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RESEARCH PRODUCT
Reactivity of Neutral Mo(S2C6H4)3 in Aqueous Media: an Alternative Functional Model of Sulfite Oxidase.
Antonio CervillaFrancisco Pérez PlaMaria PilesElisa Llopissubject
MolybdenumSpectrometry Mass Electrospray IonizationHydrogenSulfite OxidaseKineticsInorganic chemistryWaterchemistry.chemical_elementHydrogen-Ion ConcentrationAdductInorganic ChemistryReaction rateKineticschemistry.chemical_compoundchemistrySulfiteIonic strengthMolybdenumSulfite oxidaseOrganometallic CompoundsSulfitesSulfhydryl CompoundsPhysical and Theoretical ChemistryFuransdescription
The kinetics of the reaction of neutral [Mo(S2C6H4)3] with hydrogen sulfite to produce the anionic Mo(V) complex, [Mo(S2C6H4)3]-, and sulfate have been investigated. It has been shown that [Mo(S2C6H4)3] acts as the electron-proton sink in the oxygenation reaction of HSO3(-) by water. Reaction rates, monitored by UV/vis stopped-flow spectrometry, were studied in THF/water media as a function of the concentration of HSO3(-) and molybdenum complex, pH, ionic strength, and temperature. The reaction exhibits pH-dependent HSO3(-) saturation kinetics, and it is first-order in complex concentration. The kinetic data and MS-ESI spectra are consistent with the formation of [Mo O(S2C6H4)2(S2C6H5)]- (1) adduct as a crucial intermediate that transfers the oxygen atom to HSO3(-) yielding the Mo(V) species quantitatively.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2009-08-01 | Inorganic Chemistry |