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991.
992.
Since alkynes have higher symmetry than olefins, it is not easy to infer the mechanism of a triplet carbene’s addition to
an alkyne by traditional product analysis studies. Specifically, no stereochemical information which might offer insight into
the carbene’s spin state can be extracted from the cyclopropene products. In 1971, Hendrick, Baron, and Jones showed that
diphenylcarbene reacts with terminal alkynes in solution to produce indenes via a “self-trapping” vinylcarbene. They also examined the diphenylcarbene reaction with disubstituted alkynes and found at most
trace amounts of the “self-trapping” indene product.
In this work, we report the direct observation by organic matrix EPR of the vinylcarbenes generated from triplet fluorenylidene
and terminal alkynes. Our efforts to confirm the identities of these intermediates by independent synthesis, intermolecular
trapping, and an intramolecular “self-trapping” method-halogen-migration-are also recounted. These findings are among the
few instances in which fluorenylidene undergoes carbon-carbon bond formation rather than atom abstraction reactions in a low-temperature
matrix, and in which the biradical adduct of a triplet carbene and a π-bonded substrate can be directly observed. 相似文献
993.
Yu JI Kim KH Bae IH Lee DY Kim DL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2640-2642
Photoreflectance measurements were performed to investigate the optical properties in the electron beam irradiation semi-insulating GaAs(e-beam irradiation GaAs) and semi-insulating GaAs(SI-GaAs). A considerable increase of the PR amplitudes has been registered after the e-beam irradiation in comparison with the GaAs. It is that result of a higher electron scattering on the lattice defects created by the e-beam. 相似文献
994.
Lee L Wang JX Adzić RR Robinson IK Gewirth AA 《Journal of the American Chemical Society》2001,123(36):8838-8843
X-ray reflectivity, cyclic voltammetry, and scanning tunneling microscopy (STM) are used to examine the structure of alpha-SiW12O4(4-) or silicotungstic acid (STA) adsorbed on Ag(100) in acid solution. The voltammetry shows that STA passivates the Ag surface relative to electron transfer to a solution redox species. STM images reveal the formation of a series of lattice structures, one of which can be associated with a commensurate ( radical13x radical13)R33.69 degrees structural model. X-ray reflectivity measurements show uniquely that STA orients with its four-fold axis perpendicular to the Ag(100) surface and that the center of the STA molecule is 4.90 A above the top layer of the Ag substrate. Analysis of bond lengths leads to a footprint of STA on Ag(100), in which the four terminal O atoms are located near the hollow sites and have a Ag-O bond length of 2.06 A. This bond length is consistent with a strong covalent interaction between STA and the Ag surface. 相似文献
995.
Young-Joo Eo Duk-Jun Kim Byeong-Soo Bae Ki-Chang Song Tae-Young Lee Seung-Won Song 《Journal of Sol-Gel Science and Technology》1998,13(1-3):409-413
Tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) hybrid materials were prepared and the hydrolysis and condensation reactions during processing were investigated by means of 29Si NMR solution spectroscopy. The variation of drying characteristics of the coating films was examined with respect to the tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) ratio, as well as drying temperature, by FT-IR spectroscopy. It is shown that the TO mode of Si–O–Si stretching absorption was enhanced with increasing tetraethylorthosilicate (TEOS) content and drying temperature. Also, the wettability of the coating films on polymer films was independent of the solution composition but enhanced by the precoating of poly(4-hydroxystrene) (PHS) as a wetting agent. The adhesion between the coating and the films was also enhanced when the vinyltriethoxysilane (VTES) content in the coating solution was increased. 相似文献
996.
Difference in Conversions Between Dimethyl Sulfide and Methanethiol in a Cold Plasma Environment 总被引:1,自引:0,他引:1
Cheng-Hsien Tsai Wen-Jhy Lee Chuh-Yung Chen Perng-Jy Tsai Guor-Cheng Fang Minliang Shih 《Plasma Chemistry and Plasma Processing》2003,23(1):141-157
This study compared the conversion of two malodorous substances, dimethyl sulfide (CH3SCH3, DMS) and methanethiol (CH3SH) in a cold plasma reactor. The DMS and CH3SH were successfully destroyed at room temperature. DMS decomposed less than CH3SH at the same conditions. In oxygen-free condition, CS2 and hydrocarbons were the major products, while SO2 and COx were main compounds in oxygen-rich environments. The DMS/Ar plasma yielded more hydrocarbons and less CS2 than that of CH3SH/Ar plasma. In the CH3SH/O2/Ar plasma, rapid formation of SO and CO resulted in the yields much more amounts of SO2 and CO2 than those in the DMS/O2/Ar plasma; and remained only a trace of total hydrocarbons, CH2O, CH3OH, CS2, and OCS. The major differences between the reaction mechanisms of DMS and CH3SH were also proposed and discussed. 相似文献
997.
