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 - We thank the National Institute of Health (R35 GM118190) for support of this work. A.V.Z. is a Merck Fellow of the Life Sciences Research Foundation. I.J.K. is a Swiss National Science Foundation postdoctoral fellow. A.A.T. is an NIH NRSA fellow (1F32GM125163). A.M.E. is supported by the NSF Graduate Research Fellowship under grant DGE-1324585, the Ryan Fellowship, and the Northwestern University International Institute for Nanotechnology. We thank B. Elling, J. Su, and Prof. Y. Xia at Stanford University for generously facilitating our use of the GPC-MALLS and MALDI-TOF. We thank Z. Zhou and R. Nichiporuk for assistance with HRMS and G. Sethi for assistance with TGA. This work made use of the UC Berkeley Catalysis Center, managed by M. Zhang, the College of Chemistry and QB-3 Institute NMR facilities, the Stanford University Mass Spectrometry facility, and the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. Data was collected using an instrument funded by the National Science Foundation under award no. 0960140. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. DOE under contract DE-AC02-05CH11231. DFT studies were conducted at the Molecular Graphics and Computation Facility, funded by NIH grant S10OD023532.
We thank the National Institute of Health (R35 GM118190) for support of this work. A.V.Z. is a Merck Fellow of the Life Sciences Research Foundation. I.J.K. is a Swiss National Science Foundation postdoctoral fellow. A.A.T. is an NIH NRSA fellow (1F32GM125163). A.M.E. is supported by the NSF Graduate Research Fellowship under grant DGE-1324585, the Ryan Fellowship, and the Northwestern University International Institute for Nanotechnology. We thank B. Elling, J. Su, and Prof. Y. Xia at Stanford University for generously facilitating our use of the GPC-MALLS and MALDI-TOF. We thank Z. Zhou and R. Nichiporuk for assistance with HRMS and G. Sethi for assistance with TGA. This work made use of the UC Berkeley Catalysis Center, managed by M. Zhang, the College of Chemistry and QB-3 Institute NMR facilities, the Stanford University Mass Spectrometry facility, and the DuPont- Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. Data was collected using an instrument funded by the National Science Foundation under award no. 0960140. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. DOE under contract DE-AC02-05CH11231. DFT studies were conducted at the Molecular Graphics and Computation Facility, funded by NIH grant S10OD023532.
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.
UR - https://www.scopus.com/pages/publications/85064996587
UR - https://www.scopus.com/pages/publications/85064996587#tab=citedBy
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 -