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Multi-Electron Oxidation of Anthracene Derivatives by Nonheme Manganese(IV)-Oxo Complexes
- Multi-Electron Oxidation of Anthracene Derivatives by Nonheme Manganese(IV)-Oxo Complexes
- Sharma N.; Jung J.; Lee Y.-M.; Seo M.S.; Nam W.; Fukuzumi S.
- Ewha Authors
- 남원우; 이용민; Shunichi Fukuzumi; 서미숙; 정지은
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 서미숙; 정지은
- Issue Date
- Journal Title
- Chemistry - A European Journal
- Chemistry - A European Journal vol. 23, no. 29, pp. 7125 - 7131
- anthracene; bioinorganic chemistry; electron transfer; hydrogen-atom transfer; manganese
- Wiley-VCH Verlag
- SCI; SCIE; SCOPUS
- Document Type
- Six-electron oxidation of anthracene to anthraquinone by a nonheme MnIV-oxo complex, [(Bn-TPEN)MnIV(O)]2+, proceeds through a rate-determining electron transfer from anthracene to [(Bn-TPEN)MnIV(O)]2+, followed by subsequent fast oxidation reactions to give anthraquinone. The reduced MnII complex ([(Bn-TPEN)MnII]2+) is oxidized by [(Bn-TPEN)MnIV(O)]2+ rapidly to produce the μ-oxo dimer ([(Bn-TPEN)MnIII-O-MnIII(Bn-TPEN)]4+). The oxygen atoms of the anthraquinone product were found to derive from the manganese-oxo species by the 18O-labelling experiments. In the presence of Sc3+ ion, formation of an anthracene radical cation was directly detected in the electron transfer from anthracene to a Sc3+ ion-bound MnIV(O) complex, [(Bn-TPEN)MnIV(O)-(Sc(OTf)3)2]2+, followed by subsequent further oxidation to yield anthraquinone. When anthracene was replaced by 9,10-dimethylanthracene, electron transfer from 9,10-dimethylanthracene to [(Bn-TPEN)MnIV(O)-(Sc(OTf)3)2]2+ occurred rapidly to produce stable 9,10-dimethylanthracene radical cation. The driving force dependence of the rate constants of electron transfer from the anthracene derivatives to [(Bn-TPEN)MnIV(O)]2+ and [(Bn-TPEN)MnIV(O)-(Sc(OTf)3)2]2+ was well-evaluated in light of the Marcus theory of electron transfer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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