Snapshots of a Migrating H‐atom: Characterization of a Reactive Fe(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Fe(I) Isomer

We report the characterization of an S = ½ iron π‐complex, [Fe(η^6‐IndH)(depe)]^+ (Ind = Indenide (C_9H_(7^‐_), depe = 1,2‐bis(diethylphosphino)ethane), which results via C‐H elimination from a transient Fe^(III) hydride, [Fe(η^3:η^2‐Ind)(depe)H]^+. Owing to weak M‐H/C‐H bonds, these species undergo proton‐coupled electron transfer (PCET) to release H_2 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^o ≈ 0 between them). Markedly, this reactivity differs from related Fe(η^5‐Cp/Cp^*) compounds, for which terminal Fe^(III)‐H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated (indene) ring. Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and out‐lines 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.