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101.
利用IR,EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n=3,4)在NaY分子筛超笼内的合成机理.在氧化样品Pt~(2+)/NaY上300-373 K的还愿羰基化过程中,首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)=2110 cm~(-1)),然后聚集成“Pt_3(CO)_6”(σ_(CO)=2112,1896和1841 cm~(-1)),最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)=2080,1824 cm~(-1)).“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换,而[Pt_3(CO)_6]~(2-)_n(n=3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢,室温下,NO能逐步破坏Pt羰基簇合物的层间和层内Pt-Pt键,得到中间物种“Pt_3(CO)_6”和PtO(CO),同时在气相产生CO_2和N_2O.而由上述两中间物种出发,300-353 K温度下,在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物. 相似文献
102.
Principal component analysis (PCA) is applied to 32 disubstituted unsaturated compounds (Y–CH2–X): cyanides, oximes and propenes; bearing 12 -substituents: F, Cl, Br, I, OMe, OEt, SMe, SEt, NMe2, NEt2, Me, and Et. The experimental 13C chemical shifts for the -carbon and functional carbon atoms are correlated with theoretically derived molecular properties, i.e. partial charges, electronegativity, hardness, dipole moments and the nuclear repulsion energies. In the first PCA, the clustering of these three classes of organic compounds occurred mostly because of the chemical shifts and partial charges, and also of the dipole moments, hardness and electronegativity parameters as confirmed by loading graph. A strong grouping is observed in the second PCA, showing the chemical shift dependence on the type of heteroatom substituents. Therefore, sulfur, nitrogen, oxygen and neutral groups exhibit four types of C-13 SCS influences, indicating that the heteroatom (Y) properties play a significant role on the effects on chemical shifts. The -halogenated compounds represent a very heterogeneous group due to possible orbital interactions between the functional group and the substituent. The third PCA shows the grouping of F, Cl, Br and I derivatives, confirming the second PCA results that same halogen presents the same or very similar effects on the chemical shifts. 相似文献
103.
The methylation of tin(II) [Sn(II)] by iodomethane (CH3I) under environmental conditions has been further demonstrated by a 13C carbon isotope tracer method. Methylation products are mainly monomethyltin, and very small amounts of dimethyltin. The reaction of Sn(II) and CH3I was investigated at pH 2, 4, 6, 8, 10 and salinity (S) 8, 15, 22, 28, 35%; it has been found the reaction was affected by pH and salinity, the tin methylation activity being highest at about pH 6 and S = 28% . The methylation reaction is first-order for both CH3I and Sn(II), and the rate equation has been obtained as follows: . 相似文献
104.
Investigation of carbon-13 nuclear magnetic resonance spectra-structure correlation based on novel atomic distance-edge (ADE) vector 总被引:1,自引:0,他引:1
A set of novel graph-theoretical parameters,called the atomic distance-edge (ADE) vector,was developed.Based on the connecting C-C bond number between central carbon atom and the other ones,various carbon atoms of alkanes were classified as four types,i.e.,type 1,2,3 and 4 for primary,secondary,ternary and quaternary carbon,respectively; and then four regression equations were obtained to link carbon-13 chemical shift (CS) of each type of atoms.Furthermore,these regression models were used to predict the carbon-13 nuclear magnetic resonance spectra of alkanes and it was found that the estimated CS were in agreement with the experimental results. 相似文献
105.
A. Yu. Tyurin A. M. Churakov Yu. A. Strelenko M. O. Ratnikov V. A. Tartakovsky 《Russian Chemical Bulletin》2006,55(9):1648-1653
Thermolysis of o-diazidobenzotetrazine 1,3-dioxides was accompanied by cleavage of the C-C bond of the benzene ring to give nonannulated 1,2,3,4-tetrazine
1,3-dioxides. The structures of these first representatives of nonfused 1,2,3,4-tetrazines were confirmed by 13C and 14N NMR spectroscopy.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1589–1594, September, 2006. 相似文献
106.
Eckhard Herrmann Moein Nouaman Zdirad
k Gisbert Großmann Gisela Ohms 《无机化学与普通化学杂志》1994,620(11):1879-1888
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group. 相似文献
107.
M. V. Alfimov S. P. Gromov O. B. Stanislavskii E. N. Ushakov O. A. Fedorova 《Russian Chemical Bulletin》1993,42(8):1385-1389
Styryl dyes containing a crown ether group and a heteroaromatic moiety with a sulfoalkylN-substituent (1a,b) undergo photocyclodimerization in acetonitrile in the presence of Mg(ClO4)2 to give only the typeA isomer of cyclobutane derivative (2a,b). The photochemical regio- and stereoselectivity of the cycloaddition is explained by self-organization of thetrans-isomers of the styryl dyes upon complexation with the Mg2+ cations into dimers with a fixed mutual arrangement of multiple bonds.For part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1449–1452, August, 1993. 相似文献
108.
The adsorption of ovalbumin, -globulin, and lysozyme on uniform spherical hematite and chromium hydroxide particles in aqueous media has been studied as a function of the pH at a constant ionic strength. The uptake of ovalbumin and -globulin was greatest at their isoelectric points and differed little at 10–2 and 10–3 mol dm–3 NaNO3. The adsorption of lysozyme was strongly influenced by the ionic strength.The deposition of ovalbumin on hematite in the presence of Mg (NO3)2 was significantly greater than that with NaNO3 under otherwise comparable conditions. Dialysis experiments with ovalbumin against magnesium nitrate solutions showed Mg2+ to be specifically bound to the protein.The shapes of isotherms indicated monolayer coverage for ovalbumin and multilayer coating for lysozyme for both adsorbents. The shapes of isotherms of -globulin on hematite point to a rearrangement of the protein on the particle surface, while a monolayer was found on chromium hydroxide particles.Supported by the NSF Grant CHE-9108420Part of a Ph.D. thesis 相似文献
109.
110.
Lam WH Jia G Lin Z Lau CP Eisenstein O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2775-2782
Theoretical calculations on the metathesis process, [Tp(PH3)MR(eta 2-H[bond]CH3)] --> [Tp(PH3)M(CH3)(eta 2-H[bond]R)] (M=Fe, Ru, and Os; R=H and CH3), have been systematically carried out to study their detailed reaction mechanisms. Other than the one-step mechanism via a four-center transition state and the two-step mechanism through an oxidative addition/reductive elimination pathway, a new one-step mechanism, with a transition state formed under oxidative addition, has been found. Based on the intrinsic reaction coordinate calculations, we found that the trajectories of the transferring hydrogen atom in the metathesis processes studied are similar to each other regardless of the nature of reaction mechanisms. 相似文献