Abstract
Two radicals were detected by e.s.r. spectroscopy after exposure of t-butyl chloride (1H and 2H) to γ-rays at 77 K. One, the t-butyl radical, is well known, but the other, Me2Ċ—CH2Cl, probably formed by loss of a methyl hydrogen atom followed by a 1,2-chlorine shift, is novel and shows the following features. These results suggest not only that the radical is locked in a conformation in which maximum overlap between the carbon 2p-orbital of the radical and the C—Cl σ-bond is achieved, but also that considerable distortion involving movement of the chlorine atom towards the radical centre has occurred.

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