Alkoxy radicals: γ proton hyperfine couplings

Abstract

The relationship between γ proton hyperfine couplings and conformation in alkoxy radicals was investigated. It is shown that large γ proton couplings are present in alkoxy radicals in which significant spin polarization of the C_β–C_γ bonding orbitals is expected. This principle finds application in analyzing the proton hyperfine couplings observed for the alkoxy radical in irradiated deoxycytidine monophosphate. The g tensor and hyperfine coupling tensors which characterize this radical were determined from ESR and ENDOR measurements.