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Complex Leads (complex + lead)
Selected AbstractsMechanistic Insights into Acetophenone Transfer Hydrogenation Catalyzed by Half-Sandwich Ruthenium(II) Complexes Containing 2-(Diphenylphosphanyl)aniline , A Combined Experimental and Theoretical StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Alessia Bacchi Abstract Several new half-sandwich ruthenium(II) complexes containing 2-(diphenyphosphanyl)aniline (PNH2) of formula {Ru[(,2P,N)PNH2](p -cymene)Cl}Y [Y = Cl (1a), PF6 (1b), BF4 (1c), BPh4 (1d), TfO (1e)] were synthesized and fully characterized both in solution (1H NMR and 31P{1H} NMR spectroscopy) and in the solid state (FTIR, X-ray analysis on single crystal). Complexes 1a and 1b are active precatalysts in the hydrogen transfer reaction of acetophenone, leading to tof values up to 4440 h,1. In comparison, the {Ru[(,2P,N)PNMe2](p -cymene)Cl}Cl complex leads to a tof value of 100 h,1 under the same catalytic conditions. The mechanism through which the precatalysts operate was deeply explored by high-resolution MS (ESI) and DFT/PCM studies. The results reveal that the complexes containing PNH2 operate through a bifunctional mechanism analogous to that proposed for diamines and amino alcohol ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Ionic Iridium(III) Complexes with Bulky Side Groups for Use in Light Emitting Cells: Reduction of Concentration QuenchingADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Carsten Rothe Abstract Here, the photophysics and performance of single-layer light emitting cells (LECs) based on a series of ionic cyclometalated Ir(III) complexes of formulae and where ppy, bpy, and phen are 2-phenylpyridine, substituted bipyridine and substituted phenanthroline ligands, respectively, are reported. Substitution at the N,N ligand has little effect on the emitting metal-ligand to ligand charge-transfer (MLLCT) states and functionalization at this site of the complex leads to only modest changes in emission color. For the more bulky complexes the increase in intermolecular separation leads to reduced exciton migration, which in turn, by suppressing concentration quenching, significantly increases the lifetime of the excited state. On the other hand, the larger intermolecular separation induced by bulky ligands reduces the charge carrier mobility of the materials, which means that higher bias fields are needed to drive the diodes. A brightness of ca. 1000,cd,m,2 at 3,V is obtained for complex 5, which demonstrates a beneficial effect of bulky substituents. [source] The mechanisms used by enteropathogenic Escherichia coli to control filopodia dynamicsCELLULAR MICROBIOLOGY, Issue 2 2009Cedric N. Berger Summary Enteropathogenic Escherichia coli (EPEC) subverts actin dynamics in eukaryotic cells by injecting effector proteins via a type III secretion system. First, WxxxE effector Map triggers transient formation of filopodia. Then, following recovery from the filopodial signals, EPEC triggers robust actin polymerization via a signalling complex comprising Tir and the adaptor proteins Nck. In this paper we show that Map triggers filopodia formation by activating Cdc42; expression of dominant-negative Cdc42 or knock-down of Cdc42 by siRNA impaired filopodia formation. In addition, Map binds PDZ1 of NHERF1. We show that Map,NHERF1 interaction is needed for filopodia stabilization in a process involving ezrin and the RhoA/ROCK cascade; expression of dominant-negative ezrin and RhoA or siRNA knock-down of RhoA lead to rapid elimination of filopodia. Moreover, we show that formation of the Tir-Nck signalling complex leads to filopodia withdrawal. Recovery from the filopodial signals requires phosphorylation of a Tir tyrosine (Y474) residue and actin polymerization pathway as both infection of cells with EPEC expressing TirY474S or infection of Nck knockout cells with wild-type EPEC resulted in persistence of filopodia. These results show that EPEC effectors modulate actin dynamics by temporal subverting the Rho GTPases and other actin polymerization pathways for the benefit of the adherent pathogen. [source] Asymmetric Hydrogenation with Highly Active IndolPhos,Rh Catalysts: Kinetics and Reaction MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2010Jeroen Wassenaar Abstract The mechanism of the IndolPhos,Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis,Menten kinetics. A large value of KM (KM=5.01±0.16,M) is obtained, which indicates that the Rh,solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate,catalyst complexes, which are undetectable by experimental means, suggest that the major substrate,catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism of asymmetric hydrogenation reactions with C1 -symmetric heteroditopic and monodentate ligands. [source] Tuning the Magnetic Properties of LixCrTi0.25Se2 (0.03,x,0.7) by Directed Deintercalation of LithiumCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2008Malte Behrens Dr. Abstract X-ray diffraction (XRD), in situ energy-dispersive X-ray diffraction (EDXRD), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and magnetic measurements were applied to investigate the effects of lithium deintercalation on pseudolayered Li0.70CrTi0.25Se2. A detailed picture of structural changes during the deintercalation process was obtained by combining the results of EDXRD and EXAFS. Removal of Li from the host,guest complex leads to anisotropic contraction of the unit cell with stronger impact on the c axis, which is the stacking axis of the layers. The EDXRD experiments evidence that the shrinkage of the lattice parameters with decreasing xLi in LixCrTi0.25Se2 is nonlinear in the beginning and then becomes linear. Analysis of the EXAFS spectra clearly shows that the Cr/TiSe distances are affected in a different manner by Li removal. The CrSe bond lengths decrease, whereas the TiSe bonds lengthen when the Li content is reduced, which is consistent with XRD data. Magnetic measurements reveal a change from predominantly antiferromagnetic exchange (,p=,300,K) interactions for the pristine material to ferromagnetic exchange interactions (,=25,K) for the fully intercalated material. Thus, the magnetic properties can be altered under ambient conditions by directed adjustment of the dominant magnetic exchange. The unusual magnetic behavior can be explained on the basis of the variation of the metal,metal distances and the Cr-Se-Cr angles with x, which were determined by Rietveld refinements. Owing to competing ferromagnetic and antiferromagnetic exchange interactions and disorder, the magnetic ground state of the intercalated materials is characterized by spin-glass or spin-glass-like behavior. [source] Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2004Stefan Dilsky Abstract The syntheses and some typical reactions of diastereomeric rhenium complexes [CpRe(NO)(CO){P(Ph)(R)(R,)}]BF4 (R = Me, Ph; R, = 2-C6H4OMe, CH2C4H3S, CH2C4H7O) (3a,e) are described. Reduction of the carbonyl ligand with NaBH4 in THF gave the corresponding methyl complexes [CpRe(NO){P(Ph)(R)(R,)}(CH3)] (4a,e). Acid treatment of the methyl complexes leads to liberation of methane and coordination of the additional donor site of the potentially bidentate phosphane ligand. Of the chelate complexes 5a,e, those with R, = 2-C6H4OMe (5a, d) decomposed in solution at room temperature. In donor solvents, the chelate ring opens giving the stable solvated complexes [CpRe(NO){P(Ph)(R)(R,)}](solvent)]BF4 (solvent = CH3CN, THF) (6b,e, 7d). The new compounds are thus suitable starting materials for the syntheses of diastereomeric rhenium complexes [CpRe(NO){P(Ph)(R)(R,)}(L)]BF4. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Investigation of binary polymer/surfactant or ternary polymer/surfactant/Cu2+ complexes in aqueous solution through Nile red probingPOLYMER INTERNATIONAL, Issue 8 2010Zacharoula Iatridi Abstract The optical properties (absorption and emission) of Nile red have been widely used for staining or probing purposes in diverse aqueous systems. However, the applications of Nile red for the determination of the critical aggregation concentration of polymer/surfactant complexes or for the investigation of ternary polymer/surfactant/Cu2+ systems are very limited. The interactions between anionic polyelectrolytes and the oppositely charged surfactant N,N,N,N -dodecyltrimethylammonium chloride were investigated in dilute aqueous solution, exploiting the optical properties of Nile red. It is shown that the emission properties of Nile red present better sensitivity than its absorption properties, concerning the detection of the hydrophobic polymer/surfactant complexes formed in aqueous solution. Moreover, it is found that the formation of ternary polymer/surfactant/Cu2+ complexes leads to a pronounced quenching of the luminescence of Nile red. The corresponding Stern,Volmer plots indicate that quenching is more favourable when coordination of Cu2+ ions with poly(sodium acrylate) takes place, as compared to simple electrostatic binding of these ions with poly(sodium styrene sulfonate). Nile red is a sensitive and accurate tool, as an alternative to pyrene, for the characterization of binary polymer/surfactant complexes or for obtaining information on the local arrangement of ternary polymer/surfactant/Cu2+ systems in aqueous solution. Copyright © 2010 Society of Chemical Industry [source] Synthetic and antimicrobial studies on new gold(I) complexes of imidazolidin-2-ylidenesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 7 2004smail Özdemir Abstract Six new 1,3-diorganylimidazolidin-2-ylidene (NHC) gold(I) complexes of the type [Au(NHC)2]+ (1,6), were synthesized by reacting [AuCl(PPh)3] with 1,3-dimesitylimidazolidin-2-ylidene or bis(1,3-dialkylimidazolidin-2-ylidene). The complexes 1,6 were fully characterized by elemental analyses and spectroscopic data. The placement of mesityl or para-substituted benzyl groups on the nitrogen atoms of the ring of the complexes leads to the particularly active antibacterial agents evaluated in this work. It is worth noting that the p -methoxybenzyl derivative (2) inhibited the growth of Pseudomona aeruginosa, Staphylococcus epidermidis, Staphylococcus aureus and Enterococcus faecalis with minimum inhibitory concentration (MIC) values of 3.12 µg ml,1, 6.25 µg ml,1, 3.12 µg ml,1 and 3.12 µg ml,1 respectively. In contrast, the analogous p -dimethylaminobenzyl derivative (3) is effective only against Escherichia coli (MIC = 3.12 µg ml,1). Copyright © 2004 John Wiley & Sons, Ltd. [source] | |||||||||||||