title: Water exchange rates in the diruthenium mu-oxo ion cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+).
abstract: Addition of 2 equiv of Ce(4+) to the dimeric ruthenium mu-oxo ion cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+) (formal oxidation state III-III, subsequently denoted [3,3]) or addition of 1 equiv of Ce(4+) to the corresponding [3,4] ion gave near-quantitative conversion to the [4,4] ion, confirming our recent assignment of this oxidation state as an accumulating intermediate during water oxidation by the cis,cis-[(bpy)(2)Ru(O)](2)O(4+) ([5,5]) ion. The rates of water exchange at the cis-aqua positions in the [3,3] and [3,4] ions were investigated by incubating H(2)(18)O-enriched samples in normal water for predetermined times, then oxidizing them to the [5,5] state and measuring by resonance Raman (RR) spectroscopy changes in the magnitudes of the O-isotope sensitive bands at 780 and 818 cm(-1). These bands have been assigned to Ru=(18)O and Ru=(16)O stretching modes, respectively, for ruthenyl bonds formed by deprotonation of the aqua ligands upon oxidation to the [5,5] state. An intermediate accumulated during the course of the isotope exchange reaction that gave a [5,5] ion possessing both approximately 782 and approximately 812 cm(-1) bands; this spectrum was assigned to the mixed-isotope species, (bpy)(2)Ru((16)O)(16)ORu((18)O)(bpy)(2)(4+). Kinetic analysis of solutions at various levels of oxidation indicated that only the [3,3] ion underwent substitution; the exchange rate constant obtained in 0.5 M trifluoromethanesulfonic acid, 23 degrees C, was 7 x 10(-3) s(-1), which is (10(3)-10(5))-fold larger than rate constants measured for anation of monomeric (bpy)(2)Ru(III)X(H(2)O)(3+) ions bearing simple sigma-donor ligands (X).
authors.affiliation: Department of Chemistry, National Defense Academy, 1-10-20 Hashirimizu, Yokosuka, Kanagawa 239, Japan.
authors.forename: H
authors.initials: H
authors.lastname: Yamada
authors.forename: T
authors.initials: T
authors.lastname: Koike
authors.forename: J K
authors.initials: JK
authors.lastname: Hurst
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D002412:Cations; D002563:Cerium / Q000737:chemistry; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D014867:Water / Q000737:chemistry*
chemical_list: D002412:Cations; D009942:Organometallic Compounds; D014867:Water; D002563:Cerium; D015082:2,2'-Dipyridyl; D012428:Ruthenium; D010100:Oxygen