthesis, Characterization, Stability, and Gas Adsorption Characteristics of a Highly Stable Zirconium Mesaconate Framework Material

      Mostakim SK, Soumya Bhowal and Shyam Biswas

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500374

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      The modulated synthesis, complete characterization, thermal and chemical stability properties, as well as the gas adsorption behavior of a new ZrIV mesaconate material are presented.

    6. Cooperative Phenomena

      Determining the Electronic Structure of a Series of [(phen)3M]0 (M = Ti, V, Mo) and [(pdi)2M]n+ (M = Cr, Mo) Complexes: Coordination of Neutral Ligands vs. π-Radical Anions

      Mei Wang, Thomas Weyhermüller and Karl Wieghardt

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500420

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      The appropriate oxidation levels of the tridentate ligands pyridine-2,6-diimine (pdi) and 2,9-dimethyl-1,10-phenanthroline (Mephen) as neutral species, monoanion π-radical and dianion in “low valent” octahedral complexes [M(Mephen)3]0 (M = Ti, V, Cr, Mo) and [Mo(pdi)2]n (n = 0,1+) have been experimentally determined by X-ray crystallography and by UV/Vis and EPR spectroscopy.

    7. Redox Mediators in DSSCs

      A Bis(tridentate)cobalt Polypyridine Complex as Mediator in Dye-Sensitized Solar Cells

      Andreas K. C. Mengel, Woohyung Cho, Aaron Breivogel, Kookheon Char, Yong Soo Kang and Katja Heinze

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500252

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      The depicted Co3+/2+ redox shuttle increases the short-circuit photocurrent density ISC relative to that of the standard I3/I mediator in dye-sensitized solar cells with Ru sensitizers. The higher ISC values and electron recombination lifetimes are ascribed to the high energy of the π* orbitals of the polypyridine ligands of the mediator, which retard back electron transfer from TiO2 to the Co3+ species.

    8. Nanophosphors

      Uniform Poly(acrylic acid)-Functionalized Lanthanide-Doped LaVO4 Nanophosphors with High Colloidal Stability and Biocompatibility

      Nuria O. Nuñez, Paola Zambrano, Jorge García-Sevillano, Eugenio Cantelar, Sara Rivera-Fernández, Jesús M. de la Fuente and Manuel Ocaña

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500265

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      Uniform lanthanide-doped LaVO4 nanospheres functionalized with poly(acrylic acid) are synthesized with a controllable size by a one-pot procedure. As these nanoparticles present strong red (Eu) or near-infrared (Nd) luminescence, are nontoxic for cells, and show high colloidal stability in physiological buffer, they are good candidates as optical biomarkers for in vitro applications.

    9. Phosphorus/Arsenic Homology

      Stepwise Synthesis of Siloxane-Substituted Oligoarsanes and Structural Investigation of Alkaline Earth Metal Derivatives

      Christian Clobes, Paul Jerabek, Isabell Nußbruch, Gernot Frenking and Carsten von Hänisch

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500279

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      A set of different arsane compounds based on siloxanes were synthesized and compared with their phosphorus analogues. After oxidative coupling of the cyclic compounds (HESiiPr2)2O, different product types were obtained for E = P and E = As. The courses of the different reactions are investigated in experimental and quantum chemical terms to explain the different outcomes for P and As.

    10. Cyclometalation of Phosphanes

      Cyclometalation of Phosphanes at Iridium(I): Interplay with Intramolecular Reductive Elimination Induced by the Strong π-Acceptor Ligands CO and NO+

      Hans-Christian Böttcher, Merlin Junk, Peter Mayer and Wolfgang Beck

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500363

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      The synthesis and crystal structure of the cyclometalated unsaturated complex [IrCl(H)(PtBu2C6H42P,C)(PtBu2Ph)] (2) is reported. Whereas 2 is quickly formed by oxidative addition of one PtBu2Ph ligand, contrarily, also a facile inversion of the cyclometalation with simultaneous reductive elimination in reactions with strong π-acceptor ligands such as CO or NO+ was observed.

