A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization. Academic Article

abstract

• 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.

authors

• Thomas, Andy

published proceedings

• J Am Chem Soc

altmetric score

• 7.45

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.

citation count

• 20

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

publication date

• January 2019

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• Density Functional Theory
• Methane
• Molecular Structure
• Polymerization

Digital Object Identifier (DOI)

• 10.1021/jacs.9b01532

start page

• 6473

end page

• 6478

volume

• 141

issue

• 16

URL

• http://dx.doi.org/10.1021/jacs.9b01532