Kinetics and mechanism of electron transfer to transition-metal complexes by photochemically produced tris(bipyridyl)ruthenium(1+)ion
Rate constants were determined for the one-electron reduction of Cr(H/sub 2/O)/sub 6//sup 3 +/, several organochromium cations of the family (H/sub 2/O)/sub 5/CrR/sup 2 +/, several substituted pyridine complexes in the series (H/sub 2/O)/sub 5/CrNC/sub 5/H/sub 4/X/sup 3 +/, cobalt(III) amine complexes, and miscellaneous species including Yb/sub aq//sup 3 +/ and (1R,4R,8S,11S)-Ni(tmc)/sub 2//sup +/ (where tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclo-tetradecane). The results are considered in light of the Marcus equation. The data for the pyridine complexes are correlated by the Hammett equation; the reaction constant in comparison with those of other complexes indicates that electron transfer occurs directly to the metal and not, as in certain other instances, by initial reduction of the pyridine ligand bound to chromium. The qualitative differences in rates can be rationalized by a simple MO scheme.
- Research Organization:
- Iowa State Univ., Ames
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5532370
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:13; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
AZINES
BIPYRIDINES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DE-EXCITATION
ELECTRON TRANSFER
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EQUATIONS
EXCITED STATES
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PREDICTION EQUATIONS
PYRIDINES
RADIATIONLESS DECAY
REACTION KINETICS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES