Characterization and properties of the copper(II/I) complexes of macrocyclic hexathiaether ligand [21]aneS6

The copper(II/I) complexes of hexathiaether macrocyclic ligand, 1,4,8,11,15,18-hexathiacyclohenicosane ([21]aneS6), were synthesized, and characterized by electrochemical and spectroscopic techniques. Cyclic voltammetric studies indicate that Cu([21]aneS6)2+/+ forms a reversible one-electron redox couple. The electrochemical potential obtained for Cu([21]aneS6)2+/+ (Ef = 0.89 V, against SHE) was found to be the highest potential reported to date for a Cu2+/+ macrocyclic system in aqueous solution. By employing the Nernst equation, we can infer that the practical upper limit for formal potential of Cu(II/I)L systems maybe close to this high value. Stability constant data obtained for these complexes indicate that Cu([21]aneS6)+is 12 orders of magnitude greater in stability than that of Cu([21]aneS6)2+ indicating the favorable nature of this large macrocyclic ligand towards formation of Cu(I) complexes over Cu(II) complexes. Crystal structure of Cu([21]aneS6)+ (Fig. 2) shows that four sulfurs adjacent to one another are coordinated to Cu+ ion in this complex. Bond angles and distances calculated for the crystal indicate that it is a distorted tetrahedron, a geometry commonly encountered by Cu(I) complexes. This is the first report of synthesis and characterization of a metal coordinated [21]aneS6 complex.

The copper(II/I) complexes of hexathiaether macrocyclic ligand, [21]aneS6, were synthesized, and characterized by electrochemical and spectroscopic techniques. Cu([21]aneS6)2+/+ forms a reversible one-electron redox couple bearing the highest formal potential 0.89 V (against SHE) reported to date for a Cu2+/+ macrocyclic system in aqueous solution. Stability constants were also determined for the Cu(I) and Cu(II) complexes.Figure optionsDownload as PowerPoint slide