TY - JOUR A1 - Mickler, Wulfhard A1 - Bukowsky, Heinz A1 - Holdt, Hans-Jürgen T1 - Separation of Palladium(II) with immobilized Maleonitrile-Dithiocrown ethers N2 - 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)maleo-nitrile 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 synthesis of the immobilised ligands proceeds from the 2-allyloxy-1,2-propanediol forming the dicar-bon acid which is reduced to the diole. With the help of thionylchloride the dichloro compound is synthe-sized forming the macrocycle 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 allylsubstituted crown ether is sillylated and the resulting alkoxysilane is immobilised onto activated silica gel. The extraction results with crown ethers are compared with that achieved with the help of substituted ß- diketones and 4-acyl-5-pyrazolones. 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 log D= f(log L) gives the composition of the extracted compounds as 1:1. The separa-tion is unsatisfactory in the case of Ag(I), Hg(II), Pt(II), Tl (I) and the most 3d-elements. 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 for- mation constants of selected chelates were determined. Y1 - 2002 ER - TY - BOOK A1 - Mickler, Wulfhard A1 - Holdt, Hans-Jürgen A1 - Bukowsky, Heinz T1 - Separation and Concentration of Pd(II) with Immobilized Maleonitrile-Dithiocrown Ethers N2 - 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. Y1 - 2001 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Gloe, Karsten A1 - Stephan, Holger A1 - Heitzsch, Olaf A1 - Bukowsky, Heinz A1 - Pollex, Rolf A1 - Weber, Erwin T1 - Preorganized endo-dicarboxylic host macrocycles having superior extraction selectivity for small alkaline earth metal ions Y1 - 1994 ER - TY - JOUR A1 - Kühling, Matthias A1 - Bukowsky, Heinz A1 - Kraudelt, Heide T1 - Heavy metal contents of chicken and red toads Y1 - 2001 ER - TY - JOUR A1 - Blumenstein, Oswald A1 - Bukowsky, Heinz A1 - Kraudelt, Heide A1 - Cerovsky, D. T1 - First Results of Soil Investigations in a Mining Area of South Africa Y1 - 2001 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Bukowsky, Heinz A1 - Kläui, Wolfgang T1 - Extraction of alkali metal, magnesium and calcium ions with Cyclopentadienyl-Tris(diethylphosphito-P)cobaltate(- 1) Y1 - 1996 ER -