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

doi:10.1021/acs.inorgchem.9b02403

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

18 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)Mn^IV(O)]²⁺-(HOTf)₂ [1-(H⁺)₂], and scandium triflate, [(N4Py)Mn^IV(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)Mn^IV(O)]²⁺ (1) was replaced by [(N4Py)Fe^IV(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 language	English
Pages (from-to)	13761-13765
Number of pages	5
Journal	Inorganic Chemistry
Volume	58
Issue number	20
DOIs	https://doi.org/10.1021/acs.inorgchem.9b02403
State	Published - 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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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",

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.",

author = "Namita Sharma and Lee, {Yong Min} and Li, {Xiao Xi} and Wonwoo Nam and Shunichi Fukuzumi",

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 {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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AU - Sharma, Namita

AU - Lee, Yong Min

AU - Li, Xiao Xi

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - 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.

PY - 2019/10/21

Y1 - 2019/10/21

N2 - 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.

AB - 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.

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JF - Inorganic Chemistry

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ER -

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

Abstract

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