Free radicals in photolysis of mixed phosphonium–iodonium ylides and in their reactions with acetylenes

UV irradiation of mixed phosphonium–iodonium ylide in CH2Cl2 leads to formation of free radicals with lifetimes of a few minutes detected by EPR. In mixtures of ylides with acetylenes, the structure of radicals changes, and their concentration and stability increase. In the presence of acetylenes, the radicals contain ylide and acetylene residues, and their EPR spectra have hyperfine coupling constants typical for 31P nuclei in C-radicals and for 1H nuclei, depending on the acetylene structure. It has been demonstrated that the observed radical products are formed from short-lived primary radicals.