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11.
The coordination chemistry of amine tris(phenolate) ligands around V(III) and V(V) is described for the first time. Three amine tris(phenolate) ligands were employed featuring different steric and electronic influence exerted by the phenolate substituents in the ortho and para positions being either t-Bu, Me, or Cl. V(III) complexes of all ligands (1-3) were readily obtained by reaction between the ligand precursors and VCl3(THF)3 in the presence of triethylamine. The complexes obtained were pentacoordinate, a THF ligand completing the coordination sphere of the metal, which was found to be of almost perfect TBP geometry, as revealed by crystallography. V(V) oxo complexes of all the ligands (4-6) were readily obtained by a reaction between the ligand precursors and VO(OPr)3. The oxo complexes of the alkyl-bearing ligands (4 and 5) could also be synthesized by the air oxidation of the corresponding V(III) complexes (1 and 2); however, the attempted air oxidation of the V(III) complex bound to the electron-poor ligand (3) did not yield the corresponding oxo complex 6. 1H NMR and crystallographic analysis of complexes 4 and 5 supported their TBP structures. Complex 6, on the other hand, was found to be composed of a TBP complex (6a) and an octahedral complex (6b) in equilibrium, the octahedral complex being more stable at lower temperatures. An X-ray structure of 6b revealed a mononuclear oxo complex, the sixth coordination site being occupied by an aqua ligand to which two THF molecules are H-bonded. Complexes 4-6 catalyze the epoxidation of olefins by t-BuOOH, albeit slowly. These complexes may thus be considered as structural and functional models of vanadium-dependent haloperoxidase enzymes. 相似文献
12.
The reactions of propylene, ethylene, and styrene sulfide with cotton fabrics in the form of their lithium cellulosate derivative, obtained by metallation with lithium methoxide, were studied. Both graft and homo-polymerization took place and in the reaction with propylene and ethylene sulfide, cotton fabrics with high polysulfide content were obtained. With propylene sulfide 50% of the monomer polymerized was grafted. The effects of monomer concentration, cellulosate degree of substitution, reaction time, and solvent on the polymerization were investigated. In contrast with propylene and ethylene sulfide, only small conversions were obtained in the reaction with styrene sulfide. The results were attributed to steric effects. 相似文献
13.
The adsorption of silver nitrate from aqueous solution by polyethylene sulfide-containing cotton fabrics was investigated. The adsorption could be described by a Freundlich-type isotherm with n= 1. δHos was calculated from adsorption isotherms and from the equilibrium constant of complex formation and similar results of-5.6 and -5.4 kcal/mole were obtained, respectively. At low silver nitrate concentrations most of the silver nitrate present in solution could be adsorbed. It was found that adsorption by polyethylene sulfide in the fabric was much higher than that of homo-polyethylene sulfide. 相似文献
14.
Qiu-Cheng Chen Zi-Ye Xiao Shachar Fite Dr. Amir Mizrahi Dr. Natalia Fridman Xuan Zhan Or Keisar Dr. Yair Cohen Prof. Dr. Zeev Gross 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(48):11383-11388
Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science. 相似文献
15.
Qiu-Cheng Chen Dr. Natalia Fridman Dr. Yael Diskin-Posner Prof. Dr. Zeev Gross 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9481-9485
Palladium complexes of corrole and sapphyrin were prepared in high yield and fully characterized. The corrole provides a tetradentate/trianionic square planar coordination sphere for PdII, charge balanced by pyridinium. Both one and two PdII ions may be accommodated by the pentapyrrolic skeleton of the sapphyrin, and in each case the macrocycle acts as bidentate/monoanionic ligand and the inner-sphere square planar geometry is completed by allyl anions coordinated in an η3 fashion. NMR spectroscopy and X-ray crystallography data analyses uncovered the presence of interesting stereoisomers due to the flexibility of the ally ligands and also the pyrrole ring(s) that is/are not involved in metal binding. 相似文献
16.
Comparison of the performance of three ion mobility spectrometers for measurement of biogenic amines
The performance of three different types of ion mobility spectrometer (IMS) devices: GDA2 with a radioactive ion source (Airsense, Germany), UV-IMS with a photo-ionization source (G.A.S. Germany) and VG-Test with a corona discharge source (3QBD, Israel) was studied. The gas-phase ion chemistry in the IMS devices affected the species formed and their measured reduced mobility values. The sensitivity and limit of detection for trimethylamine (TMA), putrescine and cadaverine were compared by continuous monitoring of a stream of air with a given concentration of the analyte and by measurement of headspace vapors of TMA in a sealed vial. Preprocessing of the mobility spectra and the effectiveness of multivariate curve resolution techniques (MCR-LASSO) improved the accuracy of the measurements by correcting baseline effects and adjusting for variations in drift time as well as enhancing the signal to noise ratio and deconvolution of the complex data matrix to their pure components. The limit of detection for measurement of the biogenic amines by the three IMS devices was between 0.1 and 1.2 ppm (for TMA with the VG-Test and GDA, respectively) and between 0.2 and 0.7 ppm for putrescine and cadaverine with all three devices. Considering the uncertainty in the LOD determination there is almost no statistically significant difference between the three devices although they differ in their operating temperature, ionization method, drift tube design and dopant chemistry. This finding may have general implications on the achievable performance of classic IMS devices. 相似文献
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We suggest to use stochastic differential equations for laser-plasma problems. Using this technique we solve analytically the motion of the electrons at the critical layer and calculate the density profile scaling length (L). For an Nd laser flux of 1017 W/cm2 we estimate L ≈ 0.15 μm, while for a CO2 laser flux of 1015 W/cm2 we get L ≈ 1.5 μm. 相似文献
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