Biomimetic High‐Valent Non‐Heme Iron Oxidants for the cis ‐Dihydroxylation and Epoxidation of Olefins

Pathfinding: The iron(II) complex of the bispidine ligand L1 is oxidized with H2O2 to intermediate-spin [(L1)FeIV(OH)2]2+ (1, see picture) which forms cis diols 2 from olefins, and the high-spin [(L1)FeIVO(OH2)]2+ ferryl complex (3) results in epoxidation (4). Product distributions (diol/epoxide) and 18O labeling studies are used to propose a mechanism, which is fully supported by DFT analyses.