Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 1

December 16, 2005

Volume 45, Issue 1

Pages 1–173

    1. Cover Picture: Retro-Cycloaddition Reaction of Pyrrolidinofullerenes (Angew. Chem. Int. Ed. 1/2006) (page 1)

      Nazario Martín, Margarita Altable, Salvatore Filippone, Angel Martín-Domenech, Luis Echegoyen and Claudia M. Cardona

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200690000

      Retro-cycloaddition of easily prepared pyrrolidinofullerenes affords quantitatively pristine fullerenes, and thus can be used as a new protection-deprotection protocol in the chemistry of fullerenes, as shown in the cover picture. In their Communication on page 110 ff., N. Martín, L. Echegoyen, and co-workers report on this promising finding, which has already allowed the selective isolation of the Ih constitutional isomer of Sc3N@C80.

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      All Good Things Come in Threes… (pages 4–6)

      Peter Gölitz

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200504178

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      Molecular and Polymeric Hybrids Based on Covalently Linked Polyoxometalates and Transition-Metal Complexes (page 17)

      Jeonghee Kang, Bubin Xu, Zhonghua Peng, Xiaodong Zhu, Yongge Wei and Douglas R. Powell

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200690001

      This article corrects:

      Molecular and Polymeric Hybrids Based on Covalently Linked Polyoxometalates and Transition-Metal Complexes1

      Vol. 44, Issue 42, 6902–6905, Article first published online: 5 OCT 2005

    4. Richard E. Smalley: Fullerenes (pages 26–27)

      Harold Kroto

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200504094

    5. Programmable Ligand-Controlled Riboregulators (pages 30–31)

      Ronald Micura

      Article first published online: 20 SEP 2005 | DOI: 10.1002/anie.200502700

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      A flexible platform for control of gene expression is represented by rationally designed antiswitches. These trans-acting riboregulators consist of an antisense domain and an aptamer domain. They are responsive to small ligands, modular, and fully tunable to target any gene of interest (see picture).

    6. Water Oligomers in Crystal Hydrates—What's News and What Isn't? (pages 32–36)

      Mark Mascal, Lourdes Infantes and James Chisholm

      Article first published online: 24 NOV 2005 | DOI: 10.1002/anie.200501839

      How does one find out whether an interesting water aggregate observed in an organic crystal structure is novel? The first place to look is in the Cambridge Structural Database (CSD). The data are there, but analysis is difficult and it is not routinely done. The result? Many of the water chains, rings, sheets, and clusters reported as novel in the recent literature are actually redundant with published structures in the CSD.

    7. Functional Liquid-Crystalline Assemblies: Self-Organized Soft Materials (pages 38–68)

      Takashi Kato, Norihiro Mizoshita and Kenji Kishimoto

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200501384

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      Order is power: New dynamically functional liquid crystals are formed through supramolecular self-assembly and nano-segregation. These materials exhibit anisotropic and/or enhanced properties, such as electron, ion, or molecular transport, sensory, catalytic, optical, and bio-activity.

    8. Spectrally Resolved Magnetic Resonance Imaging of a Xenon Biosensor (pages 70–73)

      Christian Hilty, Thomas J. Lowery, David E. Wemmer and Alexander Pines

      Article first published online: 28 NOV 2005 | DOI: 10.1002/anie.200502693

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      Going hyper: A continuous flow of water saturated with hyperpolarized xenon through a glass tube assembly containing a xenon biosensor attached through its biotin tag to immobilized avidin–agarose beads (see picture) packed in between two frits results in distinct NMR signals that allow detection of the immobilized avidin analyte with high sensitivity.

    9. Lanthanide–Transition-Metal Sandwich Framework Comprising {Cu3} Cluster Pillars and Layered Networks of {Er36} Wheels (pages 73–77)

      Jian-Wen Cheng, Jie Zhang, Shou-Tian Zheng, Man-Bo Zhang and Guo-Yu Yang

      Article first published online: 28 NOV 2005 | DOI: 10.1002/anie.200502917

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      Synergistic coordination between isonicotinate (ina) and 1,2-benzenedicarboxylate (bdc) ligands under hydrothermal conditions results in the formation of two new coordination polymers, [Er73-O)(μ3-OH)6(bdc)3](ina)9[Cu3X4] (X=Cl, Br). Wheel-shaped [Er363-OH)303-O)6(bdc)6]54+ ions form a 2D network (see picture), which is further pillared by [Cu3X4(ina)6]4− to give a 3D framework.

