Direct kinetic studies of atom transfer and electron transfer reactions of hydroperoxo and high-valent oxo complexes of chromium.

A macrocyclic hydroperoxo chromium complex reacts with triphenyl phosphine in an acid-catalyzed oxygen-atom transfer reaction, k = 850 M-2 s-1. In a competing process, the hydroperoxo complex is converted to a dioxo chromium(V) species, which reacts with PPh3 by electron transfer, k = 4.4 x 105 M-1 s-1.