    11. Aminodisilanes

      Synthesis, Characterization, and Thermal Properties of Chlorine-Containing 1,1,2,2-Tetraaminodisilanes and Their Potential as Chemical Vapor Deposition Precursors for Silicon Nitride Films

      Liyong Du, Wenxiang Chu, Hongyan Miao, Dawei Wang, Chongying Xu and Yuqiang Ding

      Article first published online: 18 JUN 2015 | DOI: 10.1002/ejic.201500493

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      The aminodisilanes Cl(RR′N)2Si–Si(NRR′)2Cl (R = tBu and R′ = H for 1, R = R′ = nPr for 2, R = R′ = allyl for 3) are synthesized and characterized. As they are potential chemical vapor deposition (CVD) precursors for silicon nitride (SiNx) films, their thermal properties including stability, volatility, transport behavior, and vapor pressure are evaluated by thermogravimetric analysis (TGA).

  12. Microreviews

    1. Artificial Metalloenzymes

      Latest Developments in Metalloenzyme Design and Repurposing

      Tillmann Heinisch and Thomas R. Ward

      Article first published online: 18 JUN 2015 | DOI: 10.1002/ejic.201500408

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      Artificial metalloenzymes (AMEs) combine homogeneous catalysis with enzymatic catalysis. In this microreview the authors describe recent developments in this fascinating field, ranging from artificial zinc hydrolases, metathesases, new heme protein reactions to light-driven redox reactions and enzyme models.

  13. Full Papers

    1. Terminal Ligand Effects

      Cyclometalated Diruthenium Complexes Bridged by 3,3′,5,5′-Tetra(pyrid-2-yl)biphenyl: Tuning of Electronic Properties and Intervalence Charge Transfer by Terminal Ligand Effects

      Wen-Wen Yang, Jiang-Yang Shao and Yu-Wu Zhong

      Article first published online: 16 JUN 2015 | DOI: 10.1002/ejic.201500498

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      Three symmetric and three nonsymmetric cyclometalated diruthenium complexes bridged by 3,3′,5,5′-tetra(pyrid-2-yl)biphenyl have been prepared and studied. The electronic properties and intervalence charge transfer (IVCT) transitions can be effectively tuned by terminal ligand effects. DFT and TDDFT calculations give useful information on the spin density distributions and IVCT transitions.

    2. Salts for Li-Ion Batteries

      Synthesis, Spectroscopic Characterization, Crystal Structures, Energetics, and Thermal Stabilities of Li[AlX4] (X = Cl, Br): Investigation and Performance of Their Electrolyte Solutions

      Franziska Scholz, Wiebke Unkrig, Philipp Eiden, Michael A. Schmidt, Arnd Garsuch and Ingo Krossing

      Article first published online: 16 JUN 2015 | DOI: 10.1002/ejic.201500254

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      Lithium salts of bromo- and chloroaluminates were tested and fully characterized for application as electrolytes for lithium-ion and -sulfur batteries in conventionally used solvents, as well as in o-difluorobenzene as a possible alternative. The lattice enthalpies of these salts were also investigated.

    3. Oxygenation

      Synthesis of an Iridium Peroxido Complex and Its Reactivity Towards Brønsted Acids

      Hanna Baumgarth, Thomas Braun, Beatrice Braun, Reik Laubenstein and Roy Herrmann

      Article first published online: 16 JUN 2015 | DOI: 10.1002/ejic.201500384

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      The iridium peroxido complex trans-[Ir(4-C5F4N)(O2)(CNtBu)(PiPr3)2] was synthesized by treatment of the iridium(I) complex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2] with O2 in the presence of [FeCp2]PF6. The peroxido complex reacts with CF3COOH to give H2O2 and the complex cis-[Ir(4-C5F4N)(CF3COO)2(CNtBu)(H2O)(PiPr3)].

    4. Multimodal Bioprobes

      Water-Soluble, Monodisperse, Lanthanide-Doped Y(Gd)VO4 Nanocrystals as Promising Multimodal Bioprobe

      Cailing Chen, Chunguang Li, Tao Li, Jianhua Liu, He Huang, Tianyu Bai, Zhaorui Wang, Zhan Shi and Shouhua Feng

      Article first published online: 15 JUN 2015 | DOI: 10.1002/ejic.201500212

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      Monodisperse, water-dispersible, Ln3+-doped YVO4 nanocrystals have been synthesized by a microwave-assisted hydrothermal method. GdCl3 gradually replaced YCl3·6H2O from 0 to 100 % to yield GdVO4:Ln3+ nanocrystals. Y(Gd)VO4:Ln3+ nanocrystals have potential in 3D displays and fluorescent/magnetic/CT bio-imaging applications due to their excellent properties.

    5. NHC Complexes

      NHC-Stabilized Bis(trimethylsilyl)phosphido Complexes of PdII and NiII

      Masoomeh Madadi, Bahareh Khalili Najafabadi, Mahmood Azizpoor Fard and John F. Corrigan

      Article first published online: 15 JUN 2015 | DOI: 10.1002/ejic.201500491

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      N-Heterocyclic carbenes are employed to stabilize NiII and PdII metal centres containing bis(trimethylsilyl)phosphido ligands, including the square-planar complex [PdI(iPr2-bimy)2{P(SiMe3)2}] (2) illustrated (bimy = benzimidazole-2-ylidene).

    6. Thiocyanato Coordination Polymers

      Thiocyanato Coordination Polymers with Isomeric Coordination Networks – Synthesis, Structures, and Magnetic Properties

      Julia Werner, Tomče Runčevski, Robert Dinnebier, Stefan G. Ebbinghaus, Stefan Suckert and Christian Näther

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500473

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      Thiocyanato coordination polymers of composition M(NCS)2(4-acetylpyridine)2 (M = Mn, Fe, and Ni) are prepared, and their magnetic properties are investigated. Depending on the synthesis conditions and the nature of the metal cation, compounds with 1D or 2D coordination networks are obtained.

    7. Guanidate Complexes

      Ionic and Neutral Half-Sandwich Guanidinatoruthenium(II) Complexes and Their Solution Behavior

      Ram Kishan, Robin Kumar, Sambath Baskaran, Chinnappan Sivasankar and Natesan Thirupathi

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500395

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      The guanidinate ligand in 2 adopts the syn-anti conformation in the solid state whereas in solution a mixture of syn-anti, syn-syn, anti-syn, and anti-anti conformations are observed, as detected by VT 31P{1H} NMR spectroscopy.

    8. Pincer-Type NHC Complexes

      Synthesis, Characterization, Crystal Structures, and Catalytic C–C Coupling and Hydrosilylation Reactions of Palladium(II) Complexes Derived from CNC Pincer-Type N-Heterocyclic Carbenes

      Rosenani A. Haque, Patrick O. Asekunowo, Srinivasa Budagumpi and Linjun Shao

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500393

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      A series of pincer-type Pd complexes are synthesized and their C–C and C–Si bond-forming properties are evaluated.

    9. Hydrogenase Mimics

      You have full text access to this OnlineOpen article
      N-Derivatives of peri-Substituted Dichalcogenide [FeFe]-Hydrogenase Mimics: Towards Photocatalytic Dyads for Hydrogen Production

      Carlotta Figliola, Louise Male, Sarah L. Horswell and Richard S. Grainger

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500355

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      peri-Substituted naphthalenedithiolate and diselenolate-based mimics of [FeFe]-hydrogenase, appended at the 2-position with basic amine and imine functionalities, are electrocatalysts for the conversion of protons to diatomic hydrogen. The synthesis of a molecular dyad, consisting of a zinc tetraphenylporphyrin photosensitizer covalently linked via an amine in close proximity to the catalytically active site, is also reported.

