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21.
Alexander Yu. Rulev Igor A. Ushakov Evgeniy V. Kondrashov Vasiliy M. Muzalevskiy Aleksey V. Shastin Valentine G. Nenajdenko 《Journal of fluorine chemistry》2011,132(11):945-950
The key steps of the reactions of nitrogen nucleophiles with β-halogen-β-trifluoromethylstyrenes have been studied by 19F and 1H NMR monitoring and quantum-chemical calculations. In contrast to the mechanism proposed earlier for nucleophilic vinylic substitution of captodative carbonyl-bearing haloalkenes, this reaction proceeds via either E–Ad or Ad–E sequence depending on the nature of aromatic substituents of the parent styrenes. 相似文献
22.
Potential energy curves for the X (1)Sigma(g) (+) ground state and Omega=0(u) (+), 1(u) valence states and dipole moments for the 0(u) (+), 1(u)-X transitions are obtained in an ab initio configuration interaction study of Cl(2) including spin-orbit coupling. In contrast to common assumptions, it is found that the B (3)Pi(0(+)u)-X transition moment strongly depends on internuclear distance, which has an important influence on the Cl(2) photodissociation. Computed energy curves and transition moments are employed to calculate the A, B, C<--X extinction coefficients, the total spectrum for the first absorption band, and the Cl(*)((2)P(1/2))/Cl((2)P(3/2)) branching ratio as a function of excitation wavelength. The calculated data are shown to be in good agreement with available experimental results. 相似文献
23.
The photodissociation of H(2)Te through excitation in the first absorption band is investigated by means of multireference spin-orbit configuration interaction (CI) calculations. Bending potentials for low-lying electronic states of H(2)Te are obtained in C(2v) symmetry for Te-H distances fixed at the ground state equilibrium value of 3.14a(0), as well as for the minimum energy path constrained to R(1)=R(2). Asymmetric cuts of potential energy surfaces for excited states (at R(1)=3.14a(0) and theta;=90.3 degrees ) are obtained for the first time. It is shown that vibrational structure in the 380-400 nm region of the long wavelength absorption tail is due to transitions to 3A('), which has a shallow minimum at large HTe-H separations. Transitions to this state are polarized in the molecular plane, and this state converges to the excited TeH((2)Pi(1/2))+H((2)S) limit. These theoretical data are in accord with the selectivity toward TeH((2)Pi(1/2)) relative to TeH((2)Pi(3/2)) that has been found experimentally for 355 nm H(2)Te photodissociation. The calculated 3A(')<--XA(') transition dipole moment increases rapidly with HTe-H distance; this explains the observation of 3A(') vibrational structure for low vibrational levels, despite unfavorable Franck-Condon factors. According to the calculated vertical energies and transition moment data, the maximum in the first absorption band at approximately 245 nm is caused by excitation to 4A("), which has predominantly 2(1)A(") ((1)B(1) in C(2v) symmetry) character. 相似文献
24.
Tolmachev AV Vilkov AN Bogdanov B Pasa-Tolić L Masselon CD Smith RD 《Journal of the American Society for Mass Spectrometry》2004,15(11):1616-1628
Ion transfer and storage using inhomogeneous radio frequency (RF) electric fields in combination with gas-assisted ion cooling and focusing constitutes one of the basic techniques in mass spectrometry today. The RF motion of ions in the bath gas environment involves a large number of ion-neutral collisions that leads to the internal activation of ions and their effective "heating" (when a thermal distribution of internal energies results). The degree of ion activation required in various applications may range from a minimum level (e.g., slightly raising the average internal energy) to an intense level resulting in ion fragmentation. Several research groups proposed using the effective temperature as a measure of ion activation under conditions of multiple ion-neutral collisions. Here we present approximate relationships for the effective ion temperature relevant to typical operation modes of RF multipole devices. We show that RF ion activation results in near-thermal energies for ions occupying an equilibrium position at the center of an RF trap, whereas increased ion activation can be produced by shifting ions off-center, e.g., by means of an external DC electric field. The ion dissociation in the linear quadrupole ion trap using the dipolar DC ion activation has been observed experimentally and interpreted in terms of the effective ion temperature. 相似文献
25.
