Photolysis of the Cyclooctadienyl Anion

Article abstract of DOI:10.1021/jo00139a006

Visible or long-wavelength ultraviolet excitation of alkali metal salts of cyclooctadiene leads to electron exchange.Primary photoinduced electron transfer has been used to initiate the geometrical isomerization of cis-stilbene and the photosubstitution of aryl halides.Mechanistic details for these reactions are presented.Electron exchange so dominates the excited-state reactivity of this pentadienyl anion that neither potential pericyclic reaction (i.e., electrocyclization or sigmatropic shifts) nor photoinduced cis-trans isomerization can be detected.