Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 45

November 19, 2004

Volume 43, Issue 45

Pages 6009–6217

    1. Cover Picture: Atomic-Step-Templated Formation of Single Wall Carbon Nanotube Patterns (Angew. Chem. Int. Ed. 45/2004) (page 6009)

      Ariel Ismach, Lior Segev, Ellen Wachtel and Ernesto Joselevich

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200490160

      The assembly of nanowire arrays is a critical prerequisite for the large-scale fabrication of nanocircuitry. In their Communication on pp. 6140 ff., E. Joselevich and co-workers show how single-wall carbon nanotubes are formed along the atomic steps of vicinal surfaces, to give highly aligned, dense arrays of discrete, nanometer-wide wires. The cover picture shows how the nanotubes (blue AFM image) reproduce the atomic features of the surface (red model).

    2. A Crystallographic Database for Minerals (page 6024)

      Diana Hoppe and Michael Ruck

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200462385

    3. An Octahedral Rhodium Cluster with Six Phosphine and 12 Hydride Ligands and 10 Too Few Electrons (pages 6028–6030)

      Paul J. Dyson and J. Scott McIndoe

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460924

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      Six of one and half a dozen of the other: A late-transition-metal octahedral cluster [Rh6(PiPr3)6(μ-H)12]2+ (1) with six phosphine ligands has been reported with a structure and electron count akin to that of early-transition-metal halide clusters, and provides a unique link between the two classes of cluster (see scheme). Cluster 1 is also decorated with 12 hydride ligands.

    4. Catalytic Promiscuity in Biocatalysis: Using Old Enzymes to Form New Bonds and Follow New Pathways (pages 6032–6040)

      Uwe T. Bornscheuer and Romas J. Kazlauskas

      Version of Record online: 2 NOV 2004 | DOI: 10.1002/anie.200460416

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      Unfaithful enzymes, that is, enzymes that catalyze alternative reactions, play a natural role in evolution and occasionally in the biosynthesis of secondary metabolites. In one example pyruvate decarboxylase catalyzes not only the natural reaction (A) but also the enantioselective acyloin condensation of acetaldehyde and benzaldehyde (B).

    5. Integrated Nanoparticle–Biomolecule Hybrid Systems: Synthesis, Properties, and Applications (pages 6042–6108)

      Eugenii Katz and Itamar Willner

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200400651

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      Blue-sky research bears down-to-earth applications: this describes the integration of biological materials with nanomaterials to yield systems that can be applied as biosensors or as building blocks for electronic circuitry. This review describes recent advances in the preparation and the applications of biomolecule–nanoparticle conjugates. The picture shows one such example with the magnetomechanical analysis of DNA.

    6. Biomimetic Engineering of Carbon Nanotubes by Using Cell Surface Mucin Mimics (pages 6111–6116)

      Xing Chen, Goo Soo Lee, A. Zettl and Carolyn R. Bertozzi

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460620

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      Biocompatible nanotubes: Glycosylated polymers designed to mimic natural mucins were assembled on carbon nanotubes (see picture). Carbon nanotubes coated with mucin mimics were soluble in water, resisted nonspecific protein binding, and bound specifically to biomolecules through receptor–ligand interactions.

    7. Probing the Influence of O2 on Photoinduced Reversible Electron Transfer in Perylenediimide–Triphenylamine-Based Dendrimers by Single-Molecule Spectroscopy (pages 6116–6120)

      Mircea Cotlet, Sadahiro Masuo, Marc Lor, Eduard Fron, Mark Van der Auweraer, Klaus Müllen, Johan Hofkens and Frans De Schryver

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460560

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      The dynamics of reversible photoinduced electron transfer in individual perylenediimide–triphenylamine-based donor–acceptor dendrimers immobilized in polystyrene were investigated by single-molecule spectroscopy. By changing the local concentration of oxygen, it was possible to influence the transition of the charge-separation state (CSS) either to the locally excited state (LES) or to the ground state (GS, see graphic).

