European Journal of Inorganic Chemistry

Cover image for European Journal of Inorganic Chemistry

Special Issue: f-Element Chemistry

June 2010

Volume 2010, Issue 18

Pages 2551–2876

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
  2. Editorials

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
    1. f-Element Chemistry (Eur. J. Inorg. Chem. 18/2010) (page 2553)

      Gerd Meyer

      Version of Record online: 17 JUN 2010 | DOI: 10.1002/ejic.201090051

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
  4. News

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
  5. Microreviews

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
    1. Ionic Liquids

      Ionic Liquids for Lanthanide and Actinide Chemistry (pages 2569–2581)

      Anja-Verena Mudring and Sifu Tang

      Version of Record online: 27 MAY 2010 | DOI: 10.1002/ejic.201000297

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      The widely tuneable class of ionic liquids has become important for lanthanide and actinide coordination chemistry, f-element spectroscopy, f-element electrochemistry and electrodeposition, organic synthesis and catalysis as well as inorganic nanomaterial synthesis.

    2. Solid-State Hydrides

      Solid-State Structures and Properties of Europium and Samarium Hydrides (pages 2582–2593)

      Holger Kohlmann

      Version of Record online: 25 MAY 2010 | DOI: 10.1002/ejic.201000107

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      A survey on the available crystal structural data shows that europium and samarium hydrides exhibit rich crystal chemistry, ranging from ionic to complex and interstitial type compounds. While europium is always divalent, samarium is also found to be trivalent in its hydrides. Practical solutions are given to perform neutron diffraction with highly absorbing samples, such as natEu and natSm.

    3. Modeling Actinide Compounds

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      Actinyl Compounds with Hexavalent Elements (S, Cr, Se, Mo) – Structural Diversity, Nanoscale Chemistry, and Cellular Automata Modeling (pages 2594–2603)

      Sergey V. Krivovichev

      Version of Record online: 25 MAY 2010 | DOI: 10.1002/ejic.201000168

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      Basic features of the structural chemistry of actinyl compounds with TO4 tetrahedral oxyanions (T = S, Cr, Se, and Mo) are outlined with particular attention to structural topologies, nanoscale units, and algorithmic generation of structures by using cellular automata.

  6. Short Communications

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
    1. Erbium Silsesquioxane Cluster

      Coupling of Silsesquioxane Cages in the Coordination Sphere of Erbium (pages 2605–2608)

      Volker Lorenz, Steffen Blaurock, Cristian G. Hrib and Frank T. Edelmann

      Version of Record online: 24 MAR 2010 | DOI: 10.1002/ejic.201000186

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      Reaction of in situ prepared (c-C6H11)7Si7O9(OLi)3 with ErCl3 in thf solution afforded the large heterometallic (Er/Li) metallasilsesquioxane cluster (c-C6H11)21Si21O36-(SiMe3)Er2(thf)2Li4Cl2 in goodyield (65 %). An X-ray structure determination of it revealed several unusual features, including the coupling of wo silsesquioxane cages through an –O3Si(c-C6H11)– unit as well as trimethylsilylation of an Si–OH functionality.

    2. Cluster Halides

      A Topological Link between Lanthanide and Alkali-Metal Clusters: Face-Sharing Gadolinium Octahedra Centered by Endohedral Iridium Atoms in {Ir3Gd11}Br15 (pages 2609–2611)

      Matthias Brühmann and Gerd Meyer

      Version of Record online: 22 APR 2010 | DOI: 10.1002/ejic.201000254

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      The trimeric cluster {Ir3Gd11} with a structure analogous to that of the cesium suboxide {O3Cs11} (face-sharing octahedra) was observed as embedded in the cluster complex {Ir3Gd11}Br30. These are connected according to the formulation {Ir3Gd11}Bri–i12/2Bri–a9/2Bra–i9/2.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Editorials
    4. Graphical Abstract
    5. News
    6. Microreviews
    7. Short Communications
    8. Full Papers
    1. Cluster Halides

      Eight-Coordinate Endohedral Rhenium, Osmium and Iridium Atoms in Rare-Earth Halide Cluster Complexes (pages 2613–2619)

      Sina Zimmermann, Matthias Brühmann, Frederick Casper, Oliver Heyer, Thomas Lorenz, Claudia Felser, Anja-Verena Mudring and Gerd Meyer

      Version of Record online: 5 MAY 2010 | DOI: 10.1002/ejic.201000223

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      Eight-coordinate endohedral atoms of sixth-period elements (Z = Re, Os, Ir) are present in the extended cluster complexes {ReGd4}Br4, {OsSc4}Cl4 {Ir3Sc12}Br16, and {Os3Sc12}Br16Sc with different {ZR4/2} chains for the two formula types. Chemical bonding is dominated by endohedral atom–cluster atom (Z–R) and cluster atom–halide (R–X) interactions.