Seo K Kim C Choi YS Park KA Lee YH Kim B 《Journal of the American Chemical Society》2003,125(46):13946-13947
CO2 molecule chemisorbs selectively on the zigzag tube edge without an activation barrier, whereas it physisorbs on the armchair edge of nanotubes. In addition, carbon nanotubes can be etched by an adsorbed oxygen atom of CO2 molecule. From our results, we suggest a selective etching mechanism for tuning the chirality of the mass-produced carbon nanotubes. 相似文献
998.
The electrocyclic reactions of [16]annulene have been investigated by ab initio and DFT calculations. Among the six conformers of [16]annulene identified, 3, with Cs symmetry, is taken as the starting reactant for the cyclization reactions of [16]annulene, even though it is 31.4 kJ mol(-1) less stable than the most stable conformer, 1. The pathways of the electrocyclic reactions from reactant 3 to two tricyclic products, 5 and 6, have been found. All pathways identified are stepwise, i.e., the two ring closure processes occur one after the other. Among the pathways found, the ones with the lowest overall barrier for reactions 3 --> 5 and 3 --> 6 have the same rate-determining step and hence the same overall barrier, 131.0 kJ mol(-1). Thus, based on the barriers calculated, it is not possible to determine whether 5 or 6 is the dominant product in the cyclization reaction of 3. 相似文献
999.
[reaction: see text] Molecular modeling was used to design mimetics of the HIV-1 matrix protein nuclear localization signal (NLS) in which a scaffold of two resorcinol units joined by a diamide linker presents 3-aminopropyl ethers in place of lysine side chains. Prospective mimetics with linkers of 6, 8, 10, or 12 atoms were synthesized and compared in a competition assay for binding to the nuclear import receptor subunit karyopherin alpha, showing the 10-atom linker to be best and shorter ones ineffective. 相似文献
1000.
Humeres E Debacher NA Franco JD Lee BS Martendal A 《The Journal of organic chemistry》2002,67(11):3662-3667
The acid decomposition of some p-substituted aryldithiocarbamates (arylDTCs) was observed in 20% aqueous ethanol at 25 degrees C, mu = 1.0 (KCl, for pH > 0). The pH-rate profiles showed a dumbell shape with a plateau where the observed first-order rate constant k(obs) was equal to k(o), the rate constant of the decomposition of the dithiocarbamic acid species. The acid dissociation constants of the dithiocarbamic acids (pK(a)) and their conjugate acids (pK(+)) were calculated from the pH-rate profiles. Comparatively, k(o) was more than 10(4)-fold faster than alkyldithiocarbamates (alkDTCs) with similar pK(N) (the acid dissociation constant of the parent amine). It was observed that the values of pK(a) and pK(+)were 5 and 8 units of pK, respectively, higher than the expected values from the pK(N) of alkylDTCs. The higher values were attributed to the inhibition of the delocalization of the nitrogen electron pair into the benzene ring because of the strong electron withdrawal effect of the thiocarbonyl group. Comparison of the activation parameters showed that the rate acceleration was due to a decrease in the enthalpy of activation. Proton inventory indicated the existence of a multiproton transition state, and it was consistent with an S to N proton transfer through a water molecule. There are two hydrogens contributing to a secondary SIE, and there are also two protons that are being transferred at the transition state to form a zwitterion followed by fast C-N bond cleavage. The mechanism could also be a concerted asynchronic process where the N-protonation is more advanced than the C-N bond breakdown. The kinetic barrier is similar to the torsional barrier of thioamides, suggesting that the driving force to reach the transition state is the needed torsion of the C-N bond that inhibits the resonance with the thiocarbonyl group and the aromatic moiety, increasing the basicity of the nitrogen and making the proton transfer thermodynamically favorable. 相似文献