    8. An Oriented 1D Coordination/Organometallic Dimetallic Molecular Wire with Ag[BOND]Pd Metal–Metal Bonds (pages 6120–6125)

      Pierre Braunstein, Céline Frison, Nicola Oberbeckmann-Winter, Xavier Morise, Abdelatif Messaoudi, Marc Bénard, Marie-Madeleine Rohmer and Richard Welter

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461291

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      A subtle electronic balance between covalent and dative interactions involving coordinated phosphanyl iminolate ligands results in the formation of an oriented, 1 D coordination/organometallic heterodimetallic polymer with Pd–Ag interactions (shown as purple and green, respectively). In the solid-state, the lipophilic aromatic rings of the infinite zigzag chains are all on one side of the planes of metal ions, which results in an unusual layered structure.

    9. Asymmetric Synthesis of Diarylmethyl Amines by Rhodium-Catalyzed Asymmetric Addition of Aryl Titanium Reagents to Imines (pages 6125–6128)

      Tamio Hayashi, Masahiro Kawai and Norihito Tokunaga

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461338

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      A rational tuning of the arene sulfonamide moiety (by introducing isopropyl groups onto the phenyl ring) brought about high enantioselectivity in the asymmetric synthesis of diarylmethyl amines by the title reaction (see scheme). Ar1=4-CF3C6H4, 4-ClC6H4, 4-FC6H4, 3-MeOC6H4, 4-MeOC6H4, 2-MeC6H4, 1-naphthyl, Ph; Ar2=Ph, 4-FC6H4, 3-MeOC6H4, 4-MeOC6H4.

    10. A Gallium-Coated Gold Cluster (pages 6128–6131)

      U. Anandhi and Paul R. Sharp

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461295

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      A triangular arrangement of gold atoms is observed in the complex [Au3(μ-GaI2)3(Cp*Ga)5], which results when a mixture of Cp*Ga and GaI3 capture the reduced Au fragments from [LAuX] (L=ligand, X=halide). The Au atoms are bonded only to Ga atoms and each other: two Au atoms are coordinated by two Cp*Ga units and one Au atom is coordinated by a single Cp*Ga unit.

    11. Templating Open- and Closed-Chain Structures around Metal Complexes of Macrocycles (pages 6132–6135)

      Sarah L. Heath, Rebecca H. Laye, Christopher A. Muryn, Nicola Lima, Roberta Sessoli, Rachel Shaw, Simon J. Teat, Grigore A. Timco and Richard E. P. Winpenny

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461006

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      Ringing the changes: Complexes of azamacrocycles were used for the template synthesis of extraordinary new cyclic and acyclic chromium–nickel chains, which include the “S”-shaped cluster shown (see picture) obtained when a cyclen-based template is used. The results suggest a new method for making sophisticated polymetallic architectures.

    12. Reversible Photo-Switching of the Magnetization of Iron Oxide Nanoparticles at Room Temperature (pages 6135–6139)

      Rie Mikami, Minori Taguchi, Koji Yamada, Koji Suzuki, Osamu Sato and Yasuaki Einaga

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460964

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      In the solid state at room temperature, reversible control of magnetic properties was achieved with photo-illumination of a composite material made up of γ-Fe2O3 nanoparticles encapsulated with n-octylamine and an azobenzene-containing amphiphilic compound (see picture).

    13. Atomic-Step-Templated Formation of Single Wall Carbon Nanotube Patterns (pages 6140–6143)

      Ariel Ismach, Lior Segev, Ellen Wachtel and Ernesto Joselevich

      Version of Record online: 28 SEP 2004 | DOI: 10.1002/anie.200460356

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      Mind the step! Single-wall carbon nanotubes grow along the atomic steps of vicinal α-Al2O3 surfaces to give highly aligned arrays of nanometer-wide wires on a dielectric material. The nanotubes (see blue background image) reproduce the atomic features of the surface including steps, facets, and kinks (see model). The direction and morphology of the atomic steps can be controlled by the crystal miscut.