    2. Condensed Clusters

      A Bismuth-Stabilized Metal-Rich Telluride Lu9Bi≈1.0Te≈1.0 – Synthesis and Characterization (pages 2620–2625)

      Shalabh Gupta, Paul A. Maggard and John D. Corbett

      Version of Record online: 8 APR 2010 | DOI: 10.1002/ejic.201000147

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      Incorporation of bismuth into a lutetium-rich telluride system produces the new ternary phase Lu9Bi≈1Te≈1 with the orthorhombic Sc9Te2 structure. Partial oxidationof the Lu component is evident from the significant number of empty Lu 5d states above the Fermi level (dashed line).

    3. Doped Ln Vanadate Nanocrystals

      Monazite and Zircon Type LaVO4:Eu Nanocrystals – Synthesis, Luminescent Properties, and Spectroscopic Identification of the Eu3+ Sites (pages 2626–2635)

      Chun-Jiang Jia, Ling-Dong Sun, Zheng-Guang Yan, Yu-Cheng Pang, Shao-Zhe Lü and Chun-Hua Yan

      Version of Record online: 14 APR 2010 | DOI: 10.1002/ejic.201000038

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      Pure monoclinic (m) and tetragonal (t)LaVO4:Eu nanocrystals were prepared by the facile hydrothermal method assisted with citric and EDTA anions, respectively.Relative to m-LaVO4:Eu, t-LaVO4:Eunanocrystals are promising phosphors with high quantum yields and low cost.

    4. Lithium Nitridosilicates

      Chain-Type Lithium Rare-Earth Nitridosilicates – Li5Ln5Si4N12 with Ln = La, Ce (pages 2636–2641)

      Saskia Lupart, Martin Zeuner, Sandro Pagano and Wolfgang Schnick

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/ejic.201000245

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      Two new quaternary lithium rare earthnitridosilicates Li5Ln5Si4N12 (Ln = La, Ce) with nonbranched SiN4zweier single-chains have been characterized. The method of using lithium melts in closed systems at moderate temperatures has been extended to the synthesis of rare earthelement containing compounds. The 7Li solid-state NMR spectrum of Li5La5Si4N12 is reported.

    5. Non-Centrosymmetric Crystals

      Non-Centrosymmetric Ammonium Rare Earth Nitrates (NH4)2Ln(NO3)5·4H2O – Crystal Structure, Crystal Growth and Optical Properties (pages 2642–2648)

      Ladislav Bohatý, Roland Fröhlich, Peter Held and Petra Becker

      Version of Record online: 27 MAY 2010 | DOI: 10.1002/ejic.201000179

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      Crystals of (NH4)2Ln(NO3)5·4H2O (Ln = La, Ce) are piezoelectric and pyroelectric and therefore non-centrosymmetric and polar. Crystals with Ln = La, Ce, Pr, Nd are isomorphic and belong to the space group Cc. Large single crystals of the La and the Ce compounds were grown. Their refractive indices and dispersion allow the realization of phase-matching conditions for second harmonic generation.

    6. High-Energy Lanthanide States

      Spectroscopy of High-Energy States of Lanthanide Ions (pages 2649–2654)

      Michael F. Reid, Liusen Hu, Sebastian Frank, Chang-Kui Duan, Shangda Xia and Min Yin

      Version of Record online: 26 MAY 2010 | DOI: 10.1002/ejic.201000182

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      High-energy states of lanthanide ions in crystals may be analyzed by a combination of quantum-chemical calculations and phenomenological crystal-field models. We show that sharp lines may be obtained in excited-state absorption (ESA) spectra, and hence more information about the excited states could be obtained by using ESA than broad-band ground-state absorption (GSA) spectra.

    7. Luminescent Composites

      Luminescent CaWO4:Tb3+-Loaded Mesoporous Silica Composites for the Immobilization and Release of Lysozyme (pages 2655–2662)

      Shanshan Huang, Chunxia Li, Piaoping Yang, Cuimiao Zhang, Ziyong Cheng, Yong Fan and Jun Lin

      Version of Record online: 19 MAY 2010 | DOI: 10.1002/ejic.201000110

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      Luminescent CaWO4:Tb3+-loaded mesoporous silica composites with various morphologies were synthesized to serve as supports for lysozyme immobilization and release. These composites show specific lysozyme adsorption capacities at different solution pH values. The release of the enzyme can be tracked by the change in the photoluminescence of Tb3+ in CaWO4:Tb3+@rod-like SBA-15.

    8. Dinuclear Lanthanide Complexes

      Synthesis, Chirality and Complexation Phenomena of Two Diastereoisomeric Dinuclear Lanthanide(III) Complexes (pages 2663–2672)

      Benjamin S. Murray, David Parker, Cidália M. G. dos Santos and Robert D. Peacock

      Version of Record online: 6 MAY 2010 | DOI: 10.1002/ejic.201000243

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      Complexes of LnIII (Ln = Eu, Tb, Yb) with diasteromeric ditopic ligands reveal differing anion binding profiles; circularlypolarised luminescence studies of Eu systems show significant differences in the local helicity at the metal centre.

    9. NIR Bioimaging

      NIR Bioimaging: Development of Liposome-Encapsulated, Rare-Earth-Doped Y2O3 Nanoparticles as Fluorescent Probes (pages 2673–2677)

      Kohei Soga, Kimikazu Tokuzen, Kosuke Tsuji, Tomoyoshi Yamano, Hiroshi Hyodo and Hidehiro Kishimoto

      Version of Record online: 14 MAY 2010 | DOI: 10.1002/ejic.201000201

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      Liposome-encapsulated, Er-doped Y2O3 nanoparticles were developed as near-infrared (NIR) bioimaging probes. The characteristics of the liposomes with surface modification and their distribution after injection into the body of a mouse are reported with microscopic and macroscopic NIR fluorescence images.

    10. Europium(II) Borate Fluoride

      Synthesis, Crystal Structure and Optical Spectra of Europium Borate Fluoride Eu5(BO3)3F (pages 2678–2681)

      Karolina Kazmierczak and Henning A. Höppe

      Version of Record online: 16 APR 2010 | DOI: 10.1002/ejic.201000105

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      Eu5(BO3)3F, structurally similar to fluoroapatite, is the first europium(II) boratefluoride and exhibits an ordered distribution of the O and F atoms.

    11. Lanthanides

      Luminescence Properties of Redispersible Tb3+-Doped GdPO4 Nanoparticles Prepared by an Ethylene Glycol Route (pages 2682–2687)

      Ningombam Yaiphaba, Raghumani Singh Ningthoujam, Nongmaithem Rajmuhon Singh and Rajesh Kumar Vatsa

      Version of Record online: 19 JAN 2010 | DOI: 10.1002/ejic.200900968

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      Nanoparticles of Tb3+-doped GdPO4 have been prepared at a low temperature and show green luminescence. There is a strong energy transfer from Gd3+ to Tb3+. These nanoparticles are dispersible in polar solvents and can be incorporated in polyvinyl alcohol polymer to make a film.

    12. Eu-Doped Alkyl/Siloxane Hybrids

      EuIII-Doping of Lamellar Bilayer and Amorphous Mono-Amide Cross-Linked Alkyl/Siloxane Hybrids (pages 2688–2699)

      Silvia C. Nunes, José Planelles-Aragó, Rute A. S. Ferreira, Luis D. Carlos and Verónica de Zea Bermudez

      Version of Record online: 6 MAY 2010 | DOI: 10.1002/ejic.201000166

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      Two structurally different but chemically similar series of mono-amidosil alkyl/siloxane hosts have been doped with a wide range of concentrations of Eu(CF3SO3)3. The influence of the structure of the two mono-amidosils (lamellar bilayer or amorphous matrix) on the photoluminescence features is addressed by using Eu3+ ions as a local probe.

    13. Double Europium(III) Sensitization

      Europium Complexes of Tris(dipicolinato) Derivatives Coupled to Methylumbelliferone: A Double Sensitization (pages 2700–2713)

      Julien Andres and Anne-Sophie Chauvin

      Version of Record online: 31 MAY 2010 | DOI: 10.1002/ejic.201000126

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      A dipicolinic acid ligand coupled to a polyoxyethylene chain with a coumarin chromophore at its extremity was used to complex Eu3+, which affords a stable 1:3 Eu/L complex. The sensitization of the Eu3+ can occur by an excitation of the dipicolinato part (λex = 270 nm) or through the coumarin moiety (λex = 320 nm).

    14. Heterometallic Schiff Base Complexes

      Near-Infrared Luminescent, Neutral, Cyclic Zn2Ln2 (Ln = Nd, Yb, and Er) Complexes from Asymmetric Salen-Type Schiff Base Ligands (pages 2714–2722)

      Xing-Qiang Lü, Wei-Xu Feng, Ya-Ni Hui, Tao Wei, Ji-Rong Song, Shun-Sheng Zhao, Wai-Yeung Wong, Wai-Kwok Wong and Richard A. Jones

      Version of Record online: 21 MAY 2010 | DOI: 10.1002/ejic.201000100

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      Upon excitation at 200–550 nm corresponding to the intraligand π[RIGHTWARDS ARROW]π* transitions of the Schiff base, complexes [Zn2(L1)2(py)2Ln2(NO3)4(dmf)2]·3Et2O and [Zn2(L2)2Ln2(NO3)4(dmf)4] (Ln = Nd, Yb, Er, Gd) emit strong NIR luminescence of theLn3+ ions with lifetimes in ms ranges, whereas the ligand-centered singlet (1LC) visible luminescence is mostly quenched by energy transfer from the 1LC excited state to Ln3+ ions.

    15. Lanthanide Luminescence

      Acridone-Benzimidazole Ring-Fused Ligands: A New Class of Sensitizers of Lanthanide Luminescence via Low-Energy Excitation (pages 2723–2734)

      Emmanuel Deiters, Frédéric Gumy and Jean-Claude G. Bünzli

      Version of Record online: 11 FEB 2010 | DOI: 10.1002/ejic.200901148

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      Two new tridentate ring-fused acridone-benzimidazole ligands have been prepared. They sensitize europium and ytterbium luminescence upon excitation with visible light (410–430 nm).

    16. Fluoride Sensing

      Towards Fluoride Sensing with Positively Charged Lanthanide Complexes (pages 2735–2745)

      Raphaël Tripier, Carlos Platas-Iglesias, Anne Boos, Jean-François Morfin and Loïc Charbonnière

      Version of Record online: 21 JAN 2010 | DOI: 10.1002/ejic.200901045

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      Positively charged LnIII complexes bind F anions with a high selectivity over Cl and Br. Fluoride binding replaces an inner-sphere water molecule, which results in important changes in the shape and intensity of the emission spectrum of the EuIII complex. Thus, these systems show promise in the field of fluoride sensing.

    17. Lanthanidomesogens

      Enthalpy/Entropy Compensation in the Melting of Thermotropic Nitrogen-Containing Chelating Ligands and Their Lanthanide Complexes: Successes and Failures (pages 2746–2759)

      Aude Escande, Laure Guénée, Emmanuel Terazzi, Thomas B. Jensen, Homayoun Nozary and Claude Piguet

      Version of Record online: 11 MAY 2010 | DOI: 10.1002/ejic.200901190

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      Enthalpy/entropy compensation occurs for the simple increase (n) of the length of the peripheral flexible alkyl chains in lanthanide-containing thermotropic liquid crystals. The connection of an increasing number of divergent chains in polycatenar ligands (p) circumvents this limitation and allows some deliberate tuning of the melting temperatures in lanthanidomesogens.

    18. Uranyl Salts from Ionic Liquids

      Crystallization of Uranyl Salts from Dialkylimidazolium Ionic Liquids or Their Precursors (pages 2760–2767)

      Violina Cocalia, Marcin Smiglak, Steven P. Kelley, Julia L. Shamshina, Gabriela Gurau and Robin D. Rogers

      Version of Record online: 4 MAY 2010 | DOI: 10.1002/ejic.201000162

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      Initial studies in the crystallization of uranyl species from ionic liquids or by reaction with ionic liquid precursors led to the isolation of three new imidazolium-based salts of bis-μ-hydroxo-bis[bis(nitrato-O,O)dioxouranate(VI)] and one of trichlorobis(nitrato-O,O)dioxouranate(VI).

