Vishal Yadav Ph. D. (He/Him/His)

Congratulations to the @acsbiol.bsky.social Travel Awardees to #ACSSpring2025! Michael Ansong, Merve Demir, Erika Zhang, Taiwo Ogunmilade, Anjola Adewoye, @suritra.bsky.social , @vishal7494.bsky.social , Ephraim Ezeigbo, and Ben Prather.

Nonheme Mononuclear and Dinuclear Iron(II) and Iron(III) Fluoride Complexes and Their Fluorine Radical Transfer Reactivity The nonheme iron(II) complexes containing a fluoride anion, FeII(BNPAPh2O)(F) (1) and [FeII(BNPAPh2OH)(F)(THF)](BF4) (2), were synthesized and structurally characterized. Addition of dioxygen to either 1 or 2 led to the formation of a fluoride-bridged, dinuclear iron(III) complex [Fe2III(BNPAPh2O)2(F)2(μ-F)]+ (4), which was characterized by single-crystal X-ray diffraction, 1H NMR, and elemental analysis. An iron(II)(iodide) complex, FeII(BNPAPh2O)(I) (3), was prepared and reacted with O2 to give the mononuclear complex cis-FeIII(BNPAPh2O)(OH)(I) (5). Addition of excess fluoride to 5 led to the formation of the oxo-bridged, dinuclear iron(III) complex [Fe2III(BNPAPh2O)2(F)2(μ-O)] (6), while the mononuclear iron(III)(fluoride) complex cis-FeIII(BNPAPh2O)(F)(Cl) (7) was prepared from the addition of excess F– to FeIII(BNPAPh2O)Cl2. The dinuclear complexes 4 and 6 were unreactive to fluorine radical transfer, but mononuclear 7 reacts with the radical substrate (p-MeO-C6H4)3C• to give the fluorine radical transfer products FeII(BNPAPh2O)(Cl) and (p-OMe-C6H4)3CF. These results show that a mononuclear FeIII(F) complex is capable of mediating fluorine radical transfer, even in the presence of second coordination sphere hydrogen bonds to the F– ligand. These findings are placed in context with what is known about the nonheme iron halogenases and related synthetic catalysts regarding their ability, or lack thereof, to mediate fluorine radical transfer reactions.

So excited to share my new work on nonheme iron mediated radical fluorination: pubs.acs.org/doi/10.1021/...