Highly Selective and Catalytic Oxygenations of C‐H and C=C Bonds by a Mononuclear Nonheme High‐Spin Iron(III)−Alkylperoxo Species

: The reactivity of a mononuclear high-spin iron(III)-alkylperoxo intermediate [FeIII (t-BuLUrea )(OOCm)(OH2 )]2+ (2), generated from [FeII (t-BuLUrea )(H2 O)(OTf)](OTf) (1) [t-BuLUrea =1,1'-(((pyridin-2-ylmethyl)azanediyl)bis(ethane-2,1-diyl))bis(3-(tert-butyl)urea), OTf=trifluoromethanesulfonate] with cumyl hydroperoxide (CmOOH), toward the C-H and C=C bonds of hydrocarbons is reported. 2 oxygenates the strong C-H bonds of aliphatic substrates with high chemo- and stereoselectivity in the presence of 2,6-lutidine. While 2 itself is a sluggish oxidant, 2,6-lutidine assists the heterolytic O-O bond cleavage of the metal-bound alkylperoxo, giving rise to a reactive metal-based oxidant. The roles of the urea groups on the supporting ligand, and of the base, in directing the selective and catalytic oxygenation of hydrocarbon substrates by 2 are discussed.