    19. Magnetic Ni–Ln Complexes

      Structural and Magnetic Studies of New NiII–LnIII Complexes (pages 2768–2773)

      Jean-Pierre Costes and Laure Vendier

      Version of Record online: 30 APR 2010 | DOI: 10.1002/ejic.201000081

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      ortho-Vanillin can yield two types of heterodinuclear NiII–LnIII complexes that differ by their formulation and structure, depending on the solvent used. A DNi zero field splitting (zfs) term is active in these complexes. The departure from planarity of the equatorial ortho-vanillin ligands is responsible for the slight decrease in the ferromagnetic Ni–Gd interaction.

    20. RE Metal Complex Adducts

      AlMe3, GaMe3 and InMe3 Adducts of N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Rare-Earth Metal Complexes and Their Molecular Dynamics (pages 2774–2786)

      Benjamin J. Hellmann, Andreas Mix, Beate Neumann, Hans-Georg Stammler and Norbert W. Mitzel

      Version of Record online: 4 MAY 2010 | DOI: 10.1002/ejic.201000121

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      Three in one: The N,N-bis(2-{pyrid-2-yl}ethyl)hydroxylaminato ligand allows generating heterobi- and -trimetallic complexes by adduct formation of [Cp2Ln{η2-ON(C2H4-o-Py)2}] with AlMe3, GaMe3 and InMe3. All complexes exhibit a highly dynamic behaviour in solution.

    21. Pseudo-Solid-State Syntheses

      Syntheses at Elevated Temperature and Structures of Lanthanoid/Alkaline Earth Heterobimetallic Derivatives of 2-Methyl-8-hydroxyquinoline (pages 2787–2797)

      Glen B. Deacon, Craig M. Forsyth, Peter C. Junk and Aron Urbatsch

      Version of Record online: 26 MAY 2010 | DOI: 10.1002/ejic.201000325

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      Rearrangement reactions of Ln(MQ)3 and AE(MQ)2 compounds (HMQ = 2-methyl-8-hydroxyquinoline) at elevated temperatures in a 1,2,4,5-tetramethylbenzene (TMB) flux provide a useful route to homoleptic [Ln2AE(MQ)8] complexes, and the new [Eu3Ba(MQ)11]·2TMB and [Ln3(MQ)7CO3] (Ln = Eu, Er) complexes have also been obtained by this route.

    22. Rare-Earth Nitroso Complexes

      New Approaches to 12-Coordination: Structural Consequences of Steric Stress, Lanthanoid Contraction and Hydrogen Bonding (pages 2798–2812)

      Anthony S. R. Chesman, David R. Turner, Glen B. Deacon and Stuart R. Batten

      Version of Record online: 19 MAY 2010 | DOI: 10.1002/ejic.201000257

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      Rare-earth complexes containing nitroso bonding ligands dicyanonitrosomethanide, C(CN)2(NO), and carbamoylcyanonitrosomethanide, C(CONH2)(CN)(NO), demonstrate a variety of coordination modes from symmetrical η2(N,O) to monodentate η1(O). The effects upon the coordination environment of the lanthanoid contraction. Intramolecular hydrogen bonding and steric influences of co-ligands are discussed.

    23. Rare Earth Complexes

      A Structural Investigation of Trivalent and Divalent Rare Earth Thiocyanate Complexes Synthesised by Redox Transmetallation (pages 2813–2825)

      Jacinta M. Bakker, Glen B. Deacon, Craig M. Forsyth, Peter C. Junk and Michal Wiecko

      Version of Record online: 31 MAR 2010 | DOI: 10.1002/ejic.201000111

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      Solvated rare earth thiocyanate complexes synthesised by redox transmetallation between RE metals and Hg(SCN)2 yield compounds with a wide variety of structural types featuring RE–NCS and/or RE–NCS–RE bonding.

