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 (C₉ H₇^- ), 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.