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Mechanistic Studies on the Oxidation of Glyoxylic and Pyruvic Acid by a [Mn4O6]4+ Core in Aqueous Media: Kinetics of Oxo-Bridge Protonation

✍ Scribed by Suranjana Das; Jhimli Bhattacharyya; Subrata Mukhopadhyay

Publisher
John Wiley and Sons
Year
2006
Tongue
German
Weight
108 KB
Volume
89
Category
Article
ISSN
0018-019X

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✦ Synopsis

In aqueous media (pH 2.5 -6.0), the Mn IV tetramer [Mn 4 (m-O) 6 A C H T U N G T R E N N U N G (bipy) 6 ] 4+ (1 4+ ; bipy = 2,2'-bipyridine) oxidizes both glyoxylic and pyruvic acid to formic and acetic acid, respectively, under formation of CO 2 . Kinetics studies suggest that the species 1 4+ , its oxo-bridge protonated form 5+ , the reducing acids (RH) and their conjugate bases (R À ) all take part in the reaction. The oxo-bridge protonated oxidant [1H] 5+ was found to react much faster than 1 4+ . Thereby, the gemdiol forms of the a-oxo acids (especially in the case of glyoxylic acid) are the possible reductants. A one-electron/one-proton electroprotic mechanism operates in the rate-determining step.

1 ) The hydration constants of the reducing species as found in [25] are as follows: glyoxylic acid, 1.0 10 2 -1.4 10 3 ; glyoxylate, 6.5-260; pyruvic acid, 0.61-3.1; pyruvate, 6.4 10 À2 À 0.21.

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