Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer

Yong Min Lee; Surin Kim; Kei Ohkubo; Kyung Ha Kim; Wonwoo Nam; Shunichi Fukuzumi

doi:10.1021/jacs.8b12935

Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer

Yong Min Lee, Surin Kim, Kei Ohkubo, Kyung Ha Kim, Wonwoo Nam, Shunichi Fukuzumi

Chemistry & Nanoscience

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

33 Scopus citations

Abstract

Outer-sphere electron transfer from styrene, thioanisole, and toluene derivatives to a triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complex, [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been shown to be the rate-determining step of different types of redox reactions such as epoxidation, sulfoxidation, and hydroxylation of styrene, thioanisole, and toluene derivatives, respectively, by [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂. The rate constants of HOTf-promoted epoxidation of all styrene derivatives with [(N4Py)Mn^IV(O)]²⁺ and electron transfer from electron donors to [(N4Py)Mn^V(O)]²⁺ exhibit a remarkably unified correlation with the driving force of outer-sphere electron transfer in light of the Marcus theory of electron transfer. The same electron-transfer driving force dependence is observed in the oxygen atom transfer from [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂ to thioanisole derivatives as well as in the hydrogen atom transfer from toluene derivatives to [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂. Thus, mechanisms of oxygen atom transfer (epoxidation and sulfoxidation) reactions of styrene and thioanisole derivatives and hydrogen atom transfer (hydroxylation) reactions of toluene derivatives by [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂ have been unified for the first time as the same reaction pathway via outer-sphere electron transfer, followed by the fast bond-forming step, which exhibits the singly unified electron-transfer driving force dependence of the rate constants as outer-sphere electron-transfer reactions. In the case of the epoxidation of cis-stilbene by [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂, the isomerization of cis-stilbene radical cation to trans-stilbene radical cation occurs after outer-sphere electron transfer from cis-stilbene to [(N4Py)Mn^IV(O)]²⁺-(HOTf)₂ to yield trans-stilbene oxide selectively, which is also taken as evidence for the occurrence of electron transfer in the acid-catalyzed epoxidation.

Original language	English
Pages (from-to)	2614-2622
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	141
Issue number	6
DOIs	https://doi.org/10.1021/jacs.8b12935
State	Published - 13 Feb 2019

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST).

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST).

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© 2019 American Chemical Society.

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10.1021/jacs.8b12935

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@article{7bffb33ae1854a9480593da8f4d35f55,

title = "Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer",

abstract = "Outer-sphere electron transfer from styrene, thioanisole, and toluene derivatives to a triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complex, [(N4Py)MnIV(O)]2+-(HOTf)2 (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been shown to be the rate-determining step of different types of redox reactions such as epoxidation, sulfoxidation, and hydroxylation of styrene, thioanisole, and toluene derivatives, respectively, by [(N4Py)MnIV(O)]2+-(HOTf)2. The rate constants of HOTf-promoted epoxidation of all styrene derivatives with [(N4Py)MnIV(O)]2+ and electron transfer from electron donors to [(N4Py)MnV(O)]2+ exhibit a remarkably unified correlation with the driving force of outer-sphere electron transfer in light of the Marcus theory of electron transfer. The same electron-transfer driving force dependence is observed in the oxygen atom transfer from [(N4Py)MnIV(O)]2+-(HOTf)2 to thioanisole derivatives as well as in the hydrogen atom transfer from toluene derivatives to [(N4Py)MnIV(O)]2+-(HOTf)2. Thus, mechanisms of oxygen atom transfer (epoxidation and sulfoxidation) reactions of styrene and thioanisole derivatives and hydrogen atom transfer (hydroxylation) reactions of toluene derivatives by [(N4Py)MnIV(O)]2+-(HOTf)2 have been unified for the first time as the same reaction pathway via outer-sphere electron transfer, followed by the fast bond-forming step, which exhibits the singly unified electron-transfer driving force dependence of the rate constants as outer-sphere electron-transfer reactions. In the case of the epoxidation of cis-stilbene by [(N4Py)MnIV(O)]2+-(HOTf)2, the isomerization of cis-stilbene radical cation to trans-stilbene radical cation occurs after outer-sphere electron transfer from cis-stilbene to [(N4Py)MnIV(O)]2+-(HOTf)2 to yield trans-stilbene oxide selectively, which is also taken as evidence for the occurrence of electron transfer in the acid-catalyzed epoxidation.",

author = "Lee, {Yong Min} and Surin Kim and Kei Ohkubo and Kim, {Kyung Ha} and Wonwoo Nam and Shunichi Fukuzumi",

note = "Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST). Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = feb,

day = "13",

doi = "10.1021/jacs.8b12935",

language = "English",

volume = "141",

pages = "2614--2622",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "6",

}

Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer. / Lee, Yong Min; Kim, Surin; Ohkubo, Kei et al.
In: Journal of the American Chemical Society, Vol. 141, No. 6, 13.02.2019, p. 2614-2622.

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

TY - JOUR

T1 - Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer

AU - Lee, Yong Min

AU - Kim, Surin

AU - Ohkubo, Kei

AU - Kim, Kyung Ha

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST). Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (nos. 16H02268 to S.F. and 18H04650, 17H03010, 16K13964 to K.O.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to S.F.) from Japan Science and Technology Agency (JST). Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/2/13

Y1 - 2019/2/13

N2 - Outer-sphere electron transfer from styrene, thioanisole, and toluene derivatives to a triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complex, [(N4Py)MnIV(O)]2+-(HOTf)2 (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been shown to be the rate-determining step of different types of redox reactions such as epoxidation, sulfoxidation, and hydroxylation of styrene, thioanisole, and toluene derivatives, respectively, by [(N4Py)MnIV(O)]2+-(HOTf)2. The rate constants of HOTf-promoted epoxidation of all styrene derivatives with [(N4Py)MnIV(O)]2+ and electron transfer from electron donors to [(N4Py)MnV(O)]2+ exhibit a remarkably unified correlation with the driving force of outer-sphere electron transfer in light of the Marcus theory of electron transfer. The same electron-transfer driving force dependence is observed in the oxygen atom transfer from [(N4Py)MnIV(O)]2+-(HOTf)2 to thioanisole derivatives as well as in the hydrogen atom transfer from toluene derivatives to [(N4Py)MnIV(O)]2+-(HOTf)2. Thus, mechanisms of oxygen atom transfer (epoxidation and sulfoxidation) reactions of styrene and thioanisole derivatives and hydrogen atom transfer (hydroxylation) reactions of toluene derivatives by [(N4Py)MnIV(O)]2+-(HOTf)2 have been unified for the first time as the same reaction pathway via outer-sphere electron transfer, followed by the fast bond-forming step, which exhibits the singly unified electron-transfer driving force dependence of the rate constants as outer-sphere electron-transfer reactions. In the case of the epoxidation of cis-stilbene by [(N4Py)MnIV(O)]2+-(HOTf)2, the isomerization of cis-stilbene radical cation to trans-stilbene radical cation occurs after outer-sphere electron transfer from cis-stilbene to [(N4Py)MnIV(O)]2+-(HOTf)2 to yield trans-stilbene oxide selectively, which is also taken as evidence for the occurrence of electron transfer in the acid-catalyzed epoxidation.

AB - Outer-sphere electron transfer from styrene, thioanisole, and toluene derivatives to a triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complex, [(N4Py)MnIV(O)]2+-(HOTf)2 (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been shown to be the rate-determining step of different types of redox reactions such as epoxidation, sulfoxidation, and hydroxylation of styrene, thioanisole, and toluene derivatives, respectively, by [(N4Py)MnIV(O)]2+-(HOTf)2. The rate constants of HOTf-promoted epoxidation of all styrene derivatives with [(N4Py)MnIV(O)]2+ and electron transfer from electron donors to [(N4Py)MnV(O)]2+ exhibit a remarkably unified correlation with the driving force of outer-sphere electron transfer in light of the Marcus theory of electron transfer. The same electron-transfer driving force dependence is observed in the oxygen atom transfer from [(N4Py)MnIV(O)]2+-(HOTf)2 to thioanisole derivatives as well as in the hydrogen atom transfer from toluene derivatives to [(N4Py)MnIV(O)]2+-(HOTf)2. Thus, mechanisms of oxygen atom transfer (epoxidation and sulfoxidation) reactions of styrene and thioanisole derivatives and hydrogen atom transfer (hydroxylation) reactions of toluene derivatives by [(N4Py)MnIV(O)]2+-(HOTf)2 have been unified for the first time as the same reaction pathway via outer-sphere electron transfer, followed by the fast bond-forming step, which exhibits the singly unified electron-transfer driving force dependence of the rate constants as outer-sphere electron-transfer reactions. In the case of the epoxidation of cis-stilbene by [(N4Py)MnIV(O)]2+-(HOTf)2, the isomerization of cis-stilbene radical cation to trans-stilbene radical cation occurs after outer-sphere electron transfer from cis-stilbene to [(N4Py)MnIV(O)]2+-(HOTf)2 to yield trans-stilbene oxide selectively, which is also taken as evidence for the occurrence of electron transfer in the acid-catalyzed epoxidation.

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U2 - 10.1021/jacs.8b12935

DO - 10.1021/jacs.8b12935

M3 - Article

C2 - 30646680

AN - SCOPUS:85061482025

SN - 0002-7863

VL - 141

SP - 2614

EP - 2622

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)-Oxo Complex via Outer-Sphere Electron Transfer

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