We developed the highly active catalysis for metal-catalyzed living radical polymerization (Mt-LRP) using ferrocene (FeCp2) as the cocatalyst via 'concerted redox' catalysis in conjunction with Ru main catalyst that is responsible for generating growing radicals. FeCp2 promotes the following key catalytic steps (See the attached illustration): the regeneration of the Ru catalyst through reduction of trivalent forms (XRulll ? Rull; X: halogen) and the halogen-capping reaction by the resultant trivalent ferrocenium halide (FeCp2+X�).The ferrocene-concerted catalysis allowed the synthesis of high MW polymers even with a small amount of a Ru main catalyst (50 ppm for monomer) without any loss of controllability (ref 1). In addition, ferrocene and its derivatives effectively work as cocatalysts for iron (Fe) main catalysts to realize 'all-iron' catalysis. In particular, decamethylferrocene (FeCp*2) in conjunction with FeBr2/n-Bu4NBr led to controlled polymerizations of polar functional methacrylates, such as polyethylene glycol methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA).References:  1) ?ACS Macro Lett.? ?2012  ?, ?1?, 321-323.

Ferrocene-assisted "concerted redox" in living radical polymerization: Active, versatile, and sustainable catalysis

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.