We report that a novel use of 35 GHz 1H-ENDOR spectroscopy establishes the presence in 1 of an FeIV-O⋯H-O-Fe III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4 (OCH3) (where a CH3O group has replaced the HO on the FeIII site). This result substantiates the seemingly paradoxical conclusion that the nonheme FeIV-O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the FeIII-OH unit.
ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry