Oxidation of aqueous Ru(bpy) sub 3 sup 2+ by the fluoroxysulfate ion, SO sub 4 F sup minus 1

Journal Article · Wed Aug 23 04:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00316a022· OSTI ID:5053040

Cook, R L; Sullivan, J C; Appelman, E H ^[1]; Woods, M ^[2]

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1. Argonne National Lab., IL (USA)
2. Rosary College, River Forest, IL (USA)

Stopped-flow spectrophotometry has been used to study the oxidation of the substitution-inert Ru(II) complex ion Ru(bpy){sub 3}{sup 2+} by the fluoroxysulfate ion, SO{sub 4}F{sup {minus}}. The reaction follows a bimolecular rate law and has 1:1 stoichiometry. At 13.3{degree}C, corrected to infinite dilution, k{sub 2}{degree} = 1346 {plus minus} 19 M{sup {minus}1} s{sup {minus}1}. Over the temperature range 2-24{degree}C, {Delta}H{sup {double dagger}} = 37.1 {plus minus} 1.1 kJ/mol and {Delta}S{sup {double dagger}} = {minus}55 {plus minus} 4 J/(mol K). The rate and stoichiometry are independent of whether the Ru complex is present as a chloride or a perchlorate salt, and the rate does not show a dependence on acidity. The oxidation of coordinated ligands is probably involved. The reaction is among the fastest reactions of SO{sub 4}F{sup {minus}}. 10 refs., 4 tabs.

• OSTI ID: 5053040
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:17; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
AZINES
BIPYRIDINES
CHARGED PARTICLES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PYRIDINES
REDOX REACTIONS
RUTHENIUM COMPLEXES
SULFATES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES