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Iron(IV)-oxo species are powerful oxidants that are involved as intermediates in ironcatalyzed oxidations of organic substrates. This includes their role in enzymatic oxidations which provided strong incentive to generate, characterize and explore the chemistry of novel Fe(IV) compounds from the perspective or reactivity and mechanism. The simplest iron(IV) complexes that have been prepared in solution are aqueous Fe(IV)-oxo ions. Even though these species can be conveniently generated from Fe(II) precursors and oxygen atom donors, studies of the chemistry of aqueous iron(IV) are difficult because of their short lifetime, high reactivity, and sensitivity to the surroundings. Herein we describe how changes in the pH, coordinating ligands and solvent can lead to dramatic changes in the lifetime and chemistry of aqueous Fe(IV)-oxo complexes. pH-Induced Mechanistic Changeover From Hydroxyl Radicals to Iron(IV) in the Fenton Reaction A major pathway in the reaction between Fe(II) and H2O2 at pH 6-7 in noncoordinating buffers exhibits inverse kinetic dependence on [H] and leads to oxidation of dimethyl sulfoxide (DMSO) to dimethyl sulfone (DMSO2). This step regenerates Fe(II) and makes the oxidation of DMSO catalytic, a finding that strongly supports Fe(IV) as a Fenton intermediate at near-neutral pH. This Fe(IV) is a less efficient oxidant for DMSO at pH 6-7 than is (H2O)5FeO, generated by ozone oxidation of Fe(H2O)6, in acidic solutions. Large concentrations of DMSO are needed to achieve significant turnover numbers at pH≥6 owing to the rapid competing reaction between Fe(II) and Fe(IV) that leads to irreversible loss of the catalyst. At pH 6 and ≤0.02 mM Fe(II), the ratio of apparent rate constants for the reactions of Fe(IV) with DMSO and with Fe(II) is ~10. The results at pH 6-7 stand in stark

Solvento iron(IV) oxo complexes in catalytic oxidations and electron transfer reactions