    10. Precursors for Solid-Phase Synthesis

      The Use of Malonate Coordination Polymers with CuII and BaII Atoms for Barium Cuprate Preparation

      Zhanna V. Dobrokhotova, Natalya V. Gogoleva, Ekaterina N. Zorina-Tikhonova, Mikhail A. Kiskin, Vladimir V. Chernyshev, Anna L. Emelina, Mikhail A. Bukov, Alexander S. Goloveshkin, Ivan S. Bushmarinov, Aleksey A. Sidorov, Artem S. Bogomyakov, Maksim L. Kovba, Vladimir M. Novotortsev and Igor L. Eremenko

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500243

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      Combinations of CuSO4 and barium salts of substituted malonic acids produce 3D coordination polymers with various new topologies. The solid-phase thermolysis of the anhydrous polymers under specially selected conditions results in the target BaCuO2 crystalline phase.

  14. Short Communications

    1. Bridging Thiadiazole Ligands

      A Family of Dinuclear Iron(II) SCO Compounds Based on a 1,3,4-Thiadiazole Bridging Ligand

      Christian F. Herold, Luca M. Carrella and Eva Rentschler

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500483

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      Herein we present a new 1,3,4-thiadiazole bridging ligand and three spin-crossover active dinuclear iron(II) compounds. The complexes show promising magnetic properties with a diamagnetic [LS–LS] ground state at low temperatures and represent a great starting point to explore this new family of dinuclear SCO compounds.

  15. Full Papers

    1. Bimodal MRI Probes

      Fe2+-Responsive Bimodal MRI and Fluorescent Imaging Probe Based on a Gadolinium(III) Complex

      Jian Luo, Xiao-Feng Zhu and Zhong-Ning Chen

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500411

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      An Fe2+-responsive bimodal MRI and fluorescent imaging agent based on the gadolinium(III) complex Gd-DTTA-BPP exhibits clearly enhanced relaxivity and significant turn-off luminescence in response to Fe2+.

    2. Enzyme Mimics

      A Heterodinuclear FeIIIZnII Complex as a Mimic for Purple Acid Phosphatase with Site-Specific ZnII Binding

      Asha E. Roberts, Gerhard Schenk and Lawrence R. Gahan

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500351

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      The ligand 2-{[bis(2-methoxyethyl)amino]methyl}-6-{[(2-hydroxybenzyl)(2-pyridylmethyl)amino]methyl}-4-methylphenol (BMMHPH2) with two distinct coordination sites, N2O2 (α) and NO3 (β), and the corresponding iron(III)–zinc(II) complex [FeZn(BMMHP)(CH3COO)2](BPh4) were prepared as a mimic for the active site of the plant enzyme purple acid phosphatase. The complex exhibits phosphoesterase-like activity. The centrosymmetric dimer [Fe2(BMMHPH)2(μ-OH)2](BPh4)2 and the acentrosymmetric trimer [Fe2Mg(BMMHPH)2(CH3COO)2(CH3O)2](BPh4)2 were also characterized.

    3. C≡C Insertion into Ni–H Bonds

      Synthesis of Vinylnickel and Nickelacyclopropane Complexes Containing a Chelate [P,Se]-Ligand

      Hongwei Zhou, Hongjian Sun, Tingting Zheng, Shumiao Zhang and Xiaoyan Li

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500293

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      The treatment of 2-(diphenylphosphanyl)benzeneselenol with Ni(PMe3)4 affords the hydridonickel(II) complex 1. The insertion reactions of 1 with phenylacetylene and 1-phenyl-1-propyne afford the vinylnickel(II) complexes 2 and 3, and the combination of 1 with diphenylacetylene, (trimethylsilyl)acetylene, and 1-phenyl-2-(trimethylsilyl)acetylene deliver nickelacyclopropane complexes 46.

    4. Oxygen Atom Transfer Reactions

      A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulf­oxide Reductase with Mo and W

      Jilai Li, Milica Andrejić, Ricardo A. Mata and Ulf Ryde

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500209

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      The dimethyl sulfoxide (DMSO) reductase reaction with Mo and W was studied by using 13 different DFT methods calibrated to accurate LCCSD(T0)/CBS energies. A two-step reaction was found, the second barrier being rate limiting. This barrier is about 28 kJ/mol lower for W than for Mo owing to a ca. 67 kJ/mol more exothermic reaction energy. The experimental activation enthalpy for Mo is reproduced within 5–9 kJ/mol.

    5. Layered Metal-SCN Networks

      Synthesis, Structure, and Properties of Coordination Polymers with Layered Transition-Metal Thiocyanato Networks

      Julia Werner, Zbigniew Tomkowicz, Thorben Reinert and Christian Näther

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500176

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      New layered thiocyanato coordination polymers of composition [M(NCS)2(4-tert-butylpyridine)2]n (M = Ni, Co) were prepared and investigated for their magnetic properties. The Ni compound shows a ferromagnetic transition whereas the Co compound shows a transition to a magnetic state with uncompensated magnetic moment.

    6. Black Phosphorus Field Emitters

      Electrochemically Exfoliated Black Phosphorus Nanosheets – Prospective Field Emitters

      Manisha B. Erande, Sachin R. Suryawanshi, Mahendra A. More and Dattatray J. Late

      Article first published online: 5 JUN 2015 | DOI: 10.1002/ejic.201500145

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      2D black phosphorus nanosheets, synthesized by electrochemical exfoliation, have the potential to be utilized for field emission (FE) display applications.

    7. Copper Monooxygenase Models

      Synthesis and Characterization of a Dinuclear Copper Complex Bearing a Hydrophobic Cavity as a Model for Copper-Containing Monooxygenases

      Olivier Schicke, Bruno Faure, Yannick Carissan, Michel Giorgi, Ariane Jalila Simaan and Marius Réglier

      Article first published online: 3 JUN 2015 | DOI: 10.1002/ejic.201500280

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      The synthesis and characterization of a dinuclear copper complex as a model of mononuclear Cu-containing monooxygenases are described. This model exhibits features equivalent to those of the enzymes: (1) the two Cu centers are 11.5 Å apart and (2) there is a hydrophobic pocket consisting of a cyclophane moiety in which substrates can bind near the two Cu centers.

    8. Reactivity of Red Phosphorus

      Unexpected Reactivity of Red Phosphorus in Ionic Liquids

      Matthias F. Groh, Silvia Paasch, Alexander Weiz, Michael Ruck and Eike Brunner

      Article first published online: 3 JUN 2015 | DOI: 10.1002/ejic.201500502

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      Red phosphorus readily reacts with iodine in a Lewis-acidic ionic liquid at moderate temperature. Besides iodides, phosphorus nanoparticles are formed. The latter are also obtained in a bottom-up process starting from P2I4. In situ liquid- and solid-state NMR spectroscopy reveals details of the reactions.

    9. Multimodal Imaging

      Patent Blue Derivatized Dendronized Iron Oxide Nanoparticles for Multimodal Imaging

      Lai Truong-Phuoc, Marie Kueny-Stotz, Julien Jouhannaud, Antonio Garofalo, François-Xavier Blé, Hervé Simon, Franklin Tellier, Patrick Poulet, Piero Chirco, Sylvie Begin-Colin, Geneviève Pourroy and Delphine Felder-Flesch

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500289

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      Iron oxide particles of 10 and 20 nm diameter, dendronized and derivatized with Patent Blue VF dye, survived subcutaneous injection for bimodal lymph node detection with a hand-held probe during surgery.