      Corrected by:

      Corrigendum: Lanthanide–Transition-Metal Sandwich Framework Comprising {Cu3} Cluster Pillars and Layered Networks of {Er36} Wheels

      Vol. 45, Issue 5, 689, Article first published online: 17 JAN 2006

    10. Complexation-Induced Translational Isomerism: Shuttling through Stepwise Competitive Binding (pages 77–83)

      Dana S. Marlin, Diego González Cabrera, David A. Leigh and Alexandra M. Z. Slawin

      Article first published online: 28 NOV 2005 | DOI: 10.1002/anie.200501761

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      Shuttle service: Progressive binding of a transition-metal ion to a peptide station (highlighted in green in the picture) displaces the macrocycle (blue) to an alternative station (orange) in a hydrogen-bonded molecular shuttle.

    11. Dangling Arms: A Tetrahedral Supramolecular Host with Partially Encapsulated Guests (pages 83–86)

      Bryan E. F. Tiedemann and Kenneth N. Raymond

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502209

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      A protruding tail: A guest composed of a cationic sandwich complex, an alkyl chain, and a sulfonate anionic group is partially incorporated within a host [Ga4L6]12− cluster (see scheme). The cationic head group is quickly incorporated into the cavity of the host, while the sulfonate unit at the other end of the chain is not, as the alkyl sulfonate tail protrudes through an opening in a triangular face of the tetrahedral cluster.

    12. Controlling Polymer Architecture through Host–Guest Interactions (pages 87–90)

      Liang Chen, Xinyuan Zhu, Deyue Yan, Yan Chen, Qun Chen and Yefeng Yao

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502306

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      A supramolecular method to control polymer architectures (see picture) is demonstrated with the synthesis of a series of poly(sulfone–amine) samples with various degrees of branching merely by changing the amount of host (β-cyclodextrin) present. Further modification of the polymer chains allows the preparation of condensation polymers with peculiar topological structures, functionalities, and properties.

    13. Fast Colorimetric Sensing of Adenosine and Cocaine Based on a General Sensor Design Involving Aptamers and Nanoparticles (pages 90–94)

      Juewen Liu and Yi Lu

      Article first published online: 17 NOV 2005 | DOI: 10.1002/anie.200502589

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      Apt to change color: DNA aptamers have been used to assemble DNA-functionalized gold nanoparticles to produce highly sensitive and selective colorimetric sensors with an instantaneous color response on addition of a substrate. The general method has been shown for adenosine and cocaine (see picture), but should be applicable to any aptamer of choice.

    14. Efficient Enzymatic Synthesis of Phosphoroselenoate RNA by Using Adenosine 5′-(α-P-Seleno)triphosphate (pages 94–97)

      Nicolas Carrasco, Julianne Caton-Williams, Gary Brandt, Siming Wang and Zhen Huang

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502215

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      Se the way to RNA: Adenosine 5′-(α-P-seleno)triphosphate (ATPαSe) has been synthesized and efficiently and diastereoselectively incorporated into RNA through enzymatic synthesis (see scheme). The digestion of the phosphoroselenoate RNA with phosphodiesterase is slower than that of the nonmodified RNA. This enzymatic synthesis can be generally applied in the preparation of multimilligram quantities of selenium-derivatized RNAs for X-ray crystallography.

    15. Rediscovery, Isolation, and Asymmetric Reduction of 1,2,3,4-Tetrahydronaphthalene-1,4-dione and Studies of Its [Cr(CO)3] Complex (pages 98–101)

      E. Peter Kündig, Alvaro Enríquez García, Thierry Lomberget and Gérald Bernardinelli

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502588

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      For 25 years it has been known that 1,4-dihydroxynaphthalene and tetrahydronaphthalene-1,4-dione coexist as stable tautomers; however, the dione has now emerged as an interesting starting material for synthesis. Its efficient isolation is reported, and the corresponding [Cr(CO)3] complexes of the two tautomers are prepared, thus leading to efficient desymmetrization using chiral diamine acyl-transfer catalysts (see scheme).

    16. Diels–Alder Reactivity of Binuclear Complexes with Calixarene-like Structures (pages 101–104)

      Steffen Käss, Thomas Gregor and Berthold Kersting

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200500683

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      The regioselectivity of the Diels–Alder reaction between ω-substituted dienoates and unsymmetrical dienophiles can be strictly controlled by “calixarene-like” metal complexes of type A (see scheme). The reaction of the dienoate coligand in A with acrylonitrile leads to the exclusive formation of the regioisomer adduct I, which is in striking contrast to the low regioselectivity of the background reaction.

    17. Hole-Doped Single-Walled Carbon Nanotubes: Ornamenting with Gold Nanoparticles in Water (pages 104–107)

      Dong Sik Kim, Takhee Lee and Kurt E. Geckeler

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200500234

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      A simple and facile method has been developed that allows water-soluble hybrid materials of Au nanoparticles and hole-doped single-walled carbon nanotubes (SWNTs) to be prepared. Uniformly arranged Au nanoparticles (see TEM image) were obtained by the addition of metal salts to surfactant-suspended SWNTs in water using the solution-phase dispersion technique.

    18. In Situ NMR Spectroscopic Observation of a Catalytic Intermediate in Phosphine-Catalyzed Cyclo-Oligomerization of Isocyanates (pages 107–110)

      Zoltán Pusztai, Gábor Vlád, Andrea Bodor, István T. Horváth, Hans J. Laas, Reinhard Halpaap and Frank U. Richter

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502415

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      Caught in action: A mechanistic understanding of the tri-n-butylphosphine-catalyzed cyclo-oligomerization of alkyl isocyanates (RNCO, R=nBu, nHex) to products 13 has been developed at the molecular level. One of the key catalytic intermediates A was structurally characterized by in situ NMR spectroscopic analysis.

    19. Retro-Cycloaddition Reaction of Pyrrolidinofullerenes (pages 110–114)

      Nazario Martín, Margarita Altable, Salvatore Filippone, Angel Martín-Domenech, Luis Echegoyen and Claudia M. Cardona

      Article first published online: 20 OCT 2005 | DOI: 10.1002/anie.200502556

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      All things retro: Pyrrolidinofullerenes undergo a retro-cycloaddition reaction to afford the corresponding fullerene (C60, C70, or an endohedral C80 metallofullerene; see scheme) in quantitative yield upon treatment with an excess of a dipolarophile (maleic anhydride or N-phenylmaleimide) in o-dichlorobenzene. The reaction works efficiently with higher fullerenes and has allowed the isolation of one of the constitutional isomers of Sc3N@C80.

    20. Stabilization of the DNA I-Motif Structure by Incorporation of 3′-S-Phosphorothiolate Linkages (pages 114–117)

      John A. Brazier, Julie Fisher and Richard Cosstick

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200503110

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      A stable i: The i-motif is a unique, four-stranded DNA structure associated with cytosine-rich sequences at the ends of human chromosomes. This is the first report of an i-motif stabilized by a deoxycytidine analogue and demonstrates the importance of the sugar conformation in the i-motif structure.

    21. Enantioselective Aza-Henry Reactions Assisted by ZnII and N-Methylephedrine (pages 117–120)

      Claudio Palomo, Mikel Oiarbide, Rajkumar Halder, Antonio Laso and Rosa López

      Article first published online: 17 NOV 2005 | DOI: 10.1002/anie.200502674

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      Hooray aza-Henry! A combination of zinc triflate, an amine base, and (−)-N-methylephedrine (NME), which can be easily recovered and reused, leads to high enantioselectivities in the aza-Henry reaction of N-Boc-protected aldimines and nitromethane (see scheme; Boc=tert-butyloxycarbonyl).

    22. High-Yield Generation of a Long-Lived Charge-Separated State in Diphenylacetylene-Modified DNA (pages 120–122)

      Tadao Takada, Kiyohiko Kawai, Mamoru Fujitsuka and Tetsuro Majima

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200502568

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      Base jumping: A long-lived charge-separated state has been generated in high yield for DNA modified with a diphenylacetylene derivative (DPA) through an adenine(A)-base-hopping mechanism (see diagram). Modulation of the redox properties of the photosensitizer and bridge bases (e.g., by employing a brominated adenine (BrA)) can improve the yield of the charge-separated state.

