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21.
Henri Brunner Christian Zettler Manfred Zabel 《Monatshefte für Chemie / Chemical Monthly》2003,134(9):1253-1269
Summary. The synthesis of new chiral tridentate ligands is reported which coordinate transition metals in a meridional way. The ligands contain a pyridine ring, an oxazoline ring, and a strongly coordinating diphenylphosphanyl group. The methionine-derived ligand forms a copper complex, which has been studied by X-ray crystallography. The new ligands were tested in models of enantioselective catalyses, such as hydrogenation of ketopantolactone, hydrosilylation of acetophenone, and transfer hydrogenation of acetophenone.X-ray structure analysesReceived March 4, 2003; accepted March 4, 2003
Published online August 18, 2003 相似文献
22.
23.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
24.
Time-resolved excitation spectra of xenon vapor in the 150 nm region are analysed in terms of four main fluorescence lifetimes corresponding to decays of four stable excited electronic states of the Xe dimer. The two shortest decay times, ≈ 2 ns and ≈ 60 ns, are assigned to the direct radiative relaxation of the two lowest excited ungerade states, (1Σ+u)0+u and (3Σ+u))1 u respectively. The two longest decay times, ≈ 150 ns and ≈ 500 ns, must correspond to the overall depopulation rates of the two lowest excited gerade states, (3Σ+g)1g and (1Σ+g)0+g, decaying into the gerade ground state by cascading down through the intermediate ungerade states. 相似文献
25.
Develay S Tripier R Le Baccon M Patinec V Serratrice G Handel H 《Dalton transactions (Cambridge, England : 2003)》2005,(18):3016-3024
The host-guest interaction between orthophosphate, pyrophosphate and triphosphate anions and four cyclen based bis-macrocycles ligands possessing ortho-(BOC), meta-(BMC), para-xylenyl (BPC) or 2,6-pyridinyl (BPyC) linker was investigated by potentiometric measurements and NMR spectroscopy. Each ligand gave protonated species in aqueous solution that further formed ternary complexes after binding with anions; these complexes were analyzed as a result of hydrogen bond formation and Coulombic attraction between the organic host and the inorganic guest. The equilibrium constants for all the detected species are reported and the selectivity, illustrated with species distribution diagrams, is discussed. The results unambiguously showed the importance of the distance between the two cyclen cores and underlined, especially for the triphosphate species, the contribution of the nitrogen atom of the pyridinyl spacer as a supplementary anchoring point in acidic medium. 相似文献
26.
Henri J.-M. Dou Maria Ludwikow Parina Hassanaly Jacky Kister Jacques Metzger 《Journal of heterocyclic chemistry》1980,17(2):393-395
A general study of the chemical behavior of heterocyclic anions, dianions and dianionic reagents under phase transfer catalysis conditions allowed us to synthesize various heterocyclic compounds such as imidazo[2,1-b]thiazole and derivatives; imidazo[2,1-b]thiazine and imidazo[2,1-b]benzothiazepine. Reaction conditions e.g., catalyst, solvent, temperature, etc., are indicated. 相似文献
27.
Henri J.-M. Dou Parina Hassanaly Jacques Metzger 《Journal of heterocyclic chemistry》1977,14(2):321-323
Alkylation of ambident-anions derived from 2- and 4-pyridones yield by phase transfer catalysis, 80% of N-substitution and 20% of O-substitution. Change of salts, solvents, temperature and alkyl halide do not interfere very much with the N- and O-alkylation percentage of substitution. Overall yields range from 40 to 80% with primary or secondary alkyl halides. 相似文献
28.
Par Henri Edouard Audier Arielle Milliet Jean-Claude Tabet 《Helvetica chimica acta》1980,63(2):344-358
Isomerization of Protonated Aldehyde and Ketone Ions in the Mass-Spectrography Before the Loss of Water In mass spectrometry, protonated aldehyde and ketone ions isomerize before the loss of a molecule of water. In order to specify this process, the spectra of deuterium labelled protonated aldehydes and ketones have been compared to the spectra of the corresponding isomer ions. 相似文献
29.
Hans-Gerd Janssen Henri M. J. Snijders Jacques A. Rijks Carel A. Crarners Peter J. Schoenmakers 《Journal of separation science》1991,14(7):438-445
The effects of the pressure drop across the column on retention and efficiency in SFC have been studied. Numerical methods are described which enable the prediction of hold-up time and pressure drop in both packed and open tubular columns. Predictions of both hold-up time and pressure drop are in good agreement with experimental data. The density gradient along the column can be calculated using the numerical methods and a procedure is described which enables the calculation of the overall capacity factors of the solutes from the density profile in the column. Significant variations of the capacity factor are observed along the column. The effect of the density gradient along the column on local diffusivity and dispersion is studied. The column efficiency in systems with significant pressure drops is affected by changes in: the linear velocity of the mobile phase; the diffusion coefficients; and the capacity factors of the solutes along the column. The overall efficiency of the chromatographic system can be calculated if, as is the case for open tubular columns, adequate plate height equations are available. 相似文献
30.
Jean-Claude Muller Henri Rarouz John Daly Peter Schönholzer 《Helvetica chimica acta》1982,65(5):1454-1466
The structure of new 2-oxo-2,8-dihydro-[l,2,4]oxadiazolo-[2,3-a]pyrimidine-carbamates 1 was established by correlating the IR. and NMR. data with these of analogous compounds. A X-ray crystallographic analysis of 1c gave an unequivocal proof of structural assignment. 相似文献