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Efficient Epoxidation of Styrene Derivatives by a Nonheme Iron(IV)-Oxo Complex via Proton-Coupled Electron Transfer with Triflic Acid

Title
Efficient Epoxidation of Styrene Derivatives by a Nonheme Iron(IV)-Oxo Complex via Proton-Coupled Electron Transfer with Triflic Acid
Authors
Park J.Lee Y.-M.Ohkubo K.Nam W.Fukuzumi S.
Ewha Authors
남원우Shunichi Fukuzumi이용민Kei Okubo
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus; Kei Okuboscopus
Issue Date
2015
Journal Title
Inorganic Chemistry
ISSN
0020-1669JCR Link
Citation
vol. 54, no. 12, pp. 5806 - 5812
Publisher
American Chemical Society
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Styrene derivatives are not oxidized by [(N4Py)FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at 298 K, whereas epoxidation of styrene derivatives by the iron(IV)-oxo complex occurs efficiently in the presence of triflic acid (HOTf) via proton-coupled electron transfer (PCET) from styrene derivatives to the diprotonated species of [(N4Py)FeIV(O)]2+ with HOTf. Logarithms of the first-order rate constants of HOTf-promoted expoxidation of styrene derivatives with [(N4Py)FeIV(O)]2+ and PCET from electron donors to [(N4Py)FeIV(O)]2+ in the precursor complexes exhibit a remarkably unified correlation with the driving force of PCET in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes are taken into account. The same PCET driving force dependence is obtained for the first-order rate constants of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)FeIV(O)]2+ and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)FeIV(O)]2+ in the precursor complexes. Thus, HOTf-promoted epoxidation of styrene derivatives by [(N4Py)FeIV(O)]2+ proceeds via the rate-determining electron transfer from styrene derivatives to the diprotonated species of [(N4Py)FeIV(O)]2+, as shown in the reactions of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)FeIV(O)]2+ and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)FeIV(O)]2+. © 2015 American Chemical Society.
DOI
10.1021/acs.inorgchem.5b00504
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자연과학대학 > 화학·나노과학전공 > Journal papers
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