Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 10

February 27, 2006

Volume 45, Issue 10

Pages 1485–1659

    1. Cover Picture: A Supramolecular Bundling Approach toward the Alignment of Conjugated Polymers (Angew. Chem. Int. Ed. 10/2006) (page 1485)

      Yohei Kubo, Yumiko Kitada, Rie Wakabayashi, Takanori Kishida, Masatsugu Ayabe, Kenji Kaneko, Masayuki Takeuchi and Seiji Shinkai

      Article first published online: 21 FEB 2006 | DOI: 10.1002/anie.200690032

      Synthetic bundling molecules organize conjugated polymers into aligned supramolecular assemblies in an approach inspired by actin-filament bundling proteins. In their Communication on page 1548 ff., M. Takeuchi, S. Shinkai, and co-workers describe how the use of these “aligner molecules” complements existing techniques in supramolecular assembly and provides a new means of generating complex and programmed assemblies of conjugated polymers with defined arrangements, as shown in the cover picture.

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    3. Arthur Schweiger (1946–2006) (page 1500)

      Gunnar Jeschke and Stefan Stoll

      Article first published online: 21 FEB 2006 | DOI: 10.1002/anie.200600428

    4. New Principles in Medicinal Organometallic Chemistry (pages 1504–1507)

      Ulrich Schatzschneider and Nils Metzler-Nolte

      Article first published online: 2 FEB 2006 | DOI: 10.1002/anie.200504604

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      Hard-core drugs: Recent structural and spectroscopic studies demonstrate the versatility of organometallic drug candidates, for example, as novel protein kinase inhibitors and hormone-independent breast cancer prodrugs. The presence of a transition-metal center in such systems allows both the organization of ligands in 3D space (see picture) and the control of redox-activation processes in biological systems.

    5. Measuring Orbitals: Provocation or Reality? (pages 1508–1517)

      W. H. Eugen Schwarz

      Article first published online: 9 FEB 2006 | DOI: 10.1002/anie.200501333

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      Can complex orbitals really be measured? Orbital functions can indeed be reconstructed from measured data by various approaches. Now even femtosecond measurements can be used, though the results are still less accurate than those achieved with purely theoretical methods. The HOMO of the N2 molecule (see picture) has been reconstructed directly from experimental laser-spectroscopic interference intensity measurements by means of computer algorithms.

    6. Asymmetric Catalysis by Chiral Hydrogen-Bond Donors (pages 1520–1543)

      Mark S. Taylor and Eric N. Jacobsen

      Article first published online: 21 FEB 2006 | DOI: 10.1002/anie.200503132

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      Copied from Nature: A dominant mechanism used by enzymes, substrate activation by general acid catalysis, is emerging as a powerful and versatile strategy for enantioselective synthesis with small-molecule catalysts (see scheme). The mechanistic links between natural and synthetic hydrogen-bond-donor catalysts are explored, and the remarkable recent progress in asymmetric catalysis is reviewed.

    7. Solving the Clogging Problem: Precipitate-Forming Reactions in Flow (pages 1544–1548)

      Sarah L. Poe, Meredith A. Cummings, Michael P. Haaf and D. Tyler McQuade

      Article first published online: 13 JAN 2006 | DOI: 10.1002/anie.200503925

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      Solids go with the flow: A monodisperse flow in a microreactor provides an efficient method for keeping solid products away from channel walls. The use of a carrier phase, such as mineral oil, hexane, or toluene, enables solids to be synthesized without clogging of the reactor channels. Further injection points can be added to the microreactor to perform multistep syntheses (see picture).

    8. A Supramolecular Bundling Approach toward the Alignment of Conjugated Polymers (pages 1548–1553)

      Yohei Kubo, Yumiko Kitada, Rie Wakabayashi, Takanori Kishida, Masatsugu Ayabe, Kenji Kaneko, Masayuki Takeuchi and Seiji Shinkai

      Article first published online: 9 FEB 2006 | DOI: 10.1002/anie.200503128

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      All line up together! A new concept for the alignment and assembly of conjugated polymers through the action of supramolecular bundling (“aligner”) molecules is inspired by actin-filament bundling proteins. The approach provides a general means of preparing complex, ordered assemblies of conjugated polymers.

    9. Asymmetric Sequential Allylic Transfer Reaction for the Synthesis of 2-(1-Stannylvinyl)-1,3-diols: Concise Synthesis of (−)-Avenaciolide and (−)-Isoavenaciolide (pages 1553–1556)

      Chan-Mo Yu, Jinsuop Youn and Juyoung Jung

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503863

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      More adventures of tin–tin: The stereospecific synthesis of 2-stannylvinyl-1,3-diols was achieved through a one-pot allylic transfer/distannation/allylic transfer reaction sequence (see scheme). The method was applied to the concise asymmetric syntheses of (−)-avenaciolide and (−)-isoavenaciolide.

    10. Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies (pages 1557–1559)

      Xiao-Chun Huang, Yan-Yong Lin, Jie-Peng Zhang and Xiao-Ming Chen

      Article first published online: 27 JAN 2006 | DOI: 10.1002/anie.200503778

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      Thermally robust porous metal–organic frameworks (MOFs) with zeolitic topologies were constructed by means of a ligand-directed strategy involving molecular tailoring of simple bridging imidazolates with coordinatively unimportant substituents. This led to the isolation of three new MOFs having unusually high symmetries, intriguing topologies such as the supercage shown in the picture, and high thermal stability.

    11. Biologically Driven Assembly of Polyelectrolyte Microcapsule Patterns To Fabricate Microreactor Arrays (pages 1560–1563)

      Bo Wang, Qinghe Zhao, Feng Wang and Changyou Gao

      Article first published online: 27 JAN 2006 | DOI: 10.1002/anie.200502822

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      Spaced capsules: Polyelectrolyte hollow microcapsules are individually and covalently patterned on a flexible polymer film through specific biotin–avidin recognition. ZnS quantum dots (QDs) and other nanoparticles can be spatially synthesized in situ by using the aligned capsules as microreactors (see picture). Release of the QDs can be tuned by additional layers on the capsule walls.

    12. Abasic-Site-Containing Oligodeoxynucleotides as Aptamers for Riboflavin (pages 1563–1568)

      N. B. Sankaran, Seiichi Nishizawa, Takehiro Seino, Keitaro Yoshimoto and Norio Teramae

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200502979

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      Finding flavins: A new class of DNA-duplex aptamers that bind to riboflavin by utilizing an abasic (AP) site has been developed (see model). An optimized duplex shows high selectivity for riboflavin over flavin mononucleotide and flavin adenine dinucleotide. Such riboflavin–duplex interactions are discussed as a basis for the further development of AP-site-based DNA aptamers.

    13. The Transport of Nanosized Gene Carriers Unraveled by Live-Cell Imaging (pages 1568–1572)

      Ralf Bausinger, Katharina von Gersdorff, Kevin Braeckmans, Manfred Ogris, Ernst Wagner, Christoph Bräuchle and Andreas Zumbusch

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503021

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      Tracking transport: Cationic polyethylenimine nanoparticles serve as nonviral vectors and deliver DNA to the nucleus of cells. Fluorescence live-cell imaging highlights the interactions between these polyplexes and the cytoskeleton during the subsequent stages of transfection (see picture). The analysis of the underlying transport processes gives new impulse to further chemical-synthesis approaches.

    14. Elementary Arithmetic Operations by Enzymes: A Model for Metabolic Pathway Based Computing (pages 1572–1576)

      Ronan Baron, Oleg Lioubashevski, Eugenii Katz, Tamara Niazov and Itamar Willner

      Article first published online: 27 JAN 2006 | DOI: 10.1002/anie.200503314

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      Physio-logical: A system of four enzymes, horseradish peroxidase, glucose dehydrogenase, glucose oxidase, and catalase, operate in parallel in the presence of NADH and NAD+ to yield AND and XOR gates (see picture). Glucose and H2O2 act as the inputs, and the absorbance that follows the production of gluconic acid or NADH provide the outputs of the AND and XOR gates, respectively.

    15. Ultrasensitive Detection of Proteins by Amplification of Affinity Aptamers (pages 1576–1580)

      Hongquan Zhang, Zhongwen Wang, Xing-Fang Li and X. Chris Le

      Article first published online: 27 JAN 2006 | DOI: 10.1002/anie.200503345

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      Superdetective: The detection of 180 molecules of a protein was achieved by amplification of DNA aptamers that bind to the target protein. The protein–aptamer complex is separated from the unbound aptamer by capillary electrophoresis (CE). The complex fraction is collected and the aptamer amplified by the polymerase chain reaction (PCR). Such amplification dramatically improves the sensitivity of the detection of proteins.

