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Die vorliegende Arbeit stellt eine kritische Übersicht über den Forschungsstand zu multiplen Wh-Konstruktionen im Slavischen dar. Das Ziel ist es, die Unklarheit der Datenlage und die Widersprüchlichkeit der auf solchen "unklaren" Daten basierten Theorien aufzuzeigen. Inhalt: Historischer Hintergrund (Wachowicz 1974) Einige ältere Ansätze Höhepunkt: die folgenschwere Arbeit von Rudin (1988) Probleme: - Das Problem der Zuverlässlichkeit von Daten - Das Problem der Relevanz von Daten "Harte" Fakten: - Strikte Superioritätseffekte im Bulgarischen - Obligatorische Wh-Anhebung im Slavischen Neuere Ansätze: - "Qualitative" Ansätze - "Quantitative" Ansätze - Alternative Ansätze
Especially sulphur containing compounds are suitable for the separation of noble metals[ , ]. 1,2-Dithioethenes are weak chelate-forming ligands [ ]and in the case of bis(methylthio)maleonitrile[ ] the donor power of both of the sulphur atoms is further decreased by the electron withdrawing effect of the cyanogroups. Crowned dithiomaleonitrile are macrocyclic chelate ligands which extract Pd(II) at sufficient rate in a very good yields. The reason for that extraction behaviour is the fact that Pd(II) favours the square planar coordination geometry in opposite to the 3d- elements. The synthesis of the immobilized ligands proceeds from the 2-allyloxy-1,2-propanediol forming the dicarbon acid which is reduced to the diole. With the help of thionylchloride the dichloro compound is synthesized forming together with a dithiolate (1,2-disodium-1,2-dicyanethene-1,2-dithiolate, 1,2-disodium-4-methylbenzene-1,2-dithiolate [ ]) at high dilution conditions the macrocycle. Than the allysubstituted crown ether is sillylated and the resulting alkoxysilane is immobilised onto activated silca gel. The substituent forms in the same time a spacer should be modified in the future. By immobilisation at an inactive matrix the selectivity of the ligand should be applied for the accumulation of palladium from diluted solutions. The extraction was performed from nitric acid solution with a yield of 93% into a ligand solution (chloroform, kerosine). The extraction equilibrium is reached after 10 min. By atomic absorption spectroscopy the metal concentration in the aqueous phase was determined to calculate the extraction rate. By modification of the cavity of the macrocyclus the extraction rate increases from the acyclic compound through maleonitrile-dithio-21-crown-7, maleonitrile-dithio-15-crown-5 and maleonitrile-18-crown-6. The best results can be observed at the maleonitrile-dithio-12-crown-4. The rise of the function lg D= f(lg L) gives the composition of the extracted compounds as 1:1. The separation is unsatisfactory in the case of Ag(I), Hg(II), Pt(II), Tl (I) and the most 3d-elements. Also Ni(II) as a representative for the 3d-elements shows only separations coefficients of 1.43?103 . Summarizing, a very good separation of palladium from the examined elements can be specified. Additional to the extraction experiments, as well as the crystal structures and by UV spectroscopy the formation constants of selected chelates were determined. The observed order corresponds to that found by the extraction of palladium in the system water/chloroform. In the case of maleonitrile-dithio-15-crown-5 Ag(I) is endocyclic coordinated with all donor atoms of the macrocyclus. Already maleonitrile-dithio-18-crown-6 can include the silver cation into its greater cavity. In these cases a 1:1 complex is formed. A 1:2 sandwich structure was noticed only in the case of the smaller ligand maleonitrile- dithio-12-crown-4. Obviously, the formation of that structure is not favoured in the system water/chloroform from which can be explained the unfavourable extraction results.
European monetary union and exchange rate dynamics : new approaches and application to the Euro
(2001)
Asymptotic algebras
(2001)
Proceedings of HILP 5
(2001)
The decolonizing pen : cultural diversity and the transnational imaginary in Rushdieïs fiction
(2001)
Ageing and executive control
(2001)