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

Namita Sharma, Yong Min Lee, Xiao Xi Li, Wonwoo Nam, Shunichi Fukuzumi

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15 Scopus citations

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.

Original languageEnglish
Pages (from-to)13761-13765
Number of pages5
JournalInorganic Chemistry
Volume58
Issue number20
DOIs
StatePublished - 21 Oct 2019

Bibliographical note

Funding Information:
This work was supported by JSPS KAKENHI (Grant 16H02268 to S.F.) from MEXT, Japan, and the NRF of Korea through the CRI (Grant NRF-2012R1A3A2048842 to W.N.), GRL (Grant NRF-2010-00353 to W.N.), and Basic Science Research Program (Grant 2017R1D1A1B03029982 to Y.-M.L. and Grant 2017R1D1A1B03032615 to S.F.).

Publisher Copyright:
Copyright © 2019 American Chemical Society.

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