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- Title
Mononuclear Nonheme High-Spin (S=2) versus Intermediate-Spin (S=1) Iron(IV)-Oxo Complexes in Oxidation Reactions.
- Authors
Seong Hee Bae; Mi Sook Seo; Yong-Min Lee; Kyung-Bin Cho; Won-Suk Kim; Wonwoo Nam
- 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.
- Subjects
PROTEIN spectra; HEME; OXO process; OXOACIDS; OXIDATION; CHEMICAL reactions; PHYSIOLOGY
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 28, p8027
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201603978