Format:
1 Online-Ressource (7 Seiten)
Content:
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(S2N2-cyclam)]2+ (2; S2N2-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 CoII 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.
Content:
Peer Reviewed
In:
Weinheim : Wiley-VCH, 62,6
Language:
English
DOI:
10.1002/anie.202214074
URN:
urn:nbn:de:kobv:11-110-18452/27839-6
URL:
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