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Determination of Spin Inversion Probability, H-Tunneling Correction, and Regioselectivity in the Two-State Reactivity of Nonheme Iron(IV)-Oxo Complexes
- Determination of Spin Inversion Probability, H-Tunneling Correction, and Regioselectivity in the Two-State Reactivity of Nonheme Iron(IV)-Oxo Complexes
- Kwon, Yoon Hye; Mai, Binh Khanh; Lee, Yong-Min; Dhuri, Sunder N.; Mandal, Debasish; Cho, Kyung-Bin; Kim, Yongho; Shaik, Sason; Nam, Wonwoo
- Ewha Authors
- 남원우; 이용민; Kyung-Bin Michael Cho
- SCOPUS Author ID
- 남원우; Kyung-Bin Michael Cho
- Issue Date
- Journal Title
- Journal of Physical Chemistry Letters
- vol. 6, no. 8, pp. 1472 - 1476
- AMER CHEMICAL SOC
- SCI; SCIE; SCOPUS
- 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.
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