Radiolysis of solutions of diphenyliodonium and triphenylsulfonium hexafluorophosphates in various solvents

The radiolysis of solutions of Ph2IPF6 and Ph3SPF6 was undertaken in various kinds of solvents such as alcohols, ethers, acetone, acetonitrile, and dichloromethane. The salts decompose through one-electron reduction in all of the solvents except dichloromethane. The α-hydroxyalkyl and α-alkoxyalkyl radicals derived from the oxygen-containing solvents are oxidized by Ph2IPF6 to initiate a chain reaction. The kinetic chain length depends on the oxidation potentials of the radicals. In dichloromethane, which is electron scavenger, the decomposition of the salts is much less pronounced than in the other solvents. 41 references, 2 tables, 1 figure