Electron Spin Resonance of Some Arylsulfenyl Radicals

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Abstract
Radicals formed by vapor pyrolysis of β, β′ dinaphthyl and diphenyldisulfide have been studied by electron spin resonance. In each case one of the radicals, identified as the arylsulfenyl radical, shows a large g‐value anisotropy in the spectrum. The observed anisotropies are interpreted in terms of the spin—orbit coupling which mixes two states of different orbital angular momentum. The spin densities in one of the states are calculated using a perturbation treatment, according to McLachlan, to allow for the difference in orbitals occupied by different sets of electrons in a nonclosed shell system. The energy differences of the two states are estimated using a molecular orbital approximation. The results indicate that in the ground state of the radical the unpaired electron is localized in a nonbonding orbital of the sulfur.