The mechanism of methane and dioxygen activation in the catalytic cycle of methane monooxygenase
Author:
- 27 March 1995
- journal article
- Published by Wiley in FEBS Letters
- Vol. 362 (1) , 5-9
Abstract
The binuclear structure of the active center of methane monooxygenase plays a determining role in dioxygen activation and in selectivity and specificity of alkane oxidation with this enzyme. A new mechanism is suggested for binding and activation of O2, which involves side‐on binding of O2 2− to iron atoms followed by its conversion to the bis‐μ‐oxo complex considered as an alternative of ferryl in CH4 activation. This mechanism results in the sequence of the cleavage of the O—O bond of peroxide O/O2− instead of the opposite sequence O2−/O, which takes place in the case of heme monooxygenase cytochrome P‐450. Therefore, in this case there is no necessity of the charge relay system [N.B. Gerber and S.G. Sligar, J. Am. Chem. Soc. 114 (1992) 8742] for the transformation of O2 to an active intermediate. The experiment for checking this hypothesis is suggested.Keywords
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