biostudies-literatureTang LLFoundation for the National Institutes of HealthInstitute for Green Science, Carnegie Mellon UniversityNIGMS NIH HHS9704-15https://www.ebi.ac.uk/biostudies/studies/S-EPMC5286568biostudies-literatureUnknown137(30)Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (H2O2) to dioxygen (O2) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous microreactors of reverse micelles where water is present in much lower abundance than in bulk water. n-Octane serves as a proximate reservoir supplying O2 to result in partial oxidation of Fe(III) to Fe(IV)-containing species, mostly the Fe(III)Fe(IV) (major) and Fe(IV)Fe(IV) (minor) dimers which coexist with the Fe(III) TAML monomeric species. The speciation depends on the pH and the degree of hydration w0, viz., the amount of water in the reverse micelles. The previously unknown Fe(III)Fe(IV) diJournal of the American Chemical SocietyActivation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe(III)Fe(IV) Dimer and Associated Catalytic Chemistry.PMC5286568R01 GM077387Collins TJWeitz ACTang LLGunderson WARyabov ADHendrich MPfalseActivation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe(III)Fe(IV) Dimer and Associated Catalytic Chemistry.Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (H2O2) to dioxygen (O2) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous microreactors of reverse micelles where water is present in much lower abundance than in bulk water. n-Octane serves as a proximate reservoir supplying O2 to result in partial oxidation of Fe(III) to Fe(IV)-containing species, mostly the Fe(III)Fe(IV) (major) and Fe(IV)Fe(IV) (minor) dimers which coexist with the Fe(III) TAML monomeric species. The speciation depends on the pH and the degree of hydration w0, viz., the amount of water in the reverse micelles. The previously unknown Fe(III)Fe(IV) di2015-01-01T00:00:00Z2015 Aug2025-04-04T00:10:37.387Z2019-03-27T02:35:25ZS-EPMC52865682616150410.1021/jacs.5b05229