Abstract
AbstractLigand exchange reactions are carried out exclusively at the unique iron site of a subsite‐differentiated cyclotriveratrylene [4Fe‐4S] cluster complex. The effect of a variety of thiolate, phenolate, bidentate, and bridging ligands on the redox potential of the subsite‐differentiated [4Fe‐4S] cluster complex is studied and compared with the effects of such ligands on an [Fe4S4C14]2‐ cluster. The redox potential can be modulated within the range of −1.60 to −1.80 V (vs. Fc0/+) by varying the ligand. The introduction of an electron releasing substituent shifts the redox potential to more negative values, whereas an electron withdrawing substituent has the opposite effect. A linear relationship exists between the number of substituted sites and the reduction potential of the cluster.
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