Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionation of trans-dioxoruthenium(V)

Journal Article · Wed Jun 20 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00169a027· OSTI ID:6620125

Che, Chiming; Lau, Keung; Lau, Taichu; Poon, Chungkwong ^[1]

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1. Univ. of Hong Kong (Hong Kong)

The kinetics and mechanism of the reduction of trans-(Ru{sup VI}(TMC)(O){sub 2}){sup 2+} to trans(Ru{sup IV}(TMC)O(H{sub 2}O)){sup 2+} (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in aqueous solution by outer-sphere one-electron reductants (R), trans-(Ru{sup VI}(TMC)(O){sub 2}){sup 2+} + 2R + 2H{sup +} {yields} trans-(Ru{sup IV}(TMC)O(H{sub 2}O)){sup 2+} + 2R{sup +}, have been studied. The first step of the reduction is a simple outer-sphere electron-transfer process, trans-(Ru{sup VI}(TMC)(O){sub 2}){sup 2+} + R {yields} trans-(Ru{sub V}(TMC)(O){sub 2}){sup +} + R{sup +} with rate = k{sub 2}(Ru(VI)) (R). The rate constants (k{sub 2}) with cis-(Ru{sup II}(NH{sub 3}){sub 4}bpy){sup 2+} (bpy = 2,2{prime}-bipyridine), (Ru{sup II}(NH{sub 3}){sub 5}isn){sup 2+} (isn = isonicotinamide), and (Ru{sup II}(NH{sub 3}){sub 5}py){sup 2+} (py = pyridine) have been measured and can be correlated with the Marcus cross relation.

• OSTI ID: 6620125
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:13; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
COMPLEXES
DATA
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
REDUCTION
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES