Catalytic Four-Electron Reduction of Dioxygen by Ferrocene Derivatives with a Nonheme Iron(III) TAML Complex
- 주제(기타) Chemistry, Inorganic & Nuclear
- 설명문(일반) [Lu, Xiaoyan; Lee, Yong-Min; Sankaralingam, Muniyandi; Fukuzumi, Shunichi; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Fukuzumi, Shunichi] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2020
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000175409
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/acs.inorgchem.0c02400
- PubMed https://pubmed.ncbi.nlm.nih.gov/33300784
초록/요약
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 O-2 by one-electron reductants. An iron(V)-oxo complex, [(TAML)Fe-v(O)](-) (2), was produced by oxygenation of 1 with O-2 via the formation of triacetone triperoxide (TATP), acting as an autocatalyst that shortened the induction time for the generation of 2. Decamethylferrocene (Me(10)Fc) and octamethylferrocene (Me(8)Fc) reduced 2 to 1 by two electrons in the presence of CH3COOH to produce decamethylferrocenium cation (Me(10)Fc(+)) and octamethylferrocenium cation (Me(8)Fc(+)), respectively. Then, 1 was oxygenated by O-2 to regenerate 2 via the formation of TATP. In the cases of ferrocene (Fc), bromoferrocene (BrFc) and 1,1'-dibromoferrocene (Br(2)Fc), 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 O-2 occurred.
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