Search results for " pair"
showing 10 items of 779 documents
Antimony-121 Mössbauer and infrared spectral studies on 1,10-phenanthroline adducts of antimony(III) halides
1983
Abstract The syntheses of the mono-adducts of 1,10-phenanthroline with SbX 3 (X = F, Cl, Br) and PhSbI 2 are described. These compounds and the 1:1 adduct between 2,2′-bipyridine and PhSbI 2 have been characterized mainly in the solid state by infrared and Mossbauer spectroscopic techniques. The structures of the antimony trihalide complexes appear to be based on halogen bridged polymers in which the stereochemical activity of the lone pair of electrons varies with the halogen, the highest p-character of the lone pair being observed with the trifluoride adduct. Mossbauer results for the PhSbI 2 complexes suggest a ψ-octahedral stereochemistry with the lone pair and the Ph group in trans pos…
Tantalocenehydridephosphorus chemistry.
2002
Abstract The aim of this paper is to look for a better knowledge of the behaviour of bent tantalocenes that bear hydrides, phosphorus PR2X (R=Me, Ph; X=H, lone pair) and cyclopentadienyl (Cp=C5H5, Cp′=C5H2tBu(Me)2, Cp*=C5Me5) ligands. An orbital control of regioselectivity of insertion of the PR2 phosphide fragment of chlorophosphines PR2Cl into the central TaH bond of trihydrides Cp2TaH3 leading to the formation of metallophosphonium cations is discussed. Neutralisation of cationic complexes with strong bases leads either to the Ta(V)–phosphide or to the Ta(III)–phosphine species depending on the nature of the cyclopentadienyl ligand; good electron donor Cp′ and Cp* rings favour the forma…
Über den einfluß der monomerkonzentration auf die geschwindigkeitskonstante kw der monomeraddition an das ionenpaar eines „lebenden” polymeren
1966
Fur den Zahlenwert der Geschwindigkeit skonstante kw(±) fanden die Arbeitsgruppen in Mainz und Syracuse voneinander abweichende Werte. Es wurde angenommen, das die Ursache dieser Diskrepanz die um Grosenordnungen verschiedenen Konzentrationsbereiche sind, in denen die Messungen ausgefuhrt wurden. Nachfolgend wird ein Reaktionsschema vorgeschlagen und kinetisch durchgerechnet, welches eine schneller polymerisierende Komplexverbindung zwischen dem Ionenpaar und dem Monomeren voraussetzt. The rate constant kw(±) for the addition of monomer to the ion pair of a „living” polymer was measured by workers in Mainz and in Syracuse. Their results lack agreement. It was assumed that this disparity is …
Docking and synthesis of pyrrolopyrimidodiazepinone derivatives (PPDs) and their precursors: New scaffolds for DNA-interacting agents
2007
New classes of pyrrolopyrimidodiazepinone derivatives (PPDs) and their precursors were studied in silico for their ability to form stable complex with DNA fragment. In the docking studies two binding modes can be envisaged: groove mode and intercalating mode. In the case of the best ligands the docking studies revealed a common binding mode with the chromophore intercalated between GC base pairs whereas the side chain lies close to the minor groove. Synthetic approach to the PPD ring systems is discussed.
