Catalytic four-electron reduction of dioxygen by ferrocene derivatives with a nonheme iron(III) TAML complex

Shunichi Fukuzumi; Wonwoo Nam; Xiaoyan Lu; Yong Min Lee; Muniyandi Sankaralingam

doi:10.1021/acs.inorgchem.0c02400

Catalytic four-electron reduction of dioxygen by ferrocene derivatives with a nonheme iron(III) TAML complex

Shunichi Fukuzumi, Wonwoo Nam, Xiaoyan Lu, Yong Min Lee, Muniyandi Sankaralingam

Chemistry & Nanoscience

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

8 Scopus citations

Abstract

A mononuclear nonheme iron(III) complex with a tetraamido macrocyclic ligand (TAML), [(TAML)Fe^III]⁻ (1), is a selective precatalyst for four-electron reduction of dioxygen by ferrocene derivatives in the presence of acetic acid (CH₃COOH) in acetone. This is the first work to show that a nonheme iron(III) complex catalyzes the four-electron reduction of O₂ by one-electron reductants. An iron(V)oxo complex, [(TAML)Fe^V(O)]⁻ (2), was produced by oxygenation of 1 with O₂ via the formation of triacetone triperoxide (TATP), acting as an autocatalyst that shortened the induction time for the generation of 2. Decamethylferrocene (Me₁₀Fc) and octamethylferrocene (Me₈Fc) reduced 2 to 1 by two electrons in the presence of CH₃COOH to produce decamethylferrocenium cation (Me₁₀Fc⁺) and octamethylferrocenium cation (Me₈Fc⁺), respectively. Then, 1 was oxygenated by O₂ to regenerate 2 via the formation of TATP. In the cases of ferrocene (Fc), bromoferrocene (BrFc) and 1,1′-dibromoferrocene (Br₂Fc), initial electron transfer from ferrocene derivatives to 2 occurred; however, neither a second proton-coupled electron transfer from ferrocene derivatives to 2 nor a catalytic four-electron reduction of O₂ occurred.

Original language	English
Pages (from-to)	18010-18017
Number of pages	8
Journal	Inorganic Chemistry
Volume	59
Issue number	24
DOIs	https://doi.org/10.1021/acs.inorgchem.0c02400
State	Published - 21 Dec 2020

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and Basic Science Research Program (NRF-2020R1I1A1A01074630 to Y.-M.L.), and a Grant-in-Aid (no. 16H02268 to S.F.) from MEXT, Japan.

Publisher Copyright:
© 2020 by The American Society of Hematology

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10.1021/acs.inorgchem.0c02400

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@article{9be9ed3d1eaf4b1eb3aae97e52b23ecb,

title = "Catalytic four-electron reduction of dioxygen by ferrocene derivatives with a nonheme iron(III) TAML complex",

abstract = "A mononuclear nonheme iron(III) complex with a tetraamido macrocyclic ligand (TAML), [(TAML)FeIII]− (1), is a selective precatalyst for four-electron reduction of dioxygen by ferrocene derivatives in the presence of acetic acid (CH3COOH) in acetone. This is the first work to show that a nonheme iron(III) complex catalyzes the four-electron reduction of O2 by one-electron reductants. An iron(V)oxo complex, [(TAML)FeV(O)]− (2), was produced by oxygenation of 1 with O2 via the formation of triacetone triperoxide (TATP), acting as an autocatalyst that shortened the induction time for the generation of 2. Decamethylferrocene (Me10Fc) and octamethylferrocene (Me8Fc) reduced 2 to 1 by two electrons in the presence of CH3COOH to produce decamethylferrocenium cation (Me10Fc+) and octamethylferrocenium cation (Me8Fc+), respectively. Then, 1 was oxygenated by O2 to regenerate 2 via the formation of TATP. In the cases of ferrocene (Fc), bromoferrocene (BrFc) and 1,1′-dibromoferrocene (Br2Fc), initial electron transfer from ferrocene derivatives to 2 occurred; however, neither a second proton-coupled electron transfer from ferrocene derivatives to 2 nor a catalytic four-electron reduction of O2 occurred.",

author = "Shunichi Fukuzumi and Wonwoo Nam and Xiaoyan Lu and Lee, {Yong Min} and Muniyandi Sankaralingam",

note = "Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and Basic Science Research Program (NRF-2020R1I1A1A01074630 to Y.-M.L.), and a Grant-in-Aid (no. 16H02268 to S.F.) from MEXT, Japan. Publisher Copyright: {\textcopyright} 2020 by The American Society of Hematology",

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doi = "10.1021/acs.inorgchem.0c02400",

language = "English",

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T1 - Catalytic four-electron reduction of dioxygen by ferrocene derivatives with a nonheme iron(III) TAML complex

AU - Fukuzumi, Shunichi

AU - Nam, Wonwoo

AU - Lu, Xiaoyan

AU - Lee, Yong Min

AU - Sankaralingam, Muniyandi

N1 - Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.) and Basic Science Research Program (NRF-2020R1I1A1A01074630 to Y.-M.L.), and a Grant-in-Aid (no. 16H02268 to S.F.) from MEXT, Japan. Publisher Copyright: © 2020 by The American Society of Hematology

PY - 2020/12/21

Y1 - 2020/12/21

N2 - A mononuclear nonheme iron(III) complex with a tetraamido macrocyclic ligand (TAML), [(TAML)FeIII]− (1), is a selective precatalyst for four-electron reduction of dioxygen by ferrocene derivatives in the presence of acetic acid (CH3COOH) in acetone. This is the first work to show that a nonheme iron(III) complex catalyzes the four-electron reduction of O2 by one-electron reductants. An iron(V)oxo complex, [(TAML)FeV(O)]− (2), was produced by oxygenation of 1 with O2 via the formation of triacetone triperoxide (TATP), acting as an autocatalyst that shortened the induction time for the generation of 2. Decamethylferrocene (Me10Fc) and octamethylferrocene (Me8Fc) reduced 2 to 1 by two electrons in the presence of CH3COOH to produce decamethylferrocenium cation (Me10Fc+) and octamethylferrocenium cation (Me8Fc+), respectively. Then, 1 was oxygenated by O2 to regenerate 2 via the formation of TATP. In the cases of ferrocene (Fc), bromoferrocene (BrFc) and 1,1′-dibromoferrocene (Br2Fc), initial electron transfer from ferrocene derivatives to 2 occurred; however, neither a second proton-coupled electron transfer from ferrocene derivatives to 2 nor a catalytic four-electron reduction of O2 occurred.

AB - A mononuclear nonheme iron(III) complex with a tetraamido macrocyclic ligand (TAML), [(TAML)FeIII]− (1), is a selective precatalyst for four-electron reduction of dioxygen by ferrocene derivatives in the presence of acetic acid (CH3COOH) in acetone. This is the first work to show that a nonheme iron(III) complex catalyzes the four-electron reduction of O2 by one-electron reductants. An iron(V)oxo complex, [(TAML)FeV(O)]− (2), was produced by oxygenation of 1 with O2 via the formation of triacetone triperoxide (TATP), acting as an autocatalyst that shortened the induction time for the generation of 2. Decamethylferrocene (Me10Fc) and octamethylferrocene (Me8Fc) reduced 2 to 1 by two electrons in the presence of CH3COOH to produce decamethylferrocenium cation (Me10Fc+) and octamethylferrocenium cation (Me8Fc+), respectively. Then, 1 was oxygenated by O2 to regenerate 2 via the formation of TATP. In the cases of ferrocene (Fc), bromoferrocene (BrFc) and 1,1′-dibromoferrocene (Br2Fc), initial electron transfer from ferrocene derivatives to 2 occurred; however, neither a second proton-coupled electron transfer from ferrocene derivatives to 2 nor a catalytic four-electron reduction of O2 occurred.

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U2 - 10.1021/acs.inorgchem.0c02400

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AN - SCOPUS:85098831985

SN - 0020-1669

VL - 59

SP - 18010

EP - 18017

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Catalytic four-electron reduction of dioxygen by ferrocene derivatives with a nonheme iron(III) TAML complex

Abstract

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