    14. Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara–Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans (pages 6144–6148)

      Haiming Zhang, Eric M. Ferreira and Brian M. Stoltz

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461294

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      No extra functionalization step is required for palladium(II)-catalyzed oxidative carbocyclizations like that shown, which provide highly substituted benzofuran and dihydrobenzofuran derivatives by net dehydrogenation. The mechanism is similar to that of Heck cyclizations. Products containing quaternary carbon stereocenters can be obtained in diastereomerically pure form.

    15. Changes in the Conductance of Single Peptide Molecules upon Metal-Ion Binding (pages 6148–6152)

      Xiaoyin Xiao, Bingqian Xu and Nongjian Tao

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460886

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      The binding of a guest (metal ion, M+) to a single host molecule (peptide) was studied by the measurement of the conductance of the peptide (see picture). The conductance of the peptide in the metal–peptide complexes increases by an amount that is dependent on the sequence and the length of the host.

    16. Polycationic Mn12 Single-Molecule Magnets as Electron Reservoirs with S>10 Ground States (pages 6152–6156)

      Eugenio Coronado, Alicia Forment-Aliaga, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Francisco M. Romero and Wolfgang Wernsdorfer

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460282

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      Manganese magnets: Trimethylammonio groups appended to the surface of a Mn12 single-molecule magnet lead to a highly charged magnetic cluster that behaves as an electron reservoir. This cluster spontaneously forms its two-electron reduced species which has a ground spin state S=11. The cluster is a precursor for the synthesis of network materials containing Mn12 and for their deposition onto metal and metal oxide surfaces.

    17. Cubic, Hydrogen-Bonded (10,3)-a Networks in the Family [C(NH2)3][N(CH3)4][XO4] (X=S, Cr, and Mo) (pages 6157–6160)

      Brendan F. Abrahams, Marissa G. Haywood, Timothy A. Hudson and Richard Robson

      Version of Record online: 2 NOV 2004 | DOI: 10.1002/anie.200461678

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      It takes two: The complementary sulfate and guanidinium ions in [C(NH2)3][N(CH3)4][SO4] both act as 3-connecting nodes to give a 3D hydrogen-bonded network with the chiral (10,3)-a topology (see X-ray crystal structure; O red, S yellow, H pink, N blue, C black). In contrast, the 3-connected hydrogen-bonded network in the much-studied guanidinium sulfonates is 2D.

    18. Rapidly Initiating Ruthenium Olefin-Metathesis Catalysts (pages 6161–6165)

      Patricio E. Romero, Warren E. Piers and Robert McDonald

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461374

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      Vacancies: Protonation of the ruthenium carbide compounds [Cl2(L)(PR3)Ru[TRIPLE BOND]C:] gives the 14-electron four-coordinate ruthenium phosphonium alkylidenes [Cl2(L)Ru[DOUBLE BOND]CH(PR3)]+[B(X)4] (see scheme). These compounds which already have a vacant coordination site provide direct access to the active species in olefin metathesis catalysis and thus very fast initiation.

    19. Nanozymes: Gold-Nanoparticle-Based Transphosphorylation Catalysts (pages 6165–6169)

      Flavio Manea, Florence Bodar Houillon, Lucia Pasquato and Paolo Scrimin

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460649

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      Particularly effective: The self-assembly of triazacyclonane-functionalized thiols on the surface of nanosize gold particles provides a facile entry to functional gold nanoparticles that, upon complexation with ZnII, turn into powerful catalysts for the cleavage of phosphate esters (see scheme). Because of their RNase-like behavior they are dubbed nanozymes.

    20. A General Route to Macroscopic Hierarchical 3D Nanowire Networks (pages 6169–6173)

      Donghai Wang, Hongmei Luo, Rong Kou, Maria P. Gil, Shuaigang Xiao, Vladimir O. Golub, Zhenzhong Yang, C. Jeffrey Brinker and Yunfeng Lu

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460535

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      Pulling the rug out! A templated electrodeposition technique has been applied to prepare stable 3D, organized networks of metal or semiconductor nanowires (see scheme). The process involves a) the deposition of mesoporous silica onto an electrode, b) the introduction of metals or semiconductors into the pore channels, and c) removal of the silica template to yield the nanowire network.

    21. A Catalytic Langmuir Film as a Model for Heterogeneous and Homogeneous Catalytic Processes (pages 6174–6177)

      Andrea Pasc-Banu, Claudia Sugisaki, Thierry Gharsa, Jean-Daniel Marty, Ignacio Gascon, Gianluca Pozzi, Silvio Quici, Isabelle Rico-Lattes and Christophe Mingotaud

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461007

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      An amphiphilic manganese salen complex forms Langmuir films that catalyze the epoxidation of cinnamyl alcohol with the urea/hydrogen peroxide complex (UHP) dissolved in the subphase (see picture). Compression of the monolayer changes the organization of the film and thus strongly modifies the rate of the reaction, which is enhanced for molecular areas of about 140–160 Å2.

    22. Catalytic Asymmetric Mercuriocyclization of γ-Hydroxy-cis-Alkenes (pages 6177–6180)

      Sung Ho Kang, Mihyong Kim and Suk Youn Kang

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461289

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      2-Monosubstituted tetrahydrofurans 2 are obtained with 73–95 % ee through the catalytic enantioselective mercuriocyclization of γ-hydroxy-(Z)-alkenes 1 by using Hg(OAc)2 in the presence of HgII complexed with tartrate-derived 4-(2-naphthyl)bisoxazoline 3. The chiral complex was prepared from Hg(tfa)2 (0.2 equiv) and 3 (0.3 equiv). The amount of MeOH greatly influences the enantioselectivity.

    23. Nickel-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Organozinc and Grignard Reagents with 1,3,8,10-Tetraenes as Additives (pages 6180–6182)

      Jun Terao, Hirohisa Todo, Hideyuki Watanabe, Aki Ikumi and Nobuaki Kambe

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460246

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      Essential additives: The addition of bis(1,3-butadienyl) compounds (tetraenes) was essential in the efficient Ni-catalyzed cross-coupling of organozinc reagents with alkyl bromides and a tosylate (see scheme, X=C(CO2Me)2 or NCH2Ph). The efficiency of the Ni-catalyzed cross-coupling of an alkyl fluoride with a Grignard reagent was also improved by using these tetraenes.

    24. Dramatic Enhancement of Catalytic Activity in an Ionic Liquid: Highly Practical Friedel–Crafts Alkenylation of Arenes with Alkynes Catalyzed by Metal Triflates (pages 6183–6185)

      Choong Eui Song, Da-un Jung, Su Yhen Choung, Eun Joo Roh and Sang-gi Lee

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460292

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      A simple and highly efficient method for the Friedel–Crafts alkenylation of aromatic compounds has been developed by using a metal triflate (OTf) catalyst in an ionic liquid (see scheme, bmim=1-butyl-3-methylimidazolium). Not only is the catalytic activity significantly enhanced in the ionic liquid and by-product formation decreased, but some reactions that were not possible in conventional organic solvents were shown to proceed smoothly.

    25. Nitroxide-Mediated Controlled Free-Radical Emulsion Polymerization of Styrene and n-Butyl Acrylate with a Water-Soluble Alkoxyamine as Initiator (pages 6186–6189)

      Julien Nicolas, Bernadette Charleux, Olivier Guerret and Stéphanie Magnet

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460704

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      Latex: Nitroxide-mediated emulsion polymerizations of n-butyl acrylate and styrene were successfully carried out in a multistep process, with a novel water-soluble SG1-based alkoxyamine as initiator. Fast reactions lead to stable latex particles containing polymers with controlled molar masses.

    26. [LAl(μ-S3)2AlL]: A Homobimetallic Derivative of the Sulfur Crown S8 (pages 6190–6192)

      Ying Peng, Hongjun Fan, Vojtech Jancik, Herbert W. Roesky and Regine Herbst-Irmer

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461209

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      Pieces of eight: The reaction of [LAlI] with elemental sulfur yields the crown shaped complex [LAl(μ-S3)2AlL] (L=HC(CMeNAr)2, Ar=2,6-iPr2C6H3) containing an Al2S6 eight-membered ring, in which two (μ-S3) chains are bridging two aluminum atoms (see structure). The relative stabilities of the possible [L2Al2Sn] (n=2–8) species are estimated by theoretical calculation.

    27. Preparation of [LAl(μ-S)2MCp2] (M=Ti, Zr) from the Structurally Characterized Lithium Complexes [{LAl(SH)[SLi(thf)2]}2] and [{LAl[(SLi)2(thf)3]}2]⋅2 THF (pages 6192–6196)

      Vojtech Jancik, Herbert W. Roesky, Dante Neculai, Ana M. Neculai and Regine Herbst-Irmer

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461254

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      Sulfur bridges: The reactions of [LAl(SH)2] (L=HC(CMeNAr)2, Ar=2,6-iPr2C6H3) with LiN(SiMe3)2 in molar ratio 1:2 and 1:1, respectively, lead to species with the formula [{LAl[(SLi)2(thf)3]}2]⋅2 THF and [{LAl(SH)[SLi(thf)2]}2] in high yields. These lithium salts react further with [Cp2MCl2] (M=Ti, Zr; Cp=C5H5) to give unique heterobimetallic sulfides of composition [LAl(μ-S)2MCp2] (see structure; M=Ti).

    28. The Dithieno[3,2-b:2′,3′-d]phosphole System: A Novel Building Block for Highly Luminescent π-Conjugated Materials (pages 6197–6201)

      Thomas Baumgartner, Toni Neumann and Bastian Wirges

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461301

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      Like a bolt from the blue, the blue photoluminescence of novel phosphole-based materials is extraordinarily intense. The optoelectronic properties show great stability and broad flexibility with respect to wavelength, intensity, and tuneability. The special features of the dithienophosphole system were incorporated in a high-molecular-weight smart polymer potentially suitable for optoelectronic applications.

    29. Molecular Lead Clusters—From Unexpected Discovery to Rational Synthesis (pages 6202–6204)

      Karl W. Klinkhammer, Yun Xiong and Shenglai Yao

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461670

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      Feats of lead: The cluster compounds [Pb12Hyp6] (1; see structure) and [Pb10Hyp6] (2) result from the reaction of the plumbylene [Pb{Si(SiMe3)3}2] ([PbHyp2]) with hydride sources, such as PH3 or [{(Ph3P)CuH}6]. They are the first examples of neutral lead clusters bearing σ-bonded substituents. Whereas 2 is isolated from the reaction mixture on a multigram scale, 1 is only obtained in traces.

    30. Organocatalyzed Conjugate Umpolung of α,β-Unsaturated Aldehydes for the Synthesis of γ-Butyrolactones (pages 6205–6208)

      Christian Burstein and Frank Glorius

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200461572

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      Advantage organocatalysis: N-heterocyclic carbenes can generate homoenolate equivalents under mild conditions by conjugate umpolung of α,β-unsaturated aldehydes. This organocatalytic reaction allows an efficient one-step synthesis of substituted γ-butyrolactones 1 (see scheme, Mes=mesityl).

    31. Butenyl-Substituted Alkaline-Earth Metallocenes: A First Step towards Olefin Complexes of the Alkaline-Earth Metals (pages 6208–6211)

      Herbert Schumann, Stefan Schutte, Heinz-Jürgen Kroth and Dieter Lentz

      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200460927

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      Sandwich any one? The bis(butenyltetramethylcyclopentadienyl) complexes of calcium (2), strontium and barium exhibit an interaction of the alkaline-earth metals with olefin double bonds. Whereas the magnesium derivative (1) crystallizes as a sandwich complex with coplanar cyclopentadienyl ligands and free butenyl side chains, these coordinate to the metal in the analogous but open sandwich complexes of the larger metals calcium, strontium, and barium.

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      Version of Record online: 17 NOV 2004 | DOI: 10.1002/anie.200490162