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11.
N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods
in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization
of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly
accepted. Bridged TS are formed by both the substitution mechanism S
N
2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise
N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized
upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates
of N-acylalkylation, as was demonstrated by localization of the corresponding TS.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007. 相似文献
12.
Langevin approach implemented in the inelastic cross-sections measured for the low-energy electrons colliding with metallic
clusters points out that statical form of the polarizability dominate at energies less than 1.25 eV. The dynamical form comes
into play at energies around 1.3 eV. The form of the polarizabilities indicates that polarizability of the metallic clusters
is energy-dependent. 相似文献
13.
14.
The features of interaction of a spherical metallic particle with a rarefied thermal plasma flow due to the presence o charges-electrons and ions in the gaseous phase-are considered. Analytical expressions describing charge, momentum, and energy exchange between the plasma and the particle für the cases of strong and weak Debye screening are obtained. It is illustrated that the efficiency of particle heating in the plasma considerably grows as compared with a hot molecular gas due to participation of electrons and ions in file transfer processes. 相似文献
15.
S. S. Batsanov 《Russian Chemical Bulletin》1994,43(2):199-201
Experimental data are used to determine the atomic volumes and radii of the elements of subgroups IV–VIIA in the structures of metallic phases at high pressures. Metallic radii of nonmetals are compared with values based on Pauling and Goldschmidt calculations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 220–222, February, 1994. 相似文献
16.
Heavy ion irradiation in the electronic stopping power region induces macroscopic dimensional change in metallic glasses and introduces magnetic anisotropy in some magnetic materials. The present work is on the irradiation study of ferromagnetic metallic glasses, where both dimensional change and modification of magnetic anisotropy are expected. Magnetic anisotropy was measured using Mössbauer spectroscopy of virgin and irradiated Fe40Ni40B20 and Fe40Ni38Mo4B18 metallic glass ribbons. 90 MeV 127I beam was used for the irradiations. Irradiation doses were 5×1013 and 7.5×1013 ions/cm2. The relative intensity ratios D 23 of the second and third lines of the Mössbauer spectra were measured to determine the magnetic anisotropy. The virgin samples of both the materials display in-plane magnetic anisotropy, i.e., the spins are oriented parallel to the ribbon plane. Irradiation is found to cause reduction in magnetic anisotropy. Near-complete randomization of magnetic moments is observed at high irradiation doses. Correlation is found between the residual stresses introduced by ion irradiation and the change in magnetic anisotropy. 相似文献
17.
18.
Michael C. W. Chan Dr. 《化学:亚洲杂志》2008,3(1):18-27
The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???Hβ ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis. 相似文献
19.
Wolfgang H. Binder Laura Petraru Robert Sachenshofer Ronald Zirbs 《Monatshefte für Chemie / Chemical Monthly》2006,137(7):835-841
Summary. The surface modification of nanoparticles via azide/alkine-1,3-dipolar cycloaddition-reactions is described. Ligand exchange onto various nanoparticles was monitored by
1H NMR spectroscopy and formed the basis for the attachment of ligands onto the nanoparticles and their subsequent modification
by dipolar cycloaddition reactions. Nanoparticle-surfaces were monitored by binding onto self-assembled monolayers derivatized
with matching supramolecular interactions after derivatization. 相似文献
20.
Ligia E. Zamora G. A. Perez Alcazar J. M. Greneche S. Suriñach 《Hyperfine Interactions》2006,168(1-3):1057-1063
Fe60Mn10Al20Nb10, (Fe60Mn10Al30)95Nb5 and (Fe60Mn10Al30)90Nb10 ball milled powdered alloys were investigated using X-ray diffraction, Mössbauer spectrometry, thermomagnetic (TGM) and magnetization measurements. We studied the influence of Nb content and of different milling times on the structural and magnetic properties. Two main features can be concluded: (1) the FeAlMn induces a BCC phase whatever the Nb content is, and (2) as both increasing Nb content and milling time give rise to an highly disordered state in conjunction with a decrease of the ferromagnetic behavior. 相似文献