Syntheses and investigation of metal complexes with macrocyclic polythioether ligands.

Copper(I) complexes with the macrocyclic thioether ligands 1,4,8,11-tetrathiacyclotetradecane (tetrathiacyclam, 14-S4) and 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam, 14-N2S2) were synthesised and structurally characterised. While the copper(I) complexes showed no reactivity towards dioxygen, the formation of "dioxygen adduct complexes" could be spectroscopically detected with ozone using low temperature stopped-flow techniques. Furthermore, it was possible to synthesise and characterise iron(II) and cobalt(II) complexes with the tetrathiacyclam ligand. No "dioxygen adduct" intermediates were observed when these complexes were reacted with dioxygen or ozone. Depending on the reaction conditions, the coordination of the metal ions could be controlled (endo- vs. exo-coordination and cis- vs. trans-coordination) and in addition to mononuclear complexes, also coordination polymers were obtained.