Kuznetsov AE Geletii YV Hill CL Musaev DG 《The journal of physical chemistry. A》2010,114(43):11417-11424
To probe photoinduced water oxidation catalyzed by the Mn?O?L? cubane clusters, we have computationally studied the mechanism and controlling factors of the O? formation from the [Mn?O?L?] catalyst, 6. It was demonstrated that dissociation of an L = H?PO?? ligand from 6 facilitates the direct O-O bond formation that proceeds with a 28.3 (33.4) kcal/mol rate-determining energy barrier at the transition state TS1. This step (the O-O single bond formation) of the reaction is a two-electron oxidation/reduction process, during which two oxo ligands are transformed into to μ2:η2-O?2? unit, and two ("distal") Mn centers are reduced from the 4+ to the 3+ oxidation state. Next two-electron oxidation/reduction occurs by "dancing" of the resulted O?2? fragment between the Mn1 and Mn2/Mn(2')-centers, keeping its strong coordination to the Mn(1')-center. As a result of this four-electron oxidation/reduction process Mn centers of the Mn?-core of I transform from {Mn1(III)-Mn(1')(III)-Mn2(IV)-Mn(2')(IV)} to {Mn1(II)-Mn(1')(II)-Mn2(III)-Mn(2')(III)} in IV. In other words, upon O? formation in cationic complex [Mn?O?L?](+), I, all four Mn-centers are reduced by one electron each. The overall reaction I → TS1 → II → III → TS2 → IV → TS3 → V → VI + O? is found to be exothermic by 15.4 (10.5) kcal/mol. We analyze the lowest spin states and geometries of all reactants, intermediates, transition states, and products of the targeted reaction. 相似文献
26.
Aleksey A. Goldberg Aleksey V. Shastin Valentine G. Nenajdenko 《Journal of fluorine chemistry》2010,131(3):384-5688
CF3CFBr2 was employed in catalytic olefination reactions of aromatic aldehydes. In situ prepared hydrazones of aldehydes were transformed to β-fluoro-β-(trifluoromethyl)styrenes by reaction with CF3CFBr2 under CuCl catalysis. Based on this reaction, a novel stereoselective approach towards β-fluoro-β-(trifluoromethyl)styrenes was elaborated. Nucleophilic vinylic substitution of fluorine by secondary amines, thiolates and alkoxides in β-fluoro-β-(trifluoromethyl)styrenes was also tested. 相似文献
27.
28.
Vincent Larraillet Aleksey Vorobyev Claire Brunet Jér?me Lemoine Yury O. Tsybin Rodolphe Antoine Philippe Dugourd 《Journal of the American Society for Mass Spectrometry》2010,21(4):670-680
We compare product-ion mass spectra produced by electron detachment dissociation (EDD) and electron photodetachment dissociation
(EPD) of multi-deprotonated peptides on a Fourier transform and a linear ion trap mass spectrometer, respectively. Both methods,
EDD and EPD, involve the electron emission-induced formation of a radical oxidized species from a multi-deprotonated precursor
peptide. Product-ion mass spectra display mainly fragment ions resulting from backbone cleavages of Cα-C bond ruptures yielding a and x ions. Fragment ions originating from N-Cα backbone bond cleavages are also observed, in particular by EPD. Although EDD and EPD methods involve the generation of a
charge-reduced radical anion intermediate by electron emission, the product ion abundance distributions are drastically different.
Both processes seem to be triggered by the location and the recombination of radicals (both neutral and cation radicals).
Therefore, EPD product ions are predominantly formed near tryptophan and histidine residues, whereas in EDD the negative charge
solvation sites on the backbone seem to be the most favorable for the nearby bond dissociation. 相似文献
29.
Ilya V. Mishakov Ekaterina V. Ilyina Alexander F. Bedilo Aleksey A. Vedyagin 《Reaction Kinetics and Catalysis Letters》2009,97(2):355-361
Nanocrystalline aerogel VOx/MgO catalysts for the oxidative dehydrogenation of propane with high surface area and uniform vanadium distribution were
synthesized by co-gelation followed by supercritical drying. The catalysts were shown to have superior performance compared
to nanocrystalline VOx/MgO catalysts prepared by impregnation. 相似文献
30.
Victor V. Dotsenko Arif I. Ismiev Anastasiya N. Khrustaleva Konstantin A. Frolov Sergey G. Krivokolysko Elena A. Chigorina Aleksey P. Snizhko Vladimir M. Gromenko Ivan S. Bushmarinov Rizvan K. Askerov Tatyana M. Pekhtereva Sergey Yu. Suykov Elena S. Papayanina Aleksandr V. Mazepa Abel M. Magerramov 《Chemistry of Heterocyclic Compounds》2016,52(7):473-483