Asymmetric and Symmetric Dicopper(II) Paddle-Wheel Units with Modified Nucleobases
2015
New copper(II) paddle-wheel complexes with different modified nucleobases and simple molecules in the axial positions have been prepared by direct reactions between copper(II) salts and the corresponding uracil- or thymine-1-acetic acids under inert atmosphere to produce the two homoleptic complexes, [Cu2(μ-OOCCH2-T)4(G)2] and [Cu2(μ-OOCCH2-U)4(G)2], and the heteroleptic one [Cu2(μ-OOCCH2-T)2(μ-OOCCH2-U)2(G)2] (where OOCCH2-T = thymine-1-acetate, OOCCH2-U = uracil-1-acetate, and G = dimethylformamide, water, dimethylacetamide, or dimethyl sulfoxide). Interestingly, the crystal structures of this family of closely related molecules present significant differences in their supramolecular arra…
Unravelling the mechanism of the ketene-imine Staudinger reaction. An ELF quantum topological analysis
2015
The mechanism of the ketene-imine Staudinger (KI-S) reaction between t-butyl-cyano ketene and N-phenyl phenylimine has been studied using DFT methods at the MPWB1K/6-311G(d) computational level. The reaction takes place through a two-step mechanism: (i) the first step is the nucleophilic attack of the imine nitrogen lone pair on the central carbon of the ketene yielding a zwitterionic (ZW) intermediate; (ii) the second step, which is the rate- and stereoselectivity-determining step, is a ring-closure process achieved by a nucleophilic attack of the terminal carbon atom of the ketene on the imine carbon atom. Due to the unfeasibility of a cis/trans and an E/Z stereoisomerisation at the ZW in…
Metallocenes of Nb and Ta with η2-Se2H, SeH, and Se Ligands – Crystal Structures of [Cp′2Ta(SeH)H2] and [Cp′2Ta(=Se)H·W(CO)5] (Cp′ =tBuC5H4)
1999
The reactions of [Cp#2NbBH4] (1) [Cp# = C5Me5 (Cp*) or C5Me4Et] and [Cp′2TaH3] (Cp′ = tBuC5H4) with elemental selenium give complexes of the general composition [Cp2MSe2H]. These exist in three isomeric forms, A–C, depending on the metal and the chalcogen. [Cp#2NbSe2H] (2) incorporates the novel η2-Se2H ligand (C), which is labile when exposed to light. Solutions of 2(Cp*) can be converted into [Cp*2NbSe2H] (3), which exists in two isomeric forms A or B, along with [Cp*2NbSe3H] (4) and [Cp*2NbO2H] (5). [Cp′2Ta(η2-Se2)H] (6) is the only isomer found for the Ta system. Se abstraction by means of P(OEt)3 gives [Cp′2Ta(=Se)H] (7). Complex 7 can be reduced with Na/Hg and subsequently hydrolysed …
The e-ASTROGAM gamma-ray space observatory for the multimessenger astronomy of the 2030s
2018
e-ASTROGAM is a concept for a breakthrough observatory space mission carrying a gamma-ray telescope dedicated to the study of the non-thermal Universe in the photon energy range from 0.15 MeV to 3 GeV. The lower energy limit can be pushed down to energies as low as 30 keV for gamma-ray burst detection with the calorimeter. The mission is based on an advanced space-proven detector technology, with unprecedented sensitivity, angular and energy resolution, combined with remarkable polarimetric capability. Thanks to its performance in the MeV-GeV domain, substantially improving its predecessors, e-ASTROGAM will open a new window on the non-thermal Universe, making pioneering observations of the…
Extractive Spectrophotometric Determination of Ondansetron by Ion-Pair Formation with Bromocresol Green
1996
Abstract An empirical spectrophotometric procedure for the determination of the antiemetic ondansetron is carried out. The method is based on the formation of a 1:1 ion pair with bromocresol green in the pH range over 3.2 – 4.4, extraction into chloroform layer and spectrophotometric measurement at 420.8 nm. The calibration graph is linear over the range 0.1 – 20 μg ml−1 ondansetron, with a relative standard deviation of 2.7%; the influence of foreign substances is also studied. The method is applied to ondansetron determination in human urine.
Program for the interpretive optimization of two-dimensional resolution.
2016
The challenge of fully optimizing LC × LC separations is horrendous. Yet, it is essential to address this challenge if sophisticated LC × LC instruments are to be utilized to their full potential in an efficient manner. Currently, lengthy method development is a major obstacle to the proliferation of the technique, especially in industry. A program was developed for the rigorous optimization of LC × LC separations, using gradient-elution in both dimensions. The program establishes two linear retention models (one for each dimension) based on just two LC × LC experiments. It predicts LC × LC chromatograms using a simple van-Deemter model to generalize band-broadening. Various objectives (ana…