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21.
UV/Vis-spectra of Cyclosilanes (SiX
2)
n
withX=Cl, Br, I, OMe andn=4, 5, 6 are recorded and interpreted qualitatively. The spectra exhibit increasing influence of the substituents on the Si-Si-bond system within the rings in the order Cl OMe Br I. At the low energy side of the spectra weak absorption bands, possibly due to intramolecular charge transfer transitions, appear. The strong inductive effect of the electronegative substituents is documented by a marked increase of the first IP's compared to permethylcyclosilanes. 相似文献
22.
Gröger H Hummel W Buchholz S Drauz K Nguyen TV Rollmann C Hüsken H Abokitse K 《Organic letters》2003,5(2):173-176
[reaction: see text] An enzyme-compatible biphasic reaction media for the asymmetric biocatalytic reduction of ketones with in situ cofactor regeneration has been developed. In this biphasic reaction media, which is advantageous for reactions at higher substrate concentrations, both enzymes (alcohol dehydrogenase and FDH from Candida boidinii) remain stable. The reductions with poorly water-soluble ketones were carried out at substrate concentrations of 10-200 mM, and the optically active (S)-alcohols were formed with moderate to good conversions and with up to >99% ee. 相似文献
23.
Ewald Haidl Daniel Krois Harald Lehner 《Monatshefte für Chemie / Chemical Monthly》1985,116(1):119-131
Biliverdins undergo appreciable self association in acidic solutions especially if solvents like benzene or chloroform are employed. The population of aggregates further depends on the concentration of both the acid and the solute. In chloroform and benzene solutions at high acidity a doubly protonated species is formed. This is concluded from a combinatory evaluation of the CD and electronic absorption spectra of chiral optically active biliverdins (1–6) in benzene, chloroform, and ethanol solutions containing trifluoroacetic acid or hydrochloric acid. The aggregates formed at medium acid concentrations exhibit largeCotton effects in the long-wavelength absorption bands and thus dominate the CD spectra. Similarly, agrregates are the main contributors to theCotton effects of achiral, protonated biliverdins in (S)-(–)-ethyl lactate (SICD) at usual concentrations. The consequence and relevance of these findings with regard to the recent literature is briefly discussed.Dedicated to Prof. Dr.Karl Schlögl on occasion of his 60th birthday. 相似文献
24.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
25.
26.
Chiral terpyridine ligands have been synthesized and characterized. By applying Ru(III)/Ru(II) chemistry, symmetrical as well as asymmetrical bis-terpyridine ruthenium(II) complexes were obtained. These materials were fully characterized and their optical properties investigated. While the chiral metal complexes revealed no Cotton effect in good solvents such as chloroform, CD-measurements in dodecane showed an effect in both ligand and MLCT regions, suggesting chirality transfer from the lateral alkyl chains to the complex core. This behavior points to the formation of supramolecular aggregates in dodecane. Furthermore, the analogous achiral ligand and its corresponding ruthenium(II) complexes were prepared. 相似文献
27.
Polarography and chronopotentiometry are used to study the primary processes of the reduction of 2,2′-bipyridine at mercury electrodes in aqueous solutions (12 < pH < 14). Bipyridine and its first reduction product are strongly adsorbed. The reduction is preceded by a complex equilibrium between bipyridine and the cation of the supporting electrolyte (Li, Na, K, Ba). Due to the great excess of the cations, the equilibrium is shifted completely to the side of the complex, which exists as cis- and trans-isomer. The cis-form is more stable, forming a chelate, the trans-form however is more easily reducible. The kinetic and thermodynamic data of the isomerization are determined. The first reduction product reacts irreversibly giving a substance which can be reoxidized to bipyridine via a radical intermediate. 相似文献
28.
Otmar Hofer Michael Widhalm Harald Greger 《Monatshefte für Chemie / Chemical Monthly》1984,115(10):1207-1218
The CD spectra of 16 naturally occurring sesquiterpene-umbelliferone ethers, including the complete set of farnesiferol A isomers with all acetates and 6-oxoderivatives, are reported over the significant wavelength range of 350–200 nm. 11 compounds were isolated from an Asa Foetida sample and 5 further derivatives, already known as natural products, were obtained by acetylation orJones oxidation. In addition, a new compound — kamolonol (14) — was isolated. Its structure is characterized by twofold methyl migration in the drimenol derived sesquiterpene moiety.1H-NMR, MS, IR, UV, and CD data of the new compound are discussed.Herrn Prof. Dr.K. Schlögl mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
29.
Joeng-Shein Chen Harald Berndt Günther T?lg 《Fresenius' Journal of Analytical Chemistry》1992,344(12):526-534
Summary Various possibilities for the determination of trace impurities in high-purity iron by atomic spectrometry were investigated in detail. For Ba, Bi, Cd, Co, Cr, Cu, Mn, Ni, Pb, Ti and V, flame AAS, furnace AAS and ICP-OES were firstly evaluated in terms of their power of detection. Detection limits in the g/g-range could be achieved by direct determination. For determination in the ng/g-range a removal of iron by a solvent extraction technique prior to the instrumental measurement was required. The power of detection of direct determination, and of combined procedures were compared with regard to routine applicability and a minimization of systematic errors. 相似文献
30.
Gaseous Complexes NiAl2Cl8 and NiAl3Cl11 Spectral photometric measurements of equilibria which are established by reaction of solid NiCl2 with gaseous Al2Cl6 have been made. Results see ?Inhaltsübersicht”?. 相似文献