    16. Ruthenium Half-Sandwich Complexes Bound to Protein Kinase Pim-1 (pages 1580–1585)

      Judit É. Debreczeni, Alex N. Bullock, G. Ekin Atilla, Douglas S. Williams, Howard Bregman, Stefan Knapp and Eric Meggers

      Article first published online: 28 DEC 2005 | DOI: 10.1002/anie.200503468

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      Keeping in shape with half a sandwich: The structure of a picomolar organoruthenium inhibitor bound to the ATP-binding site of the protein kinase Pim-1 (see picture) demonstrates that the ruthenium center has solely a structural role in organizing the organic ligands in the three-dimensional receptor space, thus yielding a structure that is complementary in shape and functional group presentation to the active site of Pim-1.

    17. Guest Exchange in Single Crystals of van der Waals Nanocapsules (pages 1585–1588)

      Gennady S. Ananchenko, Konstantin A. Udachin, Alix Dubes, John A. Ripmeester, Thomas Perrier and Anthony W. Coleman

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200503553

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      Currency exchange! Amphiphilic para-hexanoylcalix[4]arenes can form hydrophobic van der Waals nanocapsules (see picture) which are flexible enough to allow efficient guest exchange without destroying the crystal lattice. Purple: C (dibenzylketone), green: Cl(CHCl3), red: O, white: H.

    18. Microwave-Promoted Rhodium-Catalyzed Arylation of Heterocycles through C[BOND]H Bond Activation (pages 1589–1591)

      Jared C. Lewis, Jessica Y. Wu, Robert G. Bergman and Jonathan A. Ellman

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200504289

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      Performance-enhancing ligands: Two new bridged bicyclic phosphines 1 a,b based on the “phoban” skeleton (see structures of their naphth-2-ylmethyl bromide salts; P yellow, Br brown, C white) are central to a practical catalytic method for the direct arylation of a variety of nitrogen heterocycles using aryl bromides. Broad functional-group tolerance was observed, and the use of microwave radiation allowed for short reaction times.

    19. Spontaneous Colorimetric Sensing of the Positional Isomers of Dihydroxynaphthalene in a 1D Organogel Matrix (pages 1592–1595)

      Pritam Mukhopadhyay, Yuya Iwashita, Michihiro Shirakawa, Shin-ichiro Kawano, Norifumi Fujita and Seiji Shinkai

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503158

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      Like a color palette: A naphthalenediimide-based organogel colorimetric sensor allows recognition of the positional isomers of dihydroxynaphthalene in the gel phase with the naked eye. Intercalation of the dihydroxynaphthalene into the gel matrix produces a donor–acceptor interaction, which gives the gel a distinct color that depends on the strength of noncovalent (H-bonding, π-stacking, van der Waals) interactions.

    20. Enzymatic Synthesis and Photoswitchable Enzymatic Cleavage of a Peptide-Linked Rotaxane (pages 1596–1599)

      Andrew G. Cheetham, Michael G. Hutchings, Tim D. W. Claridge and Harry L. Anderson

      Article first published online: 3 FEB 2006 | DOI: 10.1002/anie.200504064

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      Selective digestion: α-Chymotrypsin was used to synthesize a cyclodextrin azo dye rotaxane and to digest it back to its components. E[RIGHTWARDS ARROW]Z photoisomerization of the rotaxane completely changes its affinity for the enzyme. The presence of the cyclodextrin accelerates digestion of the E isomer and prevents that of the Z isomer.

    21. Self-Assembled Bidentate Ligands for Ru-Catalyzed anti-Markovnikov Hydration of Terminal Alkynes (pages 1599–1602)

      Floris Chevallier and Bernhard Breit

      Article first published online: 31 JAN 2006 | DOI: 10.1002/anie.200503826

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      In pairs: Bidentate ligands are generated by the self-assembly of monodentate ligands through complementary hydrogen bonding. A ruthenium complex bearing such self-assembled heterodimeric ligands is used as the catalyst in the regioselective hydration of terminal alkynes. FG=functional group, Piv=pivaloyl.

