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The (E, E)-dioxime containing a dithia-dioxa-diaza macrocyclic moiety 5,6 : 11,12 : 17,18-tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecane (H 2 L) has been synthesized in high yield by a 1 + 1 addition of cyanogendi-N-oxide with 2, 3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecane (3) which was obtained from condensation reaction with 2-amino thiophenol and 1,2-bis(2-bromoethoxy)benzene, in dichloromethane at ±10°C. Two vic-Dioxime ligands coordinate with Ni(II), Cu(II) and Co(III) through its hydroxyimino nitrogen donor atoms by the loss of the oxime protons. Homo and heterotrinuclear Cu II 3 and Co III Pd II 2 complexes of this ligand have been prepared; their two ligand molecules are connected via hydroxyimino or BF 2 + -bridging groups and two of the metal ions are coordinated by a diaza-dithia mixed donor macrocyclic moiety. The macrocyclic ligand and its transition metal complexes have been characterized on the basis of 1 H-, 13 C-NMR, IR and MS spectroscopy and elemental analysis data. Synthese und Charakterisierung eines neuen vic-Dioxim-Makrocyclus und einiger seiner mono-und trinuklearen MetallkomplexeInhaltsu È bersicht. Das (E,E)-Dioxim mit dem Dithia-dioxodiaza-Makrocyclus 5,6 : 11,12 : 17 : 18-Tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecan (H 2 L) wurde in hohen Ausbeuten synthetisiert durch 1 + 1 Addition von Dicyan-di-N-oxid mit 2,3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecan (3), das durch Kondensationsreaktion von 2-Aminothiophenol und 1,2-Bis(2-bromethoxy)benzol in Dichlormethan bei ±10°C erhalten wurde. Zwei vic-Dioximliganden koordinieren mit Ni II , Cu II bzw. Co III u È ber die Hydroxoimino-Stickstoffatome unter Verlust der Oximprotonen. Homo-und heteronukleare Cu II 3 -und Co III Pd II 2 -Komplexe dieses Liganden wurden dargestellt; ihre beiden Ligandenmoleku È le sind u È ber Hydroxoimino-oder BF 2 + -Bru È cken verbunden und zwei der Metallionen werden durch die N-und S-Donoratome der makrocyclischen Einheit koordiniert. Der makrocyclische Ligand und seine Ûbergangsmetallkomplexe wurden durch 1 H-, 13 C-NMR-, IR-, MS-Spektroskopie sowie durch Elementaranalysen charakterisiert.

Two new macrocyclic ligands, (5) and (6), containing nitrogen-sulfur donor atoms were designed and synthesized in a multi-step reaction sequence. Ion extraction capability of macrocycles (5) and (6) were investigated involving solvent extraction of metal picrates such as Ag + , Hg 2+ , Cd 2+ , Zn 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Co 2+ and Pb 2+ from aqueous phase to the organic phase. The metal picrate extractions were carried out at 25 ± 0.1°C and extractions were measured by u.v.-visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated depending on the organic solvents used for extraction. The extraction constant (log K ex ) and the complex composition of each metal complex were determined using spectroscopic methods.