1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe IV=O unit

Muralidharan Shanmugam, Genqiang Xue, Lawrence Que*, Brian M Hoffman

*Corresponding author for this work

Research output: Contribution to journalArticle

9 Scopus citations


We report that a novel use of 35 GHz 1H-ENDOR spectroscopy establishes the presence in 1 of an Fe IV-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 (OCH 3) (where a CH 3O group has replaced the HO on the Fe III site). This result substantiates the seemingly paradoxical conclusion that the nonheme Fe IV-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 Fe III-OH unit.

Original languageEnglish (US)
Pages (from-to)10080-10082
Number of pages3
JournalInorganic Chemistry
Issue number19
StatePublished - Oct 1 2012


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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