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Singly Unified Driving Force Dependence of Outer-Sphere Electron-Transfer Pathways of Nonheme Manganese(IV)-Oxo Complexes in the Absence and Presence of Lewis Acids
- Title
- Singly Unified Driving Force Dependence of Outer-Sphere Electron-Transfer Pathways of Nonheme Manganese(IV)-Oxo Complexes in the Absence and Presence of Lewis Acids
- Authors
- Sharma N.; Lee Y.-M.; Li X.-X.; Nam W.; Fukuzumi S.
- Ewha Authors
- 남원우; Shunichi Fukuzumi
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi
- Issue Date
- 2019
- Journal Title
- Inorganic Chemistry
- ISSN
- 0020-1669
- Citation
- Inorganic Chemistry vol. 58, no. 20, pp. 13761 - 13765
- Publisher
- American Chemical Society
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Epoxidation of styrene derivatives, sulfoxidation of thioanisole derivatives, and hydroxylation of toluene derivatives by a nonheme manganese(IV)-oxo complex binding triflic acid, [(N4Py)MnIV(O)]2+-(HOTf)2 [1-(H+)2], and scandium triflate, [(N4Py)MnIV(O)]2+-(Sc(OTf)3)2 [1-(Sc3+)2], occur via outer-sphere electron-transfer (OSET) pathways, exhibiting singly unified driving force dependence, enabling one to predict absolute values of the second-order rate constants of these three types of substrate oxidations by the manganese(IV)-oxo complex, using the Marcus theory of electron transfer. When [(N4Py)MnIV(O)]2+ (1) was replaced by [(N4Py)FeIV(O)]2+ (2), OSET pathways were changed to inner-sphere electron-transfer (ISET) pathways. The difference in the OSET versus ISET pathways is clarified based on the difference in the Lewis basicity of the oxo moieties in 1 and 2. Copyright © 2019 American Chemical Society.
- DOI
- 10.1021/acs.inorgchem.9b02403
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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