Electronic Structure and Reactivity of Dioxygen-Derived Aliphatic Thiolate-Ligated Fe-Peroxo and Fe(IV) Oxo Compounds.

Herein, we examine the electronic and geometric structural properties of O2-derived aliphatic thiolate-ligated Fe-peroxo, Fe-hydroxo, and Fe(IV) oxo compounds. The latter cleaves strong C-H bonds (96 kcal mol-1) on par with the valine C-H bond cleaved by isopencillin N synthase (IPNS). Stopped-flow kinetics studies indicate that the barrier to O2 binding to [FeII(SMe2N4(tren))]+ (3) is extremely low (Ea = 36(2) kJ mol-1), as theoretically predicted for IPNS. Dioxygen binding to 3 is shown to be reversible, and a superoxo intermediate, [FeIII(SMe2N4(tren))(O2)]+ (6), forms in the first 25 ms of the reaction at -40 °C prior to the rate-determining (Ea = 46(2) kJ mol-1) formation of peroxo-bridged [(SMe2N4(tren))Fe(III)]2(μ-O2)2+ (7). A log(kobs) vs log([Fe]) plot for the formation of 7 is consistent with the second-order dependence on iron, and H2O2 assays are consistent with a 2:1 ratio of Fe/H2O2. Peroxo 7 is shown to convert to ferric-hydroxo [FeIII(SMe2N(tren))(OH)]+ (9, g⊥ = 2.24, g∥ = 1.96), the identity of which was determined via its independent synthesis. Rates of the conversion 7 → 9 are shown to be dependent on the X-H bond strength of the H-atom donor, with a kH/kD = 4 when CD3OD is used in place of CH3OH as a solvent. A crystallographically characterized cis thiolate-ligated high-valent iron oxo, [FeIV(O)(SMe2N4(tren))]+ (11), is shown to form en route to hydroxo 9. Electronic structure calculations were shown to be consistent with 11 being an S = 1 Fe(IV)═O with an unusually high νFe-O stretching frequency at 918 cm-1 in line with the extremely short Fe-O bond (1.603(7) Å).