Chemistry - A European Journal

Cover image for Vol. 13 Issue 5

February 2, 2007

Volume 13, Issue 5

Pages 1339–1635

  1. Cover Picture

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    1. Cover Picture: Dipyrrolyl-Functionalized Bipyridine-Based Anion Receptors for Emission-Based Selective Detection of Dihydrogen Phosphate (Chem. Eur. J. 5/2007) (page 1339)

      Patrick Plitt, Dustin E. Gross, Vincent M. Lynch and Jonathan L. Sessler

      Version of Record online: 18 JAN 2007 | DOI: 10.1002/chem.200790014

      The extremely rare (and obviously apocryphal) Big Mouth Pyrrole Anglerfish that fluoresces in its hungry state until it is well fed with phosphate anion is depicted on the cover. This cover image was produced by the authors using an image purchased with associated rights from Image Quest Marine (www.imagequestmarine.com). In their Full paper on page 1374 ff., J. L. Sessler et al. discuss the selectivity of a new pyrrole-based receptor for phosphate ions.

  2. Graphical Abstract

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  3. Concept

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    1. Recent Developments in the Metal-Catalyzed Reactions of Metallocarbenoids from Propargylic Esters (pages 1350–1357)

      José Marco-Contelles and Elena Soriano

      Version of Record online: 2 JAN 2007 | DOI: 10.1002/chem.200601522

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      The applications, scope, and limitations of transition-metal-catalyzed cycloisomerization of propargylic carboxylates that yields bicyclo[n.1.0]enol esters in a very diastereoselective manner is discussed. Mechanistic DFT results, supported by recent experimental evidence, suggest that a C[BOND]C bond-forming event takes place before the cleavage of the C[BOND]O bond.

  4. Full Papers

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    1. Intra- and Intermolecular Reactions of Indoles with Alkynes Catalyzed by Gold (pages 1358–1373)

      Catalina Ferrer, Catelijne H. M. Amijs and Antonio M. Echavarren

      Version of Record online: 8 JAN 2007 | DOI: 10.1002/chem.200601324

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      The golden touch: Indoles react intramolecularly with alkynes in the presence of gold catalysts to give from six- to eight-membered ring annulated compounds. The intermolecular reaction of indoles with alkynes proceeds to form 3-alkenylated intermediates that react with a second equivalent of indole to give bisindolyl derivatives (see scheme).

    2. Dipyrrolyl-Functionalized Bipyridine-Based Anion Receptors for Emission-Based Selective Detection of Dihydrogen Phosphate (pages 1374–1381)

      Patrick Plitt, Dustin E. Gross, Vincent M. Lynch and Jonathan L. Sessler

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/chem.200601514

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      Fishing out the phosphate: Bearing the same number of pyrrole units (i.e., two) as those present in dipyrrolyl quinoxaline derivatives, the new receptors of this report display a larger cavity size than the latter due to the substitution of the quinoxaline moiety with a bipyridine spacer. Dihydrogen phosphate quenches the emission of the RuII derivative, making these systems of potential interest as anion sensors.

    3. Osmium-Mediated C[BOND]H and C[BOND]C Bond Cleavage of a Phenolic Substrate: p-Quinone Methide and Methylene Arenium Pincer Complexes (pages 1382–1393)

      Régis M. Gauvin, Haim Rozenberg, Linda J. W. Shimon, Yehoshoa Ben-David and David Milstein

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/chem.200601385

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      C[BOND]H activation of a pincer-type diphosphine phenol compound affords osmium-complexed quinone methides as a mixture of isomers. Subsequent hydrogenolysis results in C[BOND]C bond cleavage. Reactivity of the quinone methides has been studied, providing a basis to a proposed pathway for their formation as well as to the C[BOND]C cleavage process (see scheme).

    4. Pd0.213Cd0.787 and Pd0.235Cd0.765 Structures: Their Long c Axis and Composite Crystals, Chemical Twinning, and Atomic Site Preferences (pages 1394–1410)

      Joshua Teal Schmidt, Stephen Lee, Daniel C. Fredrickson, Matthias Conrad, Junliang Sun and Bernd Harbrecht

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200600135

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      Brassed off: Pd1−xCdx intermetallic structures have chains of atoms that follow the Fibonacci sequence (1,1,2,3,5,8,13,21,‥), as illustrated here. The structures have been studied in comparison with γ-brass, which is the parent structure.

