A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization.
- Additional Document Info
- View All
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.
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.
complete list of authors
Zhukhovitskiy, Aleksandr V||Kobylianskii, Ilia J||Thomas, Andy A||Evans, Austin M||Delaney, Connor P||Flanders, Nathan C||Denmark, Scott E||Dichtel, William R||Toste, F Dean