Azidyl radical reactivity. N(sub 6)(super .-) as a kinetic probe for the addition reactions of azidyl radicals with olefins1

Time-resolved UV-vis and infrared laser flash photolysis methods help examine the reactivity of the azidyl radical, N(sub 3)(super .), with olefins, using the pseudohalogen azidyl radical anion N(sub 6)(super.-). The reaction of N(sub 3)(super .) with alkyl olefins does not involve hydrogen atom transfer, suggesting that the reaction proceeds through addition. These addition reactions are controlled by polar effects and are free of steric factors.