Rearrangement of the 1,1-diphenylethoxyl radical is not concerted but occurs through a bridged intermediate.

Recent experimental observations cast some doubt on the conclusions of earlier work that indicated that the rearrangement of 1,1-diphenylethoxyl radical occurs through a bridged intermediate. We show, by using carefully benchmarked DFT calculations, that the title rearrangement is indeed a two-step reaction.