Oxygen Reduction Catalyzed by a Fluorinated Tetraphenylporphyrin Free Base at Liquid/Liquid Interfaces
Yükleniyor...
Dosyalar
Tarih
2010
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Amer Chemical Soc
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB(-)) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.
Açıklama
Anahtar Kelimeler
Kaynak
Journal of the American Chemical Society
WoS Q Değeri
Q1
Scopus Q Değeri
Q1
Cilt
132
Sayı
39
Künye
Hatay, İ., Su, B., Mendez, M. A., Corminboeuf, C., Khoury, T., Gros, C. P., Bourdillon, M., Meyer, M., Barbe, J-M., Ersöz, M., Zális, S., Samec, Z., Girault, H. H., (2010). Oxygen Reduction Catalyzed by a Fluorinated Tetraphenylporphyrin Free Base at Liquid/Liquid Interfaces. Journal of the American Chemical Society, 132(39), 13733-13741. Doi: 10.1021/ja103460p
