The mechanism of the recently reported photocontrolled cationic polymerization of vinyl
ethers was investigated using a variety of catalysts and chain-transfer agents (CTAs) as well
as diverse spectroscopic and electrochemical analytical techniques. Our study revealed a
complex activation step characterized by one-electron oxidation of the CTA. This oxidation is
followed by mesolytic cleavage of the resulting radical cation species, which leads to the
generation of a reactive cation this species initiates the polymerization of the vinyl ether …