Snapshots of a Migrating H-Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring-Protonated Iron(I) Isomer

We report the characterization of an S=1/2 iron π‐complex, [Fe(η⁶‐IndH)(depe)]⁺ (Ind=Indenide (C₉H₇⁻), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe^(III) hydride, [Fe(η³:η²‐Ind)(depe)H]⁺. Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H₂ through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE_(C‐H) value of ≈50 kcal mol⁻¹, roughly equal to the BDFE_(Fe‐H) of its Fe^(III)−H precursor (ΔG°≈0 between them). Markedly, this reactivity differs from related Fe(η⁵‐Cp/Cp*) compounds, for which terminal Fe^(III)−H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements.