Mononuclear Nonheme High-Spin (S=2) versus Intermediate-Spin (S=1) Iron(IV)–Oxo Complexes in Oxidation Reactions

Seong Hee Bae, Mi Sook Seo, Yong Min Lee, Kyung Bin Cho, Won Suk Kim, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

Mononuclear nonheme high-spin (S=2) iron(IV)–oxo species have been identified as the key intermediates responsible for the C−H bond activation of organic substrates in nonheme iron enzymatic reactions. Herein we report that the C−H bond activation of hydrocarbons by a synthetic mononuclear nonheme high-spin (S=2) iron(IV)–oxo complex occurs through an oxygen non-rebound mechanism, as previously demonstrated in the C−H bond activation by nonheme intermediate (S=1) iron(IV)–oxo complexes. We also report that C−H bond activation is preferred over C=C epoxidation in the oxidation of cyclohexene by the nonheme high-spin (HS) and intermediate-spin (IS) iron(IV)–oxo complexes, whereas the C=C double bond epoxidation becomes a preferred pathway in the oxidation of deuterated cyclohexene by the nonheme HS and IS iron(IV)–oxo complexes. In the epoxidation of styrene derivatives, the HS and IS iron(IV) oxo complexes are found to have similar electrophilic characters.

Original languageEnglish
Pages (from-to)8027-8031
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number28
DOIs
StatePublished - 4 Jul 2016

Keywords

  • bioinorganic chemistry
  • C−H activation
  • iron
  • metalloenzymes
  • reaction mechanisms

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