Extraction Behavior of Silver Ion with Cyclic and Acyclic Tetrathio Ethers and the Molecular Structures of the Silver Complexes

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The liquid-liquid extraction of silver ion with two cyclic and four acyclic tetrathio ethers was examined. The extractability of an acyclic tetrathio ether was superior to that of the corresponding cyclic one. The mole ratio of extracted silver complexes was Ag:ligand:picrate=1:1:1, except in the case of 1, 4, 8, 11-tetrathiacyclotetradecane (TTCT). X-Ray crystallographic analysis of the extracted Ag-TTCT-picrate complex was carried out. It becomes clear that the dimeric complex cation, [Ag₂(ttct)₂]²⁺, was formed in the solid state. Each silver(I) ion has the coordination number 4 and binds with four sulfur atoms to form a distorted tetrahedral configuration. Thus, two silver(I) ions are sandwiched between two TTCT molecules. The structure of the complex cation is similar to that of previously reported silver-13, 14-benzo-1, 4, 8, 11-tetrathiacyclopentadec-13-ene picrate.