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

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13 Scopus citations

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.

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
StateAccepted/In press - 2022

Bibliographical 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:
© 2022 Wiley-VCH GmbH.

Keywords

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

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