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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

Title
Determination of Spin Inversion Probability, H-Tunneling Correction, and Regioselectivity in the Two-State Reactivity of Nonheme Iron(IV)-Oxo Complexes
Authors
Kwon, Yoon HyeMai, Binh KhanhLee, Yong-MinDhuri, Sunder N.Mandal, DebasishCho, Kyung-BinKim, YonghoShaik, SasonNam, Wonwoo
Ewha Authors
남원우이용민Kyung-Bin Michael Cho
SCOPUS Author ID
남원우scopus; Kyung-Bin Michael Choscopus
Issue Date
2015
Journal Title
Journal of Physical Chemistry Letters
ISSN
1948-7185JCR Link
Citation
vol. 6, no. 8, pp. 1472 - 1476
Publisher
AMER CHEMICAL SOC
Indexed
SCI; SCIE; SCOPUS WOS scopus
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.
DOI
10.1021/acs.jpclett.5b00527
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자연과학대학 > 화학·나노과학전공 > Journal papers
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