Quecksilber(II)‐chlorid‐ und ‐iodid‐Komplexe von Dithia‐ und Tetrathiakronenethern

Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl₂)₂((ch)₂30S₄O₆)] ( 1 ), [HgCl₂(mn21S₂O₅)] ( 2 ), [HgCl₂(ch18S₂O₄)] ( 3 ) and [HgI(meb12S₂O₂)]₂[Hg₂I₆] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl₂)₂((ch)₂30S₄O₆)] two HgCl₂ units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)₂30S₄O₆) forming a binuclear complex. HgCl₂ forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S₂O₅) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S₂O₄) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S₂O₂) ligand gave with two equivalents HgI₂ the compound [HgI(meb12S₂O₂)]₂[Hg₂I₆]. In the cation [HgI(meb12S₂O₂)]⁺ meb12S₂O₂ forms with the cation HgI⁺ a half‐sandwich complex.     

Tris(pentafluoroethyl)silanol Derivatives and the Lewis Amphoteric Tris(pentafluoroethyl)silanolate Anion, [Si(C2F5)3O]−

While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C₂F₅)₃]⁻, which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C₂F₅)₃O]⁻. In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C₂F₅)₃OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C₂F₅)₃SiOSi(C₂F₅)₃. Deprotonation of Si(C₂F₅)₃OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C₂F₅)₃O}₂]²⁻, implies Lewis amphoteric character of the monomeric [Si(C₂F₅)₃O]⁻ anion.     

Buchbesprechungen

Ohne Zusammenfassung     

Systematic Investigation of Photoinduced Electron Transfer Controlled by Internal Charge Transfer and Its Consequences for Selective PdCl2 Coordination

Fluoroionophores of fluorophore–spacer–receptor format were prepared for detection of PdCl₂ by fluorescence enhancement. The fluorescent probes 1 – 13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl₂ receptor. First, varying the length of the alkylene spacer (compounds 1 – 3 ) revealed a dominant through‐space pathway for oxidative photoinduced electron transfer (PET) in CH₂‐bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4 – 9 containing two anthracene or pyrene fragments connected through CH₂ bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (E_Ox) through electron‐withdrawing or ‐donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (ΔG_PET) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (Φ_f), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl₂ were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10 – 13 were synthesized.     

Book review

Ohne Zusammenfassung

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Book review

     

A Highly K+‐Selective Two‐Photon Fluorescent Probe

A highly K⁺‐selective two‐photon fluorescent probe for the in vitro monitoring of physiological K⁺ levels in the range of 1–100 mM is reported. The two‐photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K⁺, independently of one‐photon (OP, 430 nm) or two‐photon (TP, 860 nm) excitation and comparable K⁺‐induced FEs in the presence of competitive Na⁺ ions. The estimated dissociation constant (K_d) values in Na⁺‐free solutions (K_d^OP=(28±5) mM and K_d^TP=(36±6) mM ) and in combined K⁺/Na⁺ solutions (K_d^OP=(38±8) mM and K_d^TP=(46±25) mM ) reflecting the high K⁺/Na⁺ selectivity of the fluorescent probe. The TP absorption cross‐section (σ_2PA) of the TPEF probe+160 mM K⁺ is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K⁺.     

Quasi-homogeneous hydrogenation with platinum and palladium nanoparticles stabilized by dendritic core-multishell architectures

Platinum and palladium nanoparticles, supported and stabilized by polymeric core-shell architectures, proved to be active catalysts for hydrogenation reactions. Here, two different reactions were used as probes to investigate the influence of the polymeric support: the hydrogenation of α-methyl styrene (AMS) to cumene and the partial hydrogenation of 1,5-cyclooctadiene (COD). We found that the stability of the nanoparticles and the rate of reaction are higher in the presence of a hydrophobic octadecyl shell within a three-shell polymer system. The kinetic study of AMS hydrogenation showed much higher activities for palladium nanoparticles than for platinum nanoparticles, and the obtained results (e.g., 35 kJ/mol for the activation energy) are of the same order of magnitude as reported earlier for palladium supported on alumina. A methanol/n-heptane biphasic mixture was tested for catalyst recycling and allowed for highly efficient catalyst separation with very low metal leaching.     

Ein verallgemeinertes deterministisches Netzplanmodell

Zusammenfassung Bei der Netzplantechnik und ihren Anwendungen werden unterschiedliche Modelle und Verfahren behandelt. Unter Verwendung der Graphentheorie wird ein verallgemeinertes Netzplanmodell beschrieben, das die bekannten Modelle (Vorgangsknotennetzplan, Vorgangspfeilnetzplan, Ereignisknotennetzplan) als Sonderfälle enthält.

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Summary In network-analysis and its applications one usually distinguishes between activity-on-arrow, activity-on-node and event-on-node networks. Using the theory of graphs, a generalized deterministic network model is described, containing the well known techniques as special cases.

     

Anisotropic multiplicative elastoplasticity for the prediction of earings in sheet forming

In this work, the simulation of earings in cup drawing by means of a recently developed anisotropic combined hardening material model is discussed. The model represents a multiplicative formulation of anisotropic elastoplasticity in the finite strain regime with nonlinear kinematic and isotropic hardening. Plastic anisotropy is described by the use of second-order structure tensors as additional arguments in the representation of the yield function and the plastic flow rule. The evolution equations are integrated by a form of the exponential map that preserves the plastic volume and the symmetry of the internal variables. Finite element simulations of cylindrical cup drawing processes are performed by means of ABAQUS/Standard where the discussed material model has been implemented into a user-defined reduced integration solid-shell element. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)