Axial Ligation Impedes Proton-Coupled Electron-Transfer Reactivity of a Synthetic Compound-I Analogue.

ABSTRACT: The nature of the axial ligand in high-valent iron-oxo heme enzyme intermediates and related synthetic catalysts is a critical structural element for controlling proton-coupled electron-transfer (PCET) reactivity of these species. Herein, we describe the generation and characterization of three new 6-coordinate, iron(IV)-oxo porphyrinoid-π-cation-radical complexes and report their PCET reactivity together with a previously published 5-coordinate analogue, Fe^IV(O)(TBP₈Cz^+•) (TBP₈Cz = octakis(p-tert-butylphenyl)corrolazinato^3-) (2) (Cho, K. A high-valent iron-oxo corrolazine activates C-H bonds via hydrogen-atom transfer. J. Am. Chem. Soc. 2012, 134, 7392-7399). The new complexes Fe^IV(O)(TBP_8</

SUBMITTER: Thomas J 

PROVIDER: S-EPMC11305010 | biostudies-literature | 2024 May

REPOSITORIES: biostudies-literature