Electrochemistry of carbonyl(fulvalene)dimetal complexes (M/sub 2/ = Cr/sub 2/, Mo/sub 2/, W/sub 2/, Ru/sub 2/, Mo-Ru) in aprotic media
Electrochemical studies were carried out on a series of fulvalene-bridged metal-metal-bonded carbonyl complexes. The compounds are oxidized and reduced in 2e processes. The oxidation process is irreversible on the time scale of the CV experiment. The reduction of the compounds occurs with cleavage of the metal-metal bond in an ECE or ECEC mechanism; the resulting dianion is oxidized at relatively positive potentials to re-form the metal-metal bond. Scan rate and wave shape studies of the chromium and molybdenum dimers were carried out to study the heterogeneous-electron-transfer rates. Computer simulations of cyclic voltammetry data based on the ECE mechanism show that radical-anion intermediates of the homonuclear compounds of disproportionate at a fast rate. The electrochemistry of the products of the reaction of the dichromium and dimolybdenum dimers with I/sub 2/ and the products of the reactions of the diruthenium dimer with I/sub 2/ and Br/sub 2/ was examined. The dichromium diodide and diruthenium dibromide reduce in a 2e process to the metal-metal-bonded dimers, releasing 2 equiv of halide. The dimolybdenum and diruthenium diiodides reduce to unknown products.
- Research Organization:
- Univ. of Texas, Austin
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5455103
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400400* -- Electrochemistry
ANIONS
CARBONYLS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM COMPLEXES
COMPLEXES
DATA
DIMERS
ELECTROCHEMISTRY
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
IONS
KINETICS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
OXIDATION
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
REDUCTION
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
VOLTAMETRY