title: Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex.
abstract: The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
authors.forename: William W Y
authors.initials: WW
authors.lastname: Lam
authors.forename: Wai-Lun
authors.initials: WL
authors.lastname: Man
authors.forename: Yi-Ning
authors.initials: YN
authors.lastname: Wang
authors.forename: Tai-Chu
authors.initials: TC
authors.lastname: Lau
mesh_terms: D001965:Bromides / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry*; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D001965:Bromides; D007454:Iodides; D009942:Organometallic Compounds; D012996:Solutions; D014867:Water; D012428:Ruthenium