| Abstrakt: |
We describe the synthesis, characterization and electrochemistry of a new family of peripherally functionalised vic-dioxime, 5,6-bis-(hydroxyimino)-1,2,9,10-hydroxy-4,7-dithiadecane (LH2), with bis-(thiopropandiol) moieties attached to the oxime. Thiopolyalcohol groups containing two different heteroatoms (—S— and —O—) serve as weak exocyclic binding sites for Pd+2and Ag+ions. Novel mononuclear (LH)2M, (M = NiII, CuII, CoII, MnIIand FeII), homodinuclear (LH)2(UO2)2(OH) and heterotrinuclear (LH)2MM′2(M = NiIIand M′ = PdIIand AgI) species have been obtained with the metal:ligand ratios of 1:2, 2:2, and 3:2 respectively. Metal ions coordinate through N,Nof the oxime and S,Odonor sites of the peripherally attached groups in the presence of the base. The heterotrinuclear complexes were prepared by the interaction of the mononuclear complex, (LH)2Ni, with Pd(C5H5)2and AgNO3in an appropriate solvent. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis. spectroscopy, FT-IR., and by f.a.b-m.s. The redox properties of the complexes were studied by cyclic voltammetry. |
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