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101.
Metal-catalyzed di-tert-butylsilylene transfer was developed as a mild, operationally simple, functional-group-tolerant method for silacyclopropane formation. Di-tert-butylsilylene was transferred from cyclohexene silacyclopropane 1 to an alkene through the use of a metal salt. Silacyclopropanation occurred at temperatures as low as -27 degrees C when AgOTf or AgOC(O)CF(3) were used as catalysts. Complex silacyclopropanes were formed stereospecifically and diastereoselectively from functionalized alkenes. Silacyclopropanes reacted with various carbonyl compounds, including aldehydes, ketones, formate esters, and formamides, in an overall process that efficiently converts alkenes into oxasilacyclopentanes with defined stereochemistry. 相似文献
102.
K.D. Franz H. Tom Dieck U. Krynitz I.W. Renk 《Journal of organometallic chemistry》1973,64(3):361-366
Glyoxal- and diacetyl-bis(imine)metal tetracarbonyls (RNCR′CR′NR)M(CO)4 (M = Cr, Mo, W) are reduced with potassium in DME to give paramagnetic mono-anions. Their high-resolutior, ESR spectra show the hyperfine splittings of the magnetically active ligand atoms as well as the satellites of the metal isotopes 53Cr,95,97Mo and 183W. The coupling constants are discussed with respect to π-bonding mechanisms. 相似文献
103.
João Paulo R.F. André Hugh D. Burrows Carlos F.G.C. Geraldes Maria Da Graça M. Miguel M.Helena S.F. Teixeira L.F. Vilas Boas 《Polyhedron》1996,15(24):4331-4340
Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, 1H and 13C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M−1 and 12 M−1 for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of 1H and 13C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed. 相似文献
104.
The flavonoid composition of broccoli inflorescences has been studied by LC/UV-DAD/ESI-MSn. A large number of hydroxycinnamic acid esters of kaempferol and quercetin glucosides has been characterised. The structures of the flavonoid glycosides were analysed after alkaline hydrolysis, and were identified as 3-sophoroside/sophorotrioside-7-glucoside/sophoroside of kaempferol, quercetin and isorhamnetin (this last found in trace amount). These complex quercetin and isorhamnetin glucosides have not been previously characterised in nature. In addition, several less complex glucosides based on the same aglycones have been identified. The effect of sugar substitution and acylation on chromatographic mobility and ESI ionisation and fragmentation are discussed. 相似文献
105.
Maria Helena Araujo Maria D. Vargas Anthony G. Avent Fabrizia Grepioni 《Journal of organometallic chemistry》2004,689(22):3513-3519
The reactions of [HIr4(CO)9(Ph2PCCPh)(μ-PPh2)] (1) or [Ir4(CO)8(μ3-η2-HCCPh)(μ-PPh2)2] (2) with HCCPh gave two isomeric forms of [Ir4(CO)6(μ3-η2-HCCPh)(μ2-η4-C4H2Ph2)(μ-PPh2)2] (3 and 4) in good yields as the only products. These compounds were characterized with analytical and spectroscopic data including 1H, 13C and 31P NMR (1 and 2D) spectroscopy and their molecular structures were established by X-ray diffraction studies. Compounds 3 and 4 exhibit the same distorted butterfly metal polyhedral arrangement of metal atoms with two μ-PPh2 that occupy different positions in the structures of the two isomers. Both molecules contain a HCCPh ligand bonded in a μ3-η2-// mode to one of the wings of the butterfly and a metallacyclic ring, which resulted from head-to-tail coupling, in the case of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(H)C(Ph)}(μ-PPh2)2] (3) and tail-to-tail coupling, in that of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(Ph)C(H)}(μ-PPh2)2] (4), and which is linked to two metal atoms of the second wing of the butterfly. 相似文献
106.
A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples. 相似文献
107.
Gustavsson S Rosén A Grennberg H Bolton K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(9):2223-2227
Semiempirical and density functional electronic structure theory methods were used to study SWNT-X--R bond strengths, where the single-walled carbon nanotube (SWNT) had an armchair or zigzag structure, the link heteroatom X was O, N(H), or S and the hydrocarbon chain R was CH(2)CH(3), CH(OH)CH(3), CHCH(2), or CH(CF(3))CH(3). In all systems the hydrocarbon was bonded to the end of the nanotube. The SWNT-X--R bond (that is, the bond joining the link atom to the hydrocarbon) is more than 0.4 eV stronger for armchair than for zigzag nanotubes with the same diameters, irrespective of whether O, N, or S are used as link atoms or whether OH, C==C, or CF(3) groups are present in the hydrocarbon chain. This raises the possibility for selective manipulation of armchair/zigzag nanotubes using a variety of link atoms and hydrocarbon structures. The SWNT-O--CH(CF(3))CH(3) bond is weaker than the SWNT-O--CH(2)CH(3) bond (for both armchair and zigzag nanotubes), while inclusion of a double bond in the ethyl chain increases the bond strengths. Also, SWNT-S--CH(2)CH(3) and SWNT-N(H)--CH(2)CH(3) bonds are stronger than SWNT-O--CH(2)CH(3) bonds. 相似文献
108.
Shi G Wu JT Li Y Geleziunas R Gallagher K Emm T Olah T Unger S 《Rapid communications in mass spectrometry : RCM》2002,16(11):1092-1099
109.
PHOTOSENSITIZING PROPERTIES OF BACTERIOCHLOROPHYLLIN a and BACTERIOCHLORIN a, TWO DERIVATIVES OF BACTERIOCHLOROPHYLL a 总被引:2,自引:0,他引:2
Eva M. Beems Tom M. A. R. Dubbelman Johan Lugtenburg Jaap A. van Best Monique F. M. A. Smeets J. Pierre J. Boegheim 《Photochemistry and photobiology》1987,46(5):639-643
Abstract The photosensitizing properties of two water soluble derivatives of bacteriochlorophyll a , bacteriochlorophyllin a and bacteriochlorin a (lacking the central Mg-ion) were investigated and compared to those of hematoporphyrin derivatives. At physiological pH the oxygen consumption rate of histidine, tryptophan, dithiothreitol and guanosine upon illumination was 3 to 4 times higher when bacteriochlorin a was used as photosensitizer than when hematoporphyrin derivatives were used. Especially bacteriochlorin a proved to be an effective sensitizer for the killing of L929 cells. Because bacteriochlorin a has an absorption maximum at 765 nm in phosphate buffered saline (allowing a light penetration in tissue about ten times larger than at 630 nm) and a high molar absorption coefficient (32 000 M cm−1 ) it has promising possibilities for the application in photodynamic therapy. 相似文献
110.
Strictly localized or resonance Shockley surface states have been found on the (111), (010) and (110) faces of paramagnetic bcc iron for
,¯M and ¯N points in the corresponding surface Brillouin zones. Energy, character of wave function and its damping for these states are reported. Emphasis is laid on implications of surface states in photoemission, field-electron and -ion emission, electron energy-loss or disappearance potential spectroscopy, Auger electron spectroscopy, work function, magnetic properties, electric conductivity, as well as chemisorption and catalysis. 相似文献