    24. Bimetallic 4f–3d Arrays

      Cyano-Bridged 2D Bimetallic 4f–3d Arrays with Monolayered Stair-Like, Brick-Wall-Like, or Bilayered Topologies – Rational Syntheses and Crystal Structures (pages 2826–2835)

      Wen-Tong Chen, A-Qing Wu, Guo-Cong Guo, Ming-Sheng Wang, Li-Zhen Cai and Jin-Shun Huang

      Version of Record online: 25 MAY 2010 | DOI: 10.1002/ejic.201000112

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      Fourteen cyano-bridged 2D bimetallic 4f–3d arrays with monolayered stair-like, brick-wall-like, or bilayered topologies were rationally prepared by the ball-milling method, and their structures were also characterized. The relationship between the crystal structures and the controllable syntheses was discussed.

    25. Bora-Amidinate Complexes

      Bora-Amidinate Complexes of Lanthanide(II) Metals (pages 2836–2840)

      Sjoerd Harder and Dominik Naglav

      Version of Record online: 19 MAY 2010 | DOI: 10.1002/ejic.201000094

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      The first bora-amidinate (bam) complexes of the lanthanide metals in the +2 oxidation state could be successfully obtained by reaction of DIPP(H)N–BH-N(H)DIPP with a benzylic lanthanide(II) precursor. The crystal structures show very small N–Ln–N′ bite angles (ca. 60°) that leave a large part of the metal coordination sphere available for neutral thf ligands.

    26. Controlling ate-Complex Formation

      Rare-Earth Metal Phenyl(trimethylsilyl)amide Complexes (pages 2841–2852)

      Christoph Schädle, Christian Meermann, Karl W. Törnroos and Reiner Anwander

      Version of Record online: 23 APR 2010 | DOI: 10.1002/ejic.201000220

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      Deliberate choice of the reaction conditions gives access to monomeric alkali metal-free heteroleptic complexes Y[N(SiMe3)(C6H3iPr2-2,6)]Cl2(thf)3 and Ln[N(SiMe3)(C6H3iPr2-2,6)]2(BH4)(thf) (Ln = Nd, La; depicted) according to salt metathesis protocols, with solvent effects and type of alkali metal amide precursor deserving closer attention.

    27. Ln Polymerization Catalysts

      Aminopyridinate-Stabilized Lanthanoid Complexes: Synthesis, Structure and Polymerization of Ethylene and Isoprene (pages 2853–2860)

      Christian Döring, Winfried P. Kretschmer and Rhett Kempe

      Version of Record online: 6 APR 2010 | DOI: 10.1002/ejic.201000097

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      Aminopyridinato ligand-stabilized alkyl-lanthanoid complexes were synthesized and structurally characterized. These complexes are, after activation, active catalysts for the polymerization of ethylene and isoprene.The obtained polyisoprenes have an increased 3,4-content, which decreases with increasing metal ion radius. An ethylene polymerisation activity maximum is observed for Er.

    28. Rare-Earth Metal Alkyl Complex

      Synthesis and Characterization of Heteroscorpionate Rare-Earth Metal Dialkyl Complexes and Catalysis on MMA Polymerization (pages 2861–2866)

      Zhichao Zhang, Dongmei Cui and Alexander A. Trifonov

      Version of Record online: 13 APR 2010 | DOI: 10.1002/ejic.201000108

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      The first heteroscorpionate ligated rare-earth metal dialkyl complexes were prepared via alkane elimination. These complexes were effective catalysts for the polymerization of methyl methacrylate to produce syndiotactically enriched poly(methyl methacrylate) with narrow molecular weight distribution.

    29. Organolanthanide Catalysts

      Facile Synthesis of Lanthanidocenes by the “Borohydride/Alkyl Route” and Their Application in Isoprene Polymerization (pages 2867–2876)

      Marc Visseaux, Michael Terrier, André Mortreux and Pascal Roussel

      Version of Record online: 28 APR 2010 | DOI: 10.1002/ejic.201000184

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      Borohydridolanthanidocenes were easily prepared by a straightforward synthetic approach, starting from their tris(borohydride)s, a ligand in its protonated form, and the stoichiometric amount of dialkylmagnesium reagent. These compounds were found to be very efficient in isoprene polymerization. Our approach also enables the rapid screening of a given ligand for polymerization catalysis.

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