Oxygen Reduction Catalyzed by a Fluorinated Tetraphenylporphyrin Free Base at Liquid/Liquid Interfaces

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)FA...

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Published in:Journal of the American Chemical Society Vol. 132; no. 39; pp. 13733 - 13741
Main Authors: Hatay, Imren, Su, Bin, Mendez, Manuel A., Corminboeuf, Clemence, Khoury, Tony, Gros, Claude P., Bourdillon, Melanie, Meyer, Michel, Barbe, Jean-Michel, Ersoz, Mustafa, Zalis, Stanislav, Samec, Zdenek, Girault, Hubert H.
Format: Journal Article
Language:English
Published: WASHINGTON Amer Chemical Soc 06.10.2010
Subjects:
Catalysis
Chemistry
Chemistry, Multidisciplinary
Ethylene Dichlorides - chemistry
Ferrous Compounds - chemistry
Metallocenes
Models, Molecular
Molecular Structure
Oxidation-Reduction
Oxygen - chemistry
Physical Sciences
Porphyrins - chemical synthesis
Porphyrins - chemistry
Science & Technology
Stereoisomerism
Water - chemistry
MESO
FERROCENE DERIVATIVES
SYNTHETIC MODELS
PLESSET PERTURBATION-THEORY
IMMISCIBLE ELECTROLYTE-SOLUTIONS
POLARIZED INTERFACE
LOCAL TRIATOMICS
BASIS-SETS
MOLECULAR-OXYGEN
WATER
ISSN:0002-7863, 1520-5126, 1520-5126
Online Access:Get more information
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Summary: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.
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ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja103460p