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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)
DOI:https://doi.org/10.1021/j150605a012· OSTI ID:6869080
 [1];
  1. 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