A theoretical investigation of the structures and properties of peroxyl radicals
- Mount Saint Vincent Univ., Halifax, Nova Scotia (Canada)
- Dalhousie Univ., Halifax, Nova Scotia (Canada)
- Mount Allison Univ., Sackville, New Brunswick (Canada)
As part of a study of the mechanism of the 1,3-migration in allylperoxyl radicals, the equilibrium geometries, dipole moments, charge distributions, spin density distributions, and C-O bond dissociation energies of a variety of peroxyl radicals have been calculated with extended basis sets. It is shown that the effects of electron correlation on the structures of the peroxyl radicals are smaller than in the corresponding peroxides and that electron correlation accounts for about one-half of the C-O bond dissociation energy. The peroxyl radicals are shown to be {pi}-radicals with large dipole moments in the 2.3-2.6 D range. The majority of the negative charge resides on the inner oxygen, while the spin density is higher on the terminal oxygen. The C-O bond dissociation energy decreases with the degree of saturation of the carbon adjacent to the peroxyl group and also when the hydrocarbon radical product is resonance stabilized.
- OSTI ID:
- 6812119
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 112:15; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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