Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence

A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible‐light irradiation of dimanganese decacarbonyl (Mn 2 (CO) 10 ) in the presence of an alkyl bromide results in the formation of carbon‐centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then...