    10. Magnetic Colloids

      Long-Term Stability and Reproducibility of Magnetic Colloids are Key Issues for Steady Values of Specific Power Absorption Over Time

      Beatriz Sanz, M. Pilar Calatayud, Nicolás Cassinelli, M. Ricardo Ibarra and Gerardo F. Goya

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500303

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      The poly(ethyleneimine)-coated magnetic nanoparticles (PEI-MNPs) prepared in this work by oxidative hydrolysis show good reproducibility of size and size distribution. In addition, these PEI-MNPs show only a moderate decrease in the specific power absorption when they aggregate over time. These results render these particles suitable for applications in magnetic hyperthermia.

    11. Disiloxane–Dithiol Ligands

      The Syntheses and Crystal Structures of the First Disiloxane–1,3-Dithiol and Its Cadmium Complex

      Anna Ciborska, Eleonora Conterosito, Marco Milanesio, Katarzyna Kazimierczuk, Katarzyna Rzymowska, Krzysztof Brzozowski and Anna Dołęga

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500457

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      The silicon–sulfur compound bis-1,3-[di(2,6-diisopropylphenoxy)]disiloxane–1,3-dithiol is produced in a low yield but in a repeatable manner from silicon disulfide and 2,6-diisopropylphenol in a reaction catalyzed by imidazole or 4-(dimethylamino)pyridine (DMAP). The exchange of the aryloxy substituent for an alkoxy one strongly influences the Si–O–Si angle.

  16. Microreviews

    1. Modelling Metallobiosites

      Modelling Binuclear Metallobiosites: Insights from Pyrazole-Supported Biomimetic and Bioinspired Complexes

      Kristian E. Dalle and Franc Meyer

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500185

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      Metalloenzymes with binuclear active sites are widespread in Nature. Synthetic modelling of these active sites has helped to highlight important structural and functional aspects which can dictate reactivity, providing blueprints for the development of new bioinspired catalysts. This microreview focuses on biologically relevant insights provided by complexes of 3,5-disubstitued pyrazole ligands.

  17. Full Papers

    1. Silanechalcogenones

      Acyclic Amido-Containing Silanechalcogenones

      Yuk-Chi Chan, Yongxin Li, Rakesh Ganguly and Cheuk-Wai So

      Article first published online: 27 MAY 2015 | DOI: 10.1002/ejic.201500108

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      Reactions of the amidinate-stabilized silicon(II) bis(trimethylsilyl)amide [LSiN(SiMe3)2], {L = PhC(NtBu)2, 1} with a stiochiometric amount of elemental sulfur, selenium and tellurium afforded the first stable silanechalcogenones comprising an acyclic amido substituent, [L{N(SiMe3)2}Si=E] {E = S (2), Se (3) or Te (4)}.

  18. Microreviews

    1. Bio-Inspired Si Coatings

      Bio-Inspired Formation of Silica Thin Films: From Solid Substrates to Cellular Interfaces

      Woo Kyung Cho and Sung Ho Yang

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500308

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      The bio-inspired formation of silica thin films on the surfaces of flat solids, microparticles, nanoparticles, and living cells is reviewed.

  19. Full Papers

    1. Mn–Carboxylate Catalysts

      Too Many Cooks Spoil the Broth – Variable Potencies of Oxidizing Mn Complexes of a Hexadentate Carboxylato Ligand

      Claire Deville, Maik Finsel, David P. de Sousa, Barbara Szafranowska, Julian Behnken, Simon Svane, Andrew D. Bond, Rune Kirk Seidler-Egdal and Christine J. McKenzie

      Article first published online: 29 APR 2015 | DOI: 10.1002/ejic.201500210

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      A manganese(II) complex of a hexadentate ligand catalyzes epoxidation. However, reaction conditions are critical since several metal-based oxidants with varying potencies can be generated. This observation is probably general for related catalysts, and consequences include decreased selectivity and competing water oxidation.

