Manipulating Terminal Iron-Hydroxide Nucleophilicity through Redox.

ABSTRACT: We report changes in the reactivity profile of a high-spin, terminal ferrous hydroxo complex (^EmL)Fe(OH) as a function of oxidation states (i.e., Fe^II/Fe^III). The terminal, high-spin Fe-OH adducts were isolated within a sterically hindered dipyrrin ligand scaffold. In the ferrous state, (^EmL)Fe(OH) exhibits nucleophilic reactivity toward carbon-based electrophiles (e.g., CS₂, CO₂, nitrile, isocyanate), highlighted by the reversible capture of CO₂ to generate (^EmL)Fe(κ²-O,O-HCO₃) (ΔG° = -2.0 kcal/mol) both in solution and solid state as characterized by single-crystal X-ray crystallography, ⁵⁷Fe Mössbauer spectroscopy, and IR spectroscopy. We probed the nucleophili

SUBMITTER: Oh J 

PROVIDER: S-EPMC12856904 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature