Dependence of nonadiabatic intramolecular dissociative electron transfers on stereochemistry and driving force

► We studied intramolecular dissociative electron transfers (DETs). ► The systems were trans(cyclohexane) axial(benzoyloxy)-axial(bromide) molecules. ► DET rates were 1.1 orders of magnitude faster than for the cis equatorial, axial isomers. ► The results are discussed in the framework of the German-Kuznetsov DET theory. ► The outcome is compared with that of other nonadiabatic intramolecular DETs.