    5. Design of a Phosphinate-Based Fluorescent Probe for Superoxide Detection in Mouse Peritoneal Macrophages (pages 1411–1416)

      Kehua Xu, Xia Liu, Bo Tang, Guiwen Yang, Yong Yang and Liguo An

      Version of Record online: 30 OCT 2006 | DOI: 10.1002/chem.200600497

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      A new type of phosphinate-based fluorescent probe for imaging O2.− in living cells (see graphic) is described. Analysis experiments of fluorescence show that the sensitive fluorogenic reagent features a high selectivity for O2.− over other intracellular reactive oxygen species and biological compounds, a wide response range and low detection limit. Using fluorescence microscopy, cell-derived O2.− can be identified in living cells.

    6. Identification of 7,4′-Dihydroxy-5-methoxyflavylium in “Dragon's Blood”: To Be or Not To Be an Anthocyanin (pages 1417–1422)

      Maria J. Melo, Micaela Sousa, A. Jorge Parola, J. Sérgio Seixas de Melo, Fernando Catarino, Joaquim Marçalo and Fernando Pina

      Version of Record online: 20 NOV 2006 | DOI: 10.1002/chem.200600837

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      What's in dragon's blood? The red colour of “dragon's blood” resin, extracted from the tree Dracaena draco, was found to be attributable to the red quinoid bases of the corresponding yellow flavylium cations (see figure). Despite its natural origin, the colorant is more similar to many synthetic flavylium compounds than to natural anthocyanins or deoxyanthocyanidins.

    7. Tris-Cyclometalated Iridium(III) Complexes of Carbazole(fluorenyl)pyridine Ligands: Synthesis, Redox and Photophysical Properties, and Electrophosphorescent Light-Emitting Diodes (pages 1423–1431)

      Sylvia Bettington, Mustafa Tavasli, Martin R. Bryce, Andrew Beeby, Hameed Al-Attar and Andrew P. Monkman

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200600888

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      New light on carbazole-containing polymers: Two isomeric series of carbazole-containing phosphorescent tris-cyclometalated iridium(III) complexes (see picture) have been synthesized and their redox and photophysical properties studied; selected derivatives have been used as dopants to fabricate orange and green organic light-emitting devices.

    8. Mechanistic Study of a Pd/C-Catalyzed Reduction of Aryl Sulfonates Using the Mg–MeOH–NH4OAc System (pages 1432–1441)

      Akinori Mori, Tomoteru Mizusaki, Takashi Ikawa, Tomohiro Maegawa, Yasunari Monguchi and Hironao Sajiki

      Version of Record online: 30 OCT 2006 | DOI: 10.1002/chem.200601184

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      A simple removal: The combination of Pd/C–Mg–MeOH facilitates the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates (see scheme). The addition of NH4OAc to the system markedly accelerates the reaction rate and expands the reaction scope. NH4OAc works as a solubilizing reagent for the Mg salt and an accelerator of the electron-transfer process, thus enhancing the reaction process.

    9. Oxidation of Linear Trinuclear Ruthenium Complexes [Ru3(dpa)4Cl2] and [Ru3(dpa)4(CN)2]: Synthesis, Structures, Electrochemical and Magnetic Properties (pages 1442–1451)

      Ching-Kuo Kuo, Isiah Po-Chun Liu, Chen-Yu Yeh, Chung-Hsien Chou, Ting-Bin Tsao, Gene-Hsiang Lee and Shie-Ming Peng

      Version of Record online: 29 NOV 2006 | DOI: 10.1002/chem.200601219

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      Changing structures in ruthenium complexes: The one- and two-electron oxidized products of neutral trinuclear ruthenium compounds (shown here) have been synthesized and structurally characterized. The Ru3 unit of these oxidized compounds is in an essentially symmetrical arrangement. The Ru[BOND]Laxial bond lengths and the Ru[BOND]Ru distances show significant changes upon oxidation of the neutral triruthenium dichloro and dicyano compounds.

    10. Total Synthesis and Evaluation of the Actin-Binding Properties of Microcarpalide and a Focused Library of Analogues (pages 1452–1462)

      Alois Fürstner, Takashi Nagano, Christoph Müller, Günter Seidel and Oliver Müller

      Version of Record online: 24 NOV 2006 | DOI: 10.1002/chem.200601370

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      A comparative investigation has enabled us to validate the naturally occurring nonenolides microcarpalide and pinolidoxin as leads in the search for selective and nontoxic agents with the capacity to bind to the actin cytoskeleton (see micrograph). Most notably, the 10-membered ring can even be contracted by translactonization to a much more readily available furanone moiety without compromising the bioactivity of the compound.

    11. Manipulation of the Morphology of Semiconductor-Based Nanostructures from Core–Shell Nanoparticles to Nanocables: The Case of CdSe/SiO2 (pages 1463–1470)

      Zhenyang Wang, Qifei Lu, Mingguang Kong and Lide Zhang

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200501425

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      Controlled manipulation: CdSe/SiO2 core–shell-structured nanospheres are converted to CdSe/SiO2 nanocables by a simple vapor-transport process, and their sizes, including the thickness of the SiO2 sheath and the diameter of the CdSe core, are successfully controlled.

    12. Complex Biohopanoids Synthesis: Efficient Anchoring of Ribosyl Subunits onto a C30 Hopane (pages 1471–1480)

      Weidong Pan, Chao Sun, Yongmin Zhang, Guangyi Liang, Pierre Sinaÿ and Stéphane P. Vincent

      Version of Record online: 20 NOV 2006 | DOI: 10.1002/chem.200600659

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      Synthesis of several biohopanoid derivatives: An efficient methodology for the formation of the biohopanoid C30[BOND]C31 bond has been developed, through the use of D-ribose-derived electrophiles and a hopanyllithium intermediate (see scheme). This new method enabled us to synthesize several biohopanoids stereoselectively, including a hopanepentol bearing an additional hydroxy group at position C31.

    13. Synthesis, Fluorescence, and Two-Photon Absorption of a Series of Elongated Rodlike and Banana-Shaped Quadrupolar Fluorophores: A Comprehensive Study of Structure–Property Relationships (pages 1481–1498)

      Olivier Mongin, Laurent Porrès, Marina Charlot, Claudine Katan and Mireille Blanchard-Desce

      Version of Record online: 14 NOV 2006 | DOI: 10.1002/chem.200600689

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      Fine tuning: A comprehensive series of push–push and pull–pull fluorophores was prepared from the symmetrical functionalization of an ambivalent core with conjugated rods bearing acceptor or donor end-groups (see scheme). Their absorption, photoluminescence, and two-photon-absorption (TPA) properties were investigated. These allowed structure–property relationships and guidelines for both spectral tuning and amplification of TPA to be derived.

    14. Hydrogen-Bond Interactions of Nicotine and Acetylcholine Salts: A Combined Crystallographic, Spectroscopic, Thermodynamic and Theoretical Study (pages 1499–1510)

      Virginie Arnaud, Michel Berthelot, Michel Evain, Jérôme Graton and Jean-Yves Le Questel

      Version of Record online: 14 NOV 2006 | DOI: 10.1002/chem.200600808

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      Both the greater HB basicity of the pyridinic nitrogen over the carbonyl oxygen and the greater HB acidity of the N+H unit relative to N+CH could contribute to the higher affinity for nicotinic acetylcholine receptors (nAChRs) of nicotine-like ligands (1) relative to acetylcholine-like ligands (2) (see picture; HB: hydrogen-bond).

    15. Unprecedented Polymerization of Trimethylene Carbonate Initiated by a Samarium Borohydride Complex: Mechanistic Insights and Copolymerization with ε-Caprolactone (pages 1511–1521)

      Isabelle Palard, Michèle Schappacher, Benjamine Belloncle, Alain Soum and Sophie M. Guillaume

      Version of Record online: 13 NOV 2006 | DOI: 10.1002/chem.200600843

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      α-Hydroxy-ω-formatetelechelic PTMC: The rare-earth borohydride complex [Sm(BH4)3(thf)3] initiates the controlled ring-opening polymerization of trimethylenecarbonate (TMC) to give difunctionalized polymers HO-PTMC-OC(O)H (see scheme). Random and block copolymers with ε-caprolactone (CL), HC(O)O-PTMC-co/b-PCL-OH and block HO-PTMC-b-PCL-OH, were also synthesized.

    16. Dehalogenation of 1,3-Diiodotricyclo[3.3.0.03,7]octane: Generation of 1,3-Dehydrotricyclo[3.3.0.03,7]octane, a 2,5-Methano-Bridged [2.2.1]Propellane (pages 1522–1532)

      Carles Ayats, Pelayo Camps, José A. Fernández and Santiago Vázquez

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200600859

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      Twisted [2.2.1]propellane: Compounds isolated from the reaction of (±)-1,3-diiodotricyclo[3.3.0.03,7]octane (1) with molten sodium or tBuLi suggest the intermediate formation of 1,3-dehydro derivatives 2 (see scheme). Stereoisomeric bi(5-methylenebicyclo[2.2.1]hept-2-ylidene) derivatives 4 are produced, probably by coupling of two units of 2 of the same or different absolute configuration, followed by fragmentation.

    17. Recrystallization and Shape Control of Crystals of the Organic Dye Acid Green 27 in a Mixed Solvent (pages 1533–1538)

      Huai-Ping Cong and Shu-Hong Yu

      Version of Record online: 10 NOV 2006 | DOI: 10.1002/chem.200600881

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      Keeping in shape! Differently shaped crystals of the dye acid green 27 (figure, bottom left) can be recrystallized from a mixed solvent of alcohol and water (bottom right). This approach can be used as a new and effective synthetic tool for controlling the shapes and sizes of other organic crystals.

    18. Synthesis and Characterisation of Nonclassical Ruthenium Hydride Complexes Containing Chelating Bidentate and Tridentate Phosphine Ligands (pages 1539–1546)

      Martin H. G. Prechtl, Yehoshoa Ben-David, Daniela Giunta, Stefan Busch, Yuki Taniguchi, Wolfgang Wisniewski, Helmar Görls, Richard J. Mynott, Nils Theyssen, David Milstein and Walter Leitner

      Version of Record online: 20 NOV 2006 | DOI: 10.1002/chem.200600897

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      C[BOND]H bond activation: New nonclassical ruthenium hydride complexes containing bidentate PP and tridentate PCP and PNP pincer-type ligands (see figure) have been synthesised and characterised. These complexes offer insights into H[BOND]H and C[BOND]H bond activation.

    19. Rh-Catalyzed Enantioselective Conjugate Addition of Arylboronic Acids with a Dynamic Library of Chiral tropos Phosphorus Ligands (pages 1547–1558)

      Chiara Monti, Cesare Gennari and Umberto Piarulli

      Version of Record online: 29 NOV 2006 | DOI: 10.1002/chem.200600960

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      Remarkable synergism and notable enhancements of enantioselectivity were observed for heterocomplex catalysts formed with chiral P ligands (as illustrated). Flexible biphenolic P ligands outperformed the analogous rigid binaphtholic ones. This exemplifies catalyst self-adaptation and tuning, for which heterocomplexes perform better than the homocomplexes, and conformationally mobile systems perform better than rigid ones.

    20. Structure, Stability and Guest Affinity of Tris(3-ureidobenzyl)amine Capsules in Solution (pages 1559–1569)

      Mateo Alajarín, Aurelia Pastor, Raúl-Angel Orenes, Eloísa Martínez-Viviente, Heinz Rüegger and Paul S. Pregosin

      Version of Record online: 9 NOV 2006 | DOI: 10.1002/chem.200601022

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      Captivating capsules: Self-assembled capsules are formed in solution by dimerisation of two tris(ureidobenzyl)amine modules and an appropriate guest (see figure). The affinity between guest and capsule is dictated mainly by the electronic, size and shape complementarity between cavity and guest. A gating mechanism for guest exchange is proposed.

