Search results for "Halide"
showing 10 items of 324 documents
Real-time observation of the charge transfer to solvent dynamics
2013
Intermolecular electron-transfer reactions have a crucial role in biology, solution chemistry and electrochemistry. The first step of such reactions is the expulsion of the electron to the solvent, whose mechanism is determined by the structure and dynamical response of the latter. Here we visualize the electron transfer to water using ultrafast fluorescence spectroscopy with polychromatic detection from the ultraviolet to the visible region, upon photo-excitation of the so-called charge transfer to solvent states of aqueous iodide. The initial emission is short lived (similar to 60 fs) and it relaxes to a broad distribution of lower-energy charge transfer to solvent states upon rearrangeme…
Katalizatory i proces koordynacyjnej polimeryzacji etylenu - eksperyment i teoria
2004
Badania eksperymentalne i teoretyczne koordynacyjnej polimeryzacji etylenu przeprowadzono wobec katalizatorów otrzymanych z prekursorów - kompleksów halogenków Ti, Zr, Hf, V z organicznymi zasadami Lewisa, nośnika magnezowego [MgCl2(THF)2] i związków glinoorganicznych. Określono zależnosć pomiędzy rodzajem halogenków w prekursorze a aktywnością katalizatora wanadowego. Ustalono profile energetyczne reakcji insercji i terminacji (beta-eliminacji) oraz przeniesienia atomu wodoru beta. Obliczone wartości barier insercji, a także energii wiązania etylenu do centrum aktywnego dobrze korelują z wynikami polimeryzacji. Stwierdzono występowanie w centrach aktywnych oddziaływań agostycznych, które o…
Free-volume Study in GeS2-Ga2S3-CsCl Chalcohalide Glasses Using Positron Annihilation Technique
2015
Abstract Positron annihilation lifetime spectroscopy combined with Doppler broadening of annihilation radiation was applied to study free-volume entities in Ge-Ga-S glasses having different amount of CsCl additives. It is shown that the structural changes caused by CsCl additives can be adequately described by positron trapping modes determined within two-state model. The results testify in a favor of rather unchanged nature of corresponding free-volume voids responsible for positron trapping in the studied glasses, when mainly concentration of these traps is a subject to most significant changes with composition.
Recognition of alkali metal halide contact ion pairs by uranyl-salophen receptors bearing aromatic sidearms. The role of cation-pi interactions.
2005
Hard anions have long been known to bind strongly to the uranium of uranyl-salophen complexes. Upon functionalization of the salophen framework with one or two benzyloxy substituents, efficient ditopic receptors for alkali metal ions are obtained. The solid-state structures of complexes formed by the two-armed receptor 1 with CsF and with the chlorides of K+, Rb+, and Cs+ reported here reveal the existence of dimeric supramolecular assemblies in which two receptor units assemble into capsules fully enclosing (MX)2 ion quartets. In addition to the strong coordinative binding of the anion to the uranyl center and to electrostatic cation-anion interactions, stabilizing interactions arise from …
Unprecedented Palladium-Catalyzed Cross-Coupling Reaction of α-Bromo Sulfoxides with Boronic Acids
2003
[reaction: see text] A new Suzuki-type palladium-catalyzed reaction of boronic acids with alpha-bromo sulfoxides has been developed using a protocol similar to the well-documented reaction of boronic acids with aryl halides. Both cross-coupling and homocoupling processes were observed. The best yields in cross-coupling products were obtained when the presence of oxygen was carefully excluded using degassed solvents. The oxidative addition palladium complex intermediate could be isolated and characterized by X-ray single-crystal diffraction.
Catalytic activity of solvated and unsolvated lanthanide halides in Friedel–Crafts acylations
2000
Abstract Anhydrous lanthanide halides — chlorides and bromides — can act as homogeneous catalysts of Friedel–Crafts acylations. The catalytic activity is related to the solubility of these anhydrous salts. More soluble THF or dioxane (Diox.) neodymium and samarium adducts are more active catalysts.
Tailoring polymers through interplay of ligands within precatalysts: 8-(Nitro/benzhydryl-arylimino)-7,7-dimethyl-5,6-dihydroquinolylnickel halides in…
2017
A series of 8-(nitro/benzhydryl-substituted arylimino)-7,7-dimethyl-5,6-dihydroquinolines and the corresponding nickel halide complexes were synthesized and characterized. Molecular structures of representative nickel complexes were determined by single crystal X-ray diffraction, showing the dinuclear dimers with distorted square-pyramidal geometry around the nickel center. The binding energies determined by X-ray photoelectron spectroscopy (XPS) indicate the effective coordination between the sp2-nitrogen and nickel atoms as well as the influence of both the halogen ligands and the substituents within dihydroquinolines on the strength of the NiN bond. Ethylene polymerization with the nicke…
Halogen bonding and host–guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests
2019
Single crystal X-ray structures of halogen-bonded assemblies formed between host N-hexylammonium resorcinarene bromide (1) or N-cyclohexylammonium resorcinarene chloride (2), and 1,4-diiodooctafluorobutane and accompanying small solvent guests (methanol, acetonitrile and water) are presented. The guests’ inclusion affects the geometry of the cavity of the receptors 1 and 2, while the divalent halogen bond donor 1,4-diiodooctafluorobutane determines the overall nature of the halogen bond assembly. The crystal lattice of 1 contains two structurally different dimeric assemblies A and B, formally resulting in the mixture of a capsular dimer and a dimeric pseudo-capsule. 1H and 19F NMR analyses …
Divergent reactivity of nucleophilic 1-bora-7a-azaindenide anions
2017
The reactions of 1-bora-7a-azaindenide anions, prepared in moderate to excellent yields by reduction of the appropriate 1-bora-7a-azaindenyl chlorides with KC8 in THF, with alkyl halides and carbon dioxide were studied. With alkyl halides (CH2Cl2, CH3I and BrCH(D)CH(D)tBu), the anions behave as boron anions, alkylating the boron centre via a classic SN2 mechanism. This was established with DFT methods and via experiments utilizing the neo-hexyl stereoprobe BrCH(D)CH(D)tBu. These reactions were in part driven by a re-aromatization of the six membered pyridyl ring upon formation of the product. Conversely, in the reaction of the 1-bora-7a-azaindenide anions with CO2, a novel carboxylation of …
Novel oxybispyridylboronic acids: synthesis and study of their reactivity in Suzuki-type cross-coupling reactions
2007
Abstract This paper sets forth the synthesis of novel oxybispyridylboronic acids, which are prepared from the corresponding halo-oxybispyridines via halogen–metal exchange using n-butyllithium and treatment with triisopropylborate. A range of efficient cross-coupling reactions of these novel boronic acids with selected aryl halides is described. This strategy produces novel pyridylethers of interest in cholinergic medicinal chemistry.