Search results for "Dissociation"
showing 10 items of 531 documents
Temperature and pH Dependence of Gd-DOTA and Gd-DTPA Complexes Dissociation Studied by EXAFS
1997
The Gd L3-edge of Gd(DTPA) 2- and Gd(DOTA) - complexes, in crystalline state and aqueous solutions presenting various pH (0.15-8) at different temperatures (25-90 °C), are investigated by XAFS experiments. For the Gd(DTPA) 2- . complexes we observe a strong pH (0.15-1.5) dependence of XAFS signals. On the other hand, the XAFS signals of Gd(DOTA) - complexes exhibit a light pH (1-1.5) dependence and for pH<1 we observe a ligand decomposition. Conceming both complexes, we note just a light temperature dependence. To obtain information about the short and medium range order (up to 5 A), multiple scattering calculation is performed. For the first coordination shell, we apply multi-shell fitting…
Photodissociation of Formyl Fluoride in Rare Gas Matrixes
2006
Photodissociation of formyl fluoride (HCOF) is studied in Ar, Kr, and Xe matrixes at 248 and 193 nm excitation by following spectral changes in the infrared absorption spectra. In all matrixes, the main photodissociation products are CO/HF species, including CO-HF and OC-HF complexes and thermally unstable CO/HF species (a distorted CO/HF complex or a reaction intermediate), which indicate negligible cage exit of atoms produced via the C-F and C-H bond cleavage channels. However, the observation of traces of H, F, CO, CO(2), F(2)CO, FCO, and HRg(2)(+) (Rg = Kr or Xe) in Kr and Xe matrixes would imply some importance of other reaction channels too. The analysis of the decay curves of the pre…
ChemInform Abstract: Heterocyclic Photorearrangements. Photoinduced Rearrangement of 3-Styryl-1,2,4-oxadiazoles.
1990
The photochemical behaviour of 3-styryl-5-phenyl-(5-methyl)-1,2,4-oxadiazoles in methanol at 254 nm has been investigated. A photoinduced rearrangement to the quinoline system has been pointed out and explained as proceeding through an initial photolysis of the ring ON bond, followed by a six membered ring closure reaction involving the styryl moiety.
Low-energy decay pathways of doubly charged silver clusters $Ag_{n}^{2+}$ (n = 9 - 24)
1997
The low-energy dissociation channels of mass selected silver cluster ions Ag n 2+ (n = 9–24) are determined by collision induced dissociation (CID) in a Penning trap. While all clusters of the size n ≥ 17 evaporate neutral monomers, most smaller clusters undergo asymmetric fission of the form Ag n 2+ → Ag −3 + + Ag {3} + . However, Ag 15 2+ and Ag 11 2+ emit monomers which indicates shell or odd-even effects. The observed fragmentation pathways are different from previous reports of measurements with sputtered Ag n 2+ .
Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold
2013
In its crystal structure the one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3]n (1) (TMP = 2,3,5,6-tetramethylpyrazine) adopts a zig-zag arrangement in which pairs of silver(I) centres bridged by two fluorocarboxylate ligands are linked alternately via one or two neutral TMP ligands. This material can reversibly absorb/desorb small alcohols (ROH) in single-crystal-to-single-crystal transformations, despite the lack of porosity in the crystals, to yield a related material of formula [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2]n (1-ROH). The absorption process includes coordination of the alcohol to silver(I) centres and, in the process, insertion of the alcohol into one-quarter of the Ag–O…
ChemInform Abstract: A Theoretical Determination of the Dissociation Energy of the Nitric Oxide Dimer.
2010
Multi-reference CI methods have been applied to determine the dissociation energy and structure of thecis-N2O2 molecule. The convergence of the theoretical result has been checked with respect to a systematic expansion of the one-electron basis set and the multi-reference CI wave function. The best calculated value, 13.8 kJ/mol, is in agreement with the experimental value, 12.2 kJ/mol. It has been obtained with an extended ANO-type basis set [6s5p3d2f], including the effect of the basis set superposition error (BSSE) in the geometry optimization, and additional effects, such as the electron correlation of core electrons and relativistic corrections, using the average coupled pair functional…
Defects and Reactivity at Oxide Surfaces: Experimental Aspects of the Interaction of Hydrogen, Co And Co2 with the Nio{001} Surface
1989
This paper summarizes some previous or more recent experimental results on chemical interaction, at moderate temperatures, of H, H2, CO and CO2 with the surfaces of nickel oxide, mainly the NiO {001} surface. These results are in a general agreement with theoretical predictions. Nearly perfect surfaces of maximal valency oxides cannot react with molecules. Dissociation of molecules is often required for chemisorption. Conversely, chemical reaction is usually observed either when molecules are predissociated or the surface has defects with an energy level high enough to enable both dissociation and chemisorption. On a nearly perfect, “in situ” cleaved, NiO {001} surface, partially atomized h…
Synthesis and Properties of Some Simple Organotitanium Compounds
1986
Before embarking on a detailed discussion of the titanation of carbanions, synthetic and physical organic aspects of several typical organotitanium (IV) compounds shall be surveyed, including thermal stability, aggregation state, X-ray structural data and bond energies. Some of this information is useful in understanding reactivity and selectivity in reactions with organic substrates. Low valent Ti (II) and Ti (III) shall be mentioned only on passing; the interested reader is referred to reviews [1].
ChemInform Abstract: Photochemistry of 7-Acetoxybenzopyran Derivatives. Synthesis of Eupatoriochromene and Encecalin.
1990
Abstract The photolysis of the 7-acetoxybenzopyran derivatives 1a-5a has been carried out. Chromene 1a was found to undergo extensive photopolymerization. Chromanone 2a underwent a rather inefficient photo-Fries rearrangement to the 6 - and 8 - acetyl derivatives 2b and 2c . Diacetoxychromene 3a gave the unsaturated ketone 8 as the main product, besides its deacetylation analogue 9 and chromanone 11 . Diacetoxychroman 4a afforded a mixture of four C-acetyl products: 1b, 1c, 2b and 2c , together with Chromene 1a and chromanone 2a. Finally, irradiation of chroman 5a gave rise to a mixture of the two possible photo-Fries products 5b (43%) and 5c (52%). The mechanistic implications of the above…
Energetics and Dynamics of Naphthalene Polyaminic Derivatives. Influence of Structural Design in the Balance Static vs Dynamic Excimer Formation
2003
Two new fluorescent macrocyclic structures bearing two naphthalene (Np) units at both ends of a cyclic polyaminic chain were investigated with potentiometric, fluorescence (steady-state and time-resolved) and laser flash photolysis techniques. The fluorescence emission studies show the presence of an excimer species whose formation depends on the protonation state of the polyamine chains implying the existence of a bending movement (occurring in both the ground and in the first singlet excited state), which allows the two naphthalene units to approach and interact. For comparison purposes, one bis-chromophoric compound containing a rigid chain (piperazine unit) was also investigated. Its em…