    22. Regiospecific Ligand Oxygenation in Iron Complexes of a Carboxylate-Containing Ligand Mediated by a Proposed FeV–Oxo Species (pages 1602–1606)

      Anne Nielsen, Frank B. Larsen, Andrew D. Bond and Christine J. McKenzie

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200502656

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      Mimicked: Through biomimetic iron activation of peroxides (H2O2 or tBuOOH), the shown N4O ligands in their iron(III) complexes can be oxygenated selectively at either an aromatic carbon atom or an aliphatic nitrogen atom.

    23. Bidentate Coordination of Pyrazolate in Low-Coordinate Iron(II) and Nickel(II) Complexes (pages 1607–1611)

      Javier Vela, Sridhar Vaddadi, Savariraj Kingsley, Christine J. Flaschenriem, Rene J. Lachicotte, Thomas R. Cundari and Patrick L. Holland

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503535

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      The first FeIIand NiIIcomplexes with bidentate pyrazolate ligands have been prepared (see scheme; M=FeII, NiII; R=tBu, Me; Ar=2,6-iPr2C6H3; X=Cl, (μ-Cl)2Li(thf)2). The coordination mode of the pyrazolate ligand η2 or μ-(η11) and the geometry of the resulting complex depends on the steric bulk of the diketiminate ligand, the d-electron configuration of the metal center, the solvent, and the relative stabilities of the σ- and π-type frontier orbitals.

    24. Rhodium(I) Complexes of a PBP Ambiphilic Ligand: Evidence for a Metal[RIGHTWARDS ARROW]Borane Interaction (pages 1611–1614)

      Sébastien Bontemps, Heinz Gornitzka, Ghenwa Bouhadir, Karinne Miqueu and Didier Bourissou

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503649

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      To and fro: Diphosphanylborane derivative 1 behaves as a tridentate, ambiphilic ligand towards rhodium(I) fragments (see picture). The presence of metal[RIGHTWARDS ARROW]borane interactions in the resulting square-pyramidal complexes is highlighted by structural analyses and DFT calculations.

    25. Enantiomerically Enriched Allylglycine Derivatives through the Catalytic Asymmetric Allylation of Iminoesters and Iminophosphonates with Allylsilanes (pages 1615–1617)

      Hiroshi Kiyohara, Yoshitaka Nakamura, Ryosuke Matsubara and Shū Kobayashi

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200504196

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      α-Amino acid derivatives are obtained in high yields through the catalytic enantioselective allylation of iminoesters using environmentally benign allylsilanes as nucleophiles in the presence of a copper complex prepared from Cu(OTf)2 and a chiral diamine (see scheme; Tf=trifluoromethanesulfonyl, Nap=naphthyl). The reaction is also extended to iminophosphonates.

    26. Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites (pages 1617–1620)

      Patricia Cheung, Aditya Bhan, Glenn J. Sunley and Enrique Iglesia

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200503898

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      A simpler way: Acidic zeolites catalyze dimethyl ether carbonylation to methyl acetate at low temperatures with high selectivity and catalyst stability. This approach provides a halide-free heterogeneous catalytic route to acetic acid and methyl acetate.

    27. A Chiral [2]Catenane Precursor of the Antiarthritic Gold(I) Drug Auranofin (pages 1621–1624)

      Stephen Sin-Yin Chui, Rong Chen and Chi-Ming Che

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200503431

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      Worth its weight in gold: A homoleptic gold(I) glycosylated thiolate precursor for the antiarthritic drug auranofin has been structurally characterized. The undecagold(I) cluster forms an unusual chiral [2]catenane (see picture; Au violet, S yellow) and displays interesting photophysical behavior in the solid state and in solution.

    28. Photoswitching of the Dielectric Constant of the Spin-Crossover Complex [Fe(L)(CN)2]⋅H2O (pages 1625–1629)

      Sébastien Bonhommeau, Thomas Guillon, Latévi Max Lawson Daku, Philippe Demont, José Sanchez Costa, Jean-François Létard, Gábor Molnár and Azzedine Bousseksou

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503252

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      Photoswitching of the dielectric constant has been observed for the first time in the spin-crossover complex [Fe(L)(CN)2]⋅H2O (L=2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, see picture). The electrical detection of a photoinduced change in spin state could allow the use of such complexes in optical information-storage devices.

