Determination of Spin Inversion Probability, H‑Tunneling Correction, and Regioselectivity in the Two-State Reactivity of Nonheme Iron(IV)-Oxo Complexes
We show by experiments that nonheme FeIVO species react with cyclohexene to yield selective hydrogen atom transfer (HAT) reactions with virtually no CC epoxidation. Straightforward DFT calculations reveal, however, that CC epoxidation on the S = 2 state possesses a low-energy barrier and should co...
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Veröffentlicht in: | The journal of physical chemistry letters 2015-04, Vol.6 (8), p.1472-1476 |
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Hauptverfasser: | , , , , , , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
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Zusammenfassung: | We show by experiments that nonheme FeIVO species react with cyclohexene to yield selective hydrogen atom transfer (HAT) reactions with virtually no CC epoxidation. Straightforward DFT calculations reveal, however, that CC 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 CC epoxidation on S = 2. The model enables us to derive a SIP value by combining experimental and theoretical results. |
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ISSN: | 1948-7185 1948-7185 |
DOI: | 10.1021/acs.jpclett.5b00527 |