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11.
Protonation of parent azulene (1), homoazulene (8), representative isomeric benzazulenes (9, 9A, and 9B), and benzohomoazulenes (10, 10A, and 10B) as well as the mono- and diprotonation of isomeric azulenoazulenes (11-16) were studied by DFT at the B3LYP/6-31G(d) level. The most likely carbocations were identified based on relative protonation energies. For comparison, complete experimental 13C NMR data were obtained for parent azulenium ion 1H+ and guaiazulenium ion 2H+ in TFA. The oxidation dications derived from benzazulenes (9, 9A, and 9B), benzohomoazulenes (10, 10A, and 10B) and azulenoazulenes (11, 16) were also investigated. For azulenoazulene dications the singlet and triplet states are both minima, but except for 11(2+) and 13(2+), the triplet states are higher in energy. Structural/geometrical changes in the carbocations were examined. GIAO-NMR, NPA charges (and changes in charges), and NICS (and delta NICS) were employed to compute the NMR chemical shifts (delta delta 13C values) in order to derive charge delocalization maps and to gauge relative aromaticitylantiaromaticity in the energetically most favored carbocations and oxidation dications. The emerging trends are discussed and compared. Creation of tropylium or homotropylium entities in the carbocations (monoprotonated) and carbodications (diprotonated) is identified as an important driving force governing the protonation outcomes. Consideration of the AM1-derived delta delta Hf values (and the DFT-derived delta delta G values) suggests that the two-electron oxidation of azulenoazulenes should be experimentally feasible. Given their antiaromatic (paratropic) character, azulenoazulene dications represent interesting targets for NMR study. GIAO-derived charge delocalization mapping allows the most likely sites for nucleophilic attack on the dications to be identified.  相似文献   
12.
Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of SH2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene.  相似文献   
13.
Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes.  相似文献   
14.
Monte Carlo calculations have been carried out for pure water and an infinitely dilute aqueous solution of methanol at 298.15 K at ordinary density by the Metropolis method in NTV ensemble. The hydration structure around methanol revealed by a graphic display technique indicates a structure-forming effect near the hydrophobic group.  相似文献   
15.
Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 and 11) are transformed into their corresponding trans-dimethyldihydroethanophenanthrenium dications (14(2+) and 15(2+)) in FSO(3)H x SbF(5) (4:1) and FSO(3)H x SbF(5) (1:1) with SO(2)ClF or SO(2) as the solvent; these 10 pi-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO(3)H/SO(2)ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H(2)(2+)) and, subsequently, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1 after 1 week at low temperature. Protonation of the anti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz.  相似文献   
16.
Heating a toluene solution of Cp*(CO)(C5H5N)FeSiMe2NPh2 led to insertion of pyridine into the iron-silicon bond to form Cp*(CO)Fe[eta3(C,C,C)-C5H5NSiMe2NPh2].  相似文献   
17.
ESR saturation phenomenon was observed for various alkane cation radicals derived from cyclohexane, propane and norbornane in frozen halocarbon matrices at 4 K. In addition to spectral diffusion by spin-spin interaction between the radicals, which is a common mechanism of ESR relaxation in the solid state, isotropic hyperfine modulation by the dynamics between the equivalent distorted structures was found to be very important for those centers which show Jahn-Teller (JT) or pseudo-JT effects. The effect of annealing of the sample at 77 K is also discussed.  相似文献   
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The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.  相似文献   
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