n499947SE Academic Article uri icon


  • Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2-1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

published proceedings

  • J Am Chem Soc

author list (cited authors)

  • Zhukhovitskiy, A. V., Kobylianskii, I. J., Thomas, A. A., Evans, A. M., Delaney, C. P., Flanders, N. C., ... Toste, F. D.

publication date

  • January 1, 2019 11:11 AM