Structure and water-oxidizing capabilities of dimeric ruthenium EDTA complex ions
Journal Article
·
· Inorganic Chemistry; (USA)
- Oregon Graduate Center, Beaverton (USA)
Low-temperature resonance Raman (RR) spectra of the dimeric Ru{sup III}Ru{sup IV} ion formed by oxidation of Ru(edta)OH{sub 2}{sup {minus}} exhibited a prominent band at 433 cm{sup {minus}1}, which shifted to 431 cm{sup {minus}1} upon substitution of ({sup 18}O)-H{sub 2}O in the primary coordination sphere of the precursor ion. A second band, at 324 cm{sup {minus}1}, underwent a comparable isotope-dependent shift to lower energies. The RR spectra were insensitive to deuterium substitution. These features establish that the dimer is a {mu}-oxo ion, i.e. (Ru(edta)){sub 2}O{sup 3{minus}}; from the magnitude of the isotopic shifts, the Ru-O-Ru angle was estimated to be 165{degree}. The reduction potential for the Ru{sup IV}{sub 2}/Ru{sup III}Ru{sup IV} couple was acid-insensitive over the range pH 2-11, suggesting that the dimer does not contain coordinated H{sub 2}O in either oxidation state. Cyclic voltammographic results in neutral solution suggested that (Ru(edta)){sub 2}O{sup 2{minus}} was unstable with respect to decomposition. A reinvestigation of the water-oxidizing capabilities of this ion by polarographic, gas chromatographic, and mass spectrometric methods failed to reveal O{sub 2} among the gaseous products. Instead, copious quantities of CO{sub 2} were formed, the source of which was coordinated EDTA. 29 refs., 8 figs., 1 tab.
- DOE Contract Number:
- AC06-83ER13111
- OSTI ID:
- 6902109
- Journal Information:
- Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:2; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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OSTI ID:6967741
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Tue Dec 27 23:00:00 EST 1988
· Inorganic Chemistry; (USA)
·
OSTI ID:5447566
The electrocatalytic and stoichiometric oxidation chemistry of binuclear ruthenium complexes incorporating the anionic tripod ligand (([eta][sup 5]-C[sub 5]H[sub 5])Co[P(OCH[sub 3])[sub 2] (=O)][sub 3])[sup [minus]]
Thesis/Dissertation
·
Fri Dec 31 23:00:00 EST 1993
·
OSTI ID:7107403
Related Subjects
10 SYNTHETIC FUELS
100200 -- Synthetic Fuels-- Production-- (1990-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AMINO ACIDS
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHARGED PARTICLES
CHELATING AGENTS
CHEMICAL REACTIONS
COMPLEXES
DATA
EDTA
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDATION
OXYGEN 18
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RUTHENIUM COMPLEXES
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
WATER
100200 -- Synthetic Fuels-- Production-- (1990-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AMINO ACIDS
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHARGED PARTICLES
CHELATING AGENTS
CHEMICAL REACTIONS
COMPLEXES
DATA
EDTA
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDATION
OXYGEN 18
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RUTHENIUM COMPLEXES
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
WATER