Evidence of Sulfur Non-Innocence in [Co^II (dithiacyclam)]²⁺ -Mediated Catalytic Oxygen Reduction Reactions

In many metalloenzymes, sulfur-containing ligands participate in catalytic processes, mainly via the involvement in electron transfer reactions. In a biomimetic approach, we now demonstrate the implication of S-ligation in cobalt mediated oxygen reduction reactions (ORR). A comparative study between the catalytic ORR capabilities of the four-nitrogen bound [Co(cyclam)]²⁺ (1; cyclam=1,5,8,11-tetraaza-cyclotetradecane) and the S-containing analog [Co(S₂ N₂ -cyclam)]²⁺ (2; S₂ N₂ -cyclam=1,8-dithia-5,11-diaza-cyclotetradecane) reveals improved catalytic performance once the chalcogen is introduced in the Co coordination sphere. Trapping and characterization of the intermediates formed upon dioxygen activation at the Co^II centers in 1 and 2 point to the involvement of sulfur in the O₂ reduction process as the key for the improved catalytic ORR capabilities of 2.