  20. Short Communications

    1. Cleavage of Polyenes

      Regioselective Cleavage of Electron-Rich Double Bonds in Dienes to Carbonyl Compounds with [Fe(OTf)2(mix-BPBP)] and a Combination of H2O2 and NaIO4

      Peter Spannring, Vital A. Yazerski, Jianming Chen, Matthias Otte, Bert M. Weckhuysen, Pieter C. A. Bruijnincx and Robertus J. M. Klein Gebbink

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500213

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      The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0–50 °C) and short reaction times (70 min).

  21. Full Papers

    1. Dioxo-Mo and -W Catalysts

      Dioxomolybdenum(VI) and -Tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation

      Antoine Dupé, Md. Kamal Hossain, Jörg A. Schachner, Ferdinand Belaj, Ari Lehtonen, Ebbe Nordlander and Nadia C. Mösch-Zanetti

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500055

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      Four new molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene or hydroxyglycolene substituents were synthesized and found to catalyze olefin epoxidation reactions under eco-friendly conditions.

    2. Redox-Active Molybdopterins

      Synthesis, Structure and Redox Properties of Asymmetric (Cyclopentadienyl)(ene-1,2-dithiolate)cobalt(III) Complexes Containing Phenyl, Pyridyl and Pyrazinyl Units

      James P. Dicks, Muhammad Zubair, E. Stephen Davies, C. David Garner, Carola Schulzke, Claire Wilson and Jonathan McMaster

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500138

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      Structural, electrochemical, spectroscopic and theoretical studies of [(η5-C5H5)Co(dithiolene)] complexes suggest that the pyran ring-opened form of the molybdenum cofactor of Mo- and W-containing oxygen-atom-transfer enzymes may participate in the redox reactions involved in the catalytic cycle.

  22. Short Communications

    1. Polyoxometalate Catalysts

      Viral Nanotemplates Armed with Oxygenic Polyoxometalates for Hydrogen Peroxide Detoxification

      Debora Vilona, Antonio Sorarù, Chiara Maccato, Rossella Bortolaso, Livio Trainotti, Federica Valentini, Aldrei Boaretto, Cinzia Cepek, Marcella Bonchio and Mauro Carraro

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500155

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      A polyoxometalate with oxygenic activity was anchored on the TMV (tobacco mosaic virus). The rod-like biogenic template enables the formation of catalytic nanoarrays for H2O2 dismutation.

  23. Full Papers

    1. Mn Oxidation Catalysts

      Mechanistic Links in the in-situ Formation of Dinuclear Manganese Catalysts, H2O2 Disproportionation, and Alkene Oxidation

      Davide Angelone, Shaghayegh Abdolahzadeh, Johannes W. de Boer and Wesley R. Browne

      Article first published online: 21 APR 2015 | DOI: 10.1002/ejic.201500195

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      The in situ formation of catalytically active species through the reduction of a precatalyst, H2O2 disproportionation and alkene oxidation are linked to a common active species.

    2. Water Oxidation

      A Bioinspired System for Light-Driven Water Oxidation with a Porphyrin Sensitizer and a Tetrametallic Molecular Catalyst

      Mirco Natali, Elisa Deponti, Debora Vilona, Andrea Sartorel, Marcella Bonchio and Franco Scandola

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500063

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      The photoinduced events and the light-driven water-oxidation ability of a bioinspired, three-component catalyst/photosensitizer/acceptor molecular system are investigated.

  24. Microreviews

    1. Diiron Monooxygenases

      Controlling the Activities of the Diiron Centre in Bacterial Monooxygenases: Lessons from Mutagenesis and Biodiversity

      Tim Nichol, J. Colin Murrell and Thomas J. Smith

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500043

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      The soluble diiron monooxygenases (SDIMOs) are a diverse group of enzymes that use a diiron active centre to add oxygen to a wide range of organic molecules. Here we review how natural biodiversity and laboratory mutagenesis studies have revealed how the protein scaffold of SDIMOs controls the activity of the enzymes and the presentation of substrates to the diiron site.

