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.
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© 2015 American Chemical Society.