title: Solvent effects on the oxidation of RuIV=O to O=RuVI=O by MnO4-. hydrogen-atom versus oxygen-atom transfer.
abstract: The kinetics of the oxidation of trans-[RuIV(tmc)(O)(solv)]2+ to trans-[RuVI(tmc)(O)2]2+ (tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, a tetradentate macrocyclic tertiary amine ligand; solv = H2O or CH3CN) by MnO4- have been studied in aqueous solutions and in acetonitrile. In aqueous solutions the rate law is -d[MnO4]/dt = kH2O[RuIV][MnO4-] = (kx + (ky)/(Ka)[H+])[RuIV][MnO4-], kx = (1.49 +/- 0.09) x 101 M-1 s-1 and ky = (5.72 +/- 0.29) x 104 M-1 s-1 at 298.0 K and I = 0.1 M. The terms kx and ky are proposed to be the rate constants for the oxidation of RuIV by MnO4- and HMnO4, respectively, and Ka is the acid dissociation constant of HMnO4. At [H+] = I = 0.1 M, DeltaH and DeltaS are (9.6 +/- 0.6) kcal mol-1 and -(18 +/- 2) cal mol-1 K-1, respectively. The reaction is much slower in D2O, and the deuterium isotope effects are kx/kxD = 3.5 +/- 0.1 and ky/kyD = 5.0 +/- 0.3. The reaction is also noticeably slower in H218O, and the oxygen isotope effect is kH216O/kH218O = 1.30 +/- 0.07. 18O-labeled studies indicate that the oxygen atom gained by RuIV comes from water and not from KMnO4. These results are consistent with a mechanism that involves initial rate-limiting hydrogen-atom abstraction by MnO4- from coordinated water on RuIV. In acetonitrile the rate law is -d[MnO4-]/dt = kCH3CN[RuIV][MnO4-], kCH3CN = 1.95 +/- 0.08 M-1 s-1 at 298.0 K and I = 0.1 M. DeltaH and DeltaS are (12.0 +/- 0.3) kcal mol-1 and -(17 +/- 1) cal mol-1 K-1, respectively. 18O-labeled studies show that in this case the oxygen atom gained by RuIV comes from MnO4-, consistent with an oxygen-atom transfer mechanism.
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon Tong, Hong Kong.
authors.forename: William W Y
authors.initials: WW
authors.lastname: Lam
authors.forename: Wai-Lun
authors.initials: WL
authors.lastname: Man
authors.forename: Chi-Fai
authors.initials: CF
authors.lastname: Leung
authors.forename: Chun-Yuen
authors.initials: CY
authors.lastname: Wong
authors.forename: Tai-Chu
authors.initials: TC
authors.lastname: Lau
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011196:Potassium Permanganate / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012680:Sensitivity and Specificity; D012997:Solvents / Q000737:chemistry; D013055:Spectrophotometry, Infrared / Q000379:methods; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D012997:Solvents; D011196:Potassium Permanganate; D014867:Water; D012428:Ruthenium; D006859:Hydrogen; D010100:Oxygen