Interaction of Mn(III)Tetraphenylporphyrin with Superoxide; The Reaction Mechanism and Evidence for a Peroxo Complex

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Title:Interaction of Mn(III)Tetraphenylporphyrin with Superoxide; The Reaction Mechanism and Evidence for a Peroxo Complex
Creators:
Lang, Kamil
Vondrák, Jiří
Wagnerová, Dana M.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 59, 5, pp. 1059-1065

Abstract

<p>Cathodic one-electron reduction of Mn(III)TPP and O<sub>2</sub> in an aprotic solvent yields Mn(II)TPP and the superoxide anion radical O<sub>2</sub><sup>-</sup>. The Mn(II)TPP and O<sub>2</sub><sup>-</sup> react in solution to the side-on peroxo complex Mn(III)TPP-O<sub>2</sub><sup>2-</sup>, which is oxidized at the electrode at a peak potential of <i>E</i><sub>pa</sub> = 0.40 V <i>vs</i> NHE (<i>k</i> ≈ 10<sup>4</sup> dm<sup>3</sup> mol<sup>-1</sup> s<sup>-1</sup>). The rate-determining step of the overall two-electron oxidation is the transfer of the first electron coupled with a structure rearrangement of the peroxo complex to a superoxo complex.

Title:Interaction of Mn(III)Tetraphenylporphyrin with Superoxide; The Reaction Mechanism and Evidence for a Peroxo Complex
Creators:
Lang, Kamil
Vondrák, Jiří
Wagnerová, Dana M.
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:59
Number:5
Page Range:pp. 1059-1065
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19941059UNSPECIFIED
ID Code:523
Item Type:Article
Deposited On:06 Feb 2009 17:01
Last Modified:06 Feb 2009 16:01

Citation

Lang, Kamil; Vondrák, Jiří; Wagnerová, Dana M. (1994) Interaction of Mn(III)Tetraphenylporphyrin with Superoxide; The Reaction Mechanism and Evidence for a Peroxo Complex. Collection of Czechoslovak Chemical Communications, 59 (5). pp. 1059-1065. ISSN 0010-0765

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