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  • Title: Multiple pathways for the oxygenation of a ruthenium(II) dithiocarbamate complex: S-oxygenation and S-extrusion.
    Author: Ng S, Ziller JW, Farmer PJ.
    Journal: Inorg Chem; 2004 Dec 27; 43(26):8301-9. PubMed ID: 15606176.
    Abstract:
    The reactions of Ru(bpy)(2)(N,N-dimethyldithiocarbamate)(+), 1, with O-atom-transfer reagents such as hydrogen peroxide, m-chloroperoxybenzoic acid, and oxone have been studied and several resulting derivatives isolated and structurally characterized. Both S-oxygenation and S-extrusion may occur depending upon reagent and conditions. Excess peroxygenation leads to a stable dioxygenate, Ru(bpy)(2)(N,N-dimethylthiocarbamatesulfinate-S,S)(+), 3. Stoichiometric oxygenation leads to mixtures of products from which two forms of monooxygenated species Ru(bpy)(2)(N,N-dimethylperoxydithiocarbamate-S,S), 2a, and Ru(bpy)(2)(N,N-dimethylperoxydithiocarbamate-O,S), 2b, and an S-extruded product, Ru(bpy)(2)(N,N-dimethylmonothiocarbamate)(+), 4, have been isolated as PF(6)(-) salts. The S,S-bound monooxygenate is unstable over time toward either O-atom-transfer reactions via disproportionation or reaction with phosphines or S-extrusion yielding complex 4 in which the thiocarbamate is bonded solely through the remaining S atom. All the complexes have been characterized by (1)H NMR, UV-vis, and mass spectroscopies, and all but the highly reactive 2a structurally determined by X-ray crystallography.
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