title: Electron transfer reactions of peroxydisulfate and fluoroxysulfate reactions with the cyanide complexes M(CN)n4- (M=Fe(II), Ru(II), Os(II), Mo(IV), and W(IV)).
abstract: The stoichiometry and the kinetics of oxidation of the cyanide complexes M(CN)n4- (M = Fe(II), Ru(II), Os(II), Mo(IV), and W(IV)) by the peroxydisulfate ion, S2O8(2-), and by the much more strongly oxidizing fluoroxysulfate ion, SO4F-, were studied in aqueous solutions containing Li+. Reactions of S2O8(2-) with M(CN)n4- are known to be strongly catalyzed by Li+ and other alkali metal ions, and this applies also to the corresponding reactions of SO4F-. The primary reactions of S2O8(2-) and SO4F- have both been found to be one-electron processes in which the equally strong O-O and O-F bonds are broken. The primary reaction of S2O8(2-) consists of a single step yielding M(CN)n3-, SO4-, and SO42-, whereas the primary reaction of SO4F- comprises two parallel one-electron steps, one leading to M(CN)n3-, SO4-, and F- and the other yielding M(CN)n-1(2-), CN-, SO4- and F-. The relationship between the rate constants and the standard free energies of reaction for the Li+-catalyzed reactions of SO4F- and S2O8(2-) with M(CN)n(4-), and for the uncatalyzed reactions of S2O8(2-) with bipyridyl and phenanthroline complexes MLn2+ (M = Fe(II), Ru(II), and Os(II)) studied previously, suggests that the intrinsic barrier for all three sets of reactions is similar, i.e., unaffected by the Li+ catalysis, and that the electron transfer and the breakage of the O-O and O-F bonds are concerted processes.
authors.affiliation: Department of Chemistry, University of Aarhus, DK 8000C, Denmark.
authors.forename: Ulrik
authors.initials: U
authors.lastname: Kläning
authors.forename: Jørgen R
authors.initials: JR
authors.lastname: Byberg
authors.forename: Kim
authors.initials: K
authors.lastname: Daasbjerg
authors.forename: Knud
authors.initials: K
authors.lastname: Sehested
authors.forename: Evan H
authors.initials: EH
authors.lastname: Appelman
mesh_terms: D003486:Cyanides / Q000737:chemistry*; D004583:Electrons; D019216:Metals, Heavy / Q000737:chemistry*; D013431:Sulfates / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D003486:Cyanides; D019216:Metals, Heavy; D013431:Sulfates