    23. Highly Enantioselective Synthesis of γ-Hydroxy-α,β-acetylenic Esters by Asymmetric Alkyne Addition to Aldehydes (pages 122–125)

      Ge Gao, Qin Wang, Xiao-Qi Yu, Ru-Gang Xie and Lin Pu

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200500469

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      Alkynoates are added to aromatic and α,β-unsaturated aldehydes in the synthesis of the title compounds in optically active form. This highly enantioselective and useful method is carried out under mild reaction conditions and employs the readily available chiral 1,1′-bi-2-naphthol (binol) ligand and the metal reagents Et2Zn and [Ti(OiPr)4] (see scheme; HMPA=hexamethylphosphoramide).

    24. The Photochemical Reactivity of the “Photo-Inert” Tungsten (Fischer) Carbene Complexes (pages 125–128)

      Israel Fernández, Miguel A. Sierra, Mar Gómez-Gallego, María J. Mancheño and Fernando P. Cossío

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200501590

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      The light fantastic: Tungsten(0) Fischer carbene complexes, previously considered to be photo-inert, produce, by adequately choosing the ligands, three classes of photoproducts (see scheme). Thus, irradiation of tetracarbonyltungsten(0) carbene complexes 1 leads to syn-metalated imines 2, amino complexes 3, and α-amino esters 4. Reasonable reaction pathways are proposed for all these processes.

    25. Cobalt-Catalyzed Carbonylative Copolymerization of N-Alkylazetidines and Tetrahydrofuran (pages 129–131)

      Guosheng Liu and Li Jia

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502116

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      A living polymerization: Poly(amide-co-ester)s with either gradient or segmental ester distribution are formed by the cobalt-catalyzed polymerization of azetidine in THF in the absence or presence of LiI, respectively. Periodic addition of azetidine results in copolymers with multiple amide blocks separated by ester segments (see picture). The polymers undergo a two-stage chemical degradation.

    26. Assembly of Dendrimers with Redox-Active [{CpFe(μ3-CO)}4] Clusters at the Periphery and Their Application to Oxo-Anion and Adenosine-5′-Triphosphate Sensing (pages 132–136)

      Jaime Ruiz Aranzaes, Colette Belin and Didier Astruc

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502291

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      9, 16, or 27 [CpFe(μ3-CO)]4 clusters contain the title assemblies (see picture). The one-electron oxidation Fe4[RIGHTWARDS ARROW]Fe4+ of all Fe4 units appears as a single reversible cyclic voltammetry wave and was used in solution and with dendrimer-modified electrodes for oxo-anion recognition. ATP2− is selectively recognized and better than H2PO4. The larger the dendrimer, the easier is the re-use of the modified electrode sensor.

    27. Site-Selective Photocleavage of Proteins by Uranyl Ions (pages 137–139)

      Michael R. Duff Jr. and Challa V. Kumar

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200502344

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      Footprints of a metal: The uranyl ion (UO22+) binds to selected proteins, at specific sites, with high affinities. This property was exploited to photocleave proteins at the UO22+-binding site. Quenching studies show that free UO22+ is not responsible for the cleavage. This is the first report of protein photocleavage with high selectivity by the uranyl ion, upon excitation with visible light.

    28. Step-by-Step Assembly of Trivacant Tungstosilicates: Synthesis and Characterization of Tetrameric Anions (pages 139–142)

      Nathalie Leclerc-Laronze, Mohamed Haouas, Jérôme Marrot, Francis Taulelle and Gilbert Hervé

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502441

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      Tungstosilicate building blocks: Two dimeric anions, α-[{K(H2O)2}Si2W18O66]15−, obtained by self-association of the monomeric species [SiW9O34]10− upon acidification, can be connected directly (see picture). However, in the presence of silicic acid the anions are linked through an electrophilic [Si4O4]8+ ring.

    29. Simple and Quantitative Mechanochemical Preparation of a Porous Crystalline Material Based on a 1D Coordination Network for Uptake of Small Molecules (pages 142–146)

      Dario Braga, Marco Curzi, Anna Johansson, Marco Polito, Katia Rubini and Fabrizia Grepioni

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200502597

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      Kneading them in: A versatile porous material based on the 1D coordination network [CuCl2(dace)] (dace=trans-1,4-diaminocyclohexane) can be inexpensively prepared by a mechanochemical reaction followed by mild thermal treatment. The system is able to reversibly absorb molecules from solution or by simple kneading, while guest desorption from the product invariably leads back to the unsolvated form.

    30. Inverting the Charges of Natural Nucleobase Quartets: A Planar Platinum–Purine Quartet with Pronounced Sulfate Affinity (pages 147–150)

      Michael Roitzsch and Bernhard Lippert

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200502878

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      Variations on nature: Coordinative metal–ligand bonds instead of cyclic hydrogen bonds, an anion (sulfate) in the center rather than a cation, and an overall positive charge instead of a negative one are the major differences between the artificial platinum–purine quartet 2 (left) and the naturally occurring guanine quartet G4 (right).

    31. Arsenic Fatty Acids Are Human Urinary Metabolites of Arsenolipids Present in Cod Liver (pages 150–154)

      Ernst Schmeisser, Alice Rumpler, Manfred Kollroser, Gerald Rechberger, Walter Goessler and Kevin A. Francesconi

      Article first published online: 24 NOV 2005 | DOI: 10.1002/anie.200502706

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      Is fish a healthy food? Arsenolipids present in cod liver are metabolized by humans to arsenic-containing fatty acids. Four of these metabolites were identified in human urine after consumption of cod liver and characterized by mass spectrometry and chromatography.

    32. A General and Efficient Method for the Formylation of Aryl and Heteroaryl Bromides (pages 154–158)

      Stefan Klaus, Helfried Neumann, Alexander Zapf, Dirk Strübing, Sandra Hübner, Juan Almena, Thomas Riermeier, Peter Groß, Martin Sarich, Wolf-Rüdiger Krahnert, Kai Rossen and Matthias Beller

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502697

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      The key to the general and efficient palladium-catalyzed formylation of aryl and heteroaryl bromides is the use of the di-1-adamantyl-n-butylphosphane (cataCXium A) as ligand. Low pressure of the synthesis gas and appropriate choice of the base are also important for high yields (up to 99 %) of a broad range of (hetero)aromatic aldehydes at unprecedented low catalyst concentrations (see scheme; TMEDA= N,N,N′,N′-tetramethylethylenediamine).

    33. Highly Efficient Reagents for Br/Mg Exchange (pages 159–162)

      Arkady Krasovskiy, Bernd F. Straub and Paul Knochel

      Article first published online: 24 NOV 2005 | DOI: 10.1002/anie.200502220

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      The conversion of electron-rich aryl bromides into the corresponding Grignard compounds proceeds within 2 h at 25 °C in the presence of 0.55 equivalents of the new reagent sBu2Mg⋅LiCl. The high reactivity of magnesiates is rationalized by quantum chemical model calculations, and selected examples illustrate the benefits of aryl magnesium compounds for organic syntheses.

    34. Synthesis and Characterization of Palladium and Platinum Iminoboryl Complexes (pages 162–165)

      Holger Braunschweig, Krzysztof Radacki, Daniela Rais and Katharina Uttinger

      Article first published online: 21 NOV 2005 | DOI: 10.1002/anie.200502825

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      A terminal condition: The palladium and platinum complexes trans-[(Cy3P)2M(B[TRIPLE BOND]NSiMe3)(Br)] feature an unprecedented terminally bound iminoboryl ligand. The compounds are synthesized upon facile elimination of Me3SiBr at room temperature from the postulated intermediates trans-[(Cy3P)2M(Br){B(Br)N(SiMe3)2}], which are obtained by oxidative addition of the B[BOND]Br bond in (Me3Si)2NBBr2 to [M(PCy3)2] (M=Pd, Pt). Cy=cyclohexyl.

    35. Li2B12C2 and LiB13C2: Colorless Boron-Rich Boride Carbides of Lithium (pages 165–168)

      Natascha Vojteer and Harald Hillebrecht

      Article first published online: 22 NOV 2005 | DOI: 10.1002/anie.200502325

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      Wade was right: Li2B12C2 and LiB13C2, the first boron-rich boride carbides of lithium, are (nearly) colorless and stoichiometrically composed. Their crystal structures are characterized by B12 icosahedra and C2 and CBC units, respectively, forming a three-dimensional framework with Li cations in the voids. The charge distribution can be described by Wade's rules: (Li+)2B122−C2 and (Li+)B122−(CBC+). The synthesis succeeded in molten metals at high temperatures.

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      Preview: Angew. Chem. Int. Ed. 1/2006 (page 173)

      Article first published online: 14 DEC 2005 | DOI: 10.1002/anie.200690002

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