Reactions of an excited state and of carbon- and sulfur-centere radicals with transition metal complexes
The kinetics of the reductive quenching of the {sup 2}E excited state of CrL{sub 3}{sup 3+} (L=2,2{prime}-bipyridine, 1,10-phenanthroline and their substituted analogues) by Ti(3) were investigated at 25{degrees}C in 1.0 M LiCl-HCl. The dependence of the rate on hydrogen ion concentration indicates that both Ti(H{sub 2}O){sub 6}{sup 3+} and (H{sub 2}O){sub 5}Ti(OH){sup 2+} quench. Alkyl radicals, generated from the photohomolysis of organocobalt complexes, were allowed to react in aqueous solution with (H{sub 2}O){sub 2}CrL{sup 2+} (L=1,4,8,11-tetraazacyclopentadecane or [15]aneN{sub 4}). The reaction rates were evaluated by laser flash photolysis, using the known reaction between R* and the methyl viologen radical cation as a kinetic probe. Reactions of thiyl radicals (RS*) have been studied in aqueous solution using laser flash photolysis. One method used in this study involved generating alkyl radicals by photohomolysis of the cobalt-carbon bond in RCo([14]aneN{sub 4}){sup 2+} complexes with visible light. The carbon-centered radicals abstract a hydrogen atom from a thiol to form thiyl radicals. .
- Research Organization:
- Ames Lab., IA (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 10109243
- Report Number(s):
- IS-T-1600; ON: DE92005154
- Resource Relation:
- Other Information: TH: Thesis (Ph.D.); PBD: 3 Dec 1991
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
EXCITED STATES
QUENCHING
TRANSITION ELEMENT COMPLEXES
CHEMICAL REACTIONS
THIYL RADICALS
BIPYRIDINES
PULSED IRRADIATION
TITANIUM IONS
ORGANOMETALLIC COMPOUNDS
CHEMICAL REACTION KINETICS
EQUILIBRIUM
QUANTUM EFFICIENCY
DYE LASERS
EMISSION SPECTROSCOPY
PH VALUE
400201
400500
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES
PHOTOCHEMISTRY