Scandium‐Catalyzed Self‐Assisted Polar Co‐monomer Enchainment in Ethylene Polymerization

Direct coordinative copolymerization of ethylene with functionalized co‐monomers is a long‐sought‐after approach to introducing polyolefin functionality. However, functional‐group Lewis basicity typically depresses catalytic activity and co‐monomer incorporation. Finding alternatives to intensively studied group 4 d⁰ and late‐transition‐metal catalysts is crucial to addressing this long‐standing challenge. Shown herein is that mono‐ and binuclear organoscandium complexes with a borate cocatalyst are active for ethylene + amino olefin AO; H₂C=CH(CH₂)_nNR₂] copolymerizations in the absence of a Lewis‐acidic masking reagent. Both activity (up to 4.2×10² kg mol^?1?h^?1> atm^?1>) and AO incorporation (up to 12 % at 0.2 m AO]) are appreciable. Linker‐length‐dependent (n) AO incorporation and mechanistic probes support an unusual functional‐group‐assisted enchainment mechanism. Furthermore, the binuclear catalysts exhibit enhanced AO tolerance and enhanced long chain AO incorporation.