Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen

Jindou Yang; Ping Li; Xialiang Li; Lisi Xie; Ni Wang; Haitao Lei; Chaochao Zhang; Wei Zhang; Yong Min Lee; Weiqiang Zhang; Rui Cao; Shunichi Fukuzumi; Wonwoo Nam

doi:10.1002/anie.202208143

Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen

Jindou Yang, Ping Li, Xialiang Li, Lisi Xie, Ni Wang, Haitao Lei, Chaochao Zhang, Wei Zhang, Yong Min Lee, Weiqiang Zhang, Rui Cao, Shunichi Fukuzumi, Wonwoo Nam

Chemistry & Nanoscience

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

4 Scopus citations

Abstract

A cobalt porphyrin complex with a pendant imidazole base ([(L₁)Co^II]) is an efficient catalyst for the homogeneous catalytic two-electron reduction of dioxygen by 1,1′-dimethylferrocene (Me₂Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L₂)Co^II]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton-coupled electron transfer (PCET) from [(L₁)Co^II] to O₂ in the presence of HOTf but also to facilitate electron transfer (ET) from [(L₁)Co^II] to O₂ in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O₂ have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L₁)Co^II] for the first time.

Original language	English
Journal	Angewandte Chemie - International Edition
DOIs	https://doi.org/10.1002/anie.202208143
State	Accepted/In press - 2022

Keywords

Acid-Promoted Electron Transfer
Cobalt Porphyrin Complex
Pendant Imidazole Base
Reaction Mechanisms
Reduction of Dioxygen

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10.1002/anie.202208143

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@article{a802d0b15e594775a92635ccf0dd189b,

title = "Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen",

abstract = "A cobalt porphyrin complex with a pendant imidazole base ([(L1)CoII]) is an efficient catalyst for the homogeneous catalytic two-electron reduction of dioxygen by 1,1′-dimethylferrocene (Me2Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L2)CoII]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton-coupled electron transfer (PCET) from [(L1)CoII] to O2 in the presence of HOTf but also to facilitate electron transfer (ET) from [(L1)CoII] to O2 in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O2 have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L1)CoII] for the first time.",

keywords = "Acid-Promoted Electron Transfer, Cobalt Porphyrin Complex, Pendant Imidazole Base, Reaction Mechanisms, Reduction of Dioxygen",

author = "Jindou Yang and Ping Li and Xialiang Li and Lisi Xie and Ni Wang and Haitao Lei and Chaochao Zhang and Wei Zhang and Lee, {Yong Min} and Weiqiang Zhang and Rui Cao and Shunichi Fukuzumi and Wonwoo Nam",

note = "Funding Information: This work was supported by the NRF of Korea (NRF‐2021R1A3B1076539 to W.N and NRF‐2020R1I1A1A01074630 to Y.‐M.L.), the National Natural Science Foundation of China (21773146 and 22171176), Fok Ying‐Tong Education Foundation for Outstanding Young Teachers in University, Fundamental Research Funds for the Central Universities, Research Funds of Shaanxi Normal University to R.C., and the National Natural Science Foundation of China (22102092) and the China Postdoctoral Science Foundation (2019M663614) to X.L. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

doi = "10.1002/anie.202208143",

language = "English",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

}

TY - JOUR

T1 - Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen

AU - Yang, Jindou

AU - Li, Ping

AU - Li, Xialiang

AU - Xie, Lisi

AU - Wang, Ni

AU - Lei, Haitao

AU - Zhang, Chaochao

AU - Zhang, Wei

AU - Lee, Yong Min

AU - Zhang, Weiqiang

AU - Cao, Rui

AU - Fukuzumi, Shunichi

AU - Nam, Wonwoo

N1 - Funding Information: This work was supported by the NRF of Korea (NRF‐2021R1A3B1076539 to W.N and NRF‐2020R1I1A1A01074630 to Y.‐M.L.), the National Natural Science Foundation of China (21773146 and 22171176), Fok Ying‐Tong Education Foundation for Outstanding Young Teachers in University, Fundamental Research Funds for the Central Universities, Research Funds of Shaanxi Normal University to R.C., and the National Natural Science Foundation of China (22102092) and the China Postdoctoral Science Foundation (2019M663614) to X.L. Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022

Y1 - 2022

N2 - A cobalt porphyrin complex with a pendant imidazole base ([(L1)CoII]) is an efficient catalyst for the homogeneous catalytic two-electron reduction of dioxygen by 1,1′-dimethylferrocene (Me2Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L2)CoII]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton-coupled electron transfer (PCET) from [(L1)CoII] to O2 in the presence of HOTf but also to facilitate electron transfer (ET) from [(L1)CoII] to O2 in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O2 have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L1)CoII] for the first time.

AB - A cobalt porphyrin complex with a pendant imidazole base ([(L1)CoII]) is an efficient catalyst for the homogeneous catalytic two-electron reduction of dioxygen by 1,1′-dimethylferrocene (Me2Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L2)CoII]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton-coupled electron transfer (PCET) from [(L1)CoII] to O2 in the presence of HOTf but also to facilitate electron transfer (ET) from [(L1)CoII] to O2 in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O2 have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L1)CoII] for the first time.

KW - Acid-Promoted Electron Transfer

KW - Cobalt Porphyrin Complex

KW - Pendant Imidazole Base

KW - Reaction Mechanisms

KW - Reduction of Dioxygen

UR - http://www.scopus.com/inward/record.url?scp=85133909522&partnerID=8YFLogxK

U2 - 10.1002/anie.202208143

DO - 10.1002/anie.202208143

M3 - Article

C2 - 35730106

AN - SCOPUS:85133909522

SN - 1433-7851

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

ER -

Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen

Abstract

Keywords

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