title: Unusual oxidation of phosphines employing water as the oxygen atom source and tris(benzene-1,2-dithiolate)molybdenum(VI) as the oxidant. A functional molybdenum hydroxylase analogue system.
abstract: The kinetics of the reaction of Mo(VI)(S2C6H4)3 with organic phosphines to produce the anionic Mo(V) complex, Mo(V)(S2C6H4)3-, and phosphine oxide have been investigated. Reaction rates, monitored by UV-vis stopped-flow spectrophotometry, were studied in THF/H2O media as a function of the concentration of phosphine, molybdenum complex, pH, and water concentration. The reaction exhibits pH-dependent phosphine saturation kinetics and is first-order in complex concentration. The water concentration strongly enhances the reaction rate, which is consistent with the formation of Mo(VI)(S2C6H4)3(H2O) adduct as a crucial intermediate. The observed pH dependence of the reaction rate would arise from the distribution between acid and basic forms of this adduct. Apparently, the electrophilic attack by the phosphine at the oxygen requires the coordinated water to be in the unprotonated hydroxide form, Mo(VI)(S2C6H4)3(HO)-. This is followed by the concerted abstraction of 2e-, H+ by the Mo(VI) center to give Mo(IV)(S2C6H4)3(2-), H+, and the corresponding phosphine oxide. However, this Mo(IV) complex product is oxidized rapidly to Mo(V)(S2C6H4)3- via comproportionation with unreacted Mo(VI)(S2C6H4)3. The Mo(V) complex thus formed can be oxidized to the starting Mo(VI) complex upon admission of O2. Consequently, Mo(VI)(S2C6H4)3 is a catalyst for the autoxidation of phosphines in the presence of water. Additionally, there was a detectable variation in the reactivity for a series of tertiary phosphines. The rate of Mo(VI) complex reduction increases as does the phosphine basicity: (p-CH3C6H4)3P > (C6H5)3P > (p-ClC6H4)3P. Oxygen isotope tracing confirms that water rather than dioxygen is the source of the oxygen atom which is transferred to the phosphine. Such reactivity parallels oxidase activity of xanthine enzyme with phosphine as oxygen atom acceptor and Mo(VI)(S2C6H4)3 as electron acceptor.
authors.affiliation: ICMUV, P.O. Box 2085, Polígono La Coma, Paterna, Valencia, Spain. Antonio.cervilla@uv.es
authors.forename: Antonio
authors.initials: A
authors.lastname: Cervilla
authors.forename: Francisco
authors.initials: F
authors.lastname: Pérez-Pla
authors.forename: Elisa
authors.initials: E
authors.lastname: Llopis
authors.forename: María
authors.initials: M
authors.lastname: Piles
mesh_terms: D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D008401:Gas Chromatography-Mass Spectrometry; D007700:Kinetics; D006899:Mixed Function Oxygenases / Q000737:chemistry*; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013997:Time Factors; D014867:Water / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D016877:Oxidants; D010720:Phosphines; C519862:tris(benzene-1,2-dithiolate)molybdenum(VI); D014867:Water; D008982:Molybdenum; D006899:Mixed Function Oxygenases; D010100:Oxygen