Photochemical generation of a primary vinyl cation from (E)-bromostyrene: mechanisms of formation and reaction.

The photochemistry of (E)-bromostyrene was investigated to determine the nature of the product-forming intermediates and to clarify the mechanism of formation of vinylic cations and vinylic radicals. Both a cation- and a radical-derived product are formed, and the ionic origin of the former product is demonstrated by significant scrambling of the label, starting from specifically deuterated (E)-bromostyrene. MO calculations show that the isolated incipient primary vinyl cation is not a metastable species, but that specific interaction with a counterion in combination with a polar environment makes it metastable.