Enhanced Rates of C-H Bond Cleavage by a Hydrogen-Bonded Synthetic Heme High-Valent Iron(IV) Oxo Complex.

ABSTRACT: Secondary coordination sphere interactions are critical in facilitating the formation, stabilization, and enhanced reactivity of high-valent oxidants required for essential biochemical processes. Herein, we compare the C-H bond oxidizing capabilities of spectroscopically characterized synthetic heme iron(IV) oxo complexes, F₈Cmpd-II (F₈ = tetrakis(2,6-difluorophenyl)porphyrinate), and a 2,6-lutidinium triflate (LutH⁺) Lewis acid adduct involving ferryl O-atom hydrogen-bonding, F₈Cmpd-II(LutH⁺). Second-order rate constants utilizing C-H and C-D substrates were obtained by UV-vis spectroscopic monitoring, while products were characterized and quantified by EPR spectroscopy and gas chromatography (GC). With xanthene, F₈Cmpd-II(

SUBMITTER: Ehudin MA 

PROVIDER: S-EPMC6734939 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature