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 Citations (Scopus)

Abstract

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
Volume51
Issue number19
DOIs
StatePublished - Oct 1 2012

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Hydrogen bonds
reactivity
hydrogen bonds
hydrogen
interactions
Density functional theory
cleavage
Spectroscopy
methylidyne
density functional theory
Atoms
rings
spectroscopy
atoms
hydroxide ion

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Shanmugam, Muralidharan ; Xue, Genqiang ; Que, Lawrence ; Hoffman, Brian M. / 1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe IV=O unit. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 19. pp. 10080-10082.
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1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe IV=O unit. / Shanmugam, Muralidharan; Xue, Genqiang; Que, Lawrence; Hoffman, Brian M.

In: Inorganic Chemistry, Vol. 51, No. 19, 01.10.2012, p. 10080-10082.

Research output: Contribution to journalArticle

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AB - 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.

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