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
- 등재 SCIE, SCOPUS
- 발행기관 American Chemical Society
- 발행년도 2019
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000162362
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/acs.inorgchem.9b02403
- PubMed https://pubmed.ncbi.nlm.nih.gov/31589029
초록/요약
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.
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