Abstract
RECENT studies1 have been concerned with the mechanism of redox reactions between nitrate ions and simple mono-nuclear oxomolybdenum(V) (MovO) complexes such as [MoOCl3(OPPh3)2] to determine the function of the molybdenum centre in the nitrate reductase enzymes. In the presence of excess nitrate, the following reaction stoichiometry is obtained: MovO+NO−3→MoVIO2+NO2 (1) Kinetic studies using stopped-flow techniques identified three stages in these reactions: (1) the loss of the ligand trans to the oxo-group of the Mov complex followed by rapid, non-rate-determining coordination of nitrate at the vacated site; (2) a rearrangement of the Mov–nitrato-complex to produce a geometry suitable for rapid electron transfer resulting in the formation of NO2 and a cis-dioxomolybdenumVI (MoVIO2) complex; (3) ligand substitution(s) at the cis-MoVIO2 centre.
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