Determination of spin inversion probability, H-tunneling correction, and regioselectivity in the two-state reactivity of nonheme iron(IV)-oxo complexes

Yoon Hye Kwon, Binh Khanh Mai, Yong Min Lee, Sunder N. Dhuri, Debasish Mandal, Kyung Bin Cho, Yongho Kim, Sason Shaik, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

We show by experiments that nonheme FeIVO species react with cyclohexene to yield selective hydrogen atom transfer (HAT) reactions with virtually no C = C epoxidation. Straightforward DFT calculations reveal, however, that C = C epoxidation on the S = 2 state possesses a low-energy barrier and should contribute substantially to the oxidation of cyclohexene by the nonheme FeIVO species. By modeling the selectivity of this two-site reactivity, we show that an interplay of tunneling and spin inversion probability (SIP) reverses the apparent barriers and prefers exclusive S = 1 HAT over mixed HAT and C = C epoxidation on S = 2. The model enables us to derive a SIP value by combining experimental and theoretical results.

Original languageEnglish
Pages (from-to)1472-1476
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume6
Issue number8
DOIs
StatePublished - 16 Apr 2015

Keywords

  • density functional theory
  • kinetic isotope effect
  • spin inversion
  • tunneling
  • two-state reactivity

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