Electrochemical reduction of the cis-dioxo Mo(VI)--catechol complex, MoO 2 (cat) 22-, produces stable mononuclear Mo(V), Mo(IV), and Mo(III) complexes in weakly alkaline aqueous solution. Electrochemistry and spectroscopy are used to characterize these species and the conditions promoting their formation. Their catalytic reactions with several oxo anions are studied. Coordination reactions at sites generated by reductive removal of oxo groups stabilize the reduced monomers and also mediate the redox, spectroscopic, and catalytic properties of the molybdenum center. These results help explain the relationship between molecular structure and redox properties of a mononuclear molybdenum site. These findings are discussed in relation to the behavior of the molybdenum-containing enzymes (xanthine oxidase, sulfite oxidase, and nitrate reductase) that carry out oxygen-atom transfer reactions.'J^he molybdenum-containing enzymes aldehyde oxidase, sulfite oxidase, xanthine oxidase, and nitrate reductase catalyze reactions in which an oxygen atom is added to or removed from the substrate molecule (J, 2). Isolation of a common low-molecular weight cofactor from the last three of these species (3, 4) plus physicochemical studies of the enzymes themselves (5-17) suggest a similar environment for the molybdenum atom in these systems. Important features of the en vironment include mononuclear structure with respect to Mo, oxomolybdenum bonding, predominantly sulfur ligation in the re-0065-2393/82/0201-0709$06.25/0
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