Modeling for the Active Site of Sulfite Oxidase: Synthesis, Characterization, and Reactivity of [MoVIO2(mnt)2]2- (mnt2- = 1,2-Dicyanoethylenedithiolate)
The enzyme, hepatic sulfite oxidase, is responsible for the physiologically important oxidation of sulfite to sulfate. 1 This enzyme is dimeric with each monomer containing a single Mo cofactor and a cyt 65-type heme. 2 The conversion of sulfite or bisulfite to sulfate, a two-electron process, is presumed to occur at a Mo (VI) center, with the elements of water being used as the source of the additional oxygen atom of sulfate and the Mo (VI) is reducedto Mo (IV) state in the process l. 2 terminal oxo group appears to be present in the Mo (V) and Mo (IV) states48· 1* of the enzyme. The hydroxo ligand of the Mo (V) species is suggested to be cis tothe terminal oxo group as shown by superhyperflne splitting. 4 No oxomolybdoenzyme has yet been characterized by an X-ray crystal structure determination. However, Rajagopalan and co-workers have proposed a structure for the molybdenum cofactor from variousspectroscopic …
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