Syntheses of Monosubstituted Rhodocenium Derivatives, Monomers, and Polymers

We report the first chemoselective, high yield synthesis of monosubstituted rhodocenium through a “η⁵ → η⁴ → η⁵” strategy detailing sequential nucleophilic addition and endohydride abstraction. Monosubstituted rhodocenium derivatives are then used as versatile synthons for the preparation of the first-ever vinyl monomers that allow controlled polymerizations including ROMP and RAFT, leading to rhodocenium-containing metallopolymers. Exploratory ion-exchange and self-assembly of this new class of polyelectrolytes cultivates the potential of side-chain rhodocenium-containing polymers.