Electron-transfer reactions between pentaaquo(organo)chromium(2+) and tris(bipyridyl)ruthenium(3+) ions
The ruthenium complex Ru(bpy)/sub 3//sup 3 +/, generated by laser flash photolysis, reacts with a wide range of (H/sub 2/O)/sub 5/CrR/sup 2 +/ complexes. The first step in the sequence is attributed to the one-electron oxidation of the organochromium cation. This step is accompanied by formation of Ru(bpy)/sub 3//sup 2 +/. The rate constants (i-Pr > Et >> Me) correlate with the ionization potentials of the free radicals R/sup 0/. Values for para-substituted benzylchromium ions follow the Hammett correlation. The immediate product of electron transfer, CrR/sup 3 +/, can undergo homolysis, as found for R = Et by kinetic tests and radical trapping, or in suitably constituted cases it can react by internal electron transfer, e.g., CrCH/sub 2/OCH/sub 3//sup 3 +/ + H/sub 2/O ..-->.. Cr/sup 2 +/ + CH/sub 3/OCH/sub 2/OH + H/sup +/. 33 references, 4 figures.
- Research Organization:
- Iowa State Univ., Ames
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6980535
- Journal Information:
- Inorg. Chem.; (United States), Vol. 25:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIPYRIDINES
ELECTRON TRANSFER
PHOTOCHEMISTRY
CHROMIUM COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RUTHENIUM COMPOUNDS
AQUEOUS SOLUTIONS
EXPERIMENTAL DATA
AZINES
CHEMISTRY
DATA
DISPERSIONS
HETEROCYCLIC COMPOUNDS
INFORMATION
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
REFRACTORY METAL COMPOUNDS
SOLUTIONS
TRANSITION ELEMENT COMPOUNDS
140505* - Solar Energy Conversion- Photochemical
Photobiological
& Thermochemical Conversion- (1980-)
400201 - Chemical & Physicochemical Properties