    21. The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p-Methylstyrene Copolymerization (pages 1570–1582)

      Barbara Binotti, Gianfranco Bellachioma, Giuseppe Cardaci, Carla Carfagna, Cristiano Zuccaccia and Alceo Macchioni

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200601029

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      Size matters! The interionic structure of [Pd(η12-C8H12OMe)(Ar[BOND]N[DOUBLE BOND]C(R′)[BOND]C(R′)[DOUBLE BOND]N[BOND]Ar)]X compounds is correlated with their catalytic activity and stereoselectivity toward CO/p-methylstyrene copolymerization. The isotacticity of the copolymers produced by ortho-monosubstituted catalysts depends greatly on the counterion (see scheme). This effect is explained by a greater reduction of the copolymerization rate of Cs-symmetric isomers with respect to their C2-symmetric counterparts.

    22. Experimental and DFT Study of the Tautomeric Behavior of Cobalt-Containing Secondary Phosphine Oxides (pages 1583–1593)

      Chu-Hung Wei, Cheng-En Wu, Yi-Luen Huang, Roman G. Kultyshev and Fung-E. Hong

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200601051

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      Evidence for tautomerism between phosphine oxide 1 and its isomeric phosphinous acid form 1′ in solution has been obtained. Thus, Heck reactions employing 1/Pd(OAc)2 as the catalyst system, in which 1′ but not 1 is expected to be active, gave satisfying results. DFT studies demonstrated that the tautomeric conversion 11′ might be achieved with reasonably low activation energy through a bimolecular pathway.

    23. Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals (pages 1594–1601)

      Moballigh Ahmed, Cathleen Buch, Lucie Routaboul, Ralf Jackstell, Holger Klein, Anke Spannenberg and Matthias Beller

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200601155

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      Good yields of the desired products were obtained in the hydroaminomethylation of aromatic olefins (see scheme) employing a novel rhodium–carbene complex. The influence of different ligands and reaction parameters on the catalytic activity were also investigated in detail.

    24. Effects of 3d–4f Magnetic Exchange Interactions on the Dynamics of the Magnetization of DyIII-MII-DyIII Trinuclear Clusters (pages 1602–1609)

      Fabrice Pointillart, Kevin Bernot, Roberta Sessoli and Dante Gatteschi

      Version of Record online: 30 NOV 2006 | DOI: 10.1002/chem.200601194

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      Transmission of ferromagnetic exchange interactions: The central {M(bpca)2} unit links two terminal {Dy(hfac)3} fragments to form 3d–4f trinuclear complexes. The angle between O-C-Namide-C-O planes (shown here in yellow) is around 80°. This particular structural conformation can lead to a partial “cancellation” of the easy axis anisotropy of the ions.

    25. Kibdelones: Novel Anticancer Polyketides from a Rare Australian Actinomycete (pages 1610–1619)

      Ranjala Ratnayake, Ernest Lacey, Shaun Tennant, Jennifer H. Gill and Robert J. Capon

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/chem.200601236

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      A rareKibdelosporangiumsp. isolated from an Australian soil sample has been found to produce the kibdelones (see figure), a novel family of heterocyclic polyketides that exhibit potent and selective cytotoxicity against a panel of human tumor cell lines, and also display significant antibacterial and nematocidal properties.

    26. [40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with Palladium–Carbon Bonds (pages 1620–1628)

      Yiho Kamimura, Soji Shimizu and Atsuhiro Osuka

      Version of Record online: 23 NOV 2006 | DOI: 10.1002/chem.200601304

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      Step-by-step: meso-Pentafluorophenyl-substituted nonaphyrin(1.1.1.1.1.1.1.1.1) 1 was synthesized by using a ring-size-selective synthetic procedure. By employing a stepwise metalation protocol (see scheme), heterometal complexes (Zn–Pd–Pd and Cu–Pd–Pd) were efficiently prepared, and were found to exhibit small electrochemical HOMO–LUMO gaps.

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      Preview: Chem. Eur. J. 6/2007 (page 1635)

      Version of Record online: 18 JAN 2007 | DOI: 10.1002/chem.200790016

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