  25. Full Papers

    1. Oxygen Atom Transfer

      Electronic Fine-Tuning of Oxygen Atom Transfer Reactivity of cis-Dioxomolybdenum(VI) Complexes with Thiosemicarbazone Ligands

      Aurélien Ducrot, Bethany Scattergood, Ben Coulson, Robin N. Perutz and Anne-K. Duhme-Klair

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500059

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      Thiosemicarbazone ligands (H2LR) derived from para-substituted salicylaldehydes allow the electronic properties and catalytic activities of cis-dioxo MoVI complexes of composition [MoO2(LR)MeOH] to be fine-tuned by electron-donating or electron-withdrawing groups R.

    2. Tyrosinase Models

      Catalytic Models of Tyrosinase: Reactivity Differences between Systems Based on Mono- and Binucleating Ligands

      Julia Schottenheim, Claus Gernert, Benjamin Herzigkeit, Jan Krahmer and Felix Tuczek

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500029

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      A tyrosinase model based on the binucleating ligand Lpy2 was developed and characterized. The ligand Lpy2 contains a combination of an imine and a pyridine function in the sidearms that are bridged by a flexible alkyl spacer. The Cu2Lpy2 complex catalyzes the conversion of monophenol DTBP-H into the o-quinone DTBQ (TON = 18). An electron-poor substrate is converted into the semiquinone.

    3. Immobilized Biocatalysts

      The Electrically Wired Molybdenum Domain of Human Sulfite Oxidase is Bioelectrocatalytically Active

      Roberto Spricigo, Silke Leimkühler, Lo Gorton, Frieder W. Scheller and Ulla Wollenberger

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500034

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      Human sulfite oxidase and its catalytic molybdenum-cofactor-containing domain were wired to an electrode with poly(vinylpyridine)–[osmium(N,N′-methyl-2,2′-biimidazole)3]2+/3+, which mediated the electron transfer between either of the enzyme cofactors and the electrode, as demonstrated by electrocatalytic turnover currents.

    4. V-Catalyzed Oxidative Bromination

      Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

      Federica Sabuzi, Ekaterina Churakova, Pierluca Galloni, Ron Wever, Frank Hollmann, Barbara Floris and Valeria Conte

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500086

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      Catalysis of thymol bromination by vanadium derivatives is directly compared to catalysis by a V-dependent bromoperoxidase. All reactions were performed under mild and sustainable conditions with relatively inexpensive reagents. Appealing results were obtained in terms of selectivity and sustainability.

    5. Chiral Complexes for Oxidations

      Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand

      Maria Lucia Perrone, Eliana Lo Presti, Simone Dell'Acqua, Enrico Monzani, Laura Santagostini and Luigi Casella

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201500046

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      A dinuclear copper(II) complex derived from a chiral hexadentate nitrogen ligand is reported as a new catalyst for asymmetric oxidations. For biogenic catechols as model substrates, the best enantioselectivity is obtained in the oxidation of the methyl esters of L-/D-Dopa, for which 70 % ee is obtained in favor of the L enantiomer.

    6. Oxidase and Catalase Mimics

      Mononuclear Iron(III) Complexes as Functional Models of Catechol Oxidases and Catalases

      Elena Badetti, Blerina Gjoka, Eszter Márta Nagy, Gérald Bernardinelli, Peter E. Kündig, Cristiano Zonta and Giulia Licini

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403225

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      Amino triphenolate iron(III) complexes promote effectively, at room temperature, the aerobic auto-oxidation of 3,5-di-tert-buthylcatechol to the corresponding o-benzoquinone (oxidase mimicking) and hydrogen peroxide dismutation (catalase mimicking).


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