TY - JOUR
T1 - A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization
AU - Zhukhovitskiy, Aleksandr V.
AU - Kobylianskii, Ilia J.
AU - Thomas, Andy A.
AU - Evans, Austin M.
AU - Delaney, Connor P.
AU - Flanders, Nathan C.
AU - Denmark, Scott E.
AU - DIchtel, William R.
AU - Toste, F. Dean
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/4/24
Y1 - 2019/4/24
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.9b01532
DO - 10.1021/jacs.9b01532
M3 - Article
C2 - 30964670
AN - SCOPUS:85064996587
SN - 0002-7863
VL - 141
SP - 6473
EP - 6478
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 16
ER -