    29. Molecular Crowding Induces Telomere G-Quadruplex Formation under Salt-Deficient Conditions and Enhances its Competition with Duplex Formation (pages 1629–1632)

      Zhong-yuan Kan, Yuan Yao, Ping Wang, Xiong-hui Li, Yu-hua Hao and Zheng Tan

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200502960

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      Impact of crowding: Molecular crowding with poly(ethylene glycol) (PEG) induces the formation of a G-quadruplex structure in the guanine-rich strand of telomeric DNA at a K+-ion concentration that is unable to induce G-quadruplex formation alone. The picture shows the folding and unfolding of the telomeric DNA, revealed by fluorescence resonance energy transfer (FRET), the efficiency of which is inversely dependent on the distance between the donor (D) and acceptor (A).

    30. Formation of Heteroatom Active Sites in Zeolites by Hydrolysis and Inversion (pages 1633–1638)

      Judy To, Alexey A. Sokol, Samuel A. French, C. Richard A. Catlow, Paul Sherwood and Huub J. J. van Dam

      Article first published online: 30 JAN 2006 | DOI: 10.1002/anie.200503006

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      A break and a flip: Quantum mechanical/molecular mechanical calculations are used to investigate the structures of the active sites in silicalite doped with heteroatoms from Groups 4 and 14. These calculations reveal that tripodal (see picture; Si yellow, O red, H white, heteroatom blue) or bipodal sites, formed through hydrolysis and inversion, are preferred.

    31. A Molecular Actinide–Tellurium Bond and Comparison of Bonding in [MIII{N(TePiPr2)2}3] (M=U, La) (pages 1638–1641)

      Andrew J. Gaunt, Brian L. Scott and Mary P. Neu

      Article first published online: 6 FEB 2006 | DOI: 10.1002/anie.200503372

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      Are the actinides going soft? The first molecular complexes containing an actinide–tellurium bond, [U{N(TePiPr2)2}3] (see picture) and the isostructural complex [La{N(TePiPr2)2}3] have been crystallographically characterized. The UIII[BOND]Te bond is shorter than the LaIII[BOND]Te bond by 0.06 Å, which suggests a greater degree of covalency in the bonding of actinides with soft donors.

    32. An Unsaturated α,ω-Dianionic Oligosilane (pages 1643–1645)

      Kai Abersfelder, Deniz Güclü and David Scheschkewitz

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503975

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      A trisilenediide: The reduction of dichlorotrisilene 1 with active magnesium leads to α,ω-dianionic trisilene 2, which is characterized by NMR spectroscopy and X-ray diffraction. The potential of 2 as a precursor in the synthesis of heterocycles incorporating a Si[DOUBLE BOND]Si double bond is demonstrated by the formation of stannatrisilacyclobutene 3.

    33. Enantioselective Enzymatic Reactions in Miniemulsions as Efficient “Nanoreactors” (pages 1645–1648)

      Harald Gröger, Oliver May, Hendrik Hüsken, Sandrine Georgeon, Karlheinz Drauz and Katharina Landfester

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200502854

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      Phasing in: Miniemulsions are homogenous mixtures in which the organic phase is dispersed in the form of nanometer-scale droplets, which can act as efficient “nanoreactors” for enantioselective enzymatic transformations. Very high substrate concentrations are possible, and both α- and β-amino acids were prepared with high conversions and up to >99 % ee.

    34. Two Chloride Ions as a Template in the Formation of a Cyclic Hexaurea (pages 1648–1652)

      Denys Meshcheryakov, Volker Böhmer, Michael Bolte, Véronique Hubscher-Bruder, Françoise Arnaud-Neu, Haiko Herschbach, Alain Van Dorsselaer, Iris Thondorf and Werner Mögelin

      Article first published online: 2 FEB 2006 | DOI: 10.1002/anie.200503766

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      It takes two to template: A cyclic hexaurea with four xanthene and two diphenyl ether units is predominantly formed by reaction of two diisocyanate molecules with two diamine molecules in the presence of chloride (see picture; green Cl, blue N, red O). The formation of a 1:2 complex with chloride was confirmed by X-ray analysis, solution NMR spectroscopy, and ESI-MS. The complexation constants were determined by microcalorimetry and UV spectrometry.

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      Preview: Angew. Chem. Int. Ed. 10/2006 (page 1659)

      Article first published online: 21 FEB 2006 | DOI: 10.1002/anie.200690035

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