ESR study of dialkyl carbonate radical anions and their thermal and photochemical dissociation in the solid state. [Dimethyl, diethyl, di-n-propyl carbonates]
Journal Article
·
· J. Phys. Chem.; (United States)
- Eckerd Coll., St. Petersburg, FL
Dialkyl carbonate radical anions have been identified by ESR spectroscopy in ..gamma..-irradiated samples of the parent compounds at 77/sup 0/K. The ..cap alpha..-/sup 13/C hyperfine couplings (A/sub double vertical bar/ = 159.5 G, A/sub perpendicular to/ = 127.8 G) for the dimethyl carbonate radical anion were measured with a /sup 13/C-enriched sample, and they show that the radical is pyramidal at the ..cap alpha.. carbon, as expected. Also, comparison with analogous radicals indicates appreciable spin delocalization onto the carbonyl oxygen. These dialkyl carbonate radical anions were found to undergo both a thermal and a photochemical ..beta..-scission reaction to produce the corresponding alkyl radicals. In addition to studies on polycrystalline dimethyl carbonate and diethyl carbonate, polycrystalline and glassy samples of di-n-propyl carbonate were examined, and similar results obtained for all four systems.
- OSTI ID:
- 6869080
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:5; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ANIONS
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBONATES
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
GAMMA RADIATION
HYPERFINE STRUCTURE
INFORMATION
IONIZING RADIATIONS
IONS
ISOTOPES
LIGHT NUCLEI
LOW TEMPERATURE
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESONANCE
STABLE ISOTOPES
400600* -- Radiation Chemistry
ANIONS
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBONATES
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
GAMMA RADIATION
HYPERFINE STRUCTURE
INFORMATION
IONIZING RADIATIONS
IONS
ISOTOPES
LIGHT NUCLEI
LOW TEMPERATURE
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